WO2008062870A1

WO2008062870A1 - Optical guiding member, process for producing the same, optical waveguide and light guide plate

Info

Publication number: WO2008062870A1
Application number: PCT/JP2007/072665
Authority: WO
Inventors: Naoki Ito; Jun Okamoto; Masami Aihara; Yoshie Kamata; Yutaka Mori
Original assignee: Alps Electric Co., Ltd; Mitsubishi Chemical Corporation
Priority date: 2006-11-22
Filing date: 2007-11-22
Publication date: 2008-05-29

Abstract

An optical guiding member that excels in heat resistance, light stability, film forming property, adhesion to substratum and adhesion at lamination plane, and that even when used for a prolonged period of time, is free from cracking, peeling or coloring. The optical guiding member is one comprised of a laminate of two or more layers different from each other in refractive index, wherein at least two layers in contact with each other among the layers satisfy the following requirements that: (1) in the solid Si-nuclear magnetic resonance spectrum, the position and half-width value of peak top be as specified; (2) the silicon content be 10 wt.% or more; (3) the silanol content be in the range of 0.01 to 10 wt.%; and (4) the value of hardness (Shore A) measured by type-A durometer be in the range of 5 to 90.

Description

Specification

Light guide member, method for manufacturing the same, light guide and light guide plate

Technical field

The present invention relates to a novel light guide member, a method for manufacturing the same, and an optical waveguide and a light guide plate. Specifically, the light guide member excellent in heat resistance, light resistance, film formability, adhesion to the substrate and adhesion on the laminated surface, a method for producing the same, and an optical waveguide and a light guide plate including the light guide member About.

Background art

[0002] In recent years, the power of optical communication systems has been remarkable. Especially in optical waveguides for transmitting optical signals used in optical transceiver modules, high productivity, low cost and high quality materials have been developed. Further development is desired. Also, in so-called optical equipment, for example, when displaying a display unit of a display device such as a display, a button part of a facsimile, a telephone, a mobile phone, and other various household appliances, light emitted from a light source is emitted at a desired part. The required level of high quality is also increasing in the light guide plate.

For example, in Cited Document 1, a siloxane polymer having a specific weight-average molecular weight and number-average molecular weight is used for the purpose of providing an optical waveguide having excellent environmental reliability such as a temperature cycle with few cracks. The invention of the optical waveguide used is disclosed.

[0003] On the other hand, in the field of semiconductor light-emitting device materials different from optical waveguides and light-guide plates, for semiconductor light-emitting devices that have a specific structure and physical properties and are highly resistant to ultraviolet rays and heat! A member is disclosed (Cited document 2).

Patent Document 1: Japanese Patent Application Laid-Open No. 2004-91579

Patent Document 2: Pamphlet of International Publication No. 2006/090804

Disclosure of the invention

Problems to be solved by the invention

[0004] However, the conventional conventional light guide member including S et al., Cited reference 1 is hard and brittle, so if it is thickened or a coating is applied to a complicated substrate, it will crack. There were issues such as the occurrence of In addition, conventional light guide members include substrates and film materials that are laminated for moisture-proof purposes. There was a problem of peeling of the coating film because of insufficient adhesiveness. Further, the conventional light guide member has a problem of peeling of the coating film because the adhesion on the laminated surface is not sufficient when layers of different materials are laminated. Furthermore, the light guide member is also required to have heat resistance and light resistance that can be applied for long-term use.

[0005] On the other hand, the applicability to a light guide member used as a laminate such as an optical waveguide or a light guide plate is not predictable, and in particular, coating film peeling due to insufficient adhesion on the laminate surface. Because it is difficult to solve the problem, it is difficult to divert a general compound. Furthermore, there was no special technical motive that could immediately convert the semiconductor light-emitting device member of the cited document 2.

[0006] Also, in recent years, the background of improving the design of mobile phones and home appliances! /, And technology that emits light only in a predetermined area of the aircraft, such as push button and display buttons, is desired! . In particular, the technical value in the field related to the technology for emitting light in a predetermined shape and color in a predetermined region is very high.

However, making the light guide plate free is not desirable from the viewpoint of production technology and cost. In particular, when a free shape and color are required, mass production is not appropriate. Therefore, it is desirable to establish a manufacturing method that can freely design only the light emitting part without changing the shape of the light guide plate. However, with the conventional techniques described in Japanese Patent Laid-Open No. 2003-187624, Japanese Patent Laid-Open No. 2003-281912, Japanese Patent Laid-Open No. 2006-172785, etc., it is difficult to have the above-mentioned demand.

The present invention has been made in view of the above problems. That is, the first object of the present invention is excellent in heat resistance, light resistance, film formability, adhesion to substrates and film materials, and adhesion on the laminated surface, and cracks and peeling even after long-term use. An object of the present invention is to provide a light guide member that does not cause coloring, and an optical waveguide and a light guide plate using the same. In addition, the second object of the present invention is to have flexibility, excellent adhesion to a substrate or a film material, etc., and adhesion on a laminated surface. An object of the present invention is to provide a light guide member that does not occur, and an optical waveguide and a light guide plate using the same. In addition, a third object of the present invention is to provide a light guide member manufacturing method, a light guide member, and a light guide member capable of efficiently transmitting light source light and designing a light guide portion in a free shape and color. Optical waveguide used And it aims at obtaining a light-guide plate.

Means for solving the problem

[0008] The present inventors have found, after intensive studies in order to achieve the above object, a solid Si- nuclear magnetic Co ¹ ¼ (nuclear magnetic resonance:. Hereinafter appropriately referred to as "NMR") Oite to scan Bae Kutonore Polymers that have a specific peak, have a silicon content greater than a specific value, and have a silanol content within a specified range will cause cracks even in thick film parts where the degree of freedom in thick film design is high. As a result, it was found that peeling from the substrate and film material and peeling on the laminated surface was suppressed, and the heat resistance and light resistance were excellent, and the present invention was completed.

That is, the first light guide member of the present invention is a light guide member formed by laminating two or more layers having different refractive indexes, and at least two-layer force of the layers contacting each other. (Claim 1).

(1) In the solid Si-nuclear magnetic resonance spectrum,

(i) The peak top position is in the region of chemical shift-40 ppm or more and Oppm or less, and the peak half-value width is 0.3 ppm or more and 3. Oppm or less, and

(ii) The peak top position is in the region of chemical shift—80 ppm or more—less than 40 ppm, and the peak half-value width is 0.3 ppm or more and 5. Oppm or less.

Has at least one peak selected from the group that also has force.

(2) The content of silicon is 10% by weight or more.

(3) The content of silanol is 0.01% by weight or more and 10% by weight or less.

(4) Hardness measured by Durometer Type A (Shore A) is 5 or more and 90 or less.

[0010] The second light guide member of the present invention is a light guide member formed by laminating two or more layers having different refractive indexes, and at least two-layer force of the layers in contact with each other. (Claim 2).

(5) In the solid Si-nuclear magnetic resonance spectrum,

(i) The peak top position is in the region of chemical shift-40 ppm or more and Oppm or less, and the peak half-value width is 0.5 ppm or more and 3. Oppm or less, and

(ii) The peak top position is in the region of chemical shift—more than 80ppm and less than 40ppm The peak half-value width is 1. Oppm or more and 5. Oppm or less

Has at least one peak selected from the group that also has force.

(2) The content of silicon is 10% by weight or more.

At this time, in the first and second light guide members of the present invention, it is preferable that the refractive index of at least one of the layers in contact with each other is 1.45 or more (claim 3).

The first and second light guide members of the present invention include at least one of the layers in contact with each other.

It is also preferable that the refractive index of one layer is 1.45 or more and the refractive index of at least one other layer is less than 1.45! / ヽ (Claim 4).

[0012] The third light guide member of the present invention is a light guide member formed by laminating two or more layers having different haze values, and at least two-layer force of the layers contacting each other satisfies the following conditions: (Claim 5).

(1) In the solid Si-nuclear magnetic resonance spectrum,

Has at least one peak selected from the group that also has force.

(2) The content of silicon is 10% by weight or more.

[0013] A fourth light guide member of the present invention is a light guide member formed by laminating two or more layers having different haze values, and at least two layer forces of the layers contacting each other satisfy the following conditions: (Claim 6).

(5) In the solid Si-nuclear magnetic resonance spectrum,

Has at least one peak selected from the group that also has force.

(2) The content of silicon is 10% by weight or more.

[0014] A fifth light guide member of the present invention is a light guide member in which two or more layers having different refractive indexes are laminated, and at least one of the layers has the following characteristics and emits light: A light source having a peak dominant wavelength of 5 OOnm or less is provided (claim 7).

(6) Contain polar groups at the interface with other layers.

(7) Hardness of Shore A is 5 or more and 100 or less, or Shore D is 0 or more and 85 or less.

(8) Having a siloxane bond.

[0015] A sixth light guide member of the present invention is a light guide member formed by laminating two or more layers having different refractive indexes, and at least two-layer force of the layers in contact with each other. (Claim 8).

(6) Contain polar groups at the interface with other layers.

(8) Having a siloxane bond.

[0016] A seventh light guide member of the present invention is a light guide member in which two or more layers having different haze values are laminated, and has at least one layer force of the layer, and has the following characteristics, and emits light A light source having a peak main wavelength power of S500 nm or less is provided (claim 9).

(6) Contain polar groups at the interface with other layers.

(8) Having a siloxane bond.

[0017] An eighth light guide member of the present invention is a light guide member formed by laminating two or more layers having different haze values, and at least two-layer force of the layers in contact with each other. (Claim 10).

(6) Contain polar groups at the interface with other layers.

(8) Having a siloxane bond. [0018] In this case, in the eighth light guide member of the present invention, it is preferable that the layer satisfying the above conditions (5) to (8) contains a bull group and / or a hydrosilyl group (claim 11). ).

[0019] In addition, the third, fourth, seventh and eighth light guide members of the present invention preferably have at least one layer force S of the above-mentioned layer, and a ^ 1 value of 50 or more! / ヽ(Claim 12).

[0020] In the first to eighth light guide members of the present invention, it is preferable that at least one of the layers contains inorganic particles (claim 13). At this time, it is preferable that the median particle diameter of the inorganic particles is;! -10 nm! / ヽ (claim 14)

[0021] Further, in the first to eighth light guide members of the present invention, at least one of the layers has a median particle size of 0.

It is preferred that the inorganic particles of 05 to 50 111 are contained, and that the layer and / or at least one other layer contains inorganic particles of a median particle size;! To lOnm! / (Claim 15).

[0022] Further, in the first to eighth light guide members of the present invention, it is preferable that at least one of the layers includes a phosphor! (Claim 16).

[0023] Further, in the first to eighth light guide members of the present invention, it is preferable that an angle formed between the side surface and the laminated surface of the member is 30 degrees or more and 80 degrees or less! Section 17).

[0024] Further, it is preferable that the first to eighth light guide members of the present invention include a boundary portion penetrating at least two of the layers (claim 18).

[0025] A method for producing a light guide member of the present invention is a method for producing a light guide member comprising a light guide layer formed by curing a fluid curable material on a substrate, the method comprising: The method includes a step of providing a weir for partitioning the light guide layer, a step of coating the curable material on the substrate, and a step of curing the curable material (claim 19).

[0026] At this time, the weir is preferably provided by a dispenser (claim 20).

[0027] A ninth light guide member of the present invention is a light guide member including a substrate, a light guide layer, and a weir that partitions the light guide layer, wherein the light guide layer includes a high refractive index layer and A low refractive index layer is provided, and the weir does not have a ridgeline (claim 21).

[0028] At this time, in the ninth light guide member of the present invention, it is preferable that the light guide layer is formed by curing a curable material (claim 22).

[0029] In the ninth light guide member of the present invention, it is preferable that the light guide layer has a scattering layer (claim 23). [0030] In the ninth light guide member of the present invention, it is preferable that the light guide layer has a phosphor-containing layer (claim 24).

[0031] The optical waveguide of the present invention is formed using the first to ninth light guide members of the present invention (claim 25).

[0032] The light guide plate of the present invention is characterized by being formed using the first to ninth light guide members of the present invention (claim 26).

The invention's effect

[0033] In the first to fourth light guide members of the present invention, generation of cracks is suppressed even in the thick film portion where the degree of freedom in designing the film thickness is high, and the peeling from the substrate and the peeling on the laminated surface are suppressed. In addition, it has excellent effects in heat resistance and light resistance. Therefore, the optical waveguide and the light guide plate formed using the first to fourth light guide members of the present invention suppress the generation of cracks even in the thick film portion where the degree of freedom in the film thickness design is high, and the substrate Peeling from the surface and peeling on the laminated surface are suppressed, and the heat resistance and light resistance are excellent.

[0034] The fifth to eighth light guide members of the present invention are flexible, have excellent adhesion at the time of lamination, and can be used for a long period of time! And peeling on the laminated surface are suppressed.

The optical waveguide and the light guide plate formed by using the fifth to eighth light guide members of the present invention can freely set the film thickness to a thin film force and a thin film, and the generation of cracks is suppressed even in long-term use. Peeling from the substrate and peeling on the laminated surface are suppressed.

[0035] According to the manufacturing method of the light guide member of the present invention, and the ninth light guide member of the present invention and the light guide plate using the same, the shape and specification of the light guide member and the light guide plate can be changed. Even if it is not done, the light emitting part can be designed freely.

Brief Description of Drawings

[0036] [Fig. 1] Figs. 1 (a) to 1 (f) are specific examples of the relationship between any two layers constituting the fifth to eighth light guide members of the present invention! /, FIG.

FIG. 2 is a schematic sectional view showing an embodiment of a light guide plate using the first to eighth light guide members of the present invention.

FIG. 3 is a schematic cross section showing an embodiment of a light guide plate using the first to eighth light guide members of the present invention. FIG.

FIG. 4 is a schematic cross-sectional view showing an embodiment of a light guide plate using the first to eighth light guide members of the present invention.

FIG. 5 is a schematic cross-sectional view showing an embodiment of a light guide plate using the first to eighth light guide members of the present invention.

FIG. 6 is a schematic sectional view showing an embodiment of a light guide plate using the first to eighth light guide members of the present invention.

FIG. 7 is a schematic sectional view showing an embodiment of a light guide plate using the first to eighth light guide members of the present invention.

FIG. 8 is a schematic cross-sectional view showing an embodiment of a light guide plate using the first to eighth light guide members of the present invention.

FIG. 9 is a schematic cross-sectional view showing an embodiment of a light guide plate using the first to eighth light guide members of the present invention.

FIG. 10 is a schematic cross-sectional view showing an embodiment of a light guide plate using the first to eighth light guide members of the present invention.

FIG. 11 is a schematic cross-sectional view showing an embodiment of a light guide plate using the first to eighth light guide members of the present invention.

FIG. 12 (a) to FIG. 12 (c) are cross-sectional views schematically showing a method for manufacturing a light guide member as an eleventh embodiment of the present invention.

13] FIG. 13 (a) and FIG. 13 (b) are perspective views schematically showing a weir for explaining an embodiment of the present invention.

14] A schematic cross-sectional view of a light guide member as a twelfth embodiment of the present invention.

15] A schematic cross-sectional view of a light guide member as a thirteenth embodiment of the present invention.

16] A schematic cross-sectional view of a light guide member as a fourteenth embodiment of the present invention.

FIG. 17 is a schematic cross-sectional view of a light guide member as a fifteenth embodiment of the present invention.

18] A schematic cross-sectional view of a light guide member as a sixteenth embodiment of the present invention.

19] A schematic cross-sectional view of a light guide member as a seventeenth embodiment of the present invention.

20] A schematic cross-sectional view of a light guide member according to an eighteenth embodiment of the present invention. FIG. 21 is a schematic cross-sectional view of a light guide member as a nineteenth embodiment of the present invention.

FIG. 22 is a schematic cross-sectional view of a light guide member as a twentieth embodiment of the present invention.

FIG. 23 is a schematic cross-sectional view of a light guide member as a twenty-first embodiment of the present invention.

FIG. 24 is a schematic cross-sectional view of a light guide member as a 22nd embodiment of the present invention.

FIG. 25 is a schematic cross-sectional view of a light guide member as a 23rd embodiment of the present invention.

FIG. 26 is a schematic cross-sectional view of a light guide member as a 24th embodiment of the present invention.

FIG. 27 is a schematic cross-sectional view of a light guide member as a 25th embodiment of the present invention.

FIG. 28 is a schematic cross-sectional view of a light guide member as a 26th embodiment of the present invention.

FIG. 29 is a schematic cross-sectional view of the light-emitting device fabricated in Example C-15 of the present invention. Explanation of symbols

1 Board

1H, 5H hole

2 Semiconductor light emitting device

3 Sealing material

4 Semiconductor light emitting device

5 Low refractive index layer

5a Low refractive index part

6 High refractive index layer

6a High refractive index part

7 Light scattering layer and / or phosphor-containing layer

8 Light guide member (light guide plate)

9 Angle formed by the side surface of the light guide member and the laminated surface

10 High refractive index part and / or low refractive index part (boundary part)

11 Reflective layer

21 Board

22 Semiconductor light emitting devices

23 Encapsulant

24 Semiconductor light emitting device 25 weir

26 High refractive index layer

27 Light guide member

28 Low refractive index layer

29 Scattering layer and / or phosphor-containing layer

30 Reflective layer

21H recess

28H, 30H hole

BEST MODE FOR CARRYING OUT THE INVENTION

[0038] Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made without departing from the scope of the invention.

[0039] [A] Description of the first to fourth light guide members

[A-1] Properties of layers constituting light guide member

The first to fourth light guide members of the present invention are characterized in that two or more layers are laminated.

. And in the first to fourth light guide members of the present invention, among the stacked layers,

At least two layers in contact with each other have the following characteristics. Above all, it is preferable that the above-mentioned laminated layer has the following characteristics as V and deviation! /.

That is, in the first and third light guide members of the present invention, at least two layers in contact with each other among the layers constituting the light guide member have the following characteristics (1) to (4).

Characteristics (1) In solid Si-nuclear magnetic resonance spectrum,

Has at least one peak selected from the group that also has force.

Characteristic (2) The content of silicon is 10% by weight or more.

Characteristic (3) Silanol content is 0.01 wt% or more and 10 wt% or less. Characteristics (4) Hardness measured by Durometer Type A (Shore A) is 5 or more and 90 or less.

[0041] Further, of the layers constituting the second and fourth light guide members of the present invention, at least two layers in contact with each other have the above characteristics (2) (3) and the following characteristics (5). Have.

Characteristics (5) In solid Si nuclear magnetic resonance spectrum! /,

(ii) The peak top position is in the region where the chemical shift is 80 ppm or more and less than 40 ppm, and the peak half-value width is 1. Oppm or more and 5. Oppm or less

Has at least one peak selected from the group that also has force.

[0042] Hereinafter, of these layers (1) to (5), among the layers constituting the first to fourth light guide members of the present invention, a layer having the above-described characteristics (hereinafter referred to as appropriate). Explain the characteristics of “Specific layer A”).

[0043] [A— 1 1] Characteristics (1) and (5): Solid Si nuclear magnetic resonance spectra

The specific layer A according to the present invention satisfies the characteristics (1) or (5). That is, the specific layer A according to the present invention is formed of a material that satisfies the above characteristic (1) or (5). These materials are usually compounds having a main component of key or a composition containing the compound. The compound whose main component is Ca is expressed by the SiO 2 · ηΗ 2 示 formula, but structurally,

In addition, an oxygen atom ο is bonded to each vertex of the tetrahedron of the key atom Si, and a key atom Si is further bonded to these oxygen atoms o to have a net-like structure. The schematic diagram shown below shows the net structure of Si o ignoring the tetrahedral structure described above, but in the repeating unit of Si—O—Si o, some of the oxygen atoms o are others. Some of them are substituted with a member of (for example, H, -CH, etc.).

Three

As shown in (A) of the schematic diagram, ^four atom atoms Si (Q ⁴ ) with OSi, and as shown in the schematic diagram (B), three atom atoms Si (with OSi Si ( Q ³ ) etc. exist. In the solid Si nuclear magnetic resonance spectrum (solid Si-NMR spectrum) measurement, the peaks based on each of the above silicon atoms Si are sequentially called Q ⁴ peak, Q ³ peak,.

[0044] [Chemical 1] (A) (B)

OH

o s— I

-Si- 0 Si i I I

0 Si.

-S i- O― Si- 0― S i-

!

o

0

I

Si I

-Si-

[0045] These key atoms in which four oxygen atoms are bonded are generally referred to as Q sites. In the present invention, each Q ° Q ⁴ peak derived from the Q site is referred to as a Q ⁿ peak group. The Q ⁿ peak group of silica films that do not contain organic substituents is usually observed as multi-peaks that are continuous in the region of chemical shift – 80–130 ppm.

On the other hand, a C atom with three oxygen atoms and one other atom (usually carbon) is generally called a T site. The peaks derived from the T site are observed as T ° T ³ peaks, as in the Q site. In the present invention, each peak derived from the Τ site is referred to as Τ ^η peak group. Τ The ^η peak group is generally observed as a multimodal peak in the higher magnetic field side (usually chemical shift – 80 to 40 ppm) than the Q ⁿ peak group.

[0046] Further, a key atom in which two oxygen atoms are bonded and two other atoms (usually carbon) are bonded is generally referred to as a D site. The peaks originating from the D site are also observed as D ° D ⁿ peaks (D ⁿ peak groups), as well as the peak groups originating from the Q site and T site, and are further observed from the Q ⁿ and T ⁿ peak groups. It is observed as a multi-modal peak in the high magnetic field region (normally chemical shift 0 40 ppm region). The ratio of the area of each peak group of D ⁿ T ⁿ Q ⁿ is equal to the molar ratio of the key atoms in the environment corresponding to each peak group. In terms of molar amount, the total area of the D ⁿ peak group and the T ⁿ peak group usually corresponds to the molar amount of all the atoms bonded directly to carbon atoms. [0047] When the solid Si-NMR spectrum of the specific layer A of the first to fourth light guide members of the present invention is measured, a group of D ⁿ peaks derived from a silicon atom to which a carbon atom of an organic group is directly bonded. And the T ⁿ peak group and the Q ⁿ peak group and the force S derived from the C atom that is not bonded to the carbon atom of the organic group, appear in different regions. Of these peaks, peaks below 80 ppm correspond to Q ⁿ peaks as described above, and peaks above 80 ppm correspond to D ⁿ and T ⁿ peaks. In the specific layer A, the Q ⁿ peak is not essential, but at least one, preferably a plurality of peaks are observed in the D ⁿ and T ⁿ peak regions.

[0048] The chemical shift value of the specific layer can be calculated based on the results obtained by performing solid Si-NMR measurement using the method described later in the description of Examples, for example! it can. In addition, analysis of measurement data (half-width or silanol content analysis) is performed by dividing and extracting each peak by, for example, waveform separation analysis using a Gaussian function or a mouth-lentz function.

[0049] In the first to fourth light guide members of the present invention, the specific layer A is hardened without cracks even in the thick film portion, and has excellent adhesion to the substrate and the laminated surface between the layers. 'The above-mentioned characteristics (1) or (5) are desirable for exhibiting excellent characteristics when it is possible to obtain a cured product with excellent heat resistance. The reason is not clear. ! / Is estimated as follows.

As a method for obtaining a light guide member made of inorganic glass, a melting method in which low melting point glass is melted and sealed, and a solution obtained by hydrolyzing and polycondensing alkoxysilane or the like at a relatively low temperature is applied and dried and cured. There is a sol-gel method. Of these, the member obtained from the melting method is mainly a force S in which only the Qn peak is observed, a high temperature of at least 350 ° C is required for melting, and the light guide member is thermally deteriorated. .

[0050] On the other hand, hydrolysis' polycondensation products obtained from tetrafunctional silane compounds in the sol-gel method become completely inorganic glass and are extremely excellent in heat resistance and weather resistance. (Dehydration / dealcoholation) The cross-linking proceeds by the reaction, resulting in weight reduction and volume shrinkage due to dehydration. For this reason, ^{if the} raw material is composed only of tetrafunctional silane having a ^Qn peak, the degree of cure shrinkage becomes too large, cracks are likely to occur in the film, and it becomes impossible to increase the film thickness. In such systems, attempts have been made to increase film thickness by adding inorganic particles as aggregates or by overcoating. The limit film thickness is about m. When sol-gel glass is used as the light guide member, there is a problem that a sufficient film thickness must be secured because it is applied to a substrate having a complicated shape. In addition, as described above, in order to sufficiently reduce the residual silanol and obtain a completely inorganic glass, heating at a high temperature of 400 ° C. or more is required, and the peripheral members including the substrate are thermally deteriorated. It was not.

[0051] On the other hand, in the first to fourth light guide members of the present invention, in the specific layer A, a trifunctional having a ^Tn peak is used to adjust the crosslinking density and to make the film flexible. By introducing silane and / or a bifunctional silane having a D η peak and simultaneously carrying out hydrolysis and polycondensation, the volume reduction due to dehydrocondensation and the crosslinking density can be reduced appropriately within a range that does not hinder the function. By controlling the hydrolysis / condensation process and the drying process, it is possible to obtain a transparent glass film-like member having a film thickness of 1000 m. Therefore, in the present invention, the presence of a T ⁿ peak and / or a D ⁿ peak observed at 80 ppm or more is essential.

[0052] As described above, as a method for thickening a bifunctional or trifunctional raw material as a main component, for example, a technique of hard coat film technology such as glasses is known. is there. Since these hard coat films are thin, solvent volatilization is easy and uniform curing is possible. Differences in adhesion to the base material and linear expansion coefficient were the main causes of cracks. In contrast, in the first to fourth light guide members of the present invention having flexibility, since the film thickness is as large as the paint, the film itself has a certain degree of strength, and there is a slight difference in the linear expansion coefficient. Absorbable. If such a film is not flexible, the generation of internal stress, which is different from the case of a thin film, becomes a new problem due to volume reduction by solvent drying. That is, when molding into a deep container with a small opening area such as an LED cup, if the heat curing is performed in a state where the drying in the deep part of the film is insufficient, the solvent volatilization occurs after crosslinking and the volume is reduced. Causes surface roughness such as cracks, foam, and yuzu skin. Such a film has a large internal stress. When solid-state NMR of this film is measured, the detected D ⁿ , T ⁿ , and Q ⁿ peak groups have a siloxane bond angle that is smaller than when the internal stress is small. Distribution, each with a broader peak. This fact means that the bond angle expressed by two OSi with respect to Si has a large strain. That is, even in the case of a film made of the same raw material, as the specific layer A in the first to fourth light guide members of the present invention is smaller, the lower the half width of these peaks, the lower the As the rack rises, it becomes a high quality film.

[0053] Incidentally, a phenomenon in which the half width is increased in response to strain, every case! / The constraints of molecular motion of Si atoms, but the size! /, More than is sensitively observed, its appears Ease rather D ⁿ T ⁿ becomes Q ⁿ .

In the present invention, the half-value width of the peak observed in the region of -80 ppm or higher is smaller than the half-value width range of the light guide member known so far by the Solgenole method (narrow! /,). Features.

[0054] When organized by chemical shift, in the first and third light guide members of the present invention, the half-width of the T ⁿ peak group in which the peak top position is observed at −80 ppm or more and less than 40 ppm is usually 5 Oppm or less, preferably 4. Oppm or less, usually 0.3 ppm or more, and preferably 0.5 ppm or more (characteristic (1)).

In the second and fourth light guide members of the present invention, the half width of the T ⁿ peak group observed at a peak top position of 80 ppm or more and less than 40 ppm is usually 5. Oppm or less, preferably 4. Oppm or less, and usually 1. Oppm or more, preferably 1.5 ppm or more (Characteristic (5)).

[0055] Similarly, in the first and third guide members of the present invention, the half width of D ⁿ peak group the position of the peak top is observed below 4 Oppm above Oppm is small fry constraints of molecular motion T ⁿ sag lower than the one peak group usually 3. Oppm following general, preferably 2. Opp m or less, and the scope of the above normal 0. 3 ppm (characteristic (1)) to.

In addition, in the second and fourth light guide members of the present invention, the half-value width of the D ⁿ peak group in which the peak top position is observed at 40 ppm or more and Oppm or less is because the constraint of molecular motion is small! / ヽUsually sag lower than the one of T ⁿ peak group 3. Oppm following general, preferably 2. Oppm below, and the scope of the above normal 0. 5 ppm (characteristic (5)).

[0056] If the half-value width of the peak observed in the chemical shift region is larger than the above range, the molecular motion is constrained and the strain is large, resulting in cracks and from the coated substrate. As soon as peeling occurs, it may become a member with poor heat resistance and weather resistance. For example, when a large amount of tetrafunctional silane is used, or when a large internal stress is accumulated by rapid drying in the drying process, the full width at half maximum is larger than the above range.

[0057] If the peak half-value width is smaller than the above range! /, The Si atoms in the environment It will be not involved in hexane crosslinking, for example example only D ² peak of crosslinking portion is formed by Si- c binding dimethyl siloxane chain as a silicone resin is observed and, trifunctional silane-residual uncrosslinked state For example, there is a possibility that the material is inferior in heat resistance and weather resistance to a material formed mainly of a siloxane bond.

[0058] Further, as described above, in the solid Si-nuclear magnetic resonance spectrum of the specific layer A of the first to fourth light guide members of the present invention, at least one in the D ⁿ and T ⁿ peak regions, preferably Multiple peaks are observed. Therefore, the solid Si nuclear magnetic resonance spectrum of the specific layer of the first to fourth light guide members of the present invention is selected from the group consisting of the D ⁿ peak group and the T ⁿ peak group having a half-value width in the above-described range. It is desirable to have at least one peak, preferably two or more peaks.

[0059] [Α— 1 2] Characteristic (2): Key content

The specific layer of the first to fourth light guide members of the present invention must have a key content of 10% by weight or more (characteristic (2)). That is, the specific layer A according to the present invention must have a silicon content of 10% by weight or more of the material forming the specific layer A.

The basic skeleton of the specific layer A of the first to fourth light guide members of the present invention is the same inorganic siloxane bond as glass (silicate glass). As is apparent from the chemical bond comparison table shown in Table 1 below, this siloxane bond has the following excellent characteristics as a light guide member.

(I) Thermal decomposition with large binding energy · Light resistance is good because photodegradation is difficult.

(II) It is slightly polarized electrically.

(III) The degree of freedom of the chain structure is large and a flexible structure is possible, and the chain structure can freely rotate around the center of the siloxane chain.

(IV) The degree of oxidation is large and no further oxidation occurs.

(V) Excellent electrical insulation.

[0060] [Table 1] Table] Table 1 Chemical Bond Comparison Table

[0061] From these characteristics, the specific layer A, which is a silicone-based layer formed of a skeleton in which siloxane bonds are bonded three-dimensionally and with a high degree of cross-linking, uses other materials such as epoxy resin V, Unlike layers, it is close to inorganic substances such as glass or rock, and it can be understood that it becomes a protective film with high heat resistance and light resistance. In particular, the specific layer A having a methyl group as a substituent does not absorb in the ultraviolet region, and therefore is excellent in light resistance in which photolysis is difficult to occur.

[0062] The key layer content of the specific layer A of the first to fourth light guide members of the present invention is not less than 10% by weight as described above. Usually 20 weights as it is not necessary to contain the ingredients necessary for refractive index. / Is ₀ or more, among them preferably at least 25 wt%, more preferably 30 weight ^_0/0 above. On the other hand, the upper limit is usually 47% for the reason that the silicon content of the glass composed only of SiO is 47% by weight. / ₀ or less.

[0063] It should be noted that the content ratio of the specific layer A of the first to fourth light guide members of the present invention is determined by, for example, inductively coupled high-frequency plasma spectroscopy using a method described later in the description of the embodiments. Plasma spectrometry: hereinafter abbreviated as “ICP” where appropriate.) Analysis can be performed and calculated based on the results.

[0064] [Measurement of content of key element]

Grind the specific cured material of the specific layer A of the light guide member to about 100 m, in a platinum crucible in air, 450 ° C for 1 hour, then 750 ° C for 1 hour, and 950 ° C for 1.5 hours. After holding and firing to remove the carbon component, add 10 times or more of sodium carbonate to a small amount of the obtained residue, heat with a burner to melt, cool this, add demineralized water, and then add pH with hydrochloric acid. Adjust to a neutral level and adjust the volume to about several ppm as a key element, and perform ICP analysis.

[0065] [A- 1 3] Property (3): Silanol content

The specific layer A of the first to fourth light guide members of the present invention usually has a silanol content of 0.01. % By weight or more, preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and usually 10% by weight or less, preferably 8% by weight or less, more preferably 6% by weight or less. (Characteristic (3)). That is, in the specific layer A according to the present invention, the silanol content of the material forming the specific layer A is in the above range.

[0066] Usually, a glass body obtained by a sol-gel method using alkoxysilane as a raw material is 150 ° C,

Under moderate curing conditions of about 3 hours, a certain amount of silanol remains without being completely polymerized into an oxide. A glass body obtained only from tetraalkoxysilane has high hardness and high light resistance. However, since the degree of crosslinking is high, the degree of freedom of molecular chains is small, and complete condensation does not occur, so the amount of residual silanol is large. In addition, when the hydrolysis / condensation liquid is dried and cured, there are many cross-linking points, so that the thickening is fast and drying and curing proceed at the same time, resulting in a distorted Balta body. When such a member is used as a light guide member, new internal stresses are generated due to condensation of residual styrene during long-term use, and defects such as cracks, peeling, and disconnection are likely to occur. In addition, the fracture surface of the member has more silanol and less moisture permeability, but it has high surface hygroscopicity and is likely to invade water! /. It is possible to reduce the silanol content by high-temperature firing at 400 ° C or higher, but the heat resistance of the light guide member is almost 260 ° C or lower, which is not realistic.

[0067] On the other hand, the first to fourth light guide members of the present invention have a low silanol content in the specific layer A! /, And therefore have excellent long-term performance stability with little change over time. Low! / Excellent performance. However, since the member or layer containing no silanol is inferior in the adhesion to the substrate or the adhesion on the laminated surface when the light guide member is a laminate, the silanol content is optimal as described above in the present invention. Range exists.

[0068] In the first to fourth light guide members of the present invention, since the specific layer A contains an appropriate amount of silanol, silanol is hydrogen bonded to the polar portion present on the substrate or the laminated surface of each layer. , Adhesion is developed. Examples of the polar part include hydroxyl group and metalloxane-bonded oxygen.

The silanol content of the specific layer A of the first to fourth light guide members of the present invention is, for example, measured by a solid Si-NMR spectrum using the method described below, and derived from silanol with respect to the total peak area. From the ratio of peak area, silanol in all the key atoms Obtain the ratio ratio ((%%)) of the key element and the atomic ratio of the content of the key element that was analyzed separately. This is where you can compare the comparison here and the comparison here. .

[[00006699]] Nana, any Aerosilojiru, such as any non-inorganic inorganic particles containing Sishiraran noorru. Depending on the specific fixed layer AA may contain Sishiraranol, but it may be a force SS, or it may be a special fixed layer. As a part of the bone skeleton case, the compound compound strength SS, which forms the main body, forms the layer AA. It's a good idea to have Sicilara nonor contained here. .

[[00007700]] [[Solid Solid SSii——Calculation of NNMMRR Spectral Measurement and Calculation of the Content Ratio of Sicilanolol]]

In the present invention, the first to fourth to fourth specific light guide members of the light guide and light guide member are fixed solid layers AA, solid solid SSii——NNMMRR spectrum If you are going to perform a solid-state SSii——NNMMRR spectrum measurement and data analysis under the following conditions: I'll do it. . Next, according to the ratio of the ratio of the total area of the pipi-keke surface area to the total area of the pi-ke-keo surface area to the total area of the pi-keke surface area, The ratio ratio ((%%)) of the key element that is the silarananol of the middle is determined and analyzed separately. The content ratio of sishiraranol content can be determined by comparing with the content ratio of the key element. .

[[00007711]] It should be noted that the analysis of measurement measurement data ((Sicilara nolanol amount analysis)) is, for example, a Gagarous function number This is a method of extracting and extracting each piper cake by dividing and dividing each waveform by using waveform function separation / disassembly analysis using function functions. Let ’s go. . [[Examples of equipment placement conditions]]

Instrumentation equipment :: CChheemmaaggnneettiiccss, Inc. IInnffiinniittyy CCMMXX——440000 Nuclear magnetic resonance resonance instrumentation equipment

² ²⁹⁹ SSii co-resonant ring frequency frequency: 7799 .. 443366MMHHzz

Prolo Robe :: 77 .. 55mmmm φφ Propro Robe for CCPP // MMAASS

Measurement constant temperature temperature :: Room temperature

Number of rotations of sample material rotation: 44kkHHzz

Measurement measurement method :: Shishingugururupaparurusu method

Ye ^^ 11 dekakappupuriringu frequency frequency :: 5500kkHHzz

² ²⁹⁹ SSii Flip Lip Angle :: 9900 °°

² ²⁹⁹ SSii9900 ° Papallusus width :: 55 .. OO ^^ ss

Repeat time time :: 660000ss

Number of product integration operations :: 112288 times

Observation width: 3300kkHHzz

Base Standard Semi-Sample Material :: Solid Solid SSii—— NNMMRR Base Standard Semi-Material for Didimethicyl Lucilirico Corngoum ((Polyrigidimemethylicyl Lucirochiroki) Sun)

[Example of data processing]

With respect to the specific layer A of the first to fourth light guide members of the present invention, 512 points are taken as measurement data, zero-filled to 8192 points, and Fourier transformed.

[Example of waveform separation analysis]

For each peak of the spectrum after Fourier transform, optimization calculation is performed by nonlinear least square method with the center position, height, and half width of the peak shape created by Lorentz waveform and Gaussian waveform or a mixture of both as variable parameters. Do.

For peak identification, refer to AIChE Journal, 44 (5), p. 1141, 1998, etc.

[0074] The silanol content of the specific layer A of the first to fourth light guide members of the present invention can also be determined by the following IR measurement. Here, IR measurement is easy to identify the silanol peak, but the shape of the peak is broad, the area error occurs, and it is necessary to accurately prepare a sample with a fixed film thickness for the quantitative work immediately. Therefore, it is preferable to use solid-state Si-NMR for strict quantification. When measuring the amount of silanol using solid-state Si-NMR, if the amount of silanol is very small and difficult to detect, if multiple peaks overlap and it is difficult to isolate the silanol peak, an unknown sample If the chemical shift of the silanol peak is unknown, the concentration of silanol can be determined by complementary IR measurement.

[Calculation of silanol content by IR measurement]

'Fourier Transform Inirared Spectroscopy

• Equipment: Thermo Electron NEXUS 670 and Nic—Plan

'Resolution: 4cm— ¹

• Total number of times: 64

'Purge: N

2

Measurement example: A thin film sample with a film thickness of 200 11 m is coated on a Si wafer, and the infrared absorption spectrum of each Si wafer is measured by the transmission method to determine the total silanol peak area of wave numbers SYSlcnT ¹ and SYOlcnT ¹ . On the other hand, trimethylsilanol is anhydrous as a known concentration sample. It is possible to measure the infrared absorption spectrum by the transmission method using a liquid cell with an optical path length of 200 m after diluting in carbon tetrachloride and calculating the silanol concentration by comparing the peak area ratio with the actual sample. . In addition, in the infrared absorption spectrum, the peak derived from the sample adsorbed water is detected as the background of the silanol peak, so the sample thin film must be heated at 150 ° C for 20 minutes or more at normal pressure before measurement, Remove adsorbed water by vacuuming for 10 minutes or longer.

[0076] [A-1 -4] Characteristics (4): Hardness measurement

The hardness measurement value is an index for evaluating the hardness of the specific layer A of the first to fourth light guide members of the present invention, and is measured by the following hardness measurement method.

The specific layer A of the first to fourth light guide members of the present invention is preferably a member exhibiting an elastomeric shape. That is, the first to fourth light guide members of the present invention are forces that normally use a plurality of members having different thermal expansion coefficients in the substrate or each layer. As described above, the specific layer A is an elastomer. By exhibiting the shape, the first to fourth light guide members of the present invention using the specific layer A and the specific layer A can relieve stress due to expansion and contraction of the respective parts. Therefore, it is possible to provide a light guide member that is excellent in reflow resistance and temperature cycle resistance, which is difficult to cause peeling, cracking, and disconnection during use.

[0077] Specifically, the specific layer A of the first to fourth light guide members of the present invention has a hardness measurement value (Shore A) by durometer type A of usually 5 or more, preferably 7 or more, more preferably Is 10 or more, and usually 90 or less, preferably 80 or less, more preferably 70 or less (characteristic (4)). By having the hardness measurement value in the above range, the first to fourth light guide members of the present invention using the specific layer A and the specific layer A are resistant to reflow resistance and temperature cycle resistance. It is possible to obtain the advantage of superiority.

[Hardness measurement method]

The hardness measurement value (Shore A) can be measured by the method described in JIS K6253. Specifically, measurement can be performed using an A-type rubber hardness meter manufactured by Furusato Seiki Seisakusho.

[0079] [A— 1 5] Other physical properties

The specific layer A of the first to fourth light guide members of the present invention is mainly characterized by the above characteristics. In addition, it is preferable to have the following structure and properties.

[0080] [A 1 5— 1] Light transmittance

The specific layer A of the first to fourth light guide members of the present invention emits light from the light source with a film thickness of lmm when a semiconductor light emitting device or the like is used as a light source for an optical waveguide or a light guide plate. It is preferable that the light transmittance (transmittance) at a wavelength is usually 80% or more, particularly 85% or more, and more preferably 90% or more! /. When the specific layer A is used as a light-transmitting part in the light guide member, if the transparency of the light-transmitting part is low, the luminance of the light source using the light-transmitting part is reduced. Or it becomes difficult to obtain final products, such as a light-guide plate.

Here, the “emission wavelength of the light source”, for example, in the case of a semiconductor light emitting device, the value varies depending on the type, but is generally 300 nm or more, preferably 350 nm or more, and usually 900 nm. Hereinafter, the wavelength is preferably in the range of 500 nm or less. If the light transmittance at a wavelength in this range is low, the specific layer A absorbs light, and the light extraction efficiency decreases, making it impossible to obtain a high-intensity optical waveguide or light guide plate. Furthermore, the energy corresponding to the decrease in light extraction efficiency is changed to heat, which causes thermal deterioration of the optical waveguide or the light guide plate.

[0082] In the ultraviolet to blue region (300 nm to 500 nm), the optical material is susceptible to light degradation. Therefore, if the specific layer A having excellent durability is used as a light source having an emission wavelength in this region, the optical material Since an effect becomes large, it is preferable.

The light transmittance of the optical material such as the material of the specific layer A is measured with an ultraviolet spectrophotometer using a sample of a single cured film having a smooth surface molded to a film thickness of 1 mm, for example, by the following method. I can do that.

[0083] [Measurement of transmittance]

Using an ultraviolet spectrophotometer (Shimadzu Corporation UV-3100) using a single-cured film with a smooth surface with a thickness of about lmm that is free from scattering due to scratches and unevenness of the optical material, the wavelength is between 200 nm and 800 nm. ! /, Measure the light transmittance.

[0084] [A— 1 5— 2] Peak area ratio

The specific layer A of the first to fourth light guide members of the present invention preferably satisfies the following conditions. That is, the specific layer A of the first to fourth light guide members of the present invention is the solid Si nuclear magnetism described above. In the resonance spectrum, the ratio of (total area of peaks with chemical shift of 40 ppm or more and Oppm or less) / (total area of peaks with chemical shift of less than 40 ppm) (hereinafter referred to as “peak area ratio according to the present invention” as appropriate) is usually It is preferably 3 or more, preferably 5 or more, more preferably 10 or more, and usually 200 or less, preferably 100 or less, more preferably 50 or less.

[0085] The power of the present invention and the peak area ratio within the above range are that the specific layer A of the first to fourth light guide members of the present invention is difunctional silane, trifunctional silane or tetrafunctional. This indicates that it has more than trifunctional or higher silanes such as silane. As described above, the presence of many silanes having two or less functional groups makes it possible for the specific layer A to exhibit an elastomeric shape and to relieve stress.

However, the specific layer A may exhibit an elastomeric shape even if it does not satisfy the above-described conditions regarding the peak area ratio, which is a force of the present invention. For example, this is the case when the specific layer A is produced using a coupling agent such as an alkoxide of a metal other than silicon as a crosslinking agent. The method for causing the specific layer A to exhibit an elastomeric shape is arbitrary, and is not limited to the above-mentioned conditions!

[0086] [A— 1 5— 3] Functional group

The specific layer A of the first to fourth light guide members of the present invention includes a predetermined functional group (for example, hydroxyl group, oxygen in a metalloxane bond, etc.) present on the surface of a resin such as polyphthalamide, ceramic or metal. ) And a functional group capable of hydrogen bonding. The substrate for installing the light guide member is usually made of resin, ceramic or metal. In addition, a hydroxyl group usually exists on the surface of ceramic or metal. On the other hand, the specific layer A usually has a functional group capable of hydrogen bonding with the hydroxyl group. Therefore, the first to fourth light guide members of the present invention having the specific layer A are excellent in adhesion to the substrate by the hydrogen bond.

[0087] Examples of the functional group capable of hydrogen bonding to the hydroxyl group of the specific layer A include silanol and alkoxy group. The functional group may be one kind or two or more kinds.

The specific layer A according to the present invention has these functional groups and thus has excellent adhesion, It is a noteworthy feature that it is possible to laminate by means of. Utilizing this property, it is possible to easily produce a light guide member having a light guide function, an optical waveguide, a light guide plate, etc. by laminating two or more layers with adjusted refractive indexes.

As described above, whether or not the specific layer A has a functional group capable of hydrogen bonding to a hydroxyl group depends on solid Si-NMR, solid ¹ H-NMR, infrared absorption spectrum (IR), It can be confirmed by spectroscopic techniques such as Raman spectra.

[0088] [A— 1 5— 4] Heat resistance

The specific layer A of the first to fourth light guide members of the present invention is excellent in heat resistance. That is, even when left under high temperature conditions, the transmittance of light having a predetermined wavelength does not easily change. Specifically, the specific layer A has a transmittance maintaining power for light having a wavelength of 400 nm before and after being left at 200 ° C. for 500 hours, usually 80% or more, preferably 90% or more, more preferably 95% or more. In addition, it is usually 110% or less, preferably 105% or less, more preferably 100% or less.

The variation ratio can be measured by the transmittance measurement using an ultraviolet / visible spectrophotometer in the same manner as the light transmittance measurement method described above in [A-15 1].

[0089] [8-1 5-5] 1 resistance;

The specific layer A of the first to fourth light guide members of the present invention is excellent in light resistance. That is, even when UV (ultraviolet light) is irradiated, the transmittance with respect to light having a predetermined wavelength is not easily changed. Specifically, the specific layer A has a transmittance maintenance factor of light at a wavelength of 400 nm before and after irradiation with light having a center wavelength of 380 nm and a radiation intensity of 0.4 kW / m 2 for 72 hours. It is 90% or more, more preferably 95% or more, and usually 110% or less, preferably 105% or less, more preferably 100% or less.

[0090] [A 1 5-6] Residual amount of catalyst

The specific layer A of the first to fourth light guide members of the present invention is usually produced using an organometallic compound catalyst containing at least one element selected from zirconium, hafnium, tin, zinc, and titanium. The Therefore, these catalysts usually remain in the specific layer A. ing. Specifically, the specific layer A contains the above organometallic compound catalyst in terms of metal element, usually 0.001% by weight or more, preferably 0.01% by weight or more, more preferably 0.02% by weight or more, Further, it is usually contained in an amount of not more than 0.3% by weight, preferably not more than 0.2% by weight, more preferably not more than 0.1% by weight. However, when the oxide particles containing the above metal element are blended for the purpose of adjusting the refractive index of the specific layer A, an amount of the metal element exceeding the above range is detected.The content of the organometallic compound catalyst is as follows: It can be measured by ICP analysis.

[0091] [A— 1 5— 7] Molecular weight

The specific layer A of the first to fourth light guide members of the present invention is obtained by measuring the material forming the specific layer A (specific layer forming liquid A described later) by GPC (gel permeation chromatography). The polystyrene-reduced weight average molecular weight (Mw) is usually 500 or more, preferably 900 or more, more preferably <3200 or more, usually 400 or less, preferably <is 70,000 or less, Preferably it is 27,000 or less. If the weight average molecular weight is too small, bubbles tend to be generated during curing after substrate coating, or liquid leakage tends to occur from minute gaps between the package and the substrate. There is a tendency to increase in viscosity over time, complex shape on the board, and filling efficiency to the wiring part.

[0092] The molecular weight distribution (Mw / Mn, where Mw represents the weight average molecular weight and Mn represents the number average molecular weight) is usually 20 or less, preferably 10 or less, more preferably 6 or less. . If the molecular weight distribution is too large, the member tends to thicken over time even at low temperatures and the coating efficiency to the substrate tends to deteriorate. Mn can be measured in terms of polystyrene by GPC, the same as Mw.

[0093] The specific layer forming liquid A for the first to fourth light guide members of the present invention preferably has a low molecular weight component having a specific molecular weight or less. Specifically, the component having a molecular weight of 800 or less in the GPC area ratio in the specific layer forming liquid A is usually 10% or less, preferably 7.5% or less, more preferably 5% or less of the whole. If there are too many low molecular weight components, bubbles may be generated at the time of curing after coating the substrate, and the weight yield (solid content ratio) at the time of curing may decrease due to volatilization of the main component.

[0094] Furthermore, the specific layer forming liquid A of the first to fourth light guide members of the present invention has a specific molecular weight or more. Those having a low molecular weight component are preferred. Specifically, in the GPC analysis value of the specific layer forming liquid A, the molecular weight force at which the high molecular weight fractionation range is 5% is usually 1000000 or less, preferably 30000 or less, more preferably 110000 or less. If there are too many high molecular weight fractions in GPC,

a) The specific layer forming liquid A thickens over time even in low-temperature storage.

b) Moisture is generated by dehydration condensation during storage, making it easier to peel off from the substrate or package after application of the specific layer A.

c) Due to the high viscosity, bubbles are not easily removed during curing after coating the substrate.

There is a possibility.

[0095] In summary, the specific layer forming liquid A for the first to fourth light guide members of the present invention is preferably in the molecular weight range shown above. The following methods can be mentioned.

(i) The polymerization reaction during synthesis is sufficiently performed and unreacted raw materials are consumed.

(ii) Light boiling components are sufficiently distilled off after the synthesis reaction to remove light boiling low molecular weight residues.

(iii) The reaction rate and conditions during the synthesis reaction are appropriately controlled so that the polymerization reaction proceeds uniformly, and the molecular weight distribution is not increased more than necessary.

[0096] For example, when the specific layer A is formed from a polycondensate obtained by hydrolysis and polycondensation of a specific compound as in "[A-2] Method for producing a light guide member", the specific layer is formed. Hydrolysis during synthesis of liquid A · It is preferable to proceed the polymerization reaction uniformly while maintaining an appropriate reaction rate. Hydrolysis · Polymerization is usually in the range of 15 ° C or higher, preferably 20 ° C or higher, more preferably 40 ° C or higher, and usually 140 ° C or lower, preferably 135 ° C or lower, more preferably 130 ° C or lower. To do. The hydrolysis / polymerization time varies depending on the reaction temperature, but is usually 0.1 hour or longer, preferably 1 hour or longer, more preferably 3 hours or longer, and usually 100 hours or shorter, preferably 20 hours or shorter, more preferably 15 hours. It is carried out in the range of less than time. If the reaction time is shorter than this, the force that does not reach the required molecular weight, i.e., the reaction proceeds non-uniformly, resulting in the presence of high molecular weight components while the low molecular weight raw material remains, resulting in poor cured product quality and storage stability. May become poor. Also, if the reaction time is longer than this, the polymerization catalyst may be deactivated, or the synthesis may take a long time and the productivity may deteriorate. [0097] When the reaction activity of the raw material is low and the reaction is difficult to proceed, if necessary, for example, an inert gas such as argon gas, helium gas, nitrogen gas, etc. is circulated so that moisture generated in the condensation reaction can be reduced. The reaction may be accelerated by removing the alcohol accompanied. The reaction time is preferably adjusted as appropriate while controlling the molecular weight by GPC and viscosity measurement. Furthermore, it is preferable to adjust in consideration of the temperature rising time.

When using a solvent, it is preferable to carry out the solvent distillation at normal pressure as required. Further, when the boiling point of the solvent or the low molecular weight substance to be removed is the curing start temperature (usually 120 ° C or higher), it is preferable to carry out distillation under reduced pressure as necessary. On the other hand, depending on the purpose of use, such as thin coating of the light guide film, a part of the solvent may remain for reducing the viscosity. A solvent different from the reaction solvent may be mixed after the reaction solvent is distilled off.

Here, the upper limit and the lower limit of the molecular weight distribution of the specific layer forming liquid A are not necessarily limited to one if the upper limit and the lower limit are preferably within the above range. In addition, it is possible to mix formation liquids having different molecular weight distributions depending on the purpose such as function addition. In that case, the molecular weight distribution curve may be multimodal. For example, in order to give mechanical strength to the specific layer A, a small amount of the second specific layer forming liquid A having a low molecular weight containing a large amount of adhesion components is contained in the first specific layer forming liquid A finished to a high molecular weight. This is the case.

[0099] [A— 1 5— 8] Low boiling point component

The specific layer forming liquid A and the specific layer A of the first to fourth light guide members of the present invention are those of the heat generation gas in the range of 40 ° C to 210 ° C in the TG-mass (pyrolysis MS chromatogram). It is preferable that the chromatogram integral area is small!

TG-mass is a chromatogram integral in the temperature range of 40 ° C to 210 ° C that detects the low-boiling components in the specified layer forming solution A and the specified layer A by raising the temperature of the specified layer forming solution A. A large area indicates that low-boiling components such as water, solvent, and 3- to 5-membered cyclic siloxane are present in the component. In such a case, (i) the amount of low-boiling components increases, the generation of bubbles or bleed-out during the curing process, and the lower the adhesion to the substrate, the more insufficient the curing or the weight loss during curing. There is a possibility that it will be damaged, and (ii) there is a possibility that bubbles will be generated or bleed out due to the heat generated during reflow when the lamp emits light. Therefore, the specific layer forming liquid A and the specific layer A have few such low-boiling components. Those are preferred.

The TG-mass can be measured by the following operation under the following measurement conditions.

[TG-mass measurement conditions]

Heating furnace: Frontier 'Lab PY—2010 type

Reheating furnace heating program: 40 ° C → 10 ° C / min → 400 ° C

Interface temperature: 100 ° C

Sample cup: Platinum (25 U

Sample volume: approx. LOmg

GC: HP 6890

Column: Empty column (0.25 mm X 10m)

Carrier: Helium 1.5 mL / min

Inlet temperature: 100 ° C

Split ratio: 1/50

Oven: 150 ° C

MS: JEOL Sakai—15 type

Measurement method: EI method

Ionization voltage: 70eV

Ionization current: 300 A

Photo mano voltage: 400V

Interface temperature: 150 ° C

Ionization chamber temperature: 200 ° C

Mass range: m / z = 10-400

Scan heat: 500ms

[TG—mass measurement method]

The gas components generated from the heated sample are introduced into the gas chromatograph through an empty column and MS analysis is performed. About 10 mg of sample solution is put into a platinum cell (cup) and heated at 40 ° C to 400 ° C and 10 ° C / min under He flow. The specific layer forming liquid A is solidified at around 120 ° C .; After that, it is heated in a solid state.

[0102] In the specific layer A, examples of a method for reducing the amount of the low boiling point component detected by TG mass include the following methods.

[0103] (i) The polymerization reaction and the like are sufficiently performed. That is, by ensuring sufficient reaction temperature and reaction time, unreacted light boiling raw materials are consumed, and unreacted terminals that produce water and alcohol during curing are reduced to an appropriate amount. For example, when the specific layer Α is formed from a polycondensate obtained by hydrolysis and polycondensation of a specific compound, as described later in “[Α-2] Light guide member manufacturing method”, hydrolysis is performed at normal pressure. When polycondensation is carried out, usually 15 ° C or higher, preferably 20 ° C or higher, more preferably 40 ° C or higher, and usually 140 ° C or lower, preferably 135 ° C or lower, more preferably 130 ° C Perform hydrolysis and polycondensation within the following ranges. The hydrolysis / polycondensation reaction time varies depending on the reaction temperature, usually 0.1 hour or more, preferably 1 hour or more, more preferably 3 hours or more, and usually 100 hours or less, preferably 20 hours or less, Preferably, it is carried out for 15 hours or less. The reaction time is preferably adjusted appropriately while sequentially controlling the molecular weight by GPC and viscosity measurement. Furthermore, it is preferable to adjust the temperature in consideration of the heating time.

[0104] (ii) When the specific layer forming liquid A has a light boiling point that is not consumed by the reaction, such as a solvent or a low molecular weight cyclic siloxane, the curing start temperature during the synthesis of the specific layer forming liquid A While suppressing unnecessary polymerization at the following temperatures, natural distillation, light-boiling concomitant removal by circulation of inert gas such as argon gas, nitrogen gas, helium gas, etc. It is preferable to remove low boiling components having a boiling point of about room temperature to 260 ° C. Specifically, for example, the temperature condition when the solvent is distilled off is usually 60 ° C or higher, preferably 80 ° C or higher, more preferably 100 ° C or higher, and usually 150 ° C or lower, preferably 130 ° C or lower, more preferably 120 ° C or lower. It is also possible to remove unnecessary light-boiling substances by using a separate raw material before synthesis! /.

[0105] [A— 1 6] Other layers

The first to fourth light guide members of the present invention have layers other than the specific layer A as long as at least two of the layers of the light guide member are the specific layer A. Also good. As the layer other than the specific layer A, a known layer can be arbitrarily applied. Ma The layers other than the specific layer A may be provided with only one layer, or may be provided with two or more layers.

However, in order to obtain the effects of the present invention more remarkably, more of the layers of the first to fourth light guide members of the present invention have the characteristics as the specific layer A. It is more preferable that all the layers have the characteristics as the specific layer A described above.

[0106] [A-2] Method for manufacturing light guide member

The method for producing the first to fourth light guide members of the present invention is not particularly limited. Therefore, each layer which comprises the 1st-4th light guide member of this invention can each be manufactured by arbitrary methods. In particular, the specific layer A is obtained by, for example, hydrolyzing and polycondensing a compound represented by the following general formula (1) or general formula (2) and / or an oligomer thereof, to form a polycondensate (hydrolysis / polycondensate). ) Can be obtained by drying. However, since it is preferable that the specific layer A is mainly composed of a siloxane bond, it is desirable that the compound represented by the general formula (1) or the oligomer thereof is mainly composed of a raw material. Further, when the hydrolysis polycondensate contains a solvent, the solvent may be distilled off in advance before drying.

[0107] In the following description, the hydrolyzed polycondensate or a composition containing it is referred to as a specific layer forming liquid A that is obtained before the drying step. Therefore, when the specific layer A of the first to fourth light guide members of the present invention is manufactured by the manufacturing method described here (hereinafter referred to as “the specific layer manufacturing method according to the present invention” as appropriate), this specific What was obtained from the layer forming liquid A through the drying step is the specific layer A.

Hereinafter, a method for producing the specific layer A will be described in detail.

[0108] [A— 2-1] Raw material

As the raw material, a compound represented by the following general formula (1) (hereinafter referred to as “compound (1)”) and / or an oligomer thereof is used.

[0109] M ^{m +} XY ¹ (1)

[0110] In general formula (1), M is at least one element selected from the group consisting of silicon, aluminum, zirconium, and titanium. Of these, key is preferable.

In general formula (1), m represents the valence of M, and is an integer of 1 or more and 4 or less. “M +” means that it is a positive valence. n represents the number of X groups, and is an integer of 1 or more and 4 or less. However, m≥n.

[0111] In the general formula (1), X is a hydrolyzable group that is hydrolyzed by water in the solution or moisture in the air to form a highly reactive hydroxyl group. It can be used arbitrarily. For example, a C1-C5 lower alkoxy group, acetoxy group, butanoxime group, chloro group and the like can be mentioned. Here, Ci (i is a natural number) indicates that the number of carbon atoms is i. Furthermore, X may be a hydroxyl group. These hydrolyzable groups may be used alone or in combination of two or more in any combination and ratio.

[0112] Among them, a C1-C5 lower alkoxy group is preferable because a component liberated after the reaction is neutral. In particular, a methoxy group or an ethoxy group is preferable because it is highly reactive and the solvent to be liberated is light boiling.

Furthermore, in the general formula (1), when X is a acetoxy group or a chloro group, acetic acid and hydrochloric acid are liberated after the hydrolysis reaction. It is preferable to add a process to remove!

[0113] In the general formula (1), Y ¹ can be arbitrarily selected and used as a monovalent organic group of a so-called silane coupling agent. Among them, the organic group particularly useful as Y ¹ in the general formula (1) in the present invention is selected from the following group represented by Y ° (useful organic group group). Furthermore, other organic groups may be appropriately selected for improving the affinity between the specific layer and other materials, improving adhesion, adjusting the refractive index of the specific layer A, and the like.

[0114] <Useful organic group Y °>

Υ °: A monovalent or higher-valent organic group derived from an aliphatic compound, alicyclic compound, aromatic compound, or aliphatic aromatic compound.

The carbon number of the organic group belonging to the group is usually 1 or more, usually 1000 or less, preferably 500 or less, more preferably 100 or less, and still more preferably 50 or less.

[0115] Further, at least a part of the hydrogen atoms of the organic group belonging to the group may be substituted with a substituent such as the atoms and / or organic functional groups exemplified below. At this time, a plurality of hydrogen atoms of the organic group belonging to the group Υ ° are substituted with the following substituents. In this case, it may be substituted by one or a combination of two or more selected from the substituents shown below!

[0116] Examples of substituents that can be substituted with hydrogen atoms of organic groups belonging to the group Y ° include atoms such as F, Cl, Br, and I; bur group, methacryloxy group, attaryloxy group, styryl group, mercapto group, Organic functional groups such as epoxy group, epoxycyclohexyl group, glycidoxy group, amino group, cyano group, nitro group, sulfonic acid group, carboxy group, hydroxy group, acyl group, alkoxy group, imino group, and phenyl group Etc.

[0117] In all of the above cases, among the substituents that can be substituted with the hydrogen atom of the organic group belonging to the group Y °, the organic functional group is at least one of the hydrogen atoms of the organic functional group. Some may be substituted with halogen atoms such as F, Cl, Br, and I. However, among those exemplified as substituents capable of substituting hydrogen for organic groups belonging to the group Y °, organic functional groups are examples of those that are easy to introduce, and various other types of physical chemistry depending on the purpose of use. An organic functional group having functional functionality may be introduced.

[0118] The organic group belonging to the group Υ ° may have various atoms or atomic groups such as ◯, Ν, or S as a linking group.

In general formula (1), Y ¹ is a group capable of selecting various groups depending on the purpose from the organic groups belonging to the useful organic group group Y ° described above. From the viewpoint of excellent ultraviolet resistance and heat resistance, a methyl group is The main body is preferable.

[0119] Specific examples of the compound (1) are as follows. Examples of the compound in which Μ is a _key include phenyloxysilane, _{butyltrimethoxysilane,} butyltriethoxysilane, _{butylmethoxysilane, and} orange. Sid alkoxy prop Honoré triethoxysilane, beta i (3, 4-Epokishishi black to Kishinore) E Chino Les trimethoxysilane, _gamma - (3, 4-epoxy Kishinore cyclohexylene) Echinore triethoxysilane, _gamma - (meth) Atarirokishi Provirtrimethoxysilane, phenyltrimethoxy

—Black mouth propyltrimethoxysilane, 13-cyanoethyltriethoxysilane, methyltrimethoxysilane, methinotritriethoxysilane, methinotritripropoxysilane, methinotributoxy Lan, Etyltrimethoxysilane, Ethyltriethoxysilane, Tetramethoxysilane, Tetraphenyldichlorosilane, Methylphenyldimethoxysilane, Trimethylmethoxysilane, Trimethylethoxysilane, Trimethylchlorosilane, Methyltrichlorosilane, γ-Acinopropyl Triethoxysilane, 4-Acinobutyltriethoxysilane, ρ Aminophenyltrimethoxysilane, Ν— (2 Aminoethyl) 3 Aminopropyltrimethoxysilane, Aminoethyl

— (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, Ν— (6-amino) Xylyl) aminopropyltrimethoxysilane, 3-chloropropyl trimethoxysilane, 3-chloropropyltrichlorosilane, (ρ chloromethyl) phenyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, 3- Methacryloxypropyl trimethoxysilane

Examples include trichlorosilane, butururis (2-methoxyethoxy) silane, trifluoropropyltrimethoxysilane, and the like.

[0120] Among the compounds (1), examples of the compound in which ある is aluminum include, for example, aluminum triisopropoxide, aluminum tri-η butoxide, aluminum tri-t-butoxide

And aluminum triethoxide.

Examples of the compound (1) in which M is zirconium include, for example, zirconium tetramethoxide, zirconium tetraethoxide, and zirconium tetra n propoxide.

Zirconium tetra i propoxide, Zirconium tetra n butoxide, Zirconium tetra i-butoxide, Zirconium tetra-butoxide, Zirconium dimethacrylate dibutoxide and the like.

[0121] Further, among the compounds (1), examples of the compound in which M is titanium include, for example, titanium tetrasopropoxide, titanium tetra n butoxide, titanium tetra ibutoxide, titanium methacrylate triisopropoxide, titanium tetramethoxy. Examples include propoxide, titanium tetra n propoxide, titanium tetraethoxide. However, the compounds specifically exemplified in these are some of the commercially available coupling agents that are readily available. For more details, see, for example, “Optimum Utilization Technology for Coupling Agents”, Chapter 9 Coupling agent and related product list. Of course, the coupling agents that can be used in the present invention are not limited by these examples.

[0122] Further, the compound represented by the following general formula (2) (hereinafter referred to as "compound (2)" as appropriate) and / or an oligomer thereof are also the same as the compound (1) and / or the oligomer thereof. Use with power S.

[0123] (M ³⁺ XY ¹ ) Y "(2)

[0124] In the general formula (2), M, X and Y ¹ each independently represents the same as in the general formula (1). Particularly Upsilon ^1, as in the case of the general formula (1), the organic groups belonging to useful organic group & Upsilon ° above, the force ultraviolet resistance that can select various groups depending on the purpose, high heat resistance From the point of view, it is preferable to have a methyl group as the main component.

In the general formula (2), s represents the valence of Μ and is an integer of 2 or more and 4 or less. “S +” indicates that it is a positive integer.

[0125] Furthermore, in the general formula (2), Y ² represents a u-valent organic group. However, u represents an integer of 2 or more. Therefore, in the general formula (2), Y ² can be arbitrarily selected from divalent or higher ones among the known organic groups of so-called silane coupling agents.

Yes

In general formula (2), t represents an integer of 1 or more and s−l or less. However, t≤s.

[0126] Examples of the compound (2) include various organic polymers and oligomers in which a plurality of hydrolyzable silyl groups are bonded as side chains! /, Or a hydrolyzable silyl group at multiple terminals of the molecule. Examples include those in which the group is bonded! /.

Specific examples of the compound (2) and product names thereof are listed below.

(Shin-Etsu Chemical, KBE-846)

• 2 diethoxymethylenoretinoresilinoresimethinole 2-furaninolesylane (Shin-Etsu Chemical, LS-7740)

(Manufactured by Chisso, Sila Ace XS1003)

• N—Glycidillo N, N—Bis [3- (methyldimethoxysilyl) propyl] amine

(Momentive 'Performance' Materials' Japan GK, TSL8227) • N—Glycidillo N, N—Bis [3- (trimethoxysilyl) propyl] amine

(Momentive 'Performance' Materials' Japan GK, TSL8228)

(Momentive 'Performance' Materials' Japan GK, TSL8206) • N, N-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine

(Momentive 'Performance' Materials' Japan GK, TSL8212)

(Momentive 'Performance' Materials' Japan GK, TSL8213) • N, N—bis [3- (trimethoxysilyl) propinole] amamine

(Momentive 'Performance' Materials' Japan GK, TSL8208)

(Momentive 'Performance' Materials' Japan GK, TSL8214)

(Momentive 'Performance' Materials 'Japan GK, TSL8215) • N, Ν', Ν "—Tris [3- (trimethoxysilinore) propinore] isocyanurate

(Made by Hydrasi, 12267-1)

(Shin-Etsu Chemical, LS-7325)

It is possible to use compound (1), compound (2), and / or oligomers thereof as raw materials. That is, in the method for producing a specific layer according to the present invention, as a raw material, compound (1), oligomer of compound (1), compound (2), oligomer of compound (2), and compound (1) and compound ( Any of the oligomers with 2) may be used. When an oligomer of compound (1) or an oligomer of compound (2) is used as a raw material, the molecular weight of the oligomer is The force S is arbitrary as long as the specific layer A relating to light can be obtained, usually 400 or more.

Here, when the compound (2) and / or oligomer thereof is used as a main raw material, the main chain structure in the system may be an organic bond main body and may be inferior in durability. For this reason, it is desirable to use the compound (2) in a minimum use amount mainly for imparting functions such as adhesion, refractive index adjustment, reactivity control, and inorganic particle dispersibility. When compound (1) and / or its oligomer (component derived from compound (1)) and compound (2) and / or its oligomer (component derived from compound (2)) are used at the same time, The proportion of the component (2) -derived component used is usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less.

[0129] Further, in the method for producing the specific layer forming liquid A and the specific layer A of the present invention, when the compound (1) or the oligomer of the compound (2) is used as a raw material, the oligomer is prepared in advance. However, the oligomer may be prepared in the manufacturing process. That is, a monomer such as the compound (1) or the compound (2) may be used as a raw material, and this may be used as an oligomer once in the production process, and the subsequent reaction may proceed from this oligomer.

[0130] Further, as long as the oligomer has a structure similar to that obtained from the monomer such as compound (1) or compound (2) as a result, a commercially available product having such a structure is sufficient. Can also be used. Specific examples of such oligomers include the following.

[0131] <Example of oligomer consisting only of bifunctional cage>

For example, XC96-723, XF3905, YF3057, YF3800, YF3802, YF3807, and YF3897 can be cited as examples of the hydroxy-terminated dimethylpolysiloxane manufactured by Momentive 'Performance' Materials Japan GK.

[0132] In the case of Momentive 'Performance' Materials' Hydroxy-terminated methylpolypolysiloxane manufactured by Japan GK, for example, YF3804 can be mentioned.

Examples of the both-end silanol polydimethylsiloxane manufactured by Gelest include DMS-S12 and DMS-S14.

Examples of the double-end silanol diphenylsiloxane-dimethylsiloxane copolymer manufactured by Gelest include PDS-1615. An example of the double-end silanol polydiphenylsiloxane manufactured by Gelest is PDS-9931.

[0133] <Example of oligomer containing tri- or higher functional key>

Examples of silicone alkoxy oligomers (methyl / methoxy type) manufactured by Shin-Etsu Chemical include KC-89S, KR-500, X-40-9225, X-40-9246, and X-40-9250.

[0134] Examples of silicone alkoxy oligomers (phenyl / methoxy type) manufactured by Shin-Etsu Chemical include KR-217.

Examples of silicone alkoxy oligomers (methylphenyl / methoxy type) manufactured by Shin-Etsu Chemical include KR-9218, KR-213, KR-510, X-40-9227, and X-40-9247.

[0135] Among these, the oligomer consisting only of the bifunctional cage has a great effect of giving flexibility to the specific layer A of the first to fourth light guide members of the present invention, but the mechanical functionality is obtained only with the bifunctional cage. Intensity tends to be insufficient. For this reason, the specific layer A can obtain mechanical strength useful as a sealant by polymerizing with a monomer composed of trifunctional or higher functional monomer or an oligomer containing trifunctional or higher functional cage. In addition, those having silanol as a reactive group do not need to be hydrolyzed in advance, and do not require the use of a solvent such as alcohol as a compatibilizer for adding water. In the case of using an oligomer having an alkoxy group, water for hydrolysis is required as in the case of using a monomer having an alkoxy group as a raw material.

[0136] Further, as a raw material, among these compounds (1), (2), and oligomers thereof

Use only one type! /, But two or more types may be mixed in any combination and composition. Furthermore, it is possible to use the compound (1), the compound (2) and the oligomer thereof that have been hydrolyzed in advance (that is, X is an OH group in the general formulas (1) and (2))! /. However, in the method for producing the specific layer according to the present invention, as a raw material, the compound (1), the compound (2), and the compound (1), which contain C as M and have at least one organic group Y ¹ or organic group Y ² It is necessary to use at least one oligomer (including hydrolyzed one). In addition, cross-linking in the system is mainly formed by inorganic components including siloxane bonds. Therefore, when both the compound (1) and the compound (2) are used, it is preferable that the compound (1) is mainly used.

[0137] In order to obtain the specific layer A mainly composed of a siloxane bond, it is preferable to use the compound (1) and / or an oligomer thereof as a main material. In addition, these compounds (

The oligomer of 1) and / or the oligomer of compound (2) is more preferably composed of a bifunctional composition. In particular, the bifunctional unit of the oligomer of the compound (1) and / or the oligomer of the compound (2) is preferably used as a bifunctional oligomer.

[0138] Furthermore, among the oligomers of the compound (1) and / or the oligomer of the compound (2), when a bifunctional one (hereinafter referred to as "bifunctional component oligomer") is used as a main component, these bifunctional component oligomers The amount of is usually 50% by weight or more, preferably 60% by weight or more, more preferably, based on the total weight of the raw materials (that is, the sum of the weights of compound (1), compound (2), and oligomers thereof). 70% by weight or more. The upper limit of the amount used is usually 97% by weight. This is because the use of the bifunctional component oligomer as the main ingredient is one of the factors that enable the specific layer A to be easily manufactured by the specific layer manufacturing method according to the present invention.

[0139] Hereinafter, advantages of using the bifunctional component oligomer as the main ingredient will be described in detail.

For example, in a light guide member manufactured by a conventional sol-gel method, a hydrolysis / polycondensate obtained by hydrolysis and polycondensation of the raw material (a material contained in a coating liquid (hydrolysis liquid)) is used. ) Had a high reaction activity. Therefore, if the hydrolysis / polycondensate is not diluted with a solvent such as alcohol, the polymerization in the system proceeds and cures quickly, making molding and handling difficult. For example, conventionally, when it is not diluted with a solvent, it may be cured even when the temperature is about 40 ° C to 50 ° C. Therefore, in order to ensure the polarity and properties of the hydrolyzed / polycondensate obtained after the hydrolysis, it was essential to allow a solvent to coexist in the hydrolyzed / polycondensed product.

[0140] In addition, when the hydrolysis / drying of the polycondensate is allowed to harden in the presence of a solvent in the hydrolysis / polycondensate, in addition to shrinkage due to dehydration condensation during curing, shrinkage due to desolvation (desolvation) (Shrinkage) is added. As a result, in the conventional light guide member, the internal stress of the cured product tends to be large, and cracks and peeling due to the internal stress tend to occur. Furthermore, if a bifunctional component monomer is frequently used as a raw material for the purpose of softening the light guide member in order to alleviate the above internal stress, there is a possibility that the number of low boiling rings in the polycondensate increases. Since the low boiling ring is volatilized at the time of curing, the weight yield decreases when the number of low boiling ring increases. In addition, the low boiling ring is volatilized from the cured product and causes stress generation S. Further, the light guide member containing a large amount of low-boiling annular bodies may have low heat resistance. For these reasons, it has heretofore been difficult to obtain a light guide member as a high-performance elastomeric cured body.

[0141] On the other hand, in the method for producing a specific layer according to the present invention, as a raw material, a bifunctional component is oligomerized in advance in a separate system (that is, a system that does not participate in the hydrolysis / polycondensation step) and is reactive. A material obtained by distilling off low-boiling impurities having no terminal is used as a raw material. Therefore, even if a large amount of bifunctional components (that is, the above-mentioned bifunctional component oligomers) is used, the low-boiling impurities do not volatilize, and the cured product weight yield can be improved and the performance is good. An elastomer-like cured product can be obtained.

[0142] Furthermore, by using a bifunctional component oligomer as the main raw material, the reaction activity of the hydrolyzed polycondensate can be suppressed. This is presumably due to the steric hindrance and electronic effect of the hydrolyzed polycondensate, and the decrease in the amount of silanol terminals due to the use of bifunctional component oligomers. By suppressing the reaction activity, the hydrolysis 'polycondensate does not cure without the presence of a solvent. Therefore, the hydrolysis' polycondensate can be made into a one-pack type and solvent-free system. .

[0143] Further, since the reaction activity of the hydrolyzate / polycondensate has decreased, it has become possible to raise the curing start temperature higher than in the past. Therefore, if a solvent below the hydrolysis start temperature of the hydrolysis' polycondensate is allowed to coexist in the hydrolysis' polycondensate, the hydrolysis / polycondensation product is cured when the hydrolysis' polycondensate is dried. The solvent will volatilize before it is started. As a result, even when a solvent is used, it is possible to suppress the generation of internal stress due to solvent removal shrinkage.

[0144] [A—2-2] Hydrolysis and polycondensation process In the present invention, first, the above compound (1), compound (2), and / or oligomer thereof is subjected to hydrolysis / polycondensation reaction (hydrolysis / polycondensation step). This hydrolysis / polycondensation reaction can be carried out by a known method. Hereinafter, when referring to the compound (1), the compound (2), and the oligomer thereof without distinction, they are referred to as “raw material compounds”.

[0145] Hydrolysis of raw material compound 'The theoretical amount of water used for conducting the polycondensation reaction is 1/2 mol of the total amount of hydrolyzable groups in the system based on the reaction formula shown in the following formula (3). Is the ratio.

[0146] [Chemical 2]

2 X s ϊ-… X -f II ；. o s i― 'a― s i + a x> ；. H (3}

[0147] It should be noted that the above equation (3) represents an example in which M in the general formulas (1) and (2) is a key element. “≡Si” and “Si≡” are the abbreviations of three of the four bonds of the key atom.

In this specification, the theoretical amount of water required for this hydrolysis, that is, the amount of water corresponding to a 1/2 molar ratio of the total amount of hydrolyzable groups is used as the standard (hydrolysis rate 100%). The amount of water used is expressed as a percentage of this reference amount, ie “hydrolysis rate”.

[0148] In the method for producing a specific layer according to the present invention, the amount of water used for carrying out the hydrolysis / polycondensation reaction is usually 80% or more, especially 100% when expressed by the above hydrolysis rate. A range of at least% is preferred. If the hydrolysis rate is less than this range, the hydrolysis and polymerization are insufficient, so that the raw material may volatilize during curing or the strength of the cured product may be insufficient. On the other hand, if the hydrolysis rate exceeds 200%, free water always remains in the system during curing, causing deterioration of the phosphor and other contents due to moisture, or the substrate absorbing water and foaming during curing. May cause cracking and peeling. However, what is important in the water-hydrolysis reaction is that hydrolysis-polycondensation is carried out with near 100% or more (for example, 80% or more) of water. If a process for removing free water is added before coating, 20 It is possible to apply hydrolysis rates above 0%. In this case, if an excessive amount of water is used, the amount of water to be removed and the amount of solvent used as a compatibilizer increase, the concentration process becomes complicated, and the polycondensation proceeds so much that each of the light guide members is formed. Since the coating performance of the specific layer A may deteriorate, the upper limit of the hydrolysis rate is usually 500% or less, particularly 300% or less, preferably 200% or less. [0149] When the raw material compound is subjected to hydrolysis / condensation polymerization, it is preferable to promote the hydrolysis / condensation polymerization in the presence of a catalyst or the like. In this case, examples of the catalyst used include organic acids such as acetic acid, propionic acid and butyric acid; inorganic acids such as nitric acid, hydrochloric acid, phosphoric acid and sulfuric acid; organometallic compound catalysts. Of these, in the case of a composition layer used in a portion in direct contact with the substrate, an organometallic compound catalyst that has little influence on the insulating properties is preferable. Here, the organometallic compound catalyst does not only refer to a catalyst consisting of an organometallic compound in a narrow sense in which an organic group and a metal atom are directly bonded, but an organometallic complex, a metal alkoxide, an organic acid and a metal. The catalyst which consists of an organic metal compound of a broad meaning including the salt with.

[0150] Among organometallic compound catalysts, organometallic compound catalysts containing zirconium are more preferred, which are preferred to organometallic compound catalysts containing at least one element selected from zirconium, hafnium, tin, zinc and titanium. preferable.

Specific examples of such organometallic compound catalysts containing zirconium include soot, zirconium dibutoxy diacetyl acylate, zirconium tetranormal pro-zirconium acylate, and zirconium tributoxy systemate. .

[0151] Examples of the organometallic compound catalyst containing titanium include titanium tetraisopropoxide, titanium tetranormal butoxide, butyl titanate dimer, and tetraethylacetoacetate.

An example of the organometallic compound catalyst containing zinc is zinc triacetyl acetate.

[0152] Examples of organometallic compound catalysts containing tin include tetraptyltin, monooctyltin, dioctyltin dichloride, dioctyltin oxide, tetramethyltin, dibutyltin laurate, dioctyltin. Laurate, bis (2-ethylhexanoate) tin, bis (neodecanoate) tin, di-n-butylbis (ethylhexylmalate) tin, di-normal butylbis (2,4-pentanedionate) tin, di- Normal Butinore Examples include tin laurate and dimethyldineodecanoate tin.

[0153] These organometallic compound catalysts may be used alone or in combination of two or more in any combination and ratio.

By using an organic metal compound catalyst as described above, when the raw material compound is hydrolyzed and polycondensed, the formation of low-molecular cyclic siloxane as a by-product is suppressed, and the specific layer forming liquid is produced with high yield. A can be synthesized.

[0154] Further, by using this organometallic compound catalyst, the first to fourth light guide members of the present invention using the specific layer A and the specific layer A can achieve high heat resistance. . The reason for this is not clear, but the organometallic compound not only promotes the hydrolysis / polycondensation reaction of the raw material compound as a catalyst, but also temporarily at the silanol ends of the hydrolysis / polycondensation product and its cured product. (I) prevention of oxidation of organic groups under high temperature conditions, (ii) prevention of unwanted cross-linking between polymers, (iii) ) It seems to have an effect of preventing the main chain from being broken. Hereinafter, these actions (i) to (iii) will be described.

[0155] (i) As the prevention of oxidation of organic groups, for example, when a radical is generated on a methyl group by the action of heat, the transition metal of the organometallic compound catalyst has an effect of capturing radicals. On the other hand, the transition metal itself loses its ionic valence by radical scavenging, and thus acts with oxygen to prevent organic group oxidation. As a result, it is presumed that the degradation of specific layer A will be suppressed.

(Ii) For preventing unnecessary crosslinking between polymers, for example, when a methyl group is oxidized by an oxygen molecule, it becomes formaldehyde and a hydroxyl group bonded to a silicon atom is generated. When the hydroxyl groups thus formed are dehydrated and condensed, cross-linking points are formed between the polymers, and the increase thereof may cause the specific layer A, which was originally rubbery, to become hard and brittle. However, it is presumed that the organometallic compound catalyst binds to the silanol group, thereby preventing the progress of crosslinking due to thermal decomposition.

[0157] (iii) For preventing the main chain from being broken, the organometallic compound catalyst is bonded to the silanol, so that the polymer main chain is broken by the intramolecular attack of the silanol and the cyclic siloxane. It is presumed that the heat resistance is improved by suppressing the weight loss by heating due to the formation of.

[0158] The preferred compounding amount of the organometallic compound catalyst is appropriately selected depending on the type of the catalyst used, but is usually 0.01% by weight or more, preferably not less than the total weight of the raw materials to be hydrolyzed / polycondensed. It is 0.05% by weight or more, more preferably 0.1% by weight or more, and usually 5% by weight or less, preferably 2% by weight or less, particularly preferably 1% by weight or less. If the amount of the organometallic compound catalyst is too small, it may take too much time for curing, or sufficient mechanical strength and durability may not be obtained due to insufficient curing. On the other hand, if there are too many organometallic compound catalysts, the curing will be too fast and it will be difficult to control the physical properties of the specific layer A, which is a cured product, or the catalyst will not dissolve and disperse and will precipitate and impair the transparency of the specific layer A. There is a possibility that the specific layer A, which can increase the amount of organic substances brought by the catalyst itself, may become colored when used at high temperatures.

[0159] These organometallic catalysts may be mixed into the raw material system at the time of hydrolysis and condensation, or may be divided and mixed. Further, a solvent may be used to dissolve the catalyst during hydrolysis / polycondensation, or the catalyst may be dissolved directly in the reaction solution. However, when used as the specific layer forming liquid A, it is desirable to strictly distill off the solvent after the hydrolysis and polycondensation step in order to prevent foaming during heating and coloring due to heat.

[0160] Hydrolysis · If the system is separated and becomes non-uniform during the polycondensation reaction, a solvent may be used. As the solvent, for example, C1 to C3 lower alcohols, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, methylcetosolve, ethylcellosolve, methylethylketone, toluene, water and the like can be used arbitrarily. Those which are not acidic or basic are preferred because they do not adversely affect hydrolysis and polycondensation. As the solvent, one kind may be used alone, but two kinds or more may be used in any combination and ratio. The amount of solvent used can be freely selected. However, the solvent is often removed when it is applied to the substrate and on each layer, and therefore it is preferably set to the minimum necessary amount. In order to facilitate the removal of the solvent, it is preferable to select a solvent having a boiling point of 100 ° C. or lower, more preferably 80 ° C. or lower. In addition, since a solvent such as alcohol is generated by a hydrolysis reaction without mixing a solvent from the outside, it may be heterogeneous at the beginning of the reaction or even during the reaction. [0161] When the hydrolysis / polycondensation reaction of the above raw material compound is carried out at normal pressure, it is usually 15 ° C or higher, preferably 20 ° C or higher, more preferably 40 ° C or higher, and usually 140 ° C. Hereinafter, it is preferably carried out in the range of 135 ° C or lower, more preferably 130 ° C or lower. It is better to maintain the liquid phase under pressure! /, And the force that can be performed at temperature is not to exceed 150 ° C! /. Hydrolysis / polycondensation reaction time varies depending on the reaction temperature, but is usually 0.1 hour or more, preferably 1 hour or more, more preferably 3 hours or more, and usually 100 hours or less, preferably 20 hours or less, and more Preferably, it is carried out for 15 hours or less. It is preferable to adjust the reaction time appropriately while managing the molecular weight!

[0162] Hydrolysis as described above If the time is too short or the temperature is too low under the polycondensation conditions, hydrolysis and polymerization will be insufficient, causing the raw materials to volatilize during curing or the strength of the cured product to be insufficient. There is a possibility. If the time is too long or the temperature is too high, the molecular weight of the polymer increases and the amount of silanol in the system decreases, resulting in poor adhesion during coating or the curing is too early and the structure of the cured product is not good. It becomes uniform and tends to cause cracks. Based on the above trend, it is desirable to select the conditions appropriately according to the desired physical property values.

[0163] After the hydrolysis / polycondensation reaction is completed, the obtained hydrolysis / polycondensate is stored at room temperature or lower until its use S, and polycondensation proceeds slowly during this period. Therefore, especially when used as a thick film member, it is usually within 60 days, preferably within 30 days, more preferably 15 days at room temperature storage after the completion of the hydrolysis / polycondensation reaction by heating. Preferable to use within days! /. This period can be extended by cryogenic storage in the range! It is preferable to adjust the storage period while controlling the molecular weight!

[0164] By the above operation, hydrolysis of the above raw material compound (polycondensate) is obtained. This hydrolyzed 'polycondensate is preferably liquid. However, even a solid hydrolysis-polycondensation product can be used as long as it becomes liquid by using a solvent. In addition, the liquid hydrolysis / polycondensate thus obtained is a specific layer forming liquid A that becomes the specific layer A of the first to fourth light guide members of the present invention by curing in the steps described later. is there.

[0165] [A-2-3] Evaporation of solvent When a solvent is used in the hydrolysis / polycondensation step, it is usually preferable to distill off the solvent from the hydrolysis / polycondensate before drying (solvent distillation step). Thus, the specific layer forming liquid A (liquid hydrolysis / polycondensate) containing no solvent can be obtained. As described above, conventionally, when the solvent is distilled off, the hydrolysis / polycondensation product is cured, so that it has been difficult to handle the hydrolysis / polycondensation product. However, in the method for producing a specific layer according to the present invention, when bifunctional component oligomers are used, the reactivity of the hydrolysis' polycondensate is suppressed. The condensate does not cure and the solvent can be distilled off. By distilling off the solvent before drying, cracking, peeling, disconnection, etc. due to solvent removal shrinkage can be prevented.

[0166] Usually, water used for hydrolysis is also distilled off when the solvent is distilled off. The solvent to be distilled off also includes a solvent represented by XH or the like produced by hydrolysis of the raw material compounds represented by the above general formulas (1) and (2). Furthermore, low-molecular cyclic siloxane by-produced during the reaction is also included.

The method for distilling off the solvent is arbitrary as long as the effects of the present invention are not significantly impaired. However, it should be avoided to distill off the solvent at a temperature higher than the curing start temperature of the hydrolysis and polycondensate.

[0167] The specific range of the temperature conditions when the solvent is distilled off is usually 60 ° C or higher, preferably 80 ° C or higher, more preferably 100 ° C or higher, and usually 150 ° C. C or lower, preferably 130 ° C. or lower, more preferably 120 ° C. or lower. Below the lower limit of this range, the solvent may be insufficiently distilled, and when the upper limit is exceeded, the hydrolyzate / polycondensate may gel.

[0168] The pressure condition for distilling off the solvent is usually atmospheric pressure. If necessary, reduce the pressure so that the boiling point of the reaction mixture does not reach the curing start temperature (usually 120 ° C or higher). The lower limit of the pressure is such that the main component of the hydrolysis and polycondensate does not distill.

In general, light boiling components can be efficiently distilled off under high temperature and high vacuum conditions.However, if the amount of light boiling components is very small, if it cannot be distilled off precisely due to the shape of the apparatus, the polymerization proceeds further due to high temperature operation and the molecular weight increases too much. there is a possibility. In addition, if a certain type of catalyst is used, In some cases, if subjected to a high temperature reaction for a long time, it may be deactivated and the specific layer forming liquid A may be difficult to cure. Therefore, in these cases, the light boiling component may be distilled off at low temperature and normal pressure by blowing nitrogen or steam distillation, if necessary.

[0169] In any case such as distilling under reduced pressure or nitrogen blowing, the molecular weight of the main component of the hydrolysis and polycondensate should be increased by a moderate hydrolysis / polycondensation reaction so that the main component of the polycondensate does not distill. It is desirable to keep it.

The light guide member having the specific layer A produced by using the specific layer forming liquid A from which light boiling components such as solvent, moisture, by-product low molecular cyclic siloxane, and dissolved air are sufficiently removed by these methods is light boiling. This is preferable because foaming at the time of curing due to vaporization of water and peeling from the substrate or each layer when used at a high temperature can be reduced.

[0170] However, distilling off the solvent is not an essential operation. In particular, when a solvent having a boiling point equal to or lower than the hydrolysis temperature of the hydrolysis / polycondensate is used, when the hydrolysis / polycondensation product is dried, before the hydrolysis of the hydrolysis / polycondensation product starts, Therefore, the generation of cracks and the like due to desolvation shrinkage can be prevented even without performing a solvent distillation step. However, since the volume of the hydrolysis / polycondensate may change due to volatilization of the solvent, it is preferable to distill off the solvent from the viewpoint of precisely controlling the size and shape of the light guide member.

[0171] [A— 2— 4] Application

The specific layer forming liquid A thus obtained is applied to a desired site such as a substrate to form a coating film. This coating film becomes the specific layer A by drying as described later. When the solvent is distilled off, the coating may be performed before the solvent is distilled off, or the coating may be applied after the solvent is distilled off.

[0172] At the time of application, the film thickness of the coating film may be set to an appropriate size according to the film thickness of the specific layer A to be formed. At this time, since the specific layer A according to the present invention can be made thicker than a layer formed by the conventional technique, there is an advantage that the degree of freedom of dimension setting is large.

Further, the method used for coating is not limited, but for example, a casting method, a spin method, a dipping method, or the like can be used.

[0173] [A-2-5] Drying The ability to obtain the specific layer A can be obtained by drying the hydrolysis / polycondensate obtained by the hydrolysis / polycondensation reaction described above (drying process or curing process). This hydrolyzed polycondensate is normally a liquid force as described above, and is dried in a state where it is put in a mold of the desired shape to form a specific layer A having the desired shape. Is possible. Further, by drying the hydrolyzed polycondensate applied to the target site as described above, the specific layer A can be formed directly on the target site. In the drying process, the solvent does not necessarily evaporate, but here it is called the drying process, including the phenomenon that the hydrolyzed hydrolyzate / polycondensate loses its fluidity and hardens. . Therefore, when there is no evaporation of the solvent, the above “drying” may be read as “curing”.

[0174] In the drying step, the hydrolysis / polycondensate is further polymerized to form a metalloxane bond, and the polymer is dried and cured to obtain the specific layer A.

At the time of drying, the hydrolysis / polycondensate is heated to a predetermined curing temperature to be cured. The specific temperature range is arbitrary as long as hydrolysis / drying of the polycondensate is possible. Since the metalloxane bond is usually formed efficiently at 100 ° C or higher, preferably 120 ° C or higher, more preferably Implemented above 150 ° C. However, when heating a light guide member including a light source such as a substrate or a semiconductor light-emitting device, it is usually dried at a temperature lower than the heat-resistant temperature of a component such as a light source such as a substrate or a semiconductor light-emitting device, preferably 200 ° C or lower. It is preferable to carry out.

[0175] In addition, the time for maintaining the curing temperature (curing time) for drying the hydrolyzed / polycondensate is not generally determined by the catalyst concentration, the thickness of the member, etc., but usually 0.1 hour or more, Preferably it is 0.5 hours or more, more preferably 1 hour or more, and usually 10 hours or less, preferably 5 hours or less, more preferably 3 hours or less.

In addition, the temperature raising conditions in the drying step are not particularly limited. That is, during the drying process, the temperature may be maintained at a constant temperature, or the temperature may be changed continuously or intermittently. In addition, the drying process may be further divided into a plurality of times. Furthermore, the temperature may be changed stepwise in the drying process. By changing the temperature stepwise, it is possible to obtain the advantage that foaming due to residual water vapor can be prevented. Also low When cured at a high temperature and then cured at a high temperature, it is possible to obtain an advantage that internal stress is not easily generated in the obtained specific layer A, and cracks and peeling are unlikely to occur.

[0176] However, when the hydrolysis / polycondensation reaction described above was performed in the presence of a solvent, the hydrolysis / polycondensate was not performed even if the solvent distillation step was not performed or the solvent distillation step was performed. If the solvent remains in the solvent, this drying step is dried at a temperature not lower than the boiling point of the solvent and a first drying step that substantially removes the solvent at a temperature not higher than the boiling point of the solvent. It is preferable to perform it separately from the second drying step. The “solvent” mentioned here includes a solvent represented by XH or the like and a low-molecular cyclic siloxane produced by hydrolysis / polycondensation reaction of the above-mentioned raw material compounds. In the present specification, “drying” refers to a step of hydrolysis of the above-mentioned raw material compound, in which the polycondensate loses the solvent, and further polymerizes and cures to form a metalloxane bond.

[0177] In the first drying step, hydrolysis of the raw material compound 'the contained solvent without actively proceeding further polymerization of the polycondensate is substantially removed at a temperature below the boiling point of the solvent. It is what you do. That is, the product obtained in this step is hydrolyzed prior to drying, the polycondensate is concentrated, the hydrogen-bonded viscous liquid or soft film-like force, and the solvent are removed. Hydrolysis · Polycondensate is present in liquid form.

However, it is usually preferable to perform the first drying step at a temperature lower than the boiling point of the solvent. When the first drying is performed at a temperature equal to or higher than the boiling point of the solvent, the resulting film is foamed by the vapor of the solvent, and a uniform film having no defects is obtained. This first drying process may be performed in a single step when the evaporation efficiency of the solvent is good, such as when a thin film member is used, but when the evaporation efficiency is poor, the first drying process is divided into a plurality of steps. You can warm it. In the case of a shape with extremely poor evaporation efficiency, it may be dried and concentrated beforehand in another efficient container, and then applied in a state where fluidity remains, and further dried. When the evaporation efficiency is poor, it is preferable to devise a method in which the entire member is uniformly dried without taking a means of concentrating only the surface of the member, such as ventilation drying with a large amount of air.

[0179] In the second drying step, in the state where the solvent of the above-mentioned hydrolysis 'polycondensate has substantially disappeared by the first drying step, the hydrolysis' polycondensate is heated to a temperature equal to or higher than the boiling point of the solvent. To form a metalloxane bond to form a stable cured product. This If a large amount of solvent remains in this step, the volume decreases due to evaporation of the solvent while the crosslinking reaction proceeds, resulting in a large internal stress, which causes peeling and cracking due to shrinkage. Since the metalloxane bond is usually formed efficiently at 100 ° C or higher, the second drying step is preferably performed at 100 ° C or higher, more preferably 120 ° C or higher. However, when heating a light guide member including a light source such as a substrate or a semiconductor light emitting device, the temperature is usually lower than the heat resistant temperature of a component such as a light source such as a substrate or a semiconductor light emitting device, preferably 200 ° C or lower. It is preferable to carry out drying with! The curing time in the second drying step is not generally determined depending on the catalyst concentration and the thickness of the member, but is usually 0.1 hour or more, preferably 0.5 hour or more, more preferably 1 hour or more, and usually 10 It is carried out for a period of time or less, preferably 5 hours or less, more preferably 3 hours or less.

[0180] In this way, by clearly separating the solvent removal step (first drying step) and the curing step (second drying step), even if the solvent distillation step is not performed, It is possible to obtain a specific layer A having excellent light resistance and heat resistance without cracking and peeling.

However, curing may proceed during the first drying step, and solvent removal may proceed during the second drying step. However, curing during the first drying step and removal of the solvent during the second drying step usually do not affect the effects of the present invention!

[0181] As long as the first drying step and the second drying step described above are substantially realized, the temperature raising conditions in each step are not particularly limited. That is, during each drying step, the temperature may be maintained at a constant temperature, or the temperature may be changed continuously or intermittently. In addition, each drying step may be further divided into a plurality of times. Furthermore, even if the temperature temporarily exceeds the boiling point of the solvent during the first drying step, or a period during which the temperature is lower than the boiling point of the solvent is interposed during the second drying step, In particular, as long as the solvent removal step (first drying step) and the curing step (second drying step) as described above can be achieved independently, they are included in the scope of the present invention.

[0182] Further, when using a solvent having a boiling point not higher than the curing temperature of the hydrolysis / polycondensate, preferably lower than the curing temperature as a solvent! Rulu Even when the hydrolysis / polycondensate is heated to the curing temperature without adjusting the temperature, the medium is not removed from the hydrolysis / polycondensation when the temperature reaches the boiling point during the drying process. It will be distilled off. That is, in this case, in the process of raising the hydrolysis 'polycondensate to the curing temperature in the drying step, before the hydrolysis' polycondensate is cured, the solvent is substantially removed at a temperature below the boiling point of the solvent. A removal step (first drying step) is performed. As a result, the hydrolyzed 'polycondensate becomes a liquid hydrolyzed' polycondensate containing no solvent. After that, it is dried at a temperature higher than the boiling point of the solvent (that is, the curing temperature).

The process of curing the hydrolysis / polycondensate (second drying process) proceeds. Therefore, when a solvent having a boiling point equal to or lower than the curing temperature is used as the solvent, the first drying step and the second drying step are performed even if they are not intended to be performed. . For this reason, the use of a solvent having a boiling point equal to or lower than the curing temperature of the hydrolysis polycondensate, preferably less than the above curing temperature, is that the hydrolysis / polycondensate contains a solvent during the drying step. Even if it is, the quality of the specific layer A and the light guide member provided with the specific layer A is not greatly affected.

[0183] [A— 2-6] Others

After the above-described drying process, the obtained specific layer A may be subjected to various post treatments as necessary. Examples of the post-treatment include surface treatment for improving adhesion, production of an antireflection film, production of a fine uneven surface for improving light extraction efficiency, and the like.

[0184] [A-3] Specific layer forming liquid

As described above, the specific layer forming liquid A of the present invention is a liquid material obtained by the hydrolysis / polycondensation step, and becomes the specific layer A by being cured in the drying step.

Yes

[0185] When the specific layer forming liquid A is a curable organopolysiloxane, a branched organopolysiloxane is preferred to a linear organopolysiloxane in terms of the thermal expansion coefficient of the cured product. The cured product of linear organopolysiloxane is in the form of an elastomer, and its thermal expansion coefficient is large! /, But the thermal expansion coefficient of the cured product of branched organopolysiloxane is that of linear onoreganopolysiloxane. This is because the change in optical properties accompanying thermal expansion is small because it is smaller than the thermal expansion coefficient of the product. [0186] The viscosity of the specific layer forming liquid A of the present invention is not limited, but at a liquid temperature of 25 ° C, it is usually 20 mPa's or more, preferably lOOmPa's or more, more preferably 200 mPa's or more, Usually, it is 1500 mPa's or less, preferably lOOOmPa's or less, more preferably 800 mPa's or less. The viscosity can be measured with an RV viscometer (for example, RV viscometer “R VDV-II ⁺ Proj” manufactured by Brookfield).

[0187] The weight average molecular weight and molecular weight distribution of the specific layer forming solution A of the present invention are not limited. Usually, as described in "[A-1-5-7] Molecular weight". Furthermore, it is preferable that the low-boiling component in the specific layer forming liquid A of the present invention is small, like the specific layer A of the present invention described in “[A-15-8] Low-boiling component”. .

[B188] [B] Explanation of the fifth to eighth light guide members

[B-1] Explanation of each layer constituting the light guide member

The fifth to eighth light guide members of the present invention are characterized in that two or more layers are laminated. The fifth and seventh light guide members of the present invention include a light source whose emission peak has a dominant wavelength of 500 nm or less, and at least one of the stacked layers has the following characteristics: . In the sixth and eighth light guide members of the present invention, at least two layers in contact with each other among the above layers have the characteristics shown below. Furthermore, in any of the fifth to eighth light guide members of the present invention, it is preferable that each of the stacked layers has the following characteristics.

[6] (6) It contains a polar group at the interface with other layers.

(8) Having a siloxane bond.

Hereinafter, first of all, among the layers constituting the fifth to eighth light guide members of the present invention, focusing on these characteristics (6) to (8), the layers having the above characteristics (hereinafter referred to as “specific layer B as appropriate”). ))).

[0190] [B— 1 1] Characteristics (6): Polar group

In the fifth to eighth light guide members of the present invention, the specific layer B contains a polar group at the interface with other layers. That is, the specific layer B contains a compound having a polar group so as to have a polar group at the interface with another layer. There is no limitation on the type of such a polar group. Examples include lanol groups, amino groups and derivatives thereof, alkoxysilyl groups, carbonyl groups, epoxy groups, carboxy groups, carbinol groups (one COH), methacryl groups, cyanos groups, and sulfone groups. In addition, the specific layer B may contain only one kind of polar group at any time, or may contain two or more kinds of polar groups in any combination and ratio.

As described above, the specific layer B has a polar group at the interface with other layers, so that the two layers are strongly adhered and can be stacked by overcoating.

[0191] The polar group contained in the specific layer B according to the present invention is a predetermined functional group present on the surface of a resin, ceramic or metal such as polyphthalamide (for example, a hydroxyl group or an oxygen in a metalloxane bond). Etc.) and hydrogen bond is possible, and high adhesion is expressed. The substrate for installing the light guide member is usually made of resin, ceramic or metal. Further, a hydroxyl group usually exists on the surface of the ceramic metal. On the other hand, the specific layer B usually has a functional group capable of hydrogen bonding with the hydroxyl group. Therefore, the fifth to eighth light guide members of the present invention having the specific layer B are excellent in adhesion to the substrate due to the hydrogen bond.

The presence or absence of substantial polar groups in the specific layer B can be confirmed by IR (infrared spectroscopy) analysis and NMR (nuclear magnetic resonance).

[0192] By the way, these polar groups may be added to the surface of the specific layer B later by application of a primer or surface treatment which may be contained in the specific layer B from the beginning. Therefore, from this point of view, specific examples are given of the relationship between any two layers (including the specific layer B and the layer other than the specific layer B) constituting the fifth to eighth light guide members of the present invention. The configuration shown in Fig. 1 (a) to Fig. 1 (f) can be mentioned. However, the relationship of the layers constituting the fifth to eighth light guide members of the present invention is not limited to the following specific examples.

[0193] For example, as schematically shown in Fig. 1 (a), there is a configuration in which the two laminated layers are both formed from a specific layer B S containing a polar group from the beginning. In this case, both specific layers B adhere well due to the polar group contained in the specific layer B S.

[0194] For example, as schematically shown in Fig. 1 (b), one of the two laminated layers is a specific layer BS containing a polar group from the beginning, and the other does not contain a polar group. A configuration formed of layer O can be mentioned. Even in this case, it is more dense due to the polar group contained in the specific layer BS. Wearability is improved than before.

[0195] Further, for example, as schematically shown in FIG. 1 (c), the two laminated layers are initially formed of a layer O not containing a polar group, and between the two layers O and O. The primer P is applied to In this case, polar groups are imparted to the surfaces of both layers O and O by the primer P. Thereby, adhesiveness improves. In this case, the part containing the polar group is only an interface between the two layers, which is substantially a thin film. Therefore, even if a polar group that is easily colored by light or heat is introduced, the light guide function is hardly affected. . If layer O satisfies characteristics (7) and (8), these layers O will have polar groups due to primer P, and thus function as specific layer B.

[0196] For example, as schematically shown in Fig. 1 (d), the two laminated layers are both formed from a specific layer BS containing a polar group from the beginning, and both specific layers BS, S A configuration in which primer P is applied in between is mentioned. In this case, the adhesion between the two specific layers B S and S is particularly excellent due to the primer P.

[0197] Further, for example, as schematically shown in FIG. 1 (e), one of the two laminated layers is a specific layer BS containing a polar group from the beginning, and the other contains a polar group at the beginning. An example is a configuration in which the primer P is applied between the specific layer BS and the layer O. In this case, the adhesion between the specific layer B S and the layer O is improved by the primer P as compared with the case described in FIG. Even in this case, if layer O satisfies characteristics (7) and (8), these layers O will have polar groups due to primer P. I will be in a storehouse.

[0198] Further, for example, as schematically shown in Fig. 1 (f), a specific layer BS containing a polar group is first laminated on a layer O that does not contain a polar group at first, A configuration in which the component partially soaks into layer O to assist adhesion is exemplified. Such impregnation of the component is carried out by soaking the formation liquid of the specific layer B S as the upper layer into the layer O as the lower layer.

[0199] [B-1 2] Characteristic (7): Hardness measurement

The hardness measurement value is an index for evaluating the hardness of the specific layer of the fifth to eighth light guide members of the present invention, and is measured by the following hardness measurement method. In the fifth to eighth light guide members of the present invention, the specific layer B is preferably a member having a relatively low hardness, preferably a member having an elastomeric shape. That is, the fifth to eighth light guide members of the present invention are forces that use a plurality of members having different thermal expansion coefficients in the substrate or each layer. As described above, the specific layer B has a relatively low hardness. Preferably, by exhibiting an elastomeric shape, the specific layer B and the fifth to eighth light guide members of the present invention having the specific layer can relieve stress due to expansion and contraction of the respective components. Therefore, it is possible to provide a light guide member that is excellent in reflow resistance and temperature cycle resistance, which is difficult to cause peeling, cracking, disconnection, and the like during use.

[0200] Specifically, the specific layer B has a durometer type A hardness measurement Shore A) 15 or more, preferably 7 or more, more preferably 10 or more, and usually 100 or less, preferably 80 or less. More preferably, it is 70 or less. Alternatively, the hardness measurement value (Shore D) force by durometer type D is 0 or more, and usually 85 or less, preferably 80 or less, more preferably 75 or less. By having the hardness measurement value in the above range, the fifth to eighth light guide members of the present invention having the specific layer B and the specific layer B have reflow resistance and temperature cycle resistance that are difficult to generate cracks. It is possible to obtain the advantage of superiority. In addition, when the substrate on which the specific layer B is applied is a thin substrate such as a flexible substrate, the substrate and the specific layer B may be warped due to the curing shrinkage stress force due to the lamination of the specific layer B. For this reason, it is preferable that the specific layer B is formed of a material having rubber elasticity with a Shore A of 5 to 80.

[0201] [Hardness measurement method]

The hardness measurement value (Shore A) can be measured by the method described in JIS K6253. Specifically, the measurement can be performed using an A-type rubber hardness meter manufactured by Furusato Seiki Seisakusho, while the hardness measurement value (Shore D) can be measured by the method described in JIS K6253. Specifically, measurement can be performed using a D-type plastic hardness tester manufactured by Furusato Seiki Seisakusho.

[0202] [B— 1 3] Property (8): Siloxane bond

In the fifth to eighth light guide members of the present invention, the specific layer B contains a siloxane bond. The That is, the specific layer B is formed including a compound having a siloxane bond. Examples of the compound having a siloxane bond include inorganic materials, glass materials, and organic materials. Among these, specific examples of inorganic materials include a solution containing silicon oxide, nitride nitride, oxynitride, metal alkoxide, ceramic precursor polymer or metal alkoxide by a sol-gel method. Examples thereof include inorganic materials obtained by solidifying a solution obtained by decomposition polymerization or a combination thereof. Specific examples of glass materials include glass materials such as borosilicate, phosphosilicate, and alkali silicate. Furthermore, specific examples of organic materials include organic materials (silicone materials) such as polyorganosiloxane. In addition, the compound which has a siloxane bond may use only 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

Among the compounds having a siloxane bond, a silicone material is preferable from the viewpoint of easy handling. Hereinafter, this silicone material will be described in detail.

[0203] [B— 1 3— 1] Silicone materials

The silicone-based material usually refers to an organic polymer having a siloxane bond as a main chain, and examples thereof include a compound represented by the general composition formula (4) and / or a mixture thereof.

(R'R'R'SIO) (R ⁴ R ⁵ SiO) (R ⁶ SiO) (SiO) .. Formula (4)

1/2 M 2/2 D 3/2 T 4/2 Q

[0204] In the general composition formula (4), R ¹ to R ⁶ represent those selected from the group consisting of an organic functional group, a hydroxyl group and a hydrogen atom. R ¹ to R ⁶ may be the same or different.

In the general composition formula (4), M, D, T and Q represent a number of 0 or more and less than 1. However, it is a number satisfying M + D + T + Q = 1.

In the case where the specific layer B is formed using the silicone material, the specific layer B may be sealed using a liquid silicone material and then cured by heat or light.

[0205] [B— 1 3— 2] Types of silicone materials

If silicone materials are classified according to the curing mechanism, they are usually addition-polymerized curing types.

It is possible to list silicone materials such as condensation polymerization curing type, ultraviolet curing type and peroxide crosslinking type. Among these, addition polymerization curing type (addition type silicone Are preferred to be a polymer-based material), a condensation-curing type (condensation-type silicone material), and an ultraviolet-curing type. Hereinafter, the addition type silicone material and the condensation type silicone material will be described.

[0206] [B- 1-3- 2- 1] Addition-type silicone materials

Addition-type silicone materials refer to those in which polyorganosiloxane chains are bridged by organic additional bonds. A typical example is a compound having a Si—C C Si bond at a crosslinking point obtained by reacting butylsilane and hydrosilane in the presence of an addition catalyst such as a Pt catalyst. Commercially available products can be used. Specific examples of addition polymerization curing type trade names include “LPS-1400”, “LPS-2410”, and “LPS-3400” manufactured by Shin-Etsu Chemical Co., Ltd. Note that the specific layer B formed using such an addition-type silicone material usually contains a small amount of a bur group and / or a hydrosilyl group.

[0207] The addition-type silicone material is specifically represented by, for example, (A) an alkenyl group-containing organopolysiloxane represented by the following average composition formula (5) and the following average composition formula (6). (B) Hydrosilyl group-containing organopolysiloxane and (B) the total alkenyl group in (B) are mixed in an amount ratio such that the total hydrosilyl group amount of (B) is 0.5 to 2.0 times. (C) It can be obtained by reacting in the presence of an addition reaction catalyst.

[0208] (A) The alkenyl group-containing organopolysiloxane is an organopolysiloxane having an alkenyl group bonded to at least two silicon atoms in one molecule represented by the following composition formula (5).

R SiO (5)

n ((4 n) / 2]

(In the formula (5), R is the same or different substituted or unsubstituted monovalent hydrocarbon group, alkoxy group, or hydroxyl group, and n is a positive number satisfying l≤n <2. And at least one of R is an alkenyl group.)

[0209] (B) The hydrosilyl group-containing polyorganosiloxane is an organohydrogen polysiloxane having hydrogen atoms bonded to at least two silicon atoms in one molecule represented by the following composition formula (6).

R 'H SiO (6) (In the formula (6), R ′ is the same or different substituted or unsubstituted monovalent hydrocarbon group excluding the alkenyl group, and the symbols a and b are 0.7 ≦ a ≦ 2.1, 0. 001≤b≤l. 0 and a positive number satisfying 0.8.8≤a + b≤2.

[0210] Hereinafter, the addition-type silicone material will be described in more detail.

In R of the above formula (5), the alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms such as a bur group, a allyl group, a butyr group, or a pentyl group. In addition, when R is a hydrocarbon group, an alkyl group such as a methyl group or an ethyl group, a carbon group such as a bur group or a phenyl group; one selected from monovalent hydrocarbon groups having! More preferably, they are a methyl group, an ethyl group, and a phenyl group. Each R may be different, but if UV resistance is required, 80% or more of R is preferably a methyl group! /. R may be an alkoxy group having 1 to 8 carbon atoms or a hydroxyl group, but the content of the alkoxy group or hydroxyl group is preferably 3% or less of the weight of (A)! /.

In the above composition formula (5), n is a positive force satisfying l≤n <2. If this value is 2 or more, sufficient strength as a sealing material cannot be obtained. The synthesis of this organopolysiloxane becomes difficult.

Note that only one type of (A) alkenyl group-containing organopolysiloxane may be used, or two or more types may be used in any combination and ratio.

[0211] Next, the (B) hydrosilyl group-containing polyorganosiloxane acts as a crosslinking agent for curing the composition by hydrosilylation reaction with the (A) alkenyl group-containing organopolysiloxane.

In the composition formula (6), R ′ represents a monovalent hydrocarbon group excluding an alkenyl group. Here, as R ′, a group similar to R in the composition formula (5) (however, excluding the alkenyl group) can be exemplified. In addition, when used in applications requiring UV resistance, at least 80% is preferably a methyl group.

In the composition formula (6), the symbol a is usually a positive number of 0.7 or more, preferably 0.8 or more, and usually 2.1 or less, preferably 2 or less. The sign b is a positive number that is usually 0.001 or more, preferably 0.01 or more, and usually 1.0 or less. However, a + b is 0.8 or more, preferably 1 or more, 2.6 or less, preferably 2.4 or less. Further, the (B) hydrosilyl group-containing polyorganosiloxane has at least 2, preferably 3 or more SiH bonds in one molecule.

The molecular structure of the (B) hydrosilyl group-containing polyorganosiloxane may be any of linear, cyclic, branched, and three-dimensional network structures, but the number of silicon atoms in one molecule (or polymerization) The degree) can be 3 to 1000, especially about 3 to 300.

In addition, (B) hydrosilyl group containing polyorganosiloxane may use only 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

[0212] The blending amount of the (B) hydrosilyl group-containing polyorganosiloxane depends on the total alkenyl group amount of the (A) alkenyl group-containing organopolysiloxane. Specifically, the total SiH power of (B) hydrosilyl group-containing polyorganosiloxane with respect to the total alkenyl groups of (A) anoalkenyl group-containing organopolysiloxane is usually 0.5 mol times or more, preferably 0.8 mol. The amount may be not less than twice, and usually not more than 2.0 mol times, preferably not more than 1.5 mol times.

[0213] (C) The addition reaction catalyst promotes the hydrosilylation addition reaction between (A) an alkenyl group in an alkenyl group-containing organopolysiloxane and (B) a SiH group in a hydrosilyl group-containing polyorganosiloxane. It is a catalyst. Examples of the (C) addition reaction catalyst include platinum black, platinous chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chlorophosphoric acid and olefins, platinum bismuth. Examples thereof include platinum group catalysts such as platinum catalysts such as cetoacetate, palladium catalysts and rhodium catalysts.

(C) Only one type of addition reaction catalyst may be used. Two or more types may be used in any combination and ratio.

The compounding amount of this addition reaction catalyst can be a catalytic amount, but is usually based on the total weight of (A) an alkenyl group-containing organopolysiloxane and (B) a hydrosilyl group-containing polyorganosiloxane as a platinum group metal. 1 ppm or more, particularly 2 ppm or more, and 500 ppm or less, particularly preferably 10 ppm or less.

[0214] The composition for obtaining an addition-type silicone material includes (A) an alkenyl group-containing nonreganopolysiloxane, (B) a hydrosilyl group-containing polyorganosiloxane, and (C) an addition reaction catalyst. Addition control agent to give curability and pot life as optional components In addition to linear diorganopolysiloxane having an alkenyl group for adjusting hardness and viscosity, for example, linear non-reactive organopolysiloxane, linear having about 2 to 10 key atoms or A cyclic low molecular weight organopolysiloxane or the like may be incorporated in a range that does not impair the effects of the present invention.

[0215] The curing conditions for the composition are not particularly limited, but are preferably 120 to 180 ° C, 30 to 180 minutes. When the cured product is a soft gel after curing, the linear expansion coefficient is larger than that of rubber resin or hard plastic silicone resin, so it can be cured at a low temperature around room temperature for 10 to 30 hours. Force S to suppress the generation of internal stress.

[0216] As the addition-type silicone material, a known material can be used, and an additive or an organic group for improving adhesion to metal or ceramics may be further introduced. For example, silicone materials described in Japanese Patent Nos. 39 09826, 3910080, 2003-128922, 2004 221308, and 2004-186168 are suitable.

[0217] [B— 1 3— 2-2] Condensation type silicone material

Examples of the condensation type silicone material include a compound having a Si 2 O 3 Si bond obtained by hydrolysis and polycondensation of an alkylalkoxysilane at a crosslinking point. Specific examples include a polycondensate obtained by hydrolysis and polycondensation of a compound represented by the following general formula (1) and / or (2) and / or its oligomer.

[0218] M ^{m +} XY ¹ (1)

n m— n

(In the formula (1), M represents at least one element selected from the group consisting of silicon, aluminum, zirconium, and titanium, X represents a hydrolyzable group, and Y ¹ represents a monovalent group. M represents an integer of 1 or more that represents the valence of M, and n represents an integer of 1 or more that represents the number of X groups, where m≥n.)

[0219] (M ^{s +} XY ¹ ) Y ² (2)

s-1

(In the formula (2), M represents at least one element selected from the group consisting of silicon, aluminum, zirconium, and titanium, X represents a hydrolyzable group, and Y ¹ represents a monovalent group. Y ² represents a u-valent organic group, s represents an M valence, an integer of 1 or more T represents an integer of 1 or more and s—1 or less, and u represents an integer of 2 or more. )

[0220] [B— 1 3— 3] Curing catalyst

The condensation type silicone material may contain a curing catalyst. As the curing catalyst, any catalyst can be used as long as the effects of the present invention are not significantly impaired. For example, any catalyst can be used as long as it is active in the dehydration or dealcohol condensation of an alkoxysilyl group or silanol. May be. Specific examples include metal salts such as Ti, Al, Sn, Ta, Zn, Zr, and Hf, metal chelate compounds, and amines. Of these, metal chelate compounds are preferred. The metal salt and the metal chelate compound are any force selected from the group consisting of Ti, Al, Sn, Ta, Zn and Zr, and those containing 1 or more are more preferable. Only one type of curing catalyst may be used, or two or more types may be used in any combination and ratio! /.

[0221] [B- 1-3-4] Confirmation method of siloxane bond

Whether or not the specific layer B has a siloxane bond can be confirmed by solid S-NMR and IR analysis.

[0222] [B— 1 4] Other characteristics

The specific layers B of the fifth to eighth light guide members of the present invention are mainly characterized by the above-mentioned characteristics, but preferably have the following structure and properties. .

[0223] [B— 1 4 1] UV transmittance

When the specific layer B according to the present invention is used for an optical waveguide or a light guide plate with a semiconductor light emitting element as a light source, the light transmittance (transmittance) at the emission wavelength of the light source at a film thickness of 1 mm is usually It is preferable to be 80% or more, particularly 85% or more, and more preferably 90% or more. When the specific layer B is used as the translucent part in the light guide member, if the translucency of the translucent part is low, the luminance of the light source using the translucent part is reduced. It becomes difficult to obtain the final product.

Here, the “emission wavelength of the light source” means, for example, a power that varies depending on the type of the semiconductor light emitting device. Generally, it is usually 300 nm or more, preferably 350 nm or more, and usually 900 nm or less. Preferably, it refers to a wavelength in the range of 500 nm or less. If the light transmittance at wavelengths in this range is low, the specific layer B absorbs light and the light extraction efficiency decreases, A high-intensity optical waveguide or light guide plate cannot be obtained. Furthermore, the energy corresponding to the decrease in the light extraction efficiency is changed to heat, which causes thermal deterioration of the optical waveguide or the light guide plate, which is not preferable.

[0225] In the ultraviolet to blue region (wavelength 300 nm to 500 nm), the optical material is likely to be light-degraded. Therefore, the specific layer B according to the present invention having excellent durability is used as a light source having an emission wavelength in this region. If so, the effect will be great!

The light transmittance of the optical material such as the material of the specific layer B is measured with an ultraviolet spectrophotometer using a sample of a single cured film having a smooth surface molded to a film thickness of 1 mm by the following method, for example. I can do that.

[Measurement of light transmittance]

[0227] [B— 1 4 2] Molecular weight

There is no restriction | limiting in the molecular weight of the material which forms the specific layer B which concerns on this invention. However, the coating liquid used for forming the specific layer B (specific layer forming liquid B described later) is a polystyrene-converted weight average obtained by measuring the material forming the specific layer B by GPC (gel permeation chromatography). The molecular weight (Mw) is usually 200 or more, preferably 500 or more, more preferably 900 or more, more preferably 3200 or more, and usually 400,000 or less, preferably 70,000 or less, more preferably 50,000 or less. It is. If the weight average molecular weight is too small, it will volatilize during curing or contain a high concentration of crosslinkable terminals such as alkoxy groups, hydroxyl groups, bur groups, hydrosilyl groups, etc. Therefore, when used in the vicinity of blue to ultraviolet LEDs, there is a tendency for the transmittance from the catalyst to decrease. On the other hand, if the weight average molecular weight is too large, the liquid will have a high viscosity, resulting in poor leveling during coating, penetration of fine wiring and uneven parts on the substrate, and spilling of the liquid. There is a tendency for the filling efficiency to become poor due to insufficiency.

For example, when forming a specific layer B that is cured by cross-linking of a bull group and a hydrosilyl group. In some cases, in order to achieve both storage stability and operating time, a two-component type using two or more types of specific layer forming liquid B may be used. In this case, the weight average molecular weight is the value of the specific layer forming liquid B after mixing the liquids to be used together. In addition, when the molecular weight distribution shows a shape having two or more peaks such as two peaks and three peaks, the average value over the entire section is used as the weight average molecular weight value.

[0228] [B— 1 4 3] Tackiness

The specific layer B according to the present invention preferably has a low tackiness on the surface. In general, silicone rubber has tackiness (stickiness) on the surface of the cured product. However, if the tackiness is high, the products may be stacked and may not be handled individually during the manufacturing process, or may not be transported satisfactorily.

[0229] [B— 1 4 4] Tensile stress

When an external force is applied to an object, the force that resists the object in order to maintain its original shape is called tensile stress. The specific layer B has a stress relaxation force and preferably follows external forces such as bending and deformation. The preferred tensile stress range of the specific layer B is usually 0. IMPa or more, preferably 0.3 MPa or more, more preferably 0.4 MPa or more, and the upper limit is usually 50 MPa or less, preferably 30 MPa or less. Preferably it is 20 MPa or less. If the tensile stress is too small, the mechanical strength is insufficient and may be unsuitable for light guide plate applications. If it is too large, the material may be a hard material with insufficient stress relaxation force. However, when the specific layer B is provided on a thick substrate where deformation such as twisting and warping is not likely to occur, the tensile stress of the specific layer B is arbitrary. In addition, when the specific layer B is provided on a flexible substrate having a thickness of 500 m or less, it is particularly preferable that the specific layer B can relieve stress and that the tensile stress is 0. IMPa or more and 2 OMPa or less! /, .

The tensile stress can be measured based on JIS K6250.

[0230] [B— 1 5 Other layers]

The fifth to eighth light guide members of the present invention may have layers other than the specific layer B. As such a layer other than the specific layer B, a known layer can be arbitrarily applied. In addition to the specific layer B, only one layer may be provided, or two or more layers may be provided. However, in order to obtain the effect of the present invention more remarkably, more of the layers of the fifth to eighth light guide members of the present invention have the characteristics as the specific layer B. It is more preferable that all the layers have the characteristics as the specific layer B described above.

[0231] [B— 1 6] Method for producing each layer of light guide member

The method for producing the fifth to eighth light guide members of the present invention is not particularly limited. Therefore, each layer constituting the fifth to eighth light guide members of the present invention can be manufactured by any method. Usually, a liquid material (that is, a forming solution) for each layer is applied to a desired site to form a coating film, and the coating film is cured by heat or light. Therefore, the specific layer B is formed by, for example, applying a liquid material of the specific layer B (hereinafter referred to as “specific layer forming liquid B”) to a desired part to form a coating film. It can be made by curing with heat or light.

[0232] Furthermore, when producing the specific layer B, it is preferable to appropriately perform primer treatment in order to ensure that the specific layer B has the above-mentioned preferable characteristics. In general, when an upper layer is laminated on the underlayer, if the upper layer is laminated directly on the underlayer, the self-adhesive property of the upper layer may be insufficient and peeling may occur. In order to prevent this, if necessary, an adhesive layer having adhesiveness to both the base layer and the upper layer may be applied as an intermediate layer between the base layer and the upper layer. Applying such an adhesive intermediate layer on the underlayer is called primer treatment, and the coating solution is called a primer. By this primer treatment, two layers that are inherently insufficient in adhesion can be easily laminated with high adhesion. It is also possible to improve the adhesion with an upper layer not containing a polar group by applying a primer to the base layer not containing a polar group. In this case, the primer itself works in the same way as the polar group at the interface. The film thickness of the primer layer formed by the primer treatment is an arbitrary force as long as the effect of the present invention is not significantly impaired.

[0233] Further, the specific layer B or another layer or member in contact with the specific layer B may be subjected to a surface treatment. Examples of such surface treatment include, for example, formation of an adhesion improving layer using a primer-silane coupling agent, chemical surface treatment using a chemical such as acid or alkali, plasma irradiation, ion irradiation or electron beam irradiation. Used physical surface treatment, support And surface blasting by etching or fine particle coating. Other surface treatments for improving adhesion include, for example, JP-A-5-25300, Nobuhiro Inagaki “Surface Chemistry” Vol. 18 No. 9, pp21-26, Kuroo Kurosaki “Surface Chemistry” ”Vo 1.19 No. 2, pp44-51 (1998), etc., may be known surface treatment methods. Furthermore, ozone treatment can be performed.

[0234] [B-2] Light source

The fifth and seventh light guide members of the present invention include a light source. Moreover, the sixth and eighth light guide members of the present invention may include a light source. Normally, the fifth to eighth light guide members of the present invention transmit light emitted from the light source and emit the light as it is or after converting the wavelength.

However, in the fifth and seventh light guide members of the present invention, the wavelength of the main wavelength of the light emission peak of this light source is 900 nm or less, preferably 700 nm or less, more preferably 500 ηm or less. If the wavelength of the main wavelength of the light emission peak of the light source is too long, the light beam becomes a heat ray and may cause damage to the light guide member or may be absorbed by the constituent members of the light guide member to cause transmission loss. The lower limit of the wavelength of the emission peak is not limited, but is usually 300 nm or more, preferably 350 nm or more, more preferably 400 nm or more. If the wavelength of the main wavelength of the light emission peak of the light source is too short, the light beam becomes high-energy ultraviolet light, which may reduce the transmittance of the light guide member.

[0235] The type of the light source is not limited as long as it emits light having the above-described emission peak, but a semiconductor light emitting element is usually used. For example, a light emitting diode (LED) or a laser diode (LD) can be given. Of these, GaN-based LEDs and LDs using GaN-based compound semiconductors are preferred. This is because GaN-based LEDs and LDs are extremely low power and extremely low power when combined with phosphors described later, whose light output and external quantum efficiency are significantly higher than SiC LEDs that emit light in this region. The power to obtain bright light emission. For example, for a current load of 20 mA, GaN-based LEDs and LDs usually have a light emission intensity that is more than 100 times that of SiC. For GaN-based LEDs and LDs, Al Ga

X

Those having an N light emitting layer, a GaN light emitting layer, or an InGa N light emitting layer are preferred. GaN

Y X Y

Among these LEDs, those with an InGaN emission layer have a very high emission intensity. For GaN-based LDs, which are particularly preferred, multiple amounts of InGaN and GaN layers

X Y

The one with the well structure is particularly preferred because the emission intensity is very strong.

In the above, the value of X + Y is usually a value in the range of 0.8 to 1.2. In GaN-based LEDs, these light-emitting layers doped with Zn or Si or those without dopants are preferred for adjusting the light emission characteristics.

GaN-based LEDs have these light-emitting layers, p-layers, n-layers, electrodes, and substrates as basic components. The light-emitting layers are n-type and p-type AlGaN layers, GaN layers, or InGaN layers. Etc.

X Y X Y

Those having a heterostructure in the form of a neutral switch are preferred because the luminous efficiency is high, and those having a heterostructure in the quantum well structure are more preferred because the luminous efficiency is further high.

[0237] Note that the fifth to eighth light guide members of the present invention may include only one light source or two or more light sources in any combination and ratio. Further, the fifth to eighth light guide members of the present invention may include another light source that does not have the main wavelength of the emission peak in the above wavelength range, in addition to the above light source. In addition, the light source is equipped with a combination of multiple light sources with different emission colors such as red, green, and blue!

[0238] [C. Description of matters common to first to eighth light guide members]

[C 1] Other ingredients

The specific layer A and the specific layer B (hereinafter, when the specific layer A and the specific layer B are referred to without distinction, they may be referred to as “specific layer” as appropriate. In addition, the specific layer forming liquid A and the specific layer forming liquid B When referring to them without distinction, they may be referred to as “specific layer forming liquid” as appropriate.) Any component can be contained without departing from the gist of the present invention. Therefore, depending on the application, the specific layer and the specific layer forming liquid may contain other components in addition to the above-mentioned hydrolysis polycondensate. For example, if necessary, the specific layer and the specific layer forming liquid may contain phosphors, inorganic particles, and the like. In addition, other components may be used alone, or two or more may be used in any combination and ratio. In addition, you may contain these other components in layers other than the specific layer which comprises the 1st-8th light guide member of this invention. Hereinafter, when referring to the first to eighth light guide members of the present invention without distinction, they may be appropriately referred to as “light guide members”.

Hereinafter, the phosphor and the inorganic particles will be described. [0239] [C 1 1] phosphor

The light guide member of the present invention can contain, for example, a phosphor in a phosphor-containing layer (see [C 2-3-4]) described later. The phosphors may be used alone or in combination of two or more in any combination and ratio. Also, the phosphor is contained in two or more layers among the layers constituting the light guide member of the present invention!

[0240] [C 1 1 1] Types of phosphor

There are no particular restrictions on the composition of the phosphor, but it is typically represented by the crystal matrix Y O, Zn SiO, etc.

2 3 2 4 Metal oxides, phosphates typified by Ca (PO) C1, etc. and ZnS, SrS, CaS, etc.

5 4 3

石匕匕, Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, and other rare earth metal ions, Ag, Cu, Au, Al, A combination of metal ions such as Mn and Sb as an activator or coactivator is preferred.

[0241] Preferred examples of the crystal matrix include (Zn, Cd) S, SrGa S, SrS, ZnS, etc.

twenty four

Sulfides, oxysulfides such as Y O S, (Y, Gd) Al O, YAIO, BaMgAl O, (Ba, S

2 2 3 5 12 3 10 17

r) (Mg, Mn) Al O, (Ba, Sr, Ca) (Mg, Zn, Mn) Al O, BaAl O, CeMg

10 17 10 17 12 19

Al O, (Ba, Sr, Mg) 0 -Al O, BaAl Si O, SrAl O, Sr Al O, Y Al O

11 19 2 3 2 2 8 2 4 4 14 25 3 5 12 etc. aluminate, Y SiO, Zn SiO etc. silicate, SnO, Y O etc. oxide, GdM

2 5 2 4 2 2 3

borate such as gB 2 O 3, (Y, Gd) BO, Ca (PO 2) (F, CI), (Sr, Ca, Ba, Mg) (

5 10 3 10 4 6 2 10

Halophosphates such as PO) CI, phosphates such as SrPO, (La, Ce) PO, etc.

4 6 2 2 2 7 4

it can.

[0242] However, the above-mentioned crystal matrix and activator or coactivator are not particularly limited in element composition, and can be partially replaced with elements of the same family, and the obtained phosphor is visible from near ultraviolet. Any material that absorbs light in a region and emits visible light can be used.

Specifically, the following can be used as phosphors, and these are merely examples, and phosphors that can be used in the present invention are not limited to these. In the examples of the phosphors in this specification, phosphors that differ only in part of the structure are appropriately omitted. For example, “Y SiO: Ce ³⁺ ”, “Y SiO: Tb ³⁺ ” and “Y SiO:

2 5 2 5 2 5

“Ce ³⁺ , Tb ³⁺ ” and “Y SiO: Ce ³⁺ , Tb ³⁺ ” and “La OS: Eu”, “YOS: Eu” and “(: La

2 5 2 2 2 2

, Y) O 3: £ 11 ”together with“ (1 ^, Y) O S: Eu ”. The omitted part is a comma (,)

2 2 2 2 Shown separated by.

[C 1 1 1 1] Red phosphor

Illustrating the specific wavelength range of the fluorescence emitted by the phosphor emitting red fluorescence (hereinafter referred to as “red phosphor” as appropriate), the peak wavelength is usually 570 nm or more, preferably 580 nm or more, Usually, it is 700 nm or less, preferably 680 nm or less.

[0244] Examples of red phosphors such as two are composed of fractured particles having a red fracture surface, and emit light in the red region (Mg, Ca, Sr, Ba) SiN: Eu represented by Eu. Mouth piu

2 5 8

Activated alkaline earth silicon nitride phosphor, composed of growing particles with a nearly spherical shape as a regular crystal growth shape, and emits light in the red region (Y, La, Gd, Lu) OS: Eu The rare earth oxychalcogenide-based phosphor activated by the pyrudium represented by

twenty two

Can be mentioned.

[0245] Further, an oxynitride containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo described in JP-A-2004-300247 It is also possible to use a phosphor containing an oxysulfide and containing an oxynitride having an alpha sialon structure in which part or all of the A1 element is substituted with a Ga element. These are phosphors containing oxynitrides and / or oxysulfides.

[0246] In addition, as red phosphors, for example, Eu-activated oxysulfur such as (La, Y) O S: Eu

twenty two

Compound phosphor, Y (V, P) 0: Eu, Y ：: Eu-activated oxide phosphor such as Eu, (Ba, Sr, Ca)

4 2 3

, Mg) SiO: Eu, Mn, (Ba, Mg) SiO: Eu, Mn activated silicate phosphor such as Eu, Mn

2 4 2 4

, (Ca, Sr) S: Eu-activated sulfide phosphors such as Eu, etc. YA10: Eu-activated aluminate such as Eu

Three

Phosphor, LiY (SiO 2) O: Eu, Ca Y (SiO 2) 0: Eu, (Sr, Ba, Ca) SiO: Eu, S

9 4 6 2 2 8 4 6 2 3 5 r BaSiO: Eu-activated silicate phosphor such as Eu, (Y, Gd) Al 2 O: Ce, (Tb, Gd) Al 0

2 5 3 5 12 3 5

: Ce-activated aluminate phosphor such as Ce, (Ca, Sr, Ba) Si N: Eu, (Mg, Ca, Sr,

12 2 5 8

Ba) SiN: Eu, (Mg, Ca, Sr, Ba) AlSiN: Eu-activated nitride phosphors such as Eu, (Mg,

twenty three

Ca, Sr, Ba) AlSiN: Ce-activated nitride phosphors such as Ce, (Sr, Ca, Ba, Mg) (PO)

3 10 4 6

CI: Eu, Mn-activated halophosphate phosphors such as Eu, Mn, (Ba Mg) Si O: Eu, Mn, (B

2 3 2 8

a, Sr, Ca, Mg) (Zn, Mg) Si O: Eu, Mn activated silicate phosphor such as Eu, Mn, etc.

3 2 8

MgO-0.5 MgF -GeO: Mn-activated germanate phosphor such as Mn, Eu-activated α sizer Eu-activated oxynitride phosphors such as Ron, Eu, Bi-activated such as (Gd, Y, Lu, La) 2 O: Eu, Bi

twenty three

Oxide phosphor, (Gd, Y, Lu, La) O S: Eu, Bi activated oxysulfide phosphor such as Eu, Bi, etc.

twenty two

(Gd, Y, Lu, La) VO: Eu, Bi-activated vanadate phosphor such as Eu, Bi, etc., SrY S: Eu

4 2 4

Eu, Ce activated sulfide phosphor such as Ce, Ce, CaLa S: Ce activated sulfide phosphor such as Ce, (B

twenty four

a, Sr, Ca) MgP ○: Eu, Mn (Sr, Ca, Ba, Mg, Zn) P ○: Eu, Eu, Mn, etc.

2 7 2 2 7

Mn-activated phosphate phosphor, (Y, Lu) WO: Eu, Mo-activated tungstic acid such as Eu and Mo

2 6

Salt phosphor, (Ba, Sr, Ca) Si N: Eu, Ce (where x, y, z are integers of 1 or more), Eu, x y z

Ce-activated nitride phosphor, (Ca, Sr, Ba, Mg) (PO) (F, CI, Br, OH): Eu, Mn, etc.

10 4

Eu, Mn-activated halophosphate phosphor, ((Y, Lu, Gd, ₂ (Ca, Mg) 卜

It is also possible to use Ce-activated silicate phosphors such as (Mg, Zn) Si Ge O

2 + r z-q q 12+ δ

[0247] Examples of the red phosphor include: / 3 diketonate, β-diketone, aromatic carboxylic acid, or a red organic phosphor composed of a rare earth ion complex having an anion such as Bronsted acid as a ligand, a perylene pigment (For example, dibenzo {[f, f ']-4,4', 7,7'-tetraphenyl} diindeno [1,2,3-cd: l ', 2', 3'-lm] perylene) , Anthraquinone pigments, lake pigments, azo pigments, quinacridone pigments, anthracene pigments, isoindoline pigments, isoindolinone pigments, phthalocyanine pigments, triphenylmethane basic dyes, indanthrone pigments Indophenol pigments, cyanine pigments and dioxazine pigments can also be used.

[0248] Among red phosphors, those having a peak wavelength in the range of 580 nm or more, preferably 590 nm or more, and 620 nm or less, preferably 610 nm or less can be suitably used as an orange phosphor. . Examples of such orange phosphors are (Sr, Ba) SiO 2: Eu, (

3 5

Sr, Mg) (PO): Sn ²⁺ , SrCaAlSiN: Eu, Eu-activated Eu-activated oxynitride such as α-sialon

3 4 2 3

Compound phosphor and the like.

[0249] [C 1 1 1 2] Green phosphor

Illustrating the specific wavelength range of the fluorescence emitted by the phosphor emitting green fluorescence (hereinafter referred to as “green phosphor” as appropriate), the peak wavelength is usually 490 nm or more, preferably 500 nm or more, Usually, it is 570 nm or less, preferably 550 nm or less. As such a green phosphor, for example, it is composed of fractured particles having a fracture surface, and emits light in the green region (Mg, Ca, Sr, Ba) Si ON: with a plutonium represented by Eu.

2 2 2

Active alkaline earth silicon oxynitride phosphor, composed of fractured particles with fractured surface, and emits light in the green region (Ba, Ca, Sr, Mg) SiO: Eu mouth expressed by Eu

twenty four

Examples include a palladium-activated alkaline earth silicate phosphor.

[0250] Besides, as the green phosphor, for example, SrAlO: Eu, (Ba, Sr, Ca) Al

4 14 25 2

O: Eu-activated aluminate phosphor such as Eu, (Sr, Ba) Al Si O: Eu, (Ba, Mg) SiO

4 2 2 8 2 4

: Eu, (Ba, Sr, Ca, Mg) SiO: Eu, (Ba, Sr, Ca) (Mg, Zn) Si O: Eu such as Eu

2 4 2 2 7

Activated silicate phosphor, Y SiO: Ce, Tb activated silicate phosphor such as Ce, Tb, Sr P O—

2 5 2 2 7

Sr B O: Eu-activated boric acid phosphor such as Eu, Sr Si O 2 SrCl: Eu such as Eu

2 2 5 2 3 8 2

Active halosilicate phosphor, ZnSiO: Mn-activated silicate phosphor such as Mn, CeMgAl 2 O:

2 4 11 19

Tb, Y Al O: Tb activated aluminate phosphor such as Tb, Ca Y (SiO 2) O: Tb, La G

3 5 12 2 8 4 6 2 3 a SiO: Tb-activated silicate phosphor such as Tb, (Sr, Ba, Ca) Ga S: E such as Eu, Tb, Sm

5 14 2 4

u, Tb, Sm activated thiogallate phosphor, Y (Al, Ga) O: Ce, (Y, Ga, Tb, La, Sm

3 5 12

Pr, Lu) (Al, Ga) O: Ce-activated aluminate phosphor such as Ce, Ca Sc Si O: Ce

3 5 12 3 2 3 12

Ca (Sc, Mg, Na, Li) Si O: Ce-activated silicate phosphor such as Ce, CaSc O: Ce, etc.

3 2 3 12 2 4 Ce-activated oxide phosphor, SrSi ON: Eu, (Sr, Ba, Ca) Si ON: Eu, Eu-activated / 3

2 2 2 2 2 2

Eu-activated oxynitride phosphors such as sialon, BaMgAl 2 O: Eu, Mn, etc.

10 17

Activated aluminate phosphor, Eu-activated aluminate phosphor such as SrAl 2 O 3: Eu, (La, Gd,

twenty four

Y) Os: Tb-activated oxysulfide phosphors such as Tb, LaP〇: Ce, Tb-activated phosphoric acid such as Ce, Tb

2 2 4

Salt phosphors, sulfide phosphors such as ZnS: Cu, Al, ZnS: Cu, Au, Al, (Y, Ga, Lu, Sc, La) BO: Ce, Tb T Na Gd B〇: Ce, Tb, (Ba, Sr) (Ca, Mg, Zn) B〇: K, C

3 2 2 2 7 2 2 6 e, Ce, Tb activated borate phosphors such as Tb, Ca Mg (SiO 2) CI: Eu, Mn such as Eu, Mn

8 4 4 2

Activated halosilicate phosphor, (Sr, Ca, Ba) (Al, Ga, In) S: Eu activated thioal such as Eu

twenty four

Minate phosphor and thiogallate phosphor, (Ca, Sr) (Mg, Zn) (SiO) CI: Eu, Mn

8 4 4 2

It is also possible to use Eu, Mn activated halosilicate phosphors, etc.

[0251] Examples of green phosphors include pyridine-phthalimide condensed derivatives, benzoxazinone-based, quinazolinone-based, coumarin-based, quinophthalone-based, and naltalimide-based fluorescent materials. It is also possible to use an organic phosphor such as a terbium complex having a dye or hexyl salicylate as a ligand.

[0252] [C 1 1 1 3] Blue phosphor

Illustrating the specific wavelength range of the fluorescence emitted by the phosphor emitting blue fluorescence (hereinafter referred to as “blue phosphor” as appropriate!), The peak wavelength is usually 420 nm or more, preferably 440 nm or more, Usually, it is 480 nm or less, preferably 470 nm or less.

As such a blue phosphor, for example, a growing particle force having a substantially hexagonal shape as a regular crystal growth shape is configured, and BaMgAl 2 O 3: Eu that emits light in a blue region.

10 17 This is composed of Pt-activated norlium magnesium aluminate-based phosphor, which is composed of grown particles having a nearly spherical shape as a regular crystal growth shape, and emits light in the blue region (Ca, Sr, Ba) (PO) CI: Eu-pium-activated halophosphate calcium represented by Eu

5 4 3

Phosphors, which are composed of growing particles having a regular cubic crystal growth shape and emit light in the blue region (Ca, Sr, Ba) B O CI: Eu

2 5 9

Pium-activated alkaline earth chloroborate phosphor, composed of fractured particles with fractured surfaces, and emits light in the blue-green region (Sr, Ca, Ba) Al 2 O: Eu or (Sr, Ca, Ba) Al

2 4 4 1

O: Pit-activated alkaline earth aluminate-based phosphor represented by Eu

4 25

It is done.

[0253] In addition, other examples of blue phosphors include Sn-activated phosphate phosphors such as Sr P 2 O 3: Sn.

2 2 7

Light body, Sr Al ○: Eu, BaMgAl ○: Eu, BaAl ○: Eu-activated aluminate such as Eu

4 14 25 10 17 8 13

Salt-activated phosphor, SrGa S: Ce, CaGa S: Ce-activated thiogallate phosphor such as Ce, (Ba, Sr

2 4 2 4

, Ca) MgAlO: Eu, BaMgAlO: Eu-activated aluminate fluorescence such as Eu, Tb, Sm

10 17 10 17

(Ba, Sr, Ca) MgAl O: Eu, Mn activated aluminate phosphor such as Eu, Mn, (Sr

10 17

, Ca, Ba, Mg) (PO) CI: Eu, (Ba, Sr, Ca) (PO) (CI, F, Br, OH): Eu,

10 4 6 2 5 4 3

Eu-activated halophosphate phosphors such as Mn and Sb, BaAl Si O: Eu, (Sr, Ba) MgSi 0:

2 2 8 3 2 8

Eu-activated silicate phosphor such as Eu, Eu-activated phosphate phosphor such as Sr P O: Eu, ZnS: A

2 2 7

g, sulfide phosphor such as ZnS: Ag, Al, etc., Y SiO: Ce activated silicate phosphor such as Ce, CaW

twenty five

〇 etc. tungstate phosphor, (Ba, Sr, Ca) BPO: Eu, Mn, (Sr, Ca) (PO)

4 5 10 4

• nB 2 O: Eu, 2SrO-0.84P O-0.16B O: Eu, Mn-activated boric acid phosphates such as Eu Phosphors, Eu-activated halosilicate phosphors such as SrSiO-2SrCl: Eu can also be used

2 3 8 2

Noh.

In addition, as the blue phosphor, for example, naphthalic acid imide-based, benzoxazole-based, styryl-based, coumarin-based, pyrazoline-based, triazole-based fluorescent dyes, organic phosphors such as thulium complexes, etc. may be used. Is possible.

[0254] [C 1 1 1 4] Yellow phosphor

An example of the specific wavelength range of the fluorescence emitted by a phosphor emitting yellow fluorescence (hereinafter referred to as “yellow phosphor” as appropriate) is usually 530 nm or more, preferably 540 nm or more, and more preferably 550 nm. In addition, the wavelength is usually 620 nm or less, preferably 600 mm or less, more preferably 580 nm or less. If the emission peak wavelength of the yellow phosphor is too short, the yellow component may be reduced and the color rendering may be inferior. If it is too long, the luminance of the light emitted from the light guide member may be reduced.

[0255] Examples of such yellow phosphors include various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors. In particular, RE M O: Ce (where R

3 5 12

E represents at least one element of Y, Tb, Gd, Lu, and Sm, and M represents at least one element of Al, Ga, and Sc. ) Or M ² M ³ M ⁴ O: Ce (where M ² is a divalent metal element

3 2 3 12

, M ³ is a trivalent metal element, M ⁴ is garnet phosphor having a garnet structure represented by tetravalent metal element) and the like, AE M ⁵ 0: Eu (here, AE is, Ba, Sr, Less Ca, Mg, Zn

twenty four

Both represent one kind of element, and M ⁵ represents at least one kind of element of Si and Ge. ), Etc., oxynitride phosphors obtained by substituting part of oxygen of the constituent elements of the phosphors with nitrogen, AEAlSiN: Ce (where AE is Ba , Sr, Ca, Mg

Three

, Represents at least one element of Zn. Nitride-based fluorescence with CaAlSiN structure

Three

And phosphors activated by Ce such as the body.

Further, as the yellow phosphor, for example, CaGa S: Eu (Ca, Sr) Ga S: Eu,

2 4 2 4

(Ca, Sr) (Ga, Al) S: Sulfide-based phosphors such as Eu, Ca (Si, Al) (O, N): Eu etc.

2 4 x 12 16

It is also possible to use a phosphor activated with Eu such as an oxynitride phosphor having a SiAlON structure.

[0256] [C 1 1 1 5] Other phosphors The light guide member of the present invention can contain phosphors other than those described above. For example, the layer constituting the light guide member of the present invention may be a fluorescent glass in which an ionic fluorescent material or an organic / inorganic fluorescent component is dissolved and dispersed uniformly and transparently.

[0257] Particle size of [C 1 1 2] phosphor

The particle size of the phosphor used in the present invention is not particularly limited, but the median particle size (D) is usually 0.

50

l ^ m or more, preferably 2 m or more, more preferably 5 m or more. Further, it is usually 1 OO ^ m or less, preferably 50 m or less, more preferably 20 m or less. When the median particle diameter (D) of the phosphor is in the above range, the phosphor-containing layer described later can be used as a light source.

50

The transmitted light is sufficiently scattered. In addition, since the light transmitted from the light source is sufficiently absorbed by the phosphor particles, wavelength conversion is performed with high efficiency, and light emitted from the phosphor is irradiated in all directions. As a result, primary light from a plurality of types of phosphors can be mixed to make white, and uniform white light and illuminance can be obtained. On the other hand, when the central particle size (D) of the phosphor is larger than the above range! /, The phosphor sufficiently fills the space of the light emitting part.

50

Therefore, the light transmitted from the light source may not be sufficiently absorbed by the phosphor. If the median particle size (D) of the phosphor is smaller than the above range,

50

Since the light efficiency decreases, the illuminance may decrease.

[0258] The particle size distribution (QD) of the phosphor particles is preferably smaller in order to align the dispersed state of the particles in the phosphor-containing layer, but in order to reduce the particle size, the classification yield is lowered, leading to an increase in cost. Usually, it is 0.03 or more, preferably 0.05 or more, and more preferably 0.07 or more. Further, it is usually 0.4 or less, preferably 0.3 or less, more preferably 0.2 or less. In the present invention, the median particle size (D) and particle size distribution (QD) are weight-based particle sizes.

50

It can be obtained from the distribution curve. The weight-based particle size distribution curve can be obtained by measuring the particle size distribution by a laser diffraction or scattering method. Specifically, for example, it can be measured as follows.

[0259] [Measurement method of weight-based particle size distribution curve]

(1) Disperse the phosphor in a solvent such as ethylene glycol in an environment where the temperature is 25 ° C and the humidity is 70%.

(2) With a laser diffraction particle size distribution analyzer (Horiba, Ltd. LA-300), the particle size range is 0. Measure at 1 μm to 600 μm.

(3) In this weight-based particle size distribution curve, the particle size value when the integrated value is 50% is expressed as the median particle size D. Also, the particle size values when the integrated value is 25% and 75% are D, D and

50 25 75 Notation and defined as QD = (D -D) / (D + D). Small QD means particle size distribution

75 25 75 25

Means narrow.

[0260] The shape of the phosphor particles is arbitrary as long as it does not affect the formation of the phosphor-containing layer. For example, a forming liquid for forming a phosphor-containing layer (hereinafter, referred to as “phosphor-containing layer forming liquid” as appropriate. For example, a specific layer forming liquid containing a phosphor, etc., is the same as the phosphor composition. As long as it does not affect the fluidity, etc.).

[0261] [C 1 1 3] Phosphor surface treatment

The phosphor used in the present invention may be subjected to a surface treatment for the purpose of enhancing water resistance or preventing unnecessary aggregation of the phosphor in the phosphor-containing layer. Examples of such surface treatment include surface treatments using organic materials, inorganic materials, glass materials and the like described in JP-A-2002-223008, and metal phosphates described in JP-A-2000-96045. And a known surface treatment such as a silica coating.

[0262] As specific examples of the surface treatment, for example, the following surface treatments (i) to (iii) are performed in order to coat the phosphor with the metal phosphate.

(i) a predetermined amount of a water-soluble phosphate such as potassium phosphate or sodium phosphate and an alkaline earth metal such as calcium chloride, strontium sulfate, manganese chloride or zinc nitrate, at least of Ζη and ηη One kind of water-soluble metal salt compound is mixed in the phosphor suspension and stirred.

(ii) A phosphate of at least one of the alkaline earth metals, Zn and Mn is formed in the suspension, and the generated metal phosphate is deposited on the phosphor surface.

(iii) Remove moisture.

[0263] Further, among other examples of surface treatment, preferable examples include silica coating, a method of neutralizing water glass to precipitate SiO, and surface treatment of hydrolyzed alkoxysilane.

2

(For example, Japanese Patent Laid-Open No. 3-231987) and the like to improve dispersibility O! / A method of surface treatment of hydrolyzed alkoxysilane is preferred! /.

[0264] [C 1 1 4] Phosphor mixing method

In the present invention, the method of adding phosphor particles is not particularly limited! /.

For example, when phosphor is contained in a specific layer, if the dispersion state of the phosphor particles is good, it is only necessary to post-mix in the above-mentioned specific layer forming liquid. That is, the specific layer forming solution and the phosphor are mixed, a phosphor-containing layer forming solution is prepared, and the phosphor-containing layer is prepared using this phosphor-containing layer forming solution. When aggregation of the phosphor particles is likely to occur, the phosphor particles are mixed in advance with a reaction solution containing the raw material compound before hydrolysis (hereinafter referred to as “pre-hydrolysis solution”!). When hydrolysis / polycondensation is performed in the presence of silane, the surface of the particles is partially treated with silane coupling, and the dispersed state of the phosphor particles is improved.

[0265] In addition, when the layer containing the phosphor is formed of an addition condensation type silicone resin, the phosphor surface is preliminarily provided with a crosslinkable group such as a bull group and a hydrosilyl group, or a hydrophobic group such as a methyl group. The dispersion state is improved by surface treatment using the silane coupling. If the phosphor-containing layer is formed of a dehydrated or dealkoxy-condensation type silicone resin and the phosphor particles are likely to aggregate, the phosphor particles are mixed in advance in the pre-hydrolysis solution, When hydrolysis / polycondensation is performed in the presence of phosphor particles, the surface of the particles is partially silane-coupled to improve the dispersion state of the phosphor particles.

[0266] It should be noted that some phosphors are hydrolyzable. The specific layer A of the first to fourth light guide members of the present invention is in a liquid state before application (specific layer forming liquid A). In this case, water is potentially present as a silanol body, and almost no free water is present. Therefore, even such a phosphor can be used without being hydrolyzed. Further, if the specific layer forming solution after hydrolysis and polycondensation is used after dehydration / dealcoholation treatment, there is an advantage that it can be easily used together with such a phosphor.

[0267] When a hydrolyzable phosphor is used, the use of an addition condensation type silicone resin as the material of the layer containing the phosphor means that the silicone resin generates water during curing. This is preferable. In addition, when a dehydrated or dealcoholized silicone resin is used as the material for the phosphor-containing layer, the liquid state (formation solution) before coating is not good. In addition, since water is potentially present as a silanol body and almost no free water is present, such a phosphor can be used without being hydrolyzed. Further, if the formation liquid after hydrolysis / polycondensation is used after dehydration / dealcoholation treatment, there is also an advantage that the combined use with such a phosphor becomes easy. Therefore, when the specific layer contains a phosphor, it is particularly preferable to form the specific layer with an addition condensation type, dehydration, or dealcohol type silicone resin.

[0268] When phosphor particles or inorganic particles (described later) are dispersed in a specific layer, the particle surface can be modified with an organic ligand to improve dispersibility. Conventional addition-type silicone resins that have been used as light-guide members cannot be cured and mixed with such surface-treated particles as soon as they are inhibited by such organic ligands. It was. This is because the platinum-based curing catalyst used in the addition reaction type silicone resin has a strong interaction with these organic ligands, loses the hydrosilylation ability, and causes poor curing. Such poisonous substances include organic compounds containing N, P, S, etc., ionic compounds of heavy metals such as Sn, Pb, Hg, Bi, As, acetylene groups, etc., organic compounds containing multiple bonds (flux) Amines, vinyl chloride, sulfur vulcanized rubber) and the like. On the other hand, the specific layer of the light guide member of the present invention is based on a condensation-type curing mechanism that hardly causes inhibition of curing by these poisoning substances. For this reason, the specific layer is made of phosphor particles or inorganic particles whose surface has been modified with an organic ligand, and phosphor binders that have a high degree of freedom of mixing with fluorescent components such as complex phosphors. It has excellent characteristics as an introduced transparent material.

[0269] Content of [C 1 1 5] phosphor

The phosphor content in the phosphor-containing layer of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, and the force that can be freely selected according to the application mode is usually 0.1% by weight or more, Preferably it is 1% by weight or more, more preferably 5% by weight or more, and usually 35% by weight or less, preferably 30% by weight or less, more preferably 28% by weight or less.

Yes

[0270] Also, in general, when the light emission color transmitted from the light source is mixed with the light emission color of the phosphor to obtain white, a part of the light emission color transmitted through the light source power is transmitted. ,fluorescence The body content is low and becomes a region near the lower limit of the above range. On the other hand, when white light is obtained by converting all the light transmitted from the light source into a phosphor emission color, a high concentration phosphor is preferred, and the phosphor content is in a region near the upper limit of the above range. If the phosphor content is higher than this range, the coating performance may be deteriorated, or the utilization efficiency of the phosphor may be lowered due to optical interference, and the luminance may be lowered. On the other hand, if the phosphor content is less than this range, wavelength conversion by the phosphor becomes insufficient, and the target emission color may not be obtained.

[0271] Although examples of the use of white light emission have been described above, the specific phosphor content varies depending on the target color, the light emission efficiency of the phosphor, the color mixture type, the specific gravity of the phosphor, the coating thickness, and the shape of the light guide member. Yes, this is not the case.

By the way, for example, when a phosphor is contained in a specific layer to form a phosphor-containing layer, the specific layer forming liquid has a lower viscosity than conventional light guide member forming liquids such as epoxy resins and silicone resins. In addition, there is an advantage that the coating performance can be sufficiently maintained even if a high concentration phosphor or inorganic particles having good compatibility with the phosphor and inorganic particles are dispersed. In addition, it is possible to increase the viscosity by adding a thixo material such as aerosil, if necessary, and the degree of polymerization can be increased, and the viscosity can be adjusted according to the target phosphor content. It is possible to provide a coating solution that can flexibly respond to various types of coating methods such as the type and shape of the object, as well as potting, spin coating and printing.

[0272] In addition, for example, when a phosphor is contained in a specific layer to form a phosphor-containing layer, the specific layer forming liquid may contain a thixo material such as erodyl whose polymerization degree is adjusted as necessary. Thus, it is preferable to adjust the viscosity and thixotropy according to the target phosphor content. As a result, it is possible to provide a coating solution that can flexibly cope with various types of coating methods such as potting, spin coating, and printing, as well as the type and shape of the object to be coated.

[0273] It should be noted that the phosphor content in the phosphor-containing layer is such that if the phosphor composition can be specified, the phosphor-containing sample is pulverized and pre-fired to remove the carbon component, and then subjected to hydrofluoric acid treatment. The components are removed as key hydrofluoric acid, the residue is dissolved in dilute sulfuric acid to make the main component metal element into an aqueous solution, and the main component metal element is quantified by known elemental analysis methods such as ICP, flame analysis, and fluorescent X-ray analysis. The phosphor content can be obtained by calculation. Also phosphor If the shape and particle size are uniform and the specific gravity is known, a simple method can be used in which the number of particles per unit area is obtained by image analysis of the cross-section of the coating and converted into the phosphor content.

[0274] Further, the phosphor content in the phosphor-containing layer forming liquid may be set so that the phosphor content in the phosphor-containing layer falls within the above range. Therefore, the phosphor-containing layer forming liquid does not change in weight during the drying process! / In this case, the phosphor content in the phosphor-containing layer forming liquid is the phosphor content in the phosphor-containing layer. It will be similar to the rate. In addition, when the weight of the phosphor-containing layer forming liquid changes during the drying process, such as when the phosphor-containing layer forming liquid contains a solvent, the phosphor-containing layer forming liquid excluding the solvent or the like It suffices if the phosphor content rate is the same as the phosphor content rate in the phosphor-containing layer.

[0275] [C 1 2] Inorganic particles

Further, the layer constituting the light guide member of the present invention is intended to improve optical characteristics and workability, and to obtain any of the following effects <1> to <5>. Further, inorganic particles may be included. Especially, it is preferable that the specific layer which mutually contacts among the layers which comprise the light guide member of this invention contains an inorganic particle. However, in this case, at least one of the two or more specific layers provided in the light guide member may contain inorganic particles. The inorganic particles may be contained in only one layer among the layers constituting the light guide member of the present invention, or may be contained in two or more layers.

<1> A light scattering layer described later is mixed with inorganic particles as a light scattering material, and the light transmitted from the light source is scattered to widen the directivity angle of the light emitted from the light guide member to the outside. Further, in the phosphor-containing layer, the amount of light hitting the phosphor is increased to improve the wavelength conversion efficiency.

<2> Preventing the generation of cracks by blending inorganic particles as a binder in the layers constituting the light guide member.

<3> Increasing the viscosity of the forming liquid by mixing inorganic particles as a viscosity adjusting agent in the forming liquid for constituting each layer of the light guide member.

<4> Reduce the shrinkage by blending inorganic particles in the layers that make up the light guide member <5> Incorporating inorganic particles into the layer constituting the light guide member to adjust the refractive index and improve the light extraction efficiency.

[0277] In particular, among the above cases, when the inorganic particles are contained in the specific layer, an appropriate amount of inorganic particles may be mixed in the specific layer forming liquid according to the purpose in the same manner as the phosphor powder. In this case, the effect obtained varies depending on the kind and amount of inorganic particles to be mixed.

For example, when the inorganic particles are ultrafine silica with a particle size of about 10 nm (product name: AEROSIL # 200, manufactured by Nippon Aerosil Co., Ltd.), the thixotropic property of the specific layer forming liquid increases, so Is big.

[0278] For example, when the inorganic particles are crushed silica or spherical silica having a particle size of about several μm

The effects of <2> and <4> are significant because the increase in thixotropic properties is mainly due to the role of aggregate in a specific layer.

Further, for example, when inorganic particles having a particle size of about 1 μm, which has a refractive index different from that of the compound (dried hydrolyzed polycondensate) used in the specific layer, are used at the interface between the compound and the inorganic particles. Since light scattering increases, the effect of <1> is great.

[0279] Also, for example, the refractive index of the compound (material) used in the specific layer is larger than that of the compound (material), and the median particle size is usually 1 nm or more, preferably 3 nm or more, and usually 1 Onm or less, preferably 5 nm or less. When using inorganic particles having a particle size equal to or smaller than the emission wavelength, the refractive index can be improved while maintaining the transparency of the specific layer, so the effect <5> above is great!

[0280] Therefore, the type of inorganic particles to be mixed may be selected according to the purpose. Moreover, the type may be a single type or a combination of multiple types. Moreover, in order to improve dispersibility, it may be surface-treated with a surface treatment agent such as a silane coupling agent.

[0281] [C 1 2 1] Types of inorganic particles

Examples of inorganic particles used include inorganic oxide particles such as silica, barium titanate, titanium oxide, zirconium oxide, niobium oxide, aluminum oxide, cerium oxide, yttrium oxide, and diamond particles. Depending on the choice of other substances, it is not limited to these.

[0282] The form of the inorganic particles may be any form depending on the purpose, such as powder form or slurry form. However, if it is necessary to maintain transparency, other forms contained in the layer containing the inorganic particles may be used. It is preferable to make the refractive index the same as that of the material, or add it as a water-based / solvent-based transparent sol to the liquid for forming the layer.

[0283] [C 1 2-2] Median particle size of inorganic particles

The median particle size of these inorganic particles (primary particles) is not particularly limited, but is usually about 1/10 or less of the phosphor particles. Specifically, the following median particle size is used according to the purpose. For example, if inorganic particles are used as the light scattering material, the median particle size is usually 0.05 μm or more, preferably 0.1 μm or more, and usually 50 μm or less, preferably 20 or less. is there. For example, if inorganic particles are used as the aggregate, the median particle size is preferably 1 m to 10 m. For example, if inorganic particles are used as a thickener (thixotropic agent), the central particle is preferably 10 to! OOnm. Further, for example, if inorganic particles are used as the refractive index adjusting agent, the median particle size is preferably from !! to 1 Onm. In particular, in the light guide member of the present invention, at least one of the layers in contact with each other (preferably a specific layer) contains inorganic particles having a median particle diameter of 0.05 · 50 to 50 111, and the layer and / or others. It is preferable to contain inorganic particles having a median particle diameter of 1 to 1 Onm in at least one layer.

Thus, optically, inorganic particles having a median particle diameter of! -10 nm have an advantage that various functions such as refractive index adjustment can be imparted without impairing the transmittance of the specific layer. Also

The inorganic particles having a median particle diameter of 0.05 to 50 111 can impart functions such as diffuse fluorescence as described above. For example, of the two layers in contact, the first layer contains functional inorganic particles with a median particle size of 0.05 to 50 m, and the second layer contains only inorganic particles with a median particle size of! -10 nm. When it has, the 2nd layer with a specific refractive index and transparency plays the role of a light guide layer, and a 1st layer turns into a layer light-emitted by scattering and fluorescence. In addition, for example, both the first layer and the second layer can contain inorganic particles having a median particle diameter of 1 to 10 _nm , and the first layer and the second layer can be formed by setting different contents for each layer. By arbitrarily adjusting the refractive index of this layer, it is possible to make an optical design according to the light guide distance, film thickness, scattering efficiency, and the like.

[0285] [C 1 2-3] Method of mixing inorganic particles

In the present invention, the method for mixing the inorganic particles is not particularly limited. However, when mixing inorganic particles in the forming liquid, a planetary agitation mixer or the like is usually used in the same manner as the phosphor. It is recommended to mix while degassing. For example, when mixing small particles such as Aerozinole! / When mixing small particles, after mixing the particles, if necessary, use a bead mill or three rolls to break up the agglomerated particles before mixing phosphors, etc. Large particle components may be mixed.

[0286] [C 1 2-4] Content of inorganic particles

The content of the inorganic particles in each layer of the light guide member of the present invention can be freely selected depending on the force and its application form as long as the effects of the present invention are not significantly impaired. For example, when inorganic particles are used as the light scattering agent, the content is preferably 0.01 to 10% by weight. Also, for example, when inorganic particles are used as the aggregate, the content is preferably from !! to 50% by weight. For example, when inorganic particles are used as a thickener (thixotropic agent), the content is preferably 0.;! To 20% by weight. For example, when inorganic particles are used as the refractive index adjuster, the content is preferably 10 to 80% by weight. If the amount of the inorganic particles is too small, the desired effect may not be obtained. If the amount is too large, various properties such as adhesion, transparency and hardness of the cured product may be adversely affected.

[0287] As described above, when the specific layer contains inorganic particles, the specific layer forming liquid contains inorganic particles. However, the specific layer forming liquid is a conventional conductive material such as an epoxy resin or a silicone resin. Compared to the optical member forming liquid, it has the advantage of being able to maintain sufficient coating performance even when dispersed at high concentration of inorganic particles that have good affinity with phosphors and inorganic particles. . It is also possible to increase the viscosity by adjusting the degree of polymerization if necessary, and by adding a thixo material such as aerosil, etc., and the viscosity adjustment range according to the target inorganic particle content is large. Kinds and shapes of objects, as well as potting 'spin coating • We can provide coating solutions that can flexibly support various coating methods such as printing.

[0288] The inorganic particle content in each layer of the light guide member can be measured in the same manner as the phosphor content described above.

Further, the content of the inorganic particles in the forming liquid for forming each layer may be set so that the content of the inorganic particles in each layer falls within the above range. Therefore, the weight of the forming liquid does not change during the drying process! In this case, the content of inorganic particles in the forming liquid is the same as the content of inorganic particles in each layer of the light guide member. In addition, the forming liquid contains a solvent and the like. When the weight of the forming liquid changes in the drying process, such as when it has, the content of inorganic particles in the forming liquid excluding the solvent is the same as the content of inorganic particles in each layer of the light guide member It should just become.

[C289] Layer structure of light guide member

The first and second light guide members of the present invention are characterized in that two or more layers having different refractive indexes are laminated.

In addition, the third and fourth light guide members of the present invention are characterized in that two or more layers having different values are stacked.

Furthermore, the fifth and sixth light guide members of the present invention are characterized in that two or more layers having different refractive indexes are laminated. Therefore, the fifth light guide member of the present invention is a light guide member in which two or more layers having different refractive indexes are laminated, at least one of the layers being a specific layer, and having a light emission peak. A light source with a dominant wavelength of 500 nm or less is provided. On the other hand, the sixth light guide member of the present invention is a light guide member in which two or more layers having different refractive indexes are laminated, and at least two of the layers in contact with each other are specific layers.

The seventh and eighth light guide members of the present invention are characterized in that two or more layers having different haze values are laminated. Accordingly, the seventh light guide member of the present invention is a light guide member in which two or more layers having different haze values are laminated, wherein at least one of the layers is a specific layer and has a main emission peak. A light source with a wavelength of 500 nm or less is provided. On the other hand, the eighth light guide member of the present invention is a light guide member in which two or more layers having different haze values are laminated, and at least two of the layers in contact with each other are specific layers.

In addition, when a primer is used between layers for improving adhesion, it is considered that a polar group is added to each of the two layers via the primer layer, and both layers are designated as specific layers.

Hereinafter, the layer structure of the light guide member of the present invention will be described.

[0290] [C 2-1] Refractive index

The first, second, fifth and sixth light guide members of the present invention are characterized in that two or more layers having different refractive indexes are laminated. When the first, second, fifth and sixth light guide members of the present invention are used as an optical waveguide or a light guide plate, the high refractive index layer transmits light by providing a difference in refractive index between adjacent layers. The core layer, the low refractive index layer is the cladding layer that confines light, Form each one.

[0291] The refractive index of the high refractive index layer of the first, second, fifth and sixth light guide members of the present invention is usually

1. 45 or more, preferably 1.5 or more, more preferably 1.6 or more. Although the upper limit is not particularly limited, for example, when a semiconductor light-emitting device is used as a light source, the refractive index of a general semiconductor light-emitting device is about 2.5, and is usually 2.5 or less. From the viewpoint of ease, it is preferably 2.0 or less. If the refractive index of the high refractive index layer is too small, the light extraction efficiency may not be improved. On the other hand, the light extraction efficiency is not improved even when the refractive index of the high refractive index layer is larger than the refractive index of the member constituting the light source.

[0292] The refractive index of the low refractive index layer of the first, second, fifth and sixth light guide members of the present invention is usually less than 1.45, preferably 1.43 or less, more preferably 1. 42 or less. The lower limit is usually 1.4 or more, preferably 1.41 or more.

[0293] The refractive index difference between the high-refractive index layer and the low-refractive index layer is usually 0.03 to 0.2. By appropriately adjusting this, the transmission distance of light in the high-refractive index layer It is also possible to adjust the (guide distance). In other words, when the refractive index difference is increased, the low refractive index layer (cladding layer) efficiently confines the light of the high refractive index layer (core layer), and therefore the light transmission distance with less leakage light to the low refractive index layer. Can increase the separation force S. On the other hand, if the refractive index difference is set to be as small as 0.05 or less, for example, light leakage from the high refractive index layer to the low refractive index layer increases, and the light transmission distance becomes short.

[Refractive Index Measurement Method]

The refractive index can be measured using a known method such as a Pulflich refractometer, an Abbe refractometer, a prism cover method, an interferometry, and a minimum declination method in addition to the immersion method (solid object). The refractive index measurement wavelength in the present invention can be selected from sodium D line (589 nm), which is used for general purposes when using an instrument such as an Abbe refractometer. The refractive index can be measured by various methods as described above, and the refractive index of the sample before and after curing hardly changes. Since samples after curing will be molded in various ways depending on the purpose, measurement using an Abbe refractometer using the uncured solution is the simplest and preferred!

[0295] [C 2-2] Haze straight

The third, fourth, seventh and eighth light guide members of the present invention have two or more layers having different haze values. It is characterized by being laminated. When providing the light scattering layer and / or the phosphor-containing layer in the third, fourth, seventh and eighth light guide members of the present invention, the haze value of the light scattering layer and / or the phosphor-containing layer is set. You can make it higher.

[0296] The haze value of the light scattering layer and / or the phosphor-containing layer of the third, fourth, seventh and eighth light guide members of the present invention is usually 50 or more, preferably 70 or more, more preferably 80. That's it. If the haze value of the light scattering layer and / or the phosphor-containing layer is too small, the light scattering effect, that is, the effect that light is emitted to the outside of the light guide member may not be improved. Therefore, it is preferable that the haze value of at least one of the specific layers in contact with each other falls within the range of the light scattering layer and / or the phosphor-containing layer. The haze value is a numerical value of the so-called cloudiness (cloudiness value) of a transparent member, and is a value measured based on JIS-K-7136.

[0297] [C 2-3] Role of each layer

As described above, the light guide member of the present invention includes a low refractive index layer, a high refractive index layer, a light scattering layer, and a phosphor by adjusting the refractive index and / or the haze value of each layer that is configured. The ability to provide a layer S. Hereinafter, each layer will be described. The specific installation method for each layer will be explained in the section [C-3] according to each embodiment!

[0298] [C 2-3-1] Low refractive index layer

As described above, when the light guide member of the present invention is used as an optical waveguide or a light guide plate, a low refractive index layer is usually provided as a cladding layer for confining light. A layer other than the specific layer may be a low refractive index layer, but the low refractive index layer is composed of a specific layer made of a compound having the characteristics described in the above-mentioned chapter [A] or [B]. It is preferable. Therefore, in the light guide member of the present invention, it is preferable that at least one of the specific layers in contact with each other is a low refractive index layer. The refractive index of the low refractive index layer is as described above. Further, the low refractive index layer may be provided with only one layer or may be provided with two or more layers.

[0299] [C 2-3—2] High refractive index layer

As described above, when the light guide member of the present invention is used as an optical waveguide or a light guide plate, a high refractive index layer is usually provided as a core layer for transmitting light. A layer other than the specific layer may be a high refractive index layer, but the high refractive index layer has the characteristics described in the above-mentioned chapter [A] or [B]. It is preferable that it is comprised by the specific layer which consists of a compound. Therefore, in the light guide member of the present invention, it is preferable that at least one of the specific layers in contact with each other is a high refractive index layer.

[0300] Further, in order to make the high refractive index layer have a higher refractive index than the low refractive index layer, for example, a phenyl group is introduced into the compound, or as described in Chapter [C-12]. In addition, it is preferable to contain inorganic particles having a median particle diameter of 1 to; The refractive index of the high refractive index layer is as described above. The high refractive index layer may be provided with only one layer or with two or more layers.

[0301] Furthermore, it is more preferable that the low refractive index layer and the high refractive index layer are both constituted by specific layers. Therefore, in the light guide member of the present invention, the refractive index of at least one of the specific layers in contact with each other is within the range of the high refractive index layer, and the refractive index of at least one other layer is the low refractive index. More preferably, it falls within the range of the rate layer.

[0302] [C 2-3-3] Light scattering layer

The light guide member of the present invention can be provided with a light scattering layer that radiates light transmitted from a light source to the outside. The light scattering layer functions to widen the directivity angle of light emitted from the light guide member to the outside. A layer other than the specific layer may be a light scattering layer, but the light scattering layer may be composed of a specific layer made of a compound having the characteristics described in the above-mentioned chapter [A] or [B]. preferable. In addition, as described in [C-12], the light scattering layer has a median particle size of usually 0.05 μm or more, preferably 0.1 μm or more as a light scattering material. It is preferable to contain inorganic particles of 50 μm or less, preferably 20 or less. The light scattering layer may be provided with only one layer, or may be provided with two or more layers.

[0303] Further, guided light can be extracted using the surface roughness of the substrate. This is because, by providing a light scattering layer on the rough surface, the guided light is scattered on the rough surface, and the light becomes perpendicular to the extraction surface, so that the light emerges on the surface. It is what I did. The rough surface can be formed on the substrate and / or on each layer. The rough surface may be formed on the upper surface (close to the light extraction surface! /, Surface), lower surface (far from the light extraction surface! /, Surface), or misaligned! The roughness of the rough surface is not particularly limited as long as it has the property of scattering light, but the height difference is usually 0.2 Hm or more, preferably 0.5 μm or more, and usually 50 μm or less, preferably 30 μ Less than m. .

[0304] The method of creating a rough surface on the substrate is not limited! /, But, for example, precision machining, blasting, powder coating, application of coating solution containing diffusing particles, particle pasting, chemical etching, optical Examples include irradiation, ink jet printing, exposure to a photosensitive curable (softening) resin, development, and heating / developing to a thermosensitive resin.

Further, as a method of roughening the surface of each layer to be laminated, for example, chemical treatment using hydrofluoric acid or alkali, blast treatment, powder coating, application of a coating solution containing diffusing particles, particle pasting, light irradiation, inkjet There is printing. In addition, for example, a method in which sedimentation or floating light diffusing particles are contained in a layer to be configured, and after coating, particles are settled or suspended so that more diffusing particles exist at the interface of each layer. It can be preferably used in the same manner as the method of forming the surface.

[0305] [C 2-3-4] Phosphor-containing layer

The light guide member of the present invention can be provided with a phosphor-containing layer in order to convert the wavelength of light transmitted from the light source force into a desired wavelength. The phosphor-containing layer refers to a layer containing a phosphor among the layers constituting the light guide member. At this time, a layer other than the specific layer becomes a phosphor-containing layer! /, But the phosphor-containing layer is made of a compound having the characteristics described in the above-mentioned chapter [A] or [B]. It is preferable that it is comprised by the specific layer. In this case, among the layers constituting the light guide member of the present invention, it is preferable that the specific layers in contact with each other contain a phosphor to constitute the phosphor-containing layer. However, in this case, at least one of the two or more specific layers provided in the light guide member may contain a phosphor.

The phosphor-containing layer is formed by containing the phosphor described in [C 1 1] in the layer. In addition, in order to increase the amount of light hitting the phosphor and improve the wavelength conversion efficiency, the phosphor-containing layer contains inorganic particles having a median particle size of 0.;! To 10 m as a light scattering material. Also good. The phosphor-containing layer may be provided with only one layer or two or more layers.

[0306] [C 2-4] Shape and dimensions of light guide member

There is no restriction | limiting in the shape and dimension of the light guide member of this invention, and it is arbitrary. For example, when used as a light guide or light guide plate of a light guide member, the shape and dimensions of the light guide member of the present invention Is determined according to the shape and size of the substrate of the optical waveguide or the light guide plate. When formed on the surface of the substrate, it is usually formed in a film shape, and its dimensions are arbitrarily set according to the application. In addition, as described above, the forming film (film forming the light guide member) is a force for laminating a plurality of films having different refractive indexes and haze values. The dimensions of each layer are arbitrarily set according to the application.

[0307] However, when the light guide member of the present invention is formed in a film shape, one of the advantages is that the specific layer can be formed in a thick film. In the conventional light guide member, when the layer constituting the light guide member is thickened, cracks or the like are generated due to internal stress or the like, and it is difficult to thicken the layer. However, in the light guide member of the present invention, It is possible to increase the film thickness stably. Specifically, when the light guide member of the present invention is used as a light guide plate, the thickness of each specific layer is usually 10 m or more, preferably 30 m or more, usually 500 m or less, preferably 300 mm or less. More preferably, it is 200 m or less. Here, when the thickness of the film is not constant, the thickness of the film refers to the thickness of the maximum thickness portion of the film. In this case, the total thickness of all layers excluding the light guide plate substrate is usually δθ ΐη or more, preferably δθ ΐη or more, usually 500 μm or less, preferably 300 μm or less, more preferably 200 μm. m or less.

[0308] [C 3] Structure of light guide member

Hereinafter, as an example of the light guide member of the present invention, a light guide plate using a semiconductor light-emitting device as a light source will be described as an example and described using an embodiment. However, these embodiments are used only for convenience of explanation, and the optical waveguide, the light guide plate, and other examples to which the light guide member of the present invention is applied are limited to these embodiments. is not. In particular, the substrate may be provided or not as required, and the thickness is not particularly limited. Furthermore, since the specific layer has high flexibility in the present invention, the use of this specific layer makes it possible to produce a layer having an arbitrary film thickness without warping or deformation of the substrate even on a thin substrate such as a flexible printed circuit board. it can.

[0309] [C 3-1] First embodiment

As shown in FIG. 2, the light guide plate 8 of the first embodiment is disposed on the substrate 1 so as to cover the semiconductor light emitting element 2 made of LED chips and optionally cover the semiconductor light emitting element 2. The semiconductor light emitting device 4 comprising the sealing material 3 is provided as a light source.

[0310] On the surface of the substrate 1, a low refractive index layer 5 is coated as a specific layer which is a part of the light guide plate 8. The low refractive index layer 5 is provided with a cylindrical or mortar-shaped hole 5H so as not to cover the semiconductor light emitting device 4!

[0311] On the upper surface of the low refractive index layer 5, a high refractive index layer 6 is provided as a specific layer in contact with the low refractive index layer 5. Further, in the present embodiment, the high refractive index layer 6 is also formed around the semiconductor light emitting device 4 in the hole 5H, so that light emitted from the semiconductor light emitting device 4 is directly incident on the high refractive index layer 6. It has become. As a result, the high refractive index layer 6 assures the function of transmitting light emitted from the light source (semiconductor light emitting device 4 in FIG. 2) as the core portion of the optical waveguide.

[0312] On the upper surface of the high refractive index layer 6, a low refractive index layer 5 'may be further provided as a specific layer in contact with the high refractive index layer 6. Even when the low refractive index layer 5 ′ is not provided, the air layer can serve as a cladding portion.

In addition, a light scattering layer and / or a phosphor-containing layer 7 can be appropriately provided on the contact surface (for example, the upper surface) of the high refractive index layer 6. The light scattering layer ensures the function of emitting light emitted from the light source transmitted by the high refractive index layer 6 to the outside. The phosphor-containing layer exhibits a wavelength conversion function of emitting light of a desired wavelength when excited by light from the light source transmitted by the high refractive index layer 6. In the light guide plate 8 of the present embodiment, since light is mainly emitted from the light scattering layer and / or the phosphor-containing layer 7, the light scattering layer and / or the phosphor-containing layer 7 is used. The position to be formed is preferably set in consideration of design.

In the present embodiment, the light scattering layer and / or the phosphor-containing layer 7 is formed in a predetermined portion on the upper surface of the high refractive index layer 6, and the low refractive index layer is formed on the other portions on the upper surface of the high refractive index layer 6. Assume that 5 'is formed.

[0313] The semiconductor light-emitting element 2 is not particularly limited, but a specific example of a light-emitting diode (LED) or laser diode (LD) that emits light having a peak wavelength in the range of 350 nm to 500 nm is preferable. ) And the like. Of these, the above-described GaN-based LEDs and LDs are preferable. [0314] The sealing material 3 exhibits functions such as a highly durable sealant, a light extraction film, and various function-added films of the semiconductor light emitting device 2. The encapsulant 3 may be used alone, but can contain any additive as long as the effects of the present invention are not significantly impaired except for the phosphor and the phosphor component. Further, since the high refractive index layer 6 can also serve as a sealing material, the sealing material 3 may not be provided.

As the sealing material 3 used, it is preferable to use the same compound (material) as the high refractive index layer 6 of the light guide member of the present invention from the viewpoint of adhesion and the like. Further, as the sealing material 3, other materials can be used. Normally, a resin (hereinafter referred to as “sealing resin” as appropriate) is used as the sealing material 3. Examples of such a sealing resin usually include a thermoplastic resin, a thermosetting resin, a photocurable resin, and the like. Specifically, for example, methacrylic resin such as polymethylmethacrylate; styrene resin such as polystyrene and styrene acrylonitrile copolymer; polycarbonate resin; polyester resin; phenoxy resin; Cellulosic resins such as chinoresenolose, sennellose acetate, sennellose acetate petitate; epoxy resins; phenol resins; silicone resins, etc. Also, inorganic materials such as metal alkoxides, ceramic precursor polymers, or solutions obtained by hydrolytic polymerization of a solution containing metal alkoxides by a sol-gel method or a combination thereof, inorganic materials such as siloxane bonds. Inorganic materials can be used. In addition, the material of the sealing material 3 such as the sealing resin may be used alone or in combination of two or more in any combination and ratio.

[0315] The encapsulant 3 may contain a phosphor, whereby the wavelength of the light source can be converted into light having a desired wavelength and then transmitted through the high refractive index layer. The amount of the phosphor used is not particularly limited, but is usually 0.01 parts by weight or more, preferably 0.1 parts by weight or more, more preferably 1 part by weight with respect to 100 parts by weight of the sealing material. In addition, it is usually 100 parts by weight or less, preferably 80 parts by weight or less, more preferably 60 parts by weight or less.

[0316] In addition, the sealing material 3 may contain components other than the phosphor and the inorganic particles. For example, it is possible to incorporate a color correction dye, an antioxidant, a processing stabilizer such as a phosphorus processing stabilizer, an oxidation and heat stabilizer, a light resistance stabilizer such as an ultraviolet absorber, and a silane coupling agent. These components can be used alone or in any combination of two or more. Also, it can be used in combination at a ratio! /.

[0317] The semiconductor light-emitting device 4 may be installed on the substrate 1 before coating, or may be installed on the substrate 1 after coating by removing the masking after coating the coating portion. When the low refractive index layer 5, the high refractive index layer 6, and the scattering layer and / or the phosphor-containing layer 7 are formed into a thin film, a specific layer forming solution diluted with a solvent such as toluene or heptane is used. It may be formed by coating.

[0318] Since the light guide plate 8 of the present embodiment is configured as described above, the light from the light source transmitted by the high refractive index layer 6 passes through the light scattering layer and / or the phosphor-containing layer 7. Then, the light is emitted to the outside of the light guide member (light guide plate 8). Therefore, when the sealing material 3 does not contain a phosphor, and when the light guide member (light guide plate 8) does not contain the phosphor-containing layer 7, the light is emitted from the light source (semiconductor light emitting element 2 in FIG. 2). Radiated to the outside in the same luminescent color.

[0319] In addition, the phosphor-containing layer 7 exhibits a wavelength conversion function of emitting light of a desired wavelength when excited by light from the light source transmitted by the high refractive index layer 6 as described above. . Therefore, the phosphor-containing layer 7 emits light obtained by wavelength-converting light emitted from the semiconductor light emitting element 2. At this time, the phosphor-containing layer 7 only needs to contain at least a fluorescent substance that is excited by light from the light source and emits light of a desired wavelength. Examples of such phosphors include the various phosphors exemplified above. As the emission color of the phosphor-containing layer 7, not only the three primary colors of red (R), green (G) and blue (B), but also white such as a fluorescent lamp and yellow such as a light bulb are possible. In short, the phosphor-containing layer 7 has a wavelength conversion function for emitting light having a desired wavelength different from the excitation light.

In the present embodiment, the light transmitted by the high refractive index layer 6 is also emitted from a portion where the high refractive index layer 6 is exposed on the side surface.

Therefore, in the light guide member (light guide plate 8) of this embodiment, the low refractive index layer 5 and the high refractive index layer 6 and the light scattering layer and / or the phosphor-containing layer 7 use a specific compound. Therefore, the light durability (light resistance) and heat durability (heat resistance) of the light guide member (light guide plate 8) can be improved. Due to the action of the polar group between 7 and the like, the adhesion is more improved than when the specific layer is used alone. Also, between the substrate 1 and the low refractive index layer 5, between the low refractive index layer 5 and the high refractive index layer 6, and / or the high refractive index layer. Cracks and peeling do not easily occur between 6 and the light scattering layer and / or the phosphor-containing layer 7. Furthermore, since the layers 5, 6, and 7 are all formed as the above-mentioned specific layers, there is an advantage that the film thickness can be freely controlled such as thickening and thinning, respectively. .

[0321] In addition, the angle 9 formed between the side surface of the light guide member (light guide plate 8) and the laminated surface may be vertical, but the light extraction effect (particularly, light from the side surface portion in the present embodiment). From the viewpoint of improving the taking-out effect), it is usually 30 ° or more, preferably 35 ° or more, more preferably 40 ° or more, and usually 80 ° or less, preferably 70 ° or less, and more preferably 60 ° or less. Note that the angle formed between the side surface of the light guide member (light guide plate 8) and the laminated surface is a guide as viewed from a direction perpendicular to the laminate surface of the light guide member (light guide plate 8), as shown in FIG. The inner angle formed by the side surface of the optical member (light guide plate 8) and the laminated surface is shown.

[0322] [C 3-2] Other embodiments

When the light guide member of the present invention is applied to an optical waveguide, a light guide plate, or the like, it is preferable to appropriately modify it according to the location to which the present invention is applied. For example, a desired number of light sources can be appropriately provided at desired positions on the substrate surface. A desired number of light scattering layers and phosphor-containing layers can be appropriately provided at desired positions of the light guide member.

[0323] Other embodiments are shown in Figs. However, the light guide member of the present invention is not limited to the embodiments exemplified below, and can be implemented with arbitrary modifications without departing from the gist of the present invention. In the following embodiments, the same reference numerals as those in the first embodiment are used for the same parts as those described in the first embodiment.

In the light guide plate 8 of the second embodiment, as shown in FIG. 3, the entire uppermost layer is a light scattering layer and / or a phosphor-containing layer 7. As a result, the light can be extracted from the entire surface of the light guide plate. Further, the light guide plate 8 according to the present embodiment is configured in the same manner as in the first embodiment except for the above-described points. Therefore, the light guide plate 8 of the present embodiment is also configured by laminating the low refractive index layer 5, the high refractive index layer 6, and the light scattering layer and / or the phosphor-containing layer 7 which are specific layers in contact with each other. Therefore, as in the first embodiment, it is possible to freely control the film thickness such as thickening, to suppress cracks and peeling, and to have excellent heat resistance and light resistance. You can get the benefits of As shown in FIG. 4, the light guide plate 8 of the third embodiment does not have the low refractive index layer 5 ′ and the light scattering layer and / or the phosphor-containing layer 7 as the uppermost layer. That is, the entire top surface of the photorefractive index layer 6 is configured to be exposed to the gas phase. In this case, the gas transmission layer acts as a cladding layer on the upper surface, thereby ensuring the optical transmission effect. In addition, as described above in section [C 2 1], by adjusting the refractive index difference between the low refractive index layer 5 and the high refractive index layer 6, the optical waveguide distance is controlled to achieve the desired effect. be able to.

In the case where the refractive index difference between the low refractive index layer 5 and the high refractive index layer 6 is made small, in order to achieve a desired effect using light entering the low refractive index layer 5, a light scattering layer and / or Alternatively, the phosphor-containing layer 7 can be provided on a part of the low refractive index layer 5 (FIG. 4).

[0326] Furthermore, the light guide plate 8 according to the present embodiment is configured in the same manner as in the first embodiment except for the points described above. Therefore, the light guide plate 8 of the present embodiment also has a low refractive index layer 5, a high refractive index layer 6, and a light scattering layer and / or a fluorescent layer formed on a part of the low refractive index layer 5, which are specific layers in contact with each other. Since the body-containing layer 7 is laminated, as in the first embodiment, it is possible to freely control the film thickness such as thickening, and to suppress cracks and peeling. There are advantages such as being excellent in heat resistance and light resistance.

[0327] The light guide plate 8 of the fourth embodiment is formed into a light scattering layer 7 by mixing a very small amount of inorganic particles as a light scattering agent in a portion corresponding to the high refractive index layer 6 of FIG. (Figure 5). In this case, light can be extracted from the entire surface of the light guide plate 8 as in the second embodiment. In addition, because of the two-layer structure, the total thickness of the light guide plate 8 can be reduced.

Further, the light guide plate 8 according to the present embodiment has the above-mentioned configuration and the configuration other than that the light scattering layer and / or the phosphor-containing layer 7 is not provided in a part of the low refractive index layer 5. The configuration is the same as that of the embodiment. Therefore, since the light guide plate 8 of the present embodiment is also configured by laminating the low refractive index layer 5 and the light scattering layer 7 which are specific layers in contact with each other, as in the third embodiment, the thick film It is possible to obtain advantages such as free control of film thickness such as crystallization, suppression of cracks and peeling, excellent heat resistance and light resistance, etc. The

As shown in FIG. 6, the light guide plate 8 of the fifth embodiment includes a high refractive index layer 6 that is an optical transmission unit. A part (high refractive index portion 6a) penetrates through the low refractive index layers 5, 5 ′, the light scattering layer and / or the phosphor-containing layer 7. The high refractive index portion 6a is a boundary portion that penetrates at least two specific layers in contact with each other. In the present embodiment, since the boundary portion is formed as the high refractive index portion 6a capable of transmitting light, the light transmission portion can be extended in a direction perpendicular to the substrate surface across each layer.

The high refractive index portion 6a functions as V, a so-called “boundary portion A”. Here, the boundary A is a high refractive index boundary formed of a material having a refractive index equivalent to that of the high refractive index layer 6, and transmits light emitted from the semiconductor light emitting device 4 to shine itself. Is. Further, the high refractive index portion 6a may use a material different from the high refractive index layer 6 in the light guide member of the present invention as the boundary portion A. In the case of this embodiment, as the boundary A, any material can be used as long as it is a material that can transmit light from the light source. For example, an inorganic or organic material having the same refractive index as that of the high refractive index layer 6 can be used. In particular, the boundary A is preferably an epoxy resin, a urethane resin, a polyimide resin, an acrylic resin, a phenol resin, or the like from the viewpoints of low moisture permeability, light blocking properties, and adhesion to the substrate 1. In addition, from the viewpoint of adhesion to the high refractive index layer 6, the low refractive index layers 5, 5 ′, the light scattering layer and / or the phosphor-containing layer 7, epoxy resins and acrylic resins are particularly preferred. preferable. Use of an epoxy resin as the boundary portion A is a particularly preferable combination because the high refractive index layer 6 as a specific layer is particularly excellent in adhesion to the epoxy resin, hardly changes in quality, and does not inhibit the effect.

[0330] There is no limitation on the method for producing such a high refractive index portion 6a. For example, when the high refractive index portion 6a is provided on the substrate 1, the low refractive index layers 5, 5 ′, the high refractive index layer 6, and the light scattering layer and / or the phosphor-containing layer 7 are laminated before coating. Then, the high refractive index portion 6a is formed, and then the low refractive index layers 5 and 5 ′, the high refractive index layer 6 and the light scattering layer and / or the phosphor-containing layer 7 may be laminated. At this time, the method used to form the high refractive index portion 6a is not limited, and for example, it can be formed by a dispenser, screen printing, a resist method, or the like. In addition, for example, after masking a portion of the substrate 1 where the high refractive index portion 6a is to be formed (hereinafter referred to as “installation portion” as appropriate), the low refractive index layers 5, 5 ′, the high refractive index layer 6 and the light A scattering layer and / or phosphor-containing layer 7 is laminated, and then the masking is removed, and the installation portion is highly refracted. The rate portion 6a may be formed. When the high refractive index portion 6a is provided on a layer other than the substrate 1, the layer is laminated on the substrate 1, and then the high refractive index portion 6a and the high refractive index portion 6a are formed on the layer according to the method described above. The low refractive index layers 5 and 5 ′, the high refractive index layer 6, and the light scattering layer and / or the phosphor-containing layer 7 may be formed as necessary.

[0331] Furthermore, the light guide plate 8 according to the present embodiment is configured in the same manner as in the first embodiment except for the points described above. Therefore, the light guide plate 8 of the present embodiment also includes the low refractive index layers 5 and 5 ′, the high refractive index layer 6, and the light scattering layer and / or the phosphor-containing layer 7 that are specific layers in contact with each other. Therefore, as in the first embodiment, it is possible to freely control the film thickness such as thickening, to suppress cracks and peeling, and to improve heat resistance and light resistance. Advantages such as superiority can be obtained. Further, if the high refractive index portion 6a is formed of the same compound as that of the specific layer, the high refractive index portion 6a can also be freely controlled in film thickness such as thickening, cracks and Advantages such as suppression of peeling and excellent heat resistance and light resistance can be obtained.

As shown in FIG. 7, the light guide plate 8 of the sixth embodiment includes a portion of the low refractive index layer 5 (low refractive index portion 5a) that is a light blocking portion, the high refractive index layer 6, It penetrates the light scattering layer and / or the phosphor-containing layer 7. The low refractive index portion 5a functions as a boundary portion. In the present embodiment, since the boundary portion is formed as the low refractive index portion 5a capable of blocking light, the light blocking portion can be extended in the direction perpendicular to the substrate surface across each layer.

The low refractive index portion 5a functions as V, a so-called “boundary portion B”. Here, the boundary portion B is a low refractive index boundary portion formed of a low refractive index material, which blocks light emitted from the semiconductor light emitting device 4 and divides the light guide plate 8 into an optical area. To fulfill. For this purpose, as the boundary portion B, a high refractive index boundary portion made of a material having a higher refractive index than that of the high refractive index layer 6 can be used.

[0334] Further, the low refractive index portion 5a may use a material different from the low refractive index layer 5 in the light guide member of the present invention as the boundary portion B. In the present embodiment, as the boundary B, any material can be used as long as it is a material that can block light transmitted from the light source. For example, an inorganic or organic material having a refractive index lower than that of the high refractive index layer 6 can be used. The same applies to inorganic materials and organic materials having a refractive index higher than that of the high refractive index layer 6. A similar effect can be obtained. Among these, the boundary B is preferably an epoxy resin, a urethane resin, a polyimide resin, an acrylic resin, a sol-gel glass, or the like from the viewpoints of low moisture permeability, light blocking properties, and adhesion to the substrate 1. Further, from the viewpoint of adhesion to the high refractive index layer 6, low refractive index layer 5, 5 ′, light scattering layer and / or phosphor-containing layer 7 of the present invention, epoxy resin and acrylic resin are more preferable. Epoxy resins are particularly preferred. The use of epoxy resin as the boundary B is a particularly preferred combination because the high refractive index layer 6 that is a specific layer is particularly excellent in adhesion to the epoxy resin, is difficult to be altered, and has no effect inhibition. It is.

[0335] There is no limitation on the method for producing such a low refractive index portion 5a. For example, it can be produced in the same manner as the high refractive index portion 6a described in the fifth embodiment.

Furthermore, the light guide plate 8 according to the present embodiment is configured in the same manner as in the first embodiment, except for the above points. Therefore, the light guide plate 8 of the present embodiment also includes the low refractive index layers 5 and 5 ′, the high refractive index layer 6, and the light scattering layer and / or the phosphor-containing layer 7 that are specific layers in contact with each other. Therefore, as in the first embodiment, it is possible to freely control the film thickness such as thickening, to suppress cracks and peeling, and to improve heat resistance and light resistance. Advantages such as superiority can be obtained. Further, if the low refractive index portion 5a is formed of the same compound as that of the specific layer, the low refractive index portion 5a can also be freely controlled in film thickness such as thickening, cracks and Advantages such as suppression of peeling and excellent heat resistance and light resistance can be obtained.

As shown in FIG. 8, the light guide plate 8 of the seventh embodiment is obtained by installing a light scattering layer and / or a phosphor-containing layer 7 at a desired location in the high refractive index layer 6. is there. In this case, a light emitting surface using scattering can be formed at a desired location on the light guide plate 8. If this is used, it is possible to prevent transmission of light from far away while extracting light from a desired position.

There is no limitation on the method for producing such a light scattering layer and / or phosphor-containing layer 7. For example, it can be produced in the same manner as the high refractive index portion 6a described in the fifth embodiment. However, in the present embodiment, since the light scattering layer and / or the phosphor-containing layer 7 is provided inside the high refractive index layer 6, the light scattering layer and / or the phosphor-containing layer 7 is provided. Then, a high refractive index layer 6 is further laminated thereon. [0338] Furthermore, the light guide plate 8 according to the present embodiment has the above-described points and the configuration other than that the light scattering layer and / or the phosphor-containing layer 7 is not provided in a part of the low refractive index layer 5. The configuration is the same as in the third embodiment. Therefore, the low-refractive index layers 5 and 5 ′, which are specific layers in contact with each other, and the high-refractive index layer 6 as well as the light scattering layer and / or the phosphor-containing layer 7 are also laminated in the light guide plate 8 of the present embodiment. Therefore, as in the third embodiment, it is possible to freely control the film thickness such as thickening, to suppress cracks and peeling, and to have heat resistance and light resistance. It has become possible to obtain advantages such as excellence

As shown in FIG. 9, the light guide plate 8 of the eighth embodiment has a high refractive index portion (boundary portion A) and / or a low refractive index portion (boundary portion B) 10 (in the description of this embodiment). , When referring to the high refractive index portion and the low refractive index portion without distinguishing each other, it is referred to as “boundary portion 10”) that penetrates each of the layers 5, 6, 5 ′. A desired optical waveguide is constructed in the vertical and horizontal directions of the substrate surface by controlling the light blocking portion.

[0340] There is no limitation on the method of manufacturing the boundary portion 10 like this. For example, it can be produced in the same manner as the high refractive index portion 6a described in the fifth embodiment.

[0341] Further, the light guide plate 8 according to the present embodiment has the above-described configuration, except that the light scattering layer and / or the phosphor-containing layer 7 is not provided on the upper surface of the high refractive index layer 6. The configuration is the same as in the first embodiment. Therefore, the light guide plate 8 of the present embodiment is also configured by laminating the low refractive index layers 5 and 5 ′ and the high refractive index layer 6 which are specific layers in contact with each other. Similarly, it is possible to obtain advantages such as being able to freely control the film thickness such as thickening, suppressing cracks and peeling, and being excellent in heat resistance and light resistance. It has become. In addition, if the boundary portion 10 is formed of the same compound as that of the specific layer, the boundary portion 10 can also be freely controlled in film thickness such as thickening, and cracks and separation can be suppressed. Advantages such as being possible and being excellent in heat resistance and light resistance can be obtained.

As shown in FIG. 10, in the light guide plate 8 of the ninth embodiment, the reflective layer 11 is laminated on the substrate 1, and the reflective layer 11 does not cover the portion of the semiconductor light emitting device 4. A cylindrical or mortar-shaped hole 11H is provided. Thereby, the high refractive index layer 6 is transmitted. Since the light is efficiently reflected on the surface of the reflective layer 11, the light emitted from the semiconductor light emitting device 4 can be used effectively. Instead of the reflective layer 11, a light scattering layer and / or a phosphor-containing layer 7 can be provided.

[0343] Here, the material constituting the reflective layer 11 is not limited. For example, a metal material such as silver or aluminum; barium sulfate, silica, titanium oxide, calcium carbonate, or the like can be used. The film thickness is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually δπι or more, preferably 10 m or more, and usually 100 m or less, preferably 50 m or less. Furthermore, although there is no restriction | limiting in the lamination | stacking method, For example, it can laminate | stack by vapor-depositing a raw material or apply | coating a white particle pigment. Further, when a white surface such as a solder resist is formed on the substrate 1, this white surface may be used as the reflective layer 11.

In addition, the light guide plate 8 according to the present embodiment has the above-described points, and a configuration other than the force that does not provide the light scattering layer and / or the phosphor-containing layer 7 on the upper surface of the high refractive index layer 6. Is configured in the same manner as in the first embodiment. Accordingly, the light guide plate 8 of the present embodiment is also configured by laminating the high refractive index layer 6 and the low refractive index layer 5 ′, which are specific layers that are in contact with each other, and is the same as in the first embodiment. In addition, it is possible to obtain advantages such as being able to freely control the film thickness such as thickening, being able to suppress cracks and peeling, and being excellent in heat resistance and light resistance. Yes.

As shown in FIG. 11, in the light guide plate 8 of the tenth embodiment, a cylindrical or mortar-shaped hole 1H is formed in the substrate 1, and the semiconductor light emitting device 4 is installed at the bottom of the hole 1H. It is composed. As a result, the thickness of the light source itself can be accommodated in the substrate 1. In addition, the thickness of the low refractive index layer 5, the high refractive index layer 6, the light scattering layer and / or the phosphor-containing layer 7 can be reduced, and the height of the semiconductor light emitting device 4 can be adjusted. It becomes possible to increase the degree of freedom of design.

[0346] The light guide plate 8 according to the present embodiment has the above-described points, and the configuration other than the provision of the light scattering layer and / or the phosphor-containing layer 7 in a part of the low refractive index layer 5, The configuration is the same as in the first embodiment. Therefore, the low-refractive index layers 5 and 5 ′, the high-refractive index layer 6, and the light scattering layer and / or the phosphor-containing layer 7, which are specific layers in contact with each other, are also laminated on the light guide plate 8 of the present embodiment. As in the first embodiment, the thick film It is possible to obtain advantages such as free control of the film thickness such as crystallization, suppression of cracks and peeling, and excellent heat resistance and light resistance.

[0347] While specific examples of the embodiments of the light guide member of the present invention have been described above, a part of each of the first to tenth embodiments is introduced or combined with other embodiments. This can be changed as appropriate.

In the above-described embodiment, as long as at least two specific layers such as the low refractive index layers 5, 5 ′, the light refractive index layer 6, the light scattering layer and / or the phosphor-containing layer 7 are laminated. Some layers constituting the light guide plate 8 may not be provided, and other layers may be further stacked. For example, since the specific layer is excellent in translucency and adhesiveness, it is preferable to provide a moisture-proof film formed of polyethylene terephthalate (PET) or the like on the outermost layer of the light guide plate 8 described above.

[0348] Further, the boundary portions such as the low refractive index portion 5a, the high refractive index portion 6a, and the boundary portion 10 may penetrate at least two of the specific layers 5, 5 ', 6, and 7 described above. Therefore, it is possible to penetrate three or more layers. Further, it may be formed of a material that does not transmit light just by forming it from a material that can transmit light. Furthermore, the boundary part may contain other components such as inorganic particles, phosphors, and coloring materials.

For the purpose of improving each function of the boundary portion, the color material can be used by appropriately selecting the material and color. For example, when two light guide layer regions that propagate different colors are separated by a boundary, if the boundary is white, the white boundary reflects the light in each region, and the light to the adjacent region It has the effect of preventing leakage and color mixing. However, if the white boundary is made very thin or thin, the light shielding effect may be insufficient. In this case, it is considered that the use of the black border can surely prevent the color mixing of light to the adjacent area that causes a loss of light guide amount due to light absorption.

In the case where a color material is included in the boundary to make it white, an inorganic and / or organic material can be used as the color material. For example, as the inorganic particles, alumina fine powder, silicon oxide, aluminum oxide, titanium oxide, Metal oxides such as zinc oxide and magnesium oxide; metal salts such as calcium carbonate, barium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide; boron nitride, alumina white, co Examples include loyal silica, aluminum silicate, zirconium silicate, aluminum borate, clay, talc, kaolin, mica, and synthetic mica. Further, the organic fine particles include, but are not limited to, forces that can include resin particles such as fluorine resin particles, guanamine resin particles, melamine resin particles, acrylic resin particles, and silicon resin particles.

In addition, when the boundary portion contains a color material to make it black, inorganic and / or organic materials can be used. For example, as the inorganic particles, titanium black, carbon black, iron oxide black, bismuth sulfate, etc. Is mentioned. In addition, the organic fine particles are not limited to any force that can include, for example, aniline black, cyanine black, and perylene black.

In addition, only one type of coloring material may be used, or two or more types may be used in any combination and ratio.

[0349] [D. Method for manufacturing light guide member]

The light guide member manufacturing method of the present invention (hereinafter referred to as “the manufacturing method of the present invention” as appropriate) includes a light guide layer obtained by curing a fluid curable material on a substrate. A step of providing a weir for partitioning the light guide layer on the substrate (hereinafter referred to as “weir formation process” as appropriate) and a step of applying a curable material on the substrate (hereinafter referred to as “curable material as appropriate”). And a process of curing the curable material (hereinafter referred to as “curable material curing process” as appropriate).

[0350] [D— 1 1] Weir formation process

In the manufacturing method of the present invention, first, a substrate is prepared, and a weir is provided on the substrate.

[0351] [D— 1 1 1] Board

A board | substrate is a part which can become a support body of the light guide member of this invention, and a light guide layer and a weir are arrange | positioned on this board | substrate.

The size and shape of the substrate can be set arbitrarily according to the purpose of the light guide member to be manufactured.

[0352] Further, the substrate may include an arbitrary member as necessary. For example, the substrate is a light emitting diode (also called “: LED”) and a semiconductor laser diode. A light emitting source such as a semiconductor light emitting device such as a semiconductor laser diode (also referred to as “LD”) may be provided. In this case, the position at which the light emitting light source is disposed can be arbitrarily set according to the purpose of the light guide member.

Further, one or more desired layers may be laminated on the substrate in advance. In this case, the weir and the light guide layer, which will be described later, are provided on the substrate via these layers.

Yes

[0353] The material for forming the substrate is optional as long as the effects of the present invention are not significantly impaired. For example, from the viewpoint of adhesion to a curable material for forming a weir or a light guide layer, ceramic, metal, glass, etc. Resins are preferred. Among the resins, those containing a polar group and those containing a filler for improving adhesiveness such as ceramic, metal and glass are preferable. In the case of a substrate provided with a light emitting light source, a substrate having wiring may be used. In this case, for example, a printed wiring board on which glass fiber reinforced epoxy resin is laminated is suitable. The substrate may be formed of only one kind of material. Two or more kinds of materials may be used in any combination and kind.

[0354] [D— 1 1 2] Formation of weir

A weir is provided on the substrate. The weir is formed of a material that can transmit or block light from the light source, and is a portion that functions as a boundary portion that partitions the light guide member into predetermined regions. When a material that transmits light is used as the material of the weir, the light source light is transmitted to the area including the weir. That is, light is transmitted to the inside of the weir. On the other hand, when a material that blocks light is used as the material of the weir, the light source light is transmitted only to the area that does not include the weir! That is, no light is transmitted inside the weir.

[0355] Role of [D l— l 2 l] weir

Usually, a light guide layer, which will be described later, is formed so as to be blocked by this weir. Even when the weir does not completely block the light guide layer (that is, when the light guide layer is formed so as to cross over the weir), the portion where the weir is formed is a part of the weir. Only the light guide layer is formed thin, and as a result, the weir functions as a boundary part that partitions the light guide layer partially. Therefore, the weir partitions the light guide layer, so to speak, the size, shape, position, etc. of the light guide layer region are set according to the size, shape, position, etc. of the drawing of the weir. Design of Will be determined.

[0356] For example, when the weir is completely damming the curable material in the curable material coating process, the planar shape of each area of the partitioned light guide layer is the size, shape, It will be set according to the layout.

[0357] Also, for example, when the weir is formed of a material capable of transmitting light, the light transmitted from the light source through the light guide layer can be emitted through the weir. The shape and pattern formed by the light emitted by the member can be set according to the size, shape, position, etc. of the weir.

[0358] In addition, for example, when the weir cannot transmit light! / Or is formed of a material! /, The light transmitted from the light source through the light guide layer is prevented from being emitted from the weir. It is possible to prevent transmission from the weir to the end, or to reduce the intensity of the light transmitted from the weir to the end, thereby reducing the shape or pattern formed by the light emitted by the light guide member. It can be set according to the dimensions, shape, position, etc. of the weir.

[0359] In addition, for example, when the weir has a function of converting the wavelength of light (that is, a wavelength conversion function), light transmitted from the light source through the light guide layer is transmitted through the weir to a desired wavelength. After being converted into light, the light can be emitted, so that the color formed by the light emitted from the light guide member can be set according to the size, shape, position, etc. of the weir.

[0360] For example, when the weir has a function of diffusing light, light transmitted from the light source through the light guide layer can be diffused with respect to light emitted from the weir. Thus, the shape or pattern formed by the light emitted from the light guide member can be set according to the size, shape, position, etc. of the weir.

[0361] [D— 1 1 2— 2] Weir material

Any material of the weir can be used as long as the effects of the present invention are not significantly impaired. Of these, epoxy resin, urethane resin, polyimide resin, acrylic resin, silicone resin, and the like are preferable from the viewpoint of low moisture permeability, light transmission or blocking characteristics, and adhesion to the substrate. Further, from the viewpoint of adhesion to the substrate and the light guide layer (curable material), epoxy resin, acrylic resin, and silicone resin are particularly preferable. Only one type of weir material may be used, or two or more types may be used in any combination and ratio. [0362] Further, the material of the weir is preferably a material (curable material) that can be cured by applying a liquid material. Among these, a material that does not cure during the coating operation but cures during the curing operation is preferable. From this viewpoint, the curable material is preferably a thermosetting resin, a photocurable resin, or the like. Of these, among thermosetting resins, those that cure at the lowest possible temperature are preferred, and the influence of alteration on the substrate and light source is small.

[0363] There is no limit to the curing rate of the curable material! /, But it is faster! /, More preferred! This is because the shape retention characteristics during application are excellent. Specifically, those that cure usually within 10 hours, especially within 5 hours, particularly within 3 hours are preferred.

Some curable materials have a viscosity that temporarily decreases during curing. From the viewpoint of preventing the strength and the shape retention characteristics from deteriorating, it is preferable to suppress the above-described decrease in viscosity. In order to realize this, it is effective to improve the properties of the curable material and utilize the above-mentioned inorganic particles.

[0364] Further, as a material of the weir, other components may be further mixed with the above-described resin or the like as long as the effects of the present invention are not significantly impaired. Other components may be used alone, or two or more may be used in any combination and ratio. Examples of other components include phosphors and inorganic particles. These phosphors and inorganic particles are the same as those described in the first to eighth light guide members of the present invention.

[0365] [D— 1 1 2— 3] Weir shape and dimensions

There is no particular limitation on the shape of the weir. Usually, it is formed as a convex member extending on the substrate surface. At this time, the weir is preferably formed in a shape having no ridgeline. Here, the ridge line means a corner continuously formed in the longitudinal direction on the surface of the weir. Therefore, the shape having no ridge line refers to a shape in which the cross section has no corners when the weir is cut along a plane intersecting the longitudinal direction. Therefore, for example, the weir is preferably formed as a member having a substantially semicircular cross-section (le, loose, force, dimpled) whose surface is formed only by a curved surface (Fig. 13 (b) See). This is because if the surface of the weir is formed only with a smooth convex curved surface, the light extraction effect in the weir is superior to the case where it is formed with a polygonal cross section. This is because the surface of the weir is formed with a smooth surface, so that the transmitted light hits the weir and is reflected from the top of the weir. This is because it is possible to extract smooth light that continues to the bonding surface with a plate or the like.

[0366] The dimensions of the weir can be arbitrarily set according to the design of the light guide member. However, the height of the weir (see height H in Fig. 12 (a)) is usually l ^ m or more, especially 5 m or more, especially 10 m or more, usually 5 mm or less, especially 2 mm or less. In particular, lmm or less is preferable. If the weir is too low, the light splitting function of the guided light may be lost, and if it is too high, the mechanical strength may be reduced and impractical.

[0367] In addition, the width of the weir (see width W in Fig. 12 (a)) is more than normal, especially 5 111 or more, especially 10 m or more, usually 20 mm or less, especially 10 mm or less, especially 5 mm or less is preferable. If the width of the weir is too narrow, the mechanical strength may be insufficient, and if it is too wide, it may be wasted.

[0368] [D— 1 1 2— 4] Weir formation method

There is no limitation on the method of forming the weir, but normally, the material of the weir is placed at a desired site on the substrate, and the desired shape is drawn with the material to form the weir. In this case, the drawing method is not limited. For example, a drawing method using an inkjet, a dispenser, etc .; a printing method such as intaglio printing, relief printing, lithographic printing, stencil printing (screen printing, etc.); a resist method, etc. should be used. I can do it. Of these, drawing with a dispenser, screen printing, and resist method are preferred.

[0369] A dispenser is a device that quantitatively measures a liquid material and discharges the liquid material quantitatively. This device usually produces highly precise controlled air pressure, time, etc., which pushes the liquid material injected into a syringe or other container into various sizes and shapes of nozzle tips. There are no restrictions on the temperature, humidity, pressure, etc. in this case, but it is normally performed at a temperature of 0 ° C to 100 ° C, a humidity of 5RH% to 90RH%, and a pressure of 1Pa to 200kPa.

[0370] In the dispenser, the liquid material discharged from the tip of the nozzle is dropped onto the object and drawn. This drawing can be performed manually or automatically. However, from the viewpoint of dimensional stability, an automatic dispensing stage (a device that can directly draw an electronic drawing by storing two-dimensional movement or controlling it by a computer) is used. It is preferable.

[0371] In addition, after injecting a liquid material into a container such as a syringe, a sufficient defoaming operation (defoaming operation) Preferably). If bubbles are mixed in the liquid material, the discharge from the nozzles may become intermittent during drawing, which may lead to a reduction in drawing accuracy. It is also desirable to remove bubbles of about 100 m or less that are difficult to see with the naked eye.

Although there is no restriction | limiting in the method of foam removal operation, For example, a liquid material can be centrifuged under a vacuum (rotation, revolution type), or foam can be removed by applying an ultrasonic wave. Further, it is preferable to perform the treatment before injection into a container such as a syringe and / or after injection into a syringe or the like. In addition, bubbles may be mixed in when the nozzle is connected to the syringe, so discharge from the nozzle sufficiently before drawing! /, And it is also preferable to stabilize the discharge! /.

[0372] Depending on the operating conditions of the dispenser and the characteristics of the liquid material, it is possible to control the weir dimensions. For example, the height of the weir is increased as the viscosity of the liquid material is higher, the thixotropy of the liquid material is higher, the nozzle diameter is larger, the drawing speed is slower, and the lowering of the viscosity during curing is smaller. That power S. Moreover, it is possible to make it even higher by overcoating. In addition, for example, the width of the weir can be increased as the viscosity of the liquid material is lower, the thixotropy is lower, the nozzle diameter is larger, the speed is lower, and the viscosity decrease is larger. Further, it can be made wider by performing multiple drawing adjacent in the horizontal direction. Furthermore, when a dispenser having a plurality of adjacent nozzles is used, it is possible to perform multiple drawing adjacent in the horizontal direction by one drawing.

[0373] Screen printing is a kind of printing technique called stencil printing, and is a printing method in which a large number of fine holes are provided in a plate and a liquid material that has passed through the holes is transferred by pressure. Specifically, a screen composed of a mesh and a mask is stacked on the object to be printed, and the screen is pressed against the stage while supplying the liquid material from above. As a result, the liquid material is discharged from the mesh corresponding to the opening of the mask, and the same image as the mask opening is formed.

[0374] The dimensions of the weir can be controlled by the operating conditions of screen printing. For example, the height of the weir can be increased as the mesh screen is thicker and the aperture ratio is larger. Further, it is possible to make it higher by repeatedly printing. The width of the weir usually follows the mask dimensions.

[0375] The resist method is a method in which a resist material is used as a weir material, the resist material is applied to a substrate, and a desired image is formed by development. As a resist material, Either a positive type or a negative type can be used. As the positive resist material, for example, a photosensitive positive resin or a resin composition can be used. On the other hand, as the negative resist material, for example, a photopolymerizable and / or heat polymerizable resin or a resin composition can be used. As a method of applying the resist material to the substrate, a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a slit 'and' spin method, a die coating method, a roll coating method, a spray coating method, etc. Can be done. After application of the resist material to the substrate, for example, when a photosensitive resist material is used, it is possible to use a force S to form a desired image after the resist application, through an exposure process, a development process, a heat treatment process, and the like.

[0376] Among these, it is preferable to provide a weir with a dispenser. When using a dispenser, the process is not complicated, so it is easy to design a variety of designs according to the order, and because the weir has a shape that does not have a ridgeline, the surface can be formed only with a smooth convex curved surface. This is because the light extraction effect at the portion is also excellent.

In addition, the above method can be carried out by combining two or more methods.

[0377] Note that when the weir is formed in a shape having no ridgeline as described above, for example, after the weir is formed by the above-described method, the surface of the weir is thermally melted. It is preferable to perform processing to form a curved surface!

[0378] [D— 1 2] Hardening material coating process

After the weir formation process, a curable material coating process is performed in which a curable material is coated on the substrate.

[0379] [D— 1 2— 1] Curable material

The curable material is a fluid-like material that is cured by performing some kind of curing treatment. Here, the fluid state means, for example, a liquid state or a gel state. In addition, the curable material ensures the role of the light guide that transmits light from the light source to a predetermined position. There is no restriction | limiting in the specific kind of such a curable material. Moreover, only one type of curable material may be used, or two or more types may be used in any combination and ratio. Therefore, as the curable material, it is also possible to use! /, Deviation of inorganic material and organic material and a mixture of both.

[0380] Examples of inorganic materials include metal alkoxides, ceramic precursor polymers, or Examples thereof include a solution obtained by hydrolytic polymerization of a solution containing a metal alkoxide by a sol-gel method, or an inorganic material (for example, an inorganic material having a siloxane bond) obtained by solidifying a combination thereof.

[0381] On the other hand, examples of the organic material include a thermosetting resin and a photocurable resin. Specific examples include methacrylic resins such as polymethylmethacrylate; styrene resins such as polystyrene and styrene acrylonitrile copolymers; polycarbonate resins; polyester resins; phenoxy resins; butyral resins; Cenorelose-based lunar essence such as cenololose acetate and cenololose acetate butyrate; epoxy resin; phenol resin; silicone resin and the like.

[0382] Among these curable materials, it is preferable to use a silicon-containing compound for the purpose of heat resistance, light resistance, etc., especially when using a high output light source! A silicon-containing compound is a compound having a silicon atom in its molecule, inorganic materials such as organic materials (silicon-based materials) such as les, le, polyorganosiloxane, silicon oxide, silicon nitride, and silicon oxynitride. And glass materials such as borosilicate, phosphosilicate, and alkali silicate. Of these, silicone-based materials are preferable from the viewpoints of transparency, adhesion, ease of handling, mechanical and thermal adaptability relaxation characteristics, and the like. Among the silicone materials, the specific layer forming liquid described in the first to eighth light guide members is more preferable.

[0383] Hydrolysis of the above-mentioned alkylalkoxysilane as a curable material. When a polycondensate is used, the hydrolysis / polycondensate is compared with other curable materials such as epoxy resins and silicone resins. It has the advantage that the coating performance can be sufficiently maintained even when high-concentration inorganic particles having low viscosity and good compatibility with phosphors and inorganic particles are dispersed. In addition, it is possible to increase the viscosity by adjusting the degree of polymerization as required, and by adding a thixo material such as aerosil, etc., and an object to be coated with a large viscosity adjustment range according to the target inorganic particle content It is possible to provide a coating solution that can be flexibly adapted to various coating methods such as potting, spin coating, and printing.

[0384] [D-1-2-2] Coating method of curable material

When coating the curable material, there is no limitation on the coating method. As examples of the coating method, a cast method, a spin method, a dip method, and the like can be used. Cast method and In this method, a predetermined amount of a liquid curable material is placed on the coated surface and spread automatically or with a brush. The spin method is a method of forming a uniform film thickness of a liquid curable material placed on an application surface by centrifugal force. Further, the dipping method is a method of attaching a predetermined amount of curable material to the coated surface by immersing the coated surface in a liquid curable material and pulling it up at a constant speed. Among them, the casting method is preferable for coating the curable material with a uniform film thickness in the range surrounded by the weir. In other methods, liquid accumulation occurs in the weir and it is difficult to achieve a uniform film thickness immediately, which may lead to deterioration of the light guide characteristics.

[0385] There are no restrictions on the coating conditions of the casting method, but normally a predetermined amount of curable material is discharged to a predetermined position using a dispenser, a clearance of the desired film thickness is provided, and a spatula-shaped scraper Squeeze the curable material with a plate and flatten it. At this time, it is preferable to make the film surface uniform by leveling and discharging a liquid curable material having a low viscosity adjusted with a dispenser to give time or vibration. In order to make the film surface uniform, it is also useful to use a multi-nozzle with a dispenser.

There are no restrictions on conditions such as temperature, humidity, and pressure when applying curable materials by the casting method, but normally the temperature is 0 ° C to 100 ° C, relative humidity is 5% to 90%, pressure 1 Pa to 200 kPa is preferable. Also, an environment that causes condensation is not preferable.

[0386] When coating curable materials, there is no limit to the thickness of the coating film to be formed, but it is usually 1 μm or more, especially 5 m or more, especially 10 m or more, and usually 5 mm or less. Of these, 2 mm or less, particularly 1 mm or less is preferred. If the coating film is too thin, the amount of light guided is limited and may become thicker. If it is too thick, it becomes heavier and larger, which may reduce the attractiveness of small parts.

[0387] However, at the time of coating, the curable material is usually controlled in the formation position of each region of the coating film by using the weir. That is, as a result of coating the curable material so as to be blocked by the weir, the planar shape of the formed coating film is different for each area partitioned by the weir according to the shape drawn by the weir. Its planar shape is controlled. For example, when the weir forms a closed frame, the coating film of the curable material is usually formed so as to be filled in the frame. Within the frame, the weirs will match the drawn shape. For example, even if the weir does not form a closed frame, At least the edge portion of the coating film of the curable material is formed along the weir at the portion in contact with the weir, so that the planar shape of the edge coincides with the shape on which the weir is drawn. In addition, a dam is provided in advance, and a curable material is applied so that the dam can be blocked, so that it is possible to design the light transmitted through the light guide layer to reach the weir without fail. Therefore, the light emitting part can be controlled by the weir.

Thus, by performing the curable material coating step after the dam formation step, the planar shape of the coating film of the curable material can be easily and freely designed by the previously provided dam. In addition, a coating film can be easily and freely designed using different weirs and different materials and layer configurations for each region partitioned by the weirs. For this reason, it is possible to freely design the light-emitting portion of the light guide member without having to change the shape and standard as in the past.

[0388] [D— 1 3] Curing material curing process

After the curable material coating step, a curable material curing step for curing the curable material coated on the substrate is performed. Thereby, the coating film of the curable material formed on the substrate is cured, and the light guide layer is formed.

[0389] The curing method may be arbitrarily selected according to the type of curable material.

Since curable materials are usually classified into photo-curing materials, thermosetting materials, and photo-thermosetting materials, the conditions should be set according to the type of each curable material! /.

[0390] For example, when the curable material is a photocurable material, light having a wavelength suitable for curing may be irradiated. Hereinafter, a specific example will be described.

There are various types of photo-curing materials such as acrylic, metal-based, and epoxy-based depending on the structure of the part that is polymerized and cured. Of these, acrylic and methacrylic ones are usually used in combination with radical generating polymerization initiators. Therefore, it is possible to cure the acrylic and meta- curable curable materials by irradiating light (for example, ultraviolet rays) having a wavelength suitable for generating radicals of the polymerization initiator. Examples of this radical-generating polymerization initiator include alkylphenone series, acylphosphine oxide series, titanocene series, and oxime ester series, and these may be used alone. The above may be used in any combination and ratio. In addition, polymerization promotion such as aminobenzoate, etc. Advancement agents may be used in combination.

[0391] Epoxy curable materials include those that are cured only by light and those that are cured by either light or heat. Usually, when curing this epoxy-based curable material, a cation generation type polymerization initiator is used in combination, and light and / or heat having a wavelength suitable for cation generation of the polymerization initiator is applied and cured. Examples of this cation-generating polymerization initiator include sulfonium salts and odonium salts, and these can be used alone or in combination of two or more in any combination and ratio. Of these, PF (hexafluorophosphate) salt is suitable for curing mainly by light alone.

6

SbF (hexafluoroantimony) salt is suitable for curing with light and heat

6

It is.

[0392] On the other hand, when the curable material is a thermosetting material, the curable material is coated and then cured by heating. There are no restrictions on the heating method, but examples include methods such as applying hot air, using electric heat from a heat block, using microwaves, and using radiant heat. Usually, it is preferable to use a stationary box oven, a hot plate, an electronic range, a far-infrared furnace, or the like.

[0393] When the curable material has a polycondensation type curing mechanism, the curable material usually contains a component that volatilizes with polymerization. Since the polymerization can be further accelerated by removing these volatile components, it is preferable that the apparatus used for curing has a means for replacing the atmosphere during curing with fresh gas. In particular, in the case of a dehydration condensation type curable material, for example, the replacement of the curing reflux gas is performed periodically, the curing is performed under the flow of the gas, the circulation gas is dried, or the curing reflux desiccant is disposed. It is preferable to do.

[0394] In addition, when heating is performed using a heating furnace, any of sheet processing, batch processing, moving belt, continuous processing that passes through the furnace, and processing in which the number of persons in charge is put together into the furnace can be used. It can be selected according to productivity. As the heating furnace, for example, a tunnel furnace, a box furnace, or the like is preferably used.

[0395] By the way, the material constituting the light guide layer, including the material forming the weir, has a force S that shrinks by curing. Therefore, these materials are preferably resistant to compression and tension. Hereinafter, this point will be described with an example. Usually, the substrate has a different coefficient of thermal expansion relative to the light guide layer. For example, when cured by heat during thermosetting, the cured thermosetting material has the ability to shrink when cooled to room temperature. If the constituent material of the light guide layer is larger than the constituent material of the substrate, a large tensile stress is applied to the light guide layer. At that time, if the stress cannot be relieved, the force concentrates on the part with weak adhesive force, which may cause peeling or cracking. Even if no peeling or cracking occurs, the substrate may be deformed. If peeling, destruction, deformation, or the like occurs, light guided there may be blocked and the light guide layer may not function. When combined with a light source, the light source usually generates heat. For this reason, in the immediate vicinity of the light source, a large stress is generated due to the difference in thermal expansion coefficient between the material constituting the light source and the material constituting the light guide layer, and adhesion failure or the like is likely to occur.

From the above viewpoint, it is preferable that the material of the light guide layer itself greatly relieves stress. Specifically, those having low hardness and / or rubber properties are preferred.

[D— 1 4] Other processes

In the range not departing from the gist of the present invention, one or more other steps before, during and after the dam formation step, the curable material coating step, and the curable material curing step described above May be performed.

For example, when the light guide layer is composed of two or more layers, a curable material coating process and a curable material hardening process are performed using a desired curable material after the curable material curing process. The light guide layer may be formed by stacking two or more layers by performing the process.

Further, for example, the surface treatment may be performed on the substrate before forming the weir and the light guide layer. Examples of such surface treatment include, for example, the formation of an adhesion improving layer using a primer silane coupling agent, chemical surface treatment using a chemical such as acid or alkali, plasma irradiation, ion irradiation, or electron beam irradiation. And surface roughening by sand blasting or etching 'fine particle coating'. Other surface treatments for improving adhesion include, for example, Japanese Patent Laid-Open No. 5-25300, Nobuhiro Inagaki “Surface Science” Vol. 18 No. 9, pp21-26, Satoshi Kurosaki. There are known surface treatment methods disclosed in the book “Surface Physics” Vol. 19 No. 2, p p44-51 (1998). In addition, ozone treatment can be performed. [0397] [D-2] Light guide member

According to the manufacturing method of the present invention described above, the ninth light guide member of the present invention described below can be realized.

A ninth light guide member of the present invention includes a substrate, a weir, and a light guide layer.

[0398] [D— 2— 1] Board

The substrate is as described in the section “[D- 1 1 1] substrate”.

[0399] [D- 2-2] ± g

The weir is as described in the section “[D-1-1] weir formation process”. However, in the ninth light guide member of the present invention, the weir is formed in a shape having no ridgeline as described above, and has a so-called kamaboko shape. In other words, the weir has a shape having no ridgeline. Here, “having no ridgeline” means that the plane that is parallel to the longitudinal direction of the weir and does not contact the substrate does not constitute two or more planes! /. When the boundary is composed of two or more surfaces, it has a ridge line at the intersection of two adjacent surfaces. The present invention can improve the light extraction effect by not having a ridge line at the boundary.

[0400] [D-2-3] Light guiding layer

The light guide layer is a layer having a role of transmitting light emitted from the light source to a predetermined position in the light guide member. As the material for the light guide layer, the curable material described above in the “[D-12] curable material coating step” is used.

Further, the light guide layer may be formed by only one layer, but may be formed by laminating two or more layers. In this case, examples of layers constituting the light guide layer include a high refractive index layer, a low refractive index layer, a scattering layer, and a phosphor-containing layer.

Hereinafter, these layers will be described.

[0401] [D— 2— 3— 1] High refractive index layer

The high refractive index layer normally functions as a core layer that transmits light. Therefore, light emitted from the light source is normally transmitted to a desired position through this high refractive index layer.

[0402] The refractive index of the high refractive index layer is arbitrary as long as the effect of the present invention is not significantly impaired. Usually 1.45 or more, preferably 1.5 or more, more preferably 1.6 or more. Although the upper limit is not particularly limited, for example, when a semiconductor light-emitting device is used as a light source, the refractive index of a general semiconductor light-emitting device is approximately 2.5, so it is usually 2.5 or less, and the refractive index is adjusted. From the viewpoint of facilitating, it is preferably 2.0 or less. If the refractive index of the high refractive index layer is too small, the light extraction efficiency may not be improved. On the other hand, even when the refractive index of the high refractive index layer is larger than the refractive index of the member constituting the light source, the light extraction efficiency is likely force ^s not improved.

[0403] Refractive index should be measured using known methods such as immersion method (solid object), Pulflich refractometer, Abbe refractometer, prism coupler method, interferometry, minimum deviation method, etc. Is possible. The refractive index measurement wavelength in the present invention can be selected from sodium D line (589 nm), which is used for general purposes when using an instrument such as an Abbe refractometer.

[0404] In order to make the refractive index of the high refractive index layer relatively high, for example, a phenyl group may be introduced into the compound. For example, as described above, inorganic particles having a median particle diameter of 1 to! Onm may be included as the refractive index adjusting agent.

Note that the high refractive index layer may be provided with only one layer or with two or more layers.

[0405] [D— 2— 3— 2] Low refractive index layer

The low refractive index layer normally functions as a cladding layer that confines light. Therefore, light transmitted through layers such as the high refractive index layer, scattering layer, and phosphor-containing layer is reflected at the interface between the layer and the low refractive index layer, and is transmitted accurately to a predetermined position. Has come to be

[0406] The refractive index of the low refractive index layer is arbitrary as long as the effects of the present invention are not significantly impaired. Usually, it is less than 1.45, preferably 1.43 or less, more preferably 1.42 or less. The lower limit is usually 1.4 or more, preferably 1.41 or more.

[0407] When the low refractive index layer and the high refractive index layer are used in combination, the refractive index difference between the high refractive index layer and the low refractive index layer is usually 0.03-0. The transmission distance (waveguide distance) of light in the high refractive index layer can also be adjusted by appropriately adjusting. That is, when the refractive index difference is increased, the low refractive index layer (cladding layer) efficiently confines the light of the high refractive index layer (core layer), so that the light transmission distance with less leakage light to the low refractive index layer. Can be lengthened . On the other hand, if the refractive index difference is set to be as small as 0.05 or less, for example, leakage light from the high refractive index layer to the low refractive index layer increases, so that the light transmission distance becomes short.

Note that the low refractive index layer may be provided with only one layer or two or more layers.

[0408] [D— 2-3—3] scattering layer

The scattering layer is a layer having a function of expanding the directivity angle of the emitted light when the light transmitted by the light source is emitted to the outside. As described above, the scattering layer preferably contains inorganic particles having a median particle diameter in a predetermined range as a light scattering material.

The scattering layer may be provided with only one layer or may be provided with two or more layers.

[0409] As another configuration of the scattering layer, guided light can be extracted using surface roughness. This is because by providing a scattering layer on the rough surface, the guided light is scattered on the rough surface, and the light becomes perpendicular to the extraction surface. It is a thing.

[0410] The rough surface can be formed on the substrate and / or on each layer. At this time, the rough surface may be formed on the upper surface (close to the light extraction surface, the surface), the lower surface (distant from the light extraction surface! /, Surface) of each layer, or shifted.

The roughness of the rough surface is not particularly limited as long as it has the property of scattering light, but the height difference is usually 0.2 to 111 m or more, preferably 0.5 m or more, and 50 m or less, preferably 30 m or less. It is below.

[0411] The method of creating a rough surface on the substrate is not limited, but, for example, precision machining, blasting, powder coating, application of a coating solution containing diffusing particles, particle pasting, chemical etching, light irradiation, inkjet printing , Exposure to photosensitive curable (softening) resin, development, heating / development to heat-sensitive curing resin, and the like.

Further, as a method of roughening the surface of each layer to be laminated, for example, chemical treatment using hydrofluoric acid or alkali, blast treatment, powder coating, application of a coating solution containing diffusing particles, particle pasting, light irradiation, inkjet There is printing. In addition, for example, a method in which sedimentation or floating light diffusing particles are contained in a layer to be configured, and after coating, particles are settled or suspended so that more diffusing particles exist at the interface of each layer. It can be preferably used in the same manner as the method of forming the surface. [0412] [D— 2-3— 4] Phosphor-containing layer

The phosphor-containing layer is a layer containing a phosphor, and has a function of converting the wavelength of light transmitted from the light source into a desired wavelength. The phosphor is as described above. The phosphor-containing layer may contain inorganic particles having a median particle size of 0.;! To 10 m as a light scattering agent in order to increase the amount of light hitting the phosphor and improve the wavelength conversion efficiency. Good. The phosphor-containing layer may be provided with only one layer or two or more layers.

[0413] [D— 2-4] Shape and dimensions of light guide member

The shape and size of the ninth light guide member of the present invention are not limited and are arbitrary. For example, when used as an optical waveguide or a light guide plate of a light guide member, the shape and size of the ninth light guide member of the present invention are determined according to the shape and size of the substrate of the optical waveguide or light guide plate. Is

[0414] However, in the ninth light guide member of the present invention, when the hydrolyzed polycondensate of alkylalkoxysilane is used as a curable material, the light guide layer is formed in a thick film. One of the advantages is that Many other light-guiding members have a thickness that could be difficult to thicken due to internal stress, etc., when the light-guiding layer is thickened. In the case of using the light guide member, such a situation does not occur, and a thick film can be stably formed. In this case, to give a specific range, when the light guide member is used as a light guide plate, the thickness of each layer constituting the light guide layer is usually ππι or more, preferably (30 111 or more, usually 500 mm). Or less (preferably less than or equal to 300 mm, more preferably less than or equal to 200 mm. Here, when the thickness of the film is not constant, the film thickness is the thickness of the maximum thickness portion of the film. In this case, the total thickness of all layers excluding the light guide plate substrate is usually 60 Hm or more, preferably 80 Hm or more, and usually 500 μm or less, preferably 300 m or less. More preferably, it is 200 m or less.

[0415] [D-3] Light guide plate

If the 9th light guide member of this invention is used, the light-guide plate provided with the said 9th light guide member of this invention will be obtained. In this case, if the ninth light guide member of the present invention is formed in a plate shape, the ninth light guide member itself of the present invention can be used as the light guide plate. In addition, the light guide plate can be configured by combining the ninth light guide member of the present invention with other members as necessary. wear.

[0416] However, the light guide plate is often applied to a surface light-emitting device. In this case, usually, a scattering layer is provided so that light can be emitted from the main surface (light emitting surface) of the ninth light guide member of the present invention, or a surface facing the light emitting surface (usually the substrate and the light guide layer). Or irregularities such as grooves, rough surfaces, and inclined surfaces.

In addition, the light guide plate is provided with a reflection member such as a reflection sheet to reflect light transmitted through the light guide layer, or a diffusion sheet or the like for diffusing light transmitted through the light guide layer. A member may be provided, or a refractive member such as a prism sheet may be provided to refract light transmitted through the light guide layer in a desired direction.

[0417] Further, since the light guide plate is an optical component intended to transmit light emitted from the light source, it is usually used in combination with the light source. The light guide plate and the light source may be configured separately. Force The light guide plate may be configured to include a light source. Also, the number of light sources may be one or more than two.

[0418] The wavelength of the main wavelength of the emission peak of the light source is not particularly limited, and a light source with a wide emission wavelength can be used. Usually, an illuminant having an emission wavelength from the near ultraviolet region to the blue region is used, and specific values are usually 300 nm or more, preferably 330 nm or more, and usually 500 nm or less, preferably 480 nm or less. A light emitter having an emission wavelength is used. In particular, when a phosphor is contained in the light guide layer, a light source having an emission wavelength that overlaps with the absorption wavelength of the phosphor is preferred.

[0419] As the light source, a semiconductor light emitting element is usually used. For example, LED or LD can be mentioned. In addition, as an example of a light source, an organic electoluminescence light emitting element, an inorganic electoluminescence light emitting element, etc. are mentioned. Of these, the GaN LEDs and LDs mentioned above are preferred!

[0420] [D-4] Embodiment

The ninth embodiment of the light guide member of the present invention will be described below with reference to the drawings. However, all of the following embodiments are exemplifications, and the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

[0421] [D— 4 1] Eleventh embodiment 12 (a) to 12 (c) are cross-sectional views schematically showing a method for manufacturing a light guide member as an eleventh embodiment of the present invention.

As shown in FIG. 12 (a), when manufacturing the light guide member 27 (see FIG. 12 (c)) in this embodiment, first, the substrate 21 is prepared. In the present embodiment, as shown in FIG. 12 (a), a semiconductor light emitting device 24 configured by covering a semiconductor light emitting element 22 with a sealing material 23 as a light source is installed on the surface of the substrate 21 in advance. It shall be. It should be noted that the semiconductor light emitting device 24 that is sealed with the sealing material 23 can also be used in the present invention.

[0422] After the substrate 21 is prepared, the weir 25 is provided at a desired position by the method described above (weir formation process). In the present embodiment, a material having a relatively low refractive index is used for the weir 25 so as to block light transmitted from the semiconductor light emitting device 24, and this material is drawn by a dispenser. It shall be provided.

However, in this embodiment, it is assumed that the weir 25 is formed in a shape having no ridgeline, and the weir 25 is formed in a so-called force, magenta shape. That is, as described above, since the shape of the weir 25 is not limited, the force that can be formed in a polygonal cross section as schematically shown in FIG. 13 (a) is shown in FIG. It is assumed that the surface is formed only with a smooth convex curved surface as schematically shown in b).

[0423] After the weir 25 is provided, as shown in Fig. 12 (b), a fluid curable material is coated on the substrate 21 by the method described above (curable material coating step). At this time, since the weir 25 is provided in advance, the curable material is blocked by the weir 25. Therefore, the coating film 26 ′ (and thus the high refractive index layer 26 obtained by curing the coating film 26 ′) formed by the curable material has a structure partitioned by the weir 25, and the curable material can be easily placed at a desired position. And can be applied accurately. In this embodiment, it is assumed that a curable material having a relatively high refractive index that can be the high refractive index layer 26 is used so that light emitted from the semiconductor light emitting device 24 can be transmitted after curing.

[0424] Then, after the application of the curable material, as shown in FIG. 12 (c), the applied curable material is cured by the above-described method (curable material curing step). As a result, the coating film 26 ′ is cured, and a high refractive index layer 26 as a light guide layer is obtained. Thus, the light guide member 27 of the present embodiment is manufactured. [0425] In the light guide member 27 of the present embodiment manufactured as described above, the light emitted from the semiconductor light emitting device 24 that is a light source is transmitted by the high refractive index layer 26 that is a light guide layer. It is emitted from the upper surface of the refractive index layer 26 in the figure. In this embodiment, since the weir 25 is made of a material having a low refractive index, most of the light cannot pass through the weir 25, and therefore light is transmitted from the side surface of the light guide member 27. Almost no radiation.

Thus, by providing ± 區 25, the planar shape of the high refractive index layer 26 is set according to the shape of the weir 25. Therefore, from which position of the light guide member 27 the light is emitted, that is, the light guide region can be controlled by ± により 25. Therefore, if the light guide member 27 is manufactured as in the present embodiment, the light emitting portion can be freely designed.

Further, in the light guide member 27 of the present embodiment, the weir 25 is formed in a shape that does not have a ridge line, so that the light extraction effect can be improved.

[0427] [D 4 2] 12th embodiment

FIG. 14 is a schematic cross-sectional view of a light guide member as a twelfth embodiment of the present invention. In FIG. 14, the same parts as those in FIGS. 12 and 13 are denoted by the same reference numerals.

In this light guide member 27, the weir 25 can transmit light from the semiconductor light emitting device 24, and is formed of a material containing a phosphor, and a high refractive index layer 26 which is a light guide layer Except for being partially partitioned by the weir 25, it is the same as in the eleventh embodiment.

[0428] Also in the case of manufacturing the light guide member of the present embodiment, a curable material coating step and a curable material curing step are performed after the weir forming step basically in the same manner as in the eleventh embodiment. You can do this.

However, in the weir formation step, as the material of the weir 25, a material that can transmit light from the semiconductor light emitting device 24 and contains a light scattering agent and / or a phosphor is used. Here, it is assumed that a composition in which a light scattering agent and / or a phosphor is dispersed in a resin having a high refractive index is used as the material of the weir 25.

Also, in the curable material coating process, the dam 25 cannot be completely dammed up. A curable material is applied as described above. Even in this case, since the dam 25 partially dams the curable material, the coating film formed of the curable material and the high refractive index layer 26 obtained by curing the coating film are at least partially partitioned by the dam 25. The structure allows the curable material to be easily and accurately applied to the desired location.

In the light guide member 27 of the present embodiment manufactured as described above, light emitted from the semiconductor light emitting device 24 that is a light source is transmitted through the high refractive index layer 26 that is a light guide layer, and has a high refractive index. Radiated from the surface of layer 26. In this embodiment, since the weir 25 can transmit light, a part of the light transmitted by the high refractive index layer 26 is emitted after passing through the weir 25. In this case, when the weir 25 contains a light scattering agent, the light emitted through the weir 25 is emitted after being scattered, so that the light extraction efficiency can be improved. Thereby, the brightness of the light at the position where the weir 25 is provided can be made higher than the other positions, and the light guide region can be controlled. On the other hand, when the weir 25 contains a phosphor, the light emitted through the weir 25 is emitted after wavelength conversion, so that the color of the light can be changed. Thereby, the color of the light at the position where the weir 25 is provided can be different from the other positions, and the light guide mode can be controlled.

[0430] As described above, when the light guide member 27 is manufactured as in the present embodiment, the light guide region and the light guide mode of the light guide member 27 can be controlled by the weir 25 by providing the weir 25. It becomes like. Therefore, if the light guide member 27 is manufactured as in the present embodiment, the light emitting portion can be freely designed.

Also in the light guide member 27 of the present embodiment, the light extraction effect can be improved because the weir 25 is formed in a shape having no ridgeline, as in the eleventh embodiment.

In addition, the same effects can be obtained based on the same configuration as that of the eleventh embodiment.

[0431] [D-4 3] Thirteenth embodiment

FIG. 15 is a schematic cross-sectional view of a light guide member as a thirteenth embodiment of the present invention. In FIG. 15, parts similar to those in FIGS. 12 to 14 are denoted by the same reference numerals.

The light guide member 27 has a low refractive index layer 28 formed below the high refractive index layer 26, and the light guide layer is composed of the high refractive index layer 26 and the low refractive index layer 28. With the eleventh embodiment The same is true.

[0432] The low refractive index layer 28 is a layer formed of a material having a relatively low refractive index on the substrate 21 so as to block light transmitted from the semiconductor light emitting device 24. The low refractive index layer 28 is provided with a cylindrical or mortar-shaped hole 28H so as not to cover the semiconductor light emitting device 24! /.

[0433] When manufacturing the light guide member of this embodiment, basically, as in the first embodiment, after the weir formation step, curing is performed corresponding to each layer constituting the light guide layer. Material and coating process and curable material curing process! Specifically, after performing the weir forming process in the eleventh embodiment, the curable material corresponding to the low refractive index layer 28 is used, and the curable material coating process and the curable material curing process are performed, A low refractive index layer 28 is formed. However, in this case, since the hole 28H is formed, the low refractive index layer 28 is not formed in the hole 28H by masking or the like. Then, after the formation of the low refractive index layer 28, the masking or the like is removed, and a curable material coating process and a curable material curing process are performed using a curable material corresponding to the high refractive index layer 26, thereby reducing the low refractive index. The high refractive index layer 26 may be formed on the layer 28.

[0434] In the light guide member 27 of the present embodiment manufactured in this way, the light emitted from the semiconductor light emitting device 24, which is a light source, is transmitted by the high refractive index layer 26 as in the eleventh embodiment. The light is emitted from the upper surface of the high refractive index layer 26 in the drawing, and no light is emitted from the side surface of the light guide member 27.

[0435] As described above, when the light guide member 27 is manufactured as in the present embodiment, the light guide region can be controlled similarly to the eleventh embodiment by providing the weir 25, and the light emitting portion can be freely set. It is possible to design to S. Furthermore, in the light guide member 27 of the present embodiment, the weir 25 is formed in a shape having no ridgeline, so that the light extraction effect can be improved.

In addition, based on the same configuration as that of the eleventh embodiment, the same effect can be obtained.

[0436] [D-4 4] Fourteenth embodiment

FIG. 16 is a schematic cross-sectional view of a light guide member as a fourteenth embodiment of the present invention. In FIG. 16, parts similar to those in FIGS. 12 to 15 are denoted by the same reference numerals. It shall be

In this light guide member 27, a scattering layer and / or a phosphor-containing layer 29 is formed on a part of the low refractive index layer 28, and the high refractive index layer 26, the low refractive index layer 28, the scattering layer and / or the fluorescent layer. The structure is the same as that of the thirteenth embodiment except that the light guide layer is composed of the body-containing layer 29.

[0437] In the present embodiment, the scattering layer and / or the phosphor-containing layer 29 is a layer formed by containing a light scattering agent and / or a phosphor in a curable material having a relatively high refractive index. Shall. By providing the scattering layer and / or the phosphor-containing layer 29, the refractive index difference between the low refractive index layer 28 and the high refractive index layer 26 can be reduced, and the light entering the low refractive index layer 28 can be used as desired. The effect of can be achieved.

[0438] When the light guide member of this embodiment is manufactured, basically, as in the thirteenth embodiment, after the weir formation process, the curability corresponding to each layer constituting the light guide layer is obtained. Materials The coating process and the curable material curing process should be performed! /. Specifically, after performing the weir formation process as in the thirteenth embodiment, the curable material coating process and the curable material curing process are performed using the curable material corresponding to the low refractive index layer 28, A low refractive index layer 28 is formed. However, in this case, unlike the thirteenth embodiment, the low refractive index layer 28 is not formed by masking or the like in the portion where the scattering layer and / or the phosphor-containing layer 29 is formed only by the hole 28H. Shall be kept. Then, after the formation of the low refractive index layer 28, the masking of the portion where the scattering layer and / or the phosphor-containing layer 29 is to be formed is removed, and a curable material coating step and a curable material curing step are performed on this portion. A scattering layer and / or a phosphor-containing layer 29 is formed. Then, the light guide member 27 may be manufactured by removing the masking or the like of the hole 28H and forming the high refractive index layer 26 thereon as in the thirteenth embodiment. Note that the scattering layer and / or the phosphor-containing layer 29 may be formed prior to the low refractive index layer 28.

[0439] In the light guide member 27 of the present embodiment manufactured as described above, light emitted from the semiconductor light emitting device 24 that is a light source is transmitted by the high refractive index layer 26 as in the thirteenth embodiment. The light is emitted from the upper surface of the high refractive index layer 26 in the drawing, and no light is emitted from the side surface of the light guide member 27. At this time, since the scattering layer and / or the phosphor-containing layer 29 is provided, the light incident on the scattering layer and / or the phosphor-containing layer 29 is scattered to extract light from the light guide member 27. Thus, the efficiency can be improved, or the wavelength of light emitted from the light guide member 27 can be controlled by converting the wavelength of light incident on the scattering layer and / or the phosphor-containing layer 29.

[0440] As described above, if the light guide member 27 is manufactured as in the present embodiment, the light guide region can be controlled similarly to the thirteenth embodiment by providing the weir 25, and further the scattering layer. In addition, since the light guide mode can be controlled by the phosphor-containing layer 29, the light emitting portion can be freely designed. Furthermore, in the light guide member 27 of the present embodiment, the weir 25 is formed in a shape having no ridgeline, so that the light extraction effect can be improved.

In addition, the same effect can be obtained based on the same configuration as that of the thirteenth embodiment.

[0441] [D-4 5] Fifteenth embodiment

FIG. 17 is a schematic cross-sectional view of a light guide member as a fifteenth embodiment of the present invention. In FIG. 17, parts similar to those in FIGS. 12 to 16 are denoted by the same reference numerals.

In this light guide member 27, a scattering layer and / or a phosphor-containing layer 29 is formed instead of the high refractive index layer 26, and light is guided from the low refractive index layer 28 and the scattering layer and / or the phosphor-containing layer 29. Except for the point that the layer is formed, the same as in the thirteenth embodiment is performed! /.

[0442] When manufacturing the light guide member 27 of the present embodiment, basically, as in the thirteenth embodiment, after performing the weir formation step, curing is performed corresponding to each layer constituting the light guide layer. Do the coating process and the curing process of the curable material! /. Specifically, instead of the high refractive index layer 26, a curable material coating step and a curable material curing step are performed using a curable material corresponding to the scattering layer and / or the phosphor-containing layer 29, and then the scattering layer. In addition, the production of the light guide member 27 of the present embodiment is performed with the force S in the same manner as the thirteenth embodiment except that the phosphor-containing layer 29 is formed.

[0443] In the light guide member 27 of the present embodiment manufactured as described above, the light emitted from the semiconductor light emitting device 24 as a light source is transmitted by the scattering layer and / or the phosphor-containing layer 29, and the scattering layer and / Or is emitted from the upper surface of the phosphor-containing layer 29 in the drawing, and no light is emitted from the side surface of the light guide member 27. At this time, since the scattering layer and / or the phosphor-containing layer 29 is provided, the directivity angle of light incident on the scattering layer and / or the phosphor-containing layer 29 is increased, The wavelength of light incident on the scattering layer and / or the phosphor-containing layer 29 can be converted to control the color of light emitted from the light guide member 27.

[0444] As described above, if the light guide member 27 is manufactured as in the present embodiment, the light guide region can be controlled similarly to the thirteenth embodiment by providing the weir 25, and further, the scattering layer In addition, since the light guide mode can be controlled by the phosphor-containing layer 29, the light emitting portion can be freely designed. Furthermore, in the light guide member 27 of the present embodiment, the weir 25 is formed in a shape having no ridgeline, so that the light extraction effect can be improved.

[0445] [D-4 6] Sixteenth embodiment

FIG. 18 is a schematic cross-sectional view of a light guide member as a sixteenth embodiment of the present invention. In FIG. 18, parts similar to those in FIGS. 12 to 17 are denoted by the same reference numerals.

In the light guide member 27, a scattering layer and / or a phosphor-containing layer 29 is formed in a predetermined region in the high refractive index layer 26, and the high refractive index layer 26, the low refractive index layer 28, the scattering layer, and / or This is the same as the thirteenth embodiment except that the light guide layer is composed of the phosphor-containing layer 29.

[0446] When the light guide member of this embodiment is manufactured, basically, as in the thirteenth embodiment, after the weir formation process, the curability corresponding to each layer constituting the light guide layer is obtained. Materials The coating process and the curable material curing process should be performed! /. Specifically, as in the thirteenth embodiment, after the weir formation step, the low refractive index layer 28 is formed, and then the curable material is applied using the curable material corresponding to the high refractive index layer 26. The high refractive index layer 26 is formed by performing the process and the curable material curing process. However, at this time, the portion where the scattering layer and / or the phosphor-containing layer 29 is to be formed should not be formed with the high refractive index layer 26 by masking or the like. After the formation of the high refractive index layer 26, the masking and the like are removed and protected by masking etc. in the curable material coating process and the curable material curing process! The containing layer 29 may be formed. Note that the scattering layer and / or the phosphor-containing layer 29 may be formed before the high refractive index layer 26. In the light guide member 27 of the present embodiment manufactured in this way, light emitted from the semiconductor light emitting device 24 that is a light source is transmitted by the high refractive index layer 26 and is shown in the drawing of the high refractive index layer 26. The light is emitted from the upper surface and the upper surface in the drawing of the scattering layer and / or the phosphor-containing layer 29, and no light is emitted from the side surface of the light guide member 27. At this time, since the scattering layer and / or the phosphor-containing layer 29 is provided, the directivity angle of light incident on the scattering layer and / or the phosphor-containing layer 29 is widened, or the scattering layer and / or the phosphor-containing layer 29 is provided. The color of the light emitted from the light guide member 27 can be controlled by converting the wavelength of the incident light.

[0448] As described above, if the light guide member 27 is manufactured as in the present embodiment, the light guide region can be controlled similarly to the thirteenth embodiment by providing the weir 25, and further, the scattering layer In addition, since the light guide mode can be controlled by the phosphor-containing layer 29, the light emitting portion can be freely designed. Furthermore, in the light guide member 27 of the present embodiment, the weir 25 is formed in a shape having no ridgeline, so that the light extraction effect can be improved.

[0449] [D-4 7] Seventeenth embodiment

FIG. 19 is a schematic cross-sectional view of a light guide member as a seventeenth embodiment of the present invention. In FIG. 19, parts similar to those in FIGS. 12 to 18 are denoted by the same reference numerals.

The light guide member 27 is the same as in the sixteenth embodiment except that the boundary portion between the high refractive index layer 26 and the scattering layer and / or the phosphor-containing layer 29 is divided by the weir 25. Yes. However, the high refractive index layer 26 and the scattering layer and / or the phosphor-containing layer 29 are in contact with each other at a portion (not shown), and light from the semiconductor light emitting device 24 passes through this portion and includes the scattering layer and / or the phosphor. It shall be transmitted up to layer 29.

[0450] When the light guide member of this embodiment is manufactured, basically, as in the thirteenth embodiment, after the weir formation step, the curability corresponding to each layer constituting the light guide layer is obtained. Materials The coating process and the curable material curing process should be performed! /. Specifically, as in the thirteenth embodiment, the low refractive index layer 28 is formed after the weir formation step, and then corresponds to the high refractive index layer 26 and the scattering layer and / or the phosphor-containing layer 29. Curing using curable materials The high-refractive index layer 26 and the scattering layer and / or the phosphor-containing layer 29 are formed by performing the material coating step and the curable material curing step, respectively. At this time, unlike the sixteenth embodiment, masking or the like is not required. Since the weir 25 is provided between the high refractive index layer 26 and the scattering layer and / or phosphor-containing layer 29, the weir 25 causes the high refractive index layer 26 and the scattering layer and / or phosphor-containing layer 29 to This is because the curable material is prevented from intermingling between them.

In the light guide member 27 of the present embodiment manufactured in this way, the light emitted from the semiconductor light emitting device 24 that is a light source is transmitted by the high refractive index layer 26 and is shown in the drawing of the high refractive index layer 26. Radiated from the upper surface. Further, part of the light is further transmitted by the scattering layer and / or the phosphor-containing layer 29 and is emitted from the upper surface of the scattering layer and / or the phosphor-containing layer 29 in the drawing. On the other hand, no light is emitted from the side surface of the light guide member 27.

[0452] As described above, if the light guide member 27 is manufactured as in the present embodiment, the light guide region can be controlled similarly to the thirteenth embodiment by providing the weir 25, and further, the scattering layer In addition, since the light guide mode can be controlled by the phosphor-containing layer 29, the light emitting portion can be freely designed. Furthermore, in the light guide member 27 of the present embodiment, the weir 25 is formed in a shape having no ridgeline, so that the light extraction effect can be improved.

In addition, based on the same configuration as that of the sixteenth embodiment, the same effect can be obtained.

[0453] [D—4 8] Eighteenth embodiment

FIG. 20 is a schematic cross-sectional view of a light guide member as an eighteenth embodiment of the present invention. In FIG. 20, parts similar to those in FIGS. 22 to 29 are denoted by the same reference numerals.

In this light guide member 27, a scattering layer and / or a phosphor-containing layer 29 is laminated on a high refractive index layer 26, and a high refractive index layer 26, a low refractive index layer 28, a scattering layer and / or a phosphor containing layer are stacked. 29 and the force are the same as in the thirteenth embodiment except that the light guide layer is configured.

[0454] When the light guide member of this embodiment is manufactured, basically, as in the thirteenth embodiment, after the weir formation step, the curability corresponding to each layer constituting the light guide layer is obtained. Materials The coating process and the curable material curing process should be performed! /. Specifically, as in the thirteenth embodiment, after the weir formation step, the low refractive index layer 28 and the high refractive index layer 26 are formed, and the After that, on the high refractive index layer 26, using the curable material corresponding to the scattering layer and / or the phosphor-containing layer 29, the scattering layer and / or the curable material coating process and the curable material curing process. The phosphor-containing layer 29 may be formed.

In the light guide member 27 of the present embodiment manufactured as described above, the light emitted from the semiconductor light emitting device 24 that is a light source is transmitted by the high refractive index layer 26 and the scattering layer and / or the phosphor-containing layer 29. The light is transmitted and emitted from the upper surface of the scattering layer and / or the phosphor-containing layer 29 in the figure, and no light is emitted from the side surface of the light guide member 27. At this time, since the scattering layer and / or the phosphor-containing layer 29 is provided, the direction angle of the light incident on the scattering layer and / or the phosphor-containing layer 29 is widened, or the scattering layer and / or the phosphor-containing layer 29 is used. It is possible to control the color of light emitted from the light guide member 27 by converting the wavelength of light incident on the light guide member 27.

[0456] As described above, if the light guide member 27 is manufactured as in the present embodiment, the light guide region can be controlled similarly to the thirteenth embodiment by providing the weir 25, and further, the scattering layer In addition, since the light guide mode can be controlled by the phosphor-containing layer 29, the light emitting portion can be freely designed. Furthermore, in the light guide member 27 of the present embodiment, the weir 25 is formed in a shape having no ridgeline, so that the light extraction effect can be improved.

[0457] [D—4 9] Nineteenth embodiment

FIG. 21 is a schematic cross-sectional view of a light guide member as a nineteenth embodiment of the present invention. In FIG. 21, parts similar to those in FIGS. 12 to 20 are denoted by the same reference numerals.

In this light guide member 27, a low refractive index layer 28 is formed instead of the scattering layer and / or the phosphor-containing layer 29, and the light guide layer is composed of the high refractive index layer 26 and the low refractive index layers 28, 28. The configuration is the same as that of the eighteenth embodiment except that the weir 25 can transmit light.

[0458] When manufacturing the light guide member of the present embodiment, a dam formation step is first performed as in the eighteenth embodiment. However, in this embodiment, it is assumed that the weir 25 is formed of a material having a relatively high refractive index so that the weir 25 can transmit light. And the shape of the weir 25 After the formation, a curable material coating step and a curable material curing step are performed corresponding to each layer constituting the light guide layer. Specifically, a low refractive index layer 28, a high refractive index layer 28, and a high light guiding layer are formed in the same manner as in the eighteenth embodiment except that the low refractive index layer 28 is formed instead of the scattering layer and / or the phosphor-containing layer 29. The refractive index layer 26 and the low refractive index layer 28 may be laminated.

In the light guide member 27 of the present embodiment manufactured as described above, the light emitted from the semiconductor light emitting device 24 that is a light source is transmitted by the high refractive index layer 26 and emitted from the weir 25. Therefore, the shape of the light emitting portion can be set according to the weir 25, and therefore, the light guide region can be controlled by the weir 25. On the other hand, since the low refractive index layer 28 is formed on the upper surface of the light guide member 27 in the drawing, no light is emitted from the surface.

[0460] As described above, when the light guide member 27 is manufactured as in the present embodiment, the light guide region can be controlled and the light emitting portion can be freely designed by providing the weir 25. is there. Furthermore, in the light guide member 27 of the present embodiment, the weir 25 is formed in a shape that does not have a ridge line, so that the light extraction effect can be improved.

In addition, based on the same configuration as that in the 18th embodiment, the same effect can be obtained.

[0461] [D 4 10] 20th embodiment

FIG. 22 is a schematic cross-sectional view of a light guide member as a twentieth embodiment of the present invention. In FIG. 22, parts similar to those in FIGS. 12 to 21 are denoted by the same reference numerals.

In the light guide member 27, a scattering layer and / or a phosphor-containing layer 29 is formed on a part of the low refractive index layer 28 formed on the high refractive index layer 26, and the low refractive index layer 26 and the low refractive index layer 26 are low. The present embodiment is the same as the nineteenth embodiment except that the light guide layer is composed of the refractive index layers 28 and 28 and the scattering layer and / or the phosphor-containing layer 29.

[0462] When the light guide member 27 of the present embodiment is manufactured, basically, as in the nineteenth embodiment, after performing the weir formation step, curing is performed corresponding to each layer constituting the light guide layer. Do the coating process and the curing process of the curable material! /. Specifically, when the low refractive index layer 28 and the scattering layer and / or the phosphor-containing layer 29 are formed on the high refractive index layer 26, the low refractive index layer 28 is formed in the same manner as in the fourteenth embodiment. Partially scattering layer and / or phosphor-containing layer 2 Except for forming 9, it may be the same as the nineteenth embodiment.

In the light guide member 27 of the present embodiment manufactured as described above, the light emitted from the semiconductor light emitting device 24 that is a light source is transmitted by the high refractive index layer 26 and emitted from the weir 25. Further, light is emitted through the scattering layer and / or the phosphor-containing layer 29 on the upper surface of the light guide member 27 in the drawing.

[0464] As described above, when the light guide member 27 is manufactured as in the present embodiment, the light guide region can be controlled by providing the weir 25, and further, the scattering layer and / or the phosphor-containing layer can be controlled. Since the light guide mode can be controlled by 29, the light emitting portion can be designed freely. Further, in the light guide member 27 of the present embodiment, the weir 25 is formed in a shape having no ridgeline, so that the light extraction effect can be improved.

In addition, based on the configuration similar to that of the nineteenth embodiment, the same effect can be obtained.

[0465] [D—4 11] 21st embodiment

FIG. 23 is a schematic cross-sectional view of a light guide member as a 21st embodiment of the present invention. In FIG. 23, parts similar to those in FIGS. 12 to 22 are denoted by the same reference numerals.

The light guide member 27 is the same as that of the twentieth embodiment except that the weir 25 is formed of a material that blocks light.

[0466] When the light guide member 27 of the present embodiment is manufactured, basically, as in the twentieth embodiment, after the weir formation step, curing is performed corresponding to each layer constituting the light guide layer. Do the coating process and the curing process of the curable material! /. Specifically, the dam 25 can be manufactured in the same manner as in the twentieth embodiment except that a material capable of blocking light is used.

[0467] In the light guide member 27 of the present embodiment manufactured as described above, light emitted from the semiconductor light emitting device 24 as a light source is transmitted by the high refractive index layer 26, and the upper part of the light guide member 27 in the figure. On the side surface, it is emitted through the scattering layer and / or the phosphor-containing layer 29. However, since the weir 25 blocks light, no light is emitted from the side surface of the light guide member 27.

[0468] As described above, when the light guide member 27 is manufactured as in the present embodiment, the weir 25 is provided. Thus, the light guide region can be controlled, and the light guide mode can be controlled by the scattering layer and / or the phosphor-containing layer 29, so that the light emitting portion can be freely designed. In the light guide member 27 of the present embodiment, since the weir 25 is formed in a shape having no ridgeline, when the weir 25 can reflect light, such as when the weir 25 is formed in white, The light extraction effect can be improved.

In addition, based on the same configuration as that of the twentieth embodiment, the same effect can be obtained.

[0469] [D-4 12] Twenty-second embodiment

FIG. 24 is a schematic cross-sectional view of a light guide member as a 22nd embodiment of the present invention. In FIG. 24, parts similar to those in FIGS. 12 to 23 are denoted by the same reference numerals.

The light guide member 27 is the same as that of the nineteenth embodiment except that the weir 25 contains a light scattering agent and / or a phosphor.

[0470] When manufacturing the light guide member 27 of the present embodiment, basically, as in the nineteenth embodiment, after performing the weir formation step, curing is performed corresponding to each layer constituting the light guide layer. Do the coating process and the curing process of the curable material! /. Specifically, the light from the semiconductor light emitting device 24 can be transmitted as the material of the weir 25, and a material containing a light scattering agent and / or a phosphor is used as in the nineteenth embodiment. Thus, the light guide member 27 can be manufactured.

In the light guide member 27 of the present embodiment manufactured as described above, the light emitted from the semiconductor light emitting device 24 that is a light source is transmitted by the high refractive index layer 26 and emitted from the weir 25. At this time, since the weir 25 contains a light scattering agent and / or a phosphor, the light directing angle is widened, or the color of the light emitted from the light guide member 27 is controlled by converting the wavelength of the light. can do. On the other hand, since the low refractive index layer 28 is formed on the upper surface of the light guide member 27 in the figure, no light is emitted from the surface.

[0472] As described above, if the light guide member 27 is manufactured as in the present embodiment, the light guide region can be controlled by providing the weir 25, and further, by the light scattering agent and / or the phosphor. Since the light guide mode can be controlled, the light emitting portion can be designed freely. In addition, this implementation In the light guide member 27 of the form, since the weir 25 is formed in a shape having no ridgeline, the light extraction effect can be improved.

[0473] [D-4 13] 23rd embodiment

FIG. 25 is a schematic cross-sectional view of a light guide member as a 23rd embodiment of the present invention. In FIG. 25, parts similar to those in FIGS. 12 to 24 are denoted by the same reference numerals.

The light guide member 27 is the same as the nineteenth embodiment except that the weir 25 is formed with different dimensions (that is, nonuniformly). Specifically, the dam 25 on the left side in the figure penetrates the entire low refractive index layers 28 and 28 and the high refractive index layer 26, whereas the dam 25 on the right side in the figure is formed low and has a high height. The refractive index layer 26 and the lower refractive index layer 28 below it penetrate, but do not penetrate the low refractive index layer 28 above the high refractive index layer 26.

[0474] When the light guide member 27 of the present embodiment is manufactured, basically, as in the nineteenth embodiment, after the weir formation step, the layers are cured corresponding to the respective layers constituting the light guide layer. What is necessary is just to perform a property material coating process and a curable material hardening process. However, in this embodiment, the dam 25 on the right side in the figure is formed low in the dam formation step. Therefore, in the process of forming the low refractive index layer 28 on the high refractive index layer 26, the curable material can be blocked by the left weir 25 in the figure, but the right dam 25 in the figure has the curable material. Can no longer be dammed up. However, even in this case, until the high refractive index layer 26 is formed, it is possible to block the curable material using the weir 25 on the right side of the figure, and the weir 25 can be freely designed for the light emitting portion. It contributes.

In the light guide member 27 of the present embodiment manufactured as described above, the light emitted from the semiconductor light emitting device 24 that is a light source is transmitted by the high refractive index layer 26 and emitted from the weir 25. At this time, light is emitted from the left weir 25 in the figure from the left direction to the upper direction in the figure, and light is emitted in an angular range, while the right weir 25 in the figure is above the weir 25. Since the low refractive index layer 28 is formed, the mode of light emission can be controlled so that light is emitted only in a relatively narrow angle range in the right direction in the figure. [0476] As described above, when the light guide member 27 is manufactured as in the present embodiment, the light guide region can be controlled by providing the weir 25, so that the light emitting portion can be freely designed. It is. Furthermore, in the light guide member 27 of the present embodiment, the weir 25 is formed in a shape having no ridgeline, so that the light extraction effect can be improved.

[0477] [D—4 14] Twenty-fourth embodiment

FIG. 26 is a schematic cross-sectional view of a light guide member as a twenty-fourth embodiment of the present invention. In FIG. 26, parts similar to those in FIGS. 12 to 25 are denoted by the same reference numerals.

The light guide member 27 is the same as the nineteenth embodiment except that the weir 25 is provided on the substrate 21 via another layer. Specifically, a part of the weir 25 (left side in the figure) is provided directly on the substrate 21 and the other part of the weir 25 (right side in the figure) is provided via the low refractive index layer 28. Yes.

[0478] When manufacturing the light guide member 27 of the present embodiment, basically, as in the nineteenth embodiment, after performing the weir formation step, curing is performed corresponding to each layer constituting the light guide layer. What is necessary is just to perform a property material coating process and a curable material hardening process. However, in the present embodiment, first, the left dam 25 in the figure is formed in the dam formation step, and then the low refractive index layer 28 is formed, and then the right dam 25 in the figure is formed on the low refractive index layer 28. After that, the high refractive index layer 26 and the low refractive index layer 28 are formed. In this case, the dam 25 on the right side of the figure can dampen the curable material when forming the high refractive index layer 26 and the low refractive index layer 28 thereon. It contributes to the free design.

In the light guide member 27 of the present embodiment manufactured as described above, the light emitted from the semiconductor light emitting device 24 that is a light source is transmitted by the high refractive index layer 26 and emitted from the weir 25. On the other hand, since the low refractive index layer 28 is formed on the upper surface of the light guide member 27 in the figure, no light is emitted from the surface.

[0480] As described above, if the light guide member 27 is manufactured as in the present embodiment, the light guide region can be controlled, so that the light emitting portion can be freely designed. Furthermore, in this embodiment In the light guide member 27, since the weir 25 is formed in a shape having no ridgeline, the light extraction effect can be improved.

[0481] [D 4 15] 25th embodiment

FIG. 27 is a schematic cross-sectional view of a light guide member as a 25th embodiment of the present invention. In FIG. 27, parts similar to those in FIGS. 12 to 26 are denoted by the same reference numerals.

The light guide member 27 is the same as the nineteenth embodiment except that a reflective layer 30 is formed between the substrate 21 and the high refractive index layer 26 constituting the light guide layer. Specifically, the reflective layer 30 is formed on the surface of the substrate 21 instead of the low refractive index layer 28.

[0482] In the case of manufacturing the light guide member 27 of the present embodiment, after forming the reflective layer 30 on the substrate 21, after performing the weir forming step, the high refractive index layer is formed as in the nineteenth embodiment. A curable material coating step and a curable material curing step may be performed corresponding to each of the 26 and the low refractive index layer 28. The reflective layer 30 can be formed by evaporating the material of the reflective layer 30, for example. During vapor deposition, a cylindrical or mortar-shaped hole 30H is formed so that the reflective layer 30 does not cover the semiconductor light emitting device 24.

In the light guide member 27 of the present embodiment manufactured as described above, the light emitted from the semiconductor light emitting device 24 that is a light source is transmitted by the high refractive index layer 26 and emitted from the weir 25. At this time, since the reflection layer 30 is formed, the light is efficiently transmitted through the high refractive index layer 26, and the light extraction efficiency from the light guide member 27 is improved. On the other hand, since the low refractive index layer 28 is formed on the upper surface of the light guide member 27 in the drawing, no light is emitted from the surface.

[0484] As described above, when the light guide member 27 is manufactured as in the present embodiment, the light guide region can be controlled and the light emitting portion can be freely designed by providing the weir 25. is there. Furthermore, in the light guide member 27 of the present embodiment, the weir 25 is formed in a shape that does not have a ridge line, so that the light extraction effect can be improved.

In addition, based on the configuration similar to that of the nineteenth embodiment, the same effect can be obtained. [0485] [D—4 16] 26th embodiment

FIG. 28 is a schematic cross-sectional view of a light guide member as a 26th embodiment of the present invention. In FIG. 28, parts similar to those in FIGS. 12 to 27 are denoted by the same reference numerals.

The light guide member 27 is the same as that of the nineteenth embodiment except that the substrate 21 is not flat. Specifically, a cylindrical or mortar-shaped recess 21H is formed in the substrate 21, and the semiconductor light emitting device 24 is installed on the bottom of the recess 21H.

[0486] When the light guide member 27 of the present embodiment is manufactured, it is the same as that of the nineteenth embodiment except that a recess 21H is formed as the substrate 21 and V is used.

[0488] As described above, when the light guide member 27 is manufactured as in the present embodiment, the light guide region can be controlled and the light emitting portion can be freely designed by providing the weir 25. is there. Furthermore, in the light guide member 27 of the present embodiment, the weir 25 is formed in a shape that does not have a ridge line, so that the light extraction effect can be improved.

[0489] [D— 4 17] Others

Although the embodiments of the present invention have been described, none of the above-described embodiments limit the present invention, and some of the embodiments may be appropriately changed by introducing or combining some of them with other embodiments. Is also possible.

[0490] Further, in the above-described embodiment, other layers may be stacked or other members may be provided without departing from the gist of the present invention.

Furthermore, ± 區 25 may be combined with different ones. For example, light scatterers and / or phosphors are included only partially when weirs with different shapes and dimensions can be used in combination with weirs with a high refractive index and a low weir. Even if you use a weir Good.

In addition, the weir 25 may divide at least a part of the light guide layer and may not divide the light guide layer completely. Therefore, it suffices that at least a part of the section is defined in the horizontal direction in the figure, and at least a part is defined in the height direction in the figure. Therefore, as in the twelfth embodiment, the weir 25 may be buried in the light guide layer.

By the way, none of the first to ninth light guide members of the present invention is in conflict. Therefore, for example, a certain light guide member may correspond to two or more of the first to ninth light guide members.

Example

[0491] Hereinafter, the present invention will be described more specifically with reference to examples. However, they are intended to explain the present invention, and are intended to limit the present invention to these embodiments. is not.

[A. Examples and comparative examples mainly related to first to fourth light guide members]

[Example A— 1 1]

[A— 1 1] Manufacture of light guide plate

A light guide plate of Example A-11 was produced according to the following procedure.

[0493] [A- 1-1 1] Synthesis of specific layer (low refractive index layer) forming solution

Momentive 'Performance' 'Materials' Japan GK Co., Ltd. Both-end silanol Dimethenoresiri 1-year-old Inore XC96— 723 1450.82g, Phenyloloxysilane 145g 3 · 190 g was prepared, weighed into a 2 L three-necked Kolben equipped with a stirring blade and a condenser, and stirred at room temperature for 15 minutes until the catalyst was sufficiently dissolved. Thereafter, the temperature of the reaction solution was raised to 120 ° C., and initial hydrolysis was carried out with stirring at 120 ° C. under total reflux for 30 minutes.

[0494] Subsequently, nitrogen was blown in with SV20 and the resulting methanol, water, and low-boiling components of by-products were distilled off and stirred at 120 ° C, and the polymerization reaction was further continued for 5 hours. Here, “SV” is an abbreviation for “Space Velocity”, and indicates the volume of blown air per unit time. Therefore, SV20 means blowing N of 20 times the volume of the reaction solution in one hour.

2

[0495] Nitrogen blowing was stopped and the reaction solution was cooled to room temperature. Transfer the reaction solution, and use a rotary evaporator to distill off trace amounts of methanol, water, and low-boiling carbon components that remain on the oil bath at 120 ° C and lkPa for 20 minutes. Layer) forming liquid (282 mPa · s) was obtained.

[0496] [A- 1-1-2] Synthesis of specific layer (high refractive index layer) forming solution

Momentive 'Performance' Materials' Japan GK Co., Ltd. Both End Silanol Dimethylol Silicone Oile XC96-723 42g, Both End Silanol Methyl Phenyl Silcon Corn Oil 98g, Phenyltrimethoxysilane 14g, and Catalyst Prepare 0.308 g of zirconium tetracetylacetonate powder, weigh it into a three-necked Kolben equipped with a stirring blade and a condenser, and stir at room temperature for 15 minutes until the catalyst is sufficiently dissolved. did. Thereafter, the temperature of the reaction solution was raised to 120 ° C, and initial hydrolysis was carried out with stirring at 120 ° C under total reflux for 2 hours.

Subsequently, nitrogen was blown in with SV20 and the resulting methanol, water, and low-boiling components of by-products were distilled off and stirred at 120 ° C, and the polymerization reaction was further continued for 6 hours.

Nitrogen blowing was stopped and the reaction solution was cooled to room temperature.After that, transfer the reaction solution to an eggplant-shaped flask, and using a rotary evaporator, the remaining methanol and methanol remaining in a minute amount at 120 ° C and lkPa for 20 minutes on an oil bath. Moisture and low boiling water components were distilled off to obtain a solvent-free specific layer (high refractive index layer) forming solution.

[0497] [A- 1-1-3] Synthesis of specific layer (light scattering layer) forming solution

As light-scattering particles, 0.75g of “Tospearl 145 (median particle size 5 m)” manufactured by Momentive 'Performance' Materials' Japan GK and Al O fine powder CR1 (median particle size 40

twenty three

0nm) 0.076g was mixed with 11.3g of the specific layer (high refractive index layer) forming liquid described above in [A-1-1-2] and 2.5g of heptane, and ultrasonic dispersion was performed. A light scattering layer) forming solution was obtained.

[0498] [A— 1 1 4] Application of specific layer forming solution

A glass fiber reinforced epoxy laminate with a blue LED mounted on it is coated with a doughnut-shaped (outside 10mmφ, hole 6mmφ) Toyo Adtec low adhesive tape “Τ120ΤW” to surround the LED. On top of this, a low-adhesive tape “T120 HW” made by Toyo Adtec Co., Ltd. with a diameter of 10 mm was pasted.

The specific layer (low refractive index layer) forming solution of [A-1 1 1] was spin-coated. Spin Coe The test was performed at 300 rpm for 5 seconds and then at 1200 rpm for 10 seconds.

When the above-mentioned low adhesive tape was peeled off and the specific layer forming solution was cured at 150 ° C. for 2 hours, the low refractive index layer could be applied by removing / excluding the LED portion.

[0499] Next, 0.8 ml of the specific layer (high refractive index layer) forming solution of [A-1 1 2] above was applied to the upper surface of the low refractive index layer, and spread so as to be uniform. When cured at 2 ° C. for 2 hours, a low refractive index layer defect including the LED and a high refractive index layer could be provided on the low refractive index layer.

Next, the above specific layer (light scattering layer) forming solution of [A-1 13] was applied to the upper surface of the high refractive index layer while flowing. Excess scattering liquid was soaked in the underlying paper. After waiting for the scattering particles to level for more than 30 minutes, it was cured in an atmosphere at 150 ° C for 2 hours to form a light scattering layer.

[0500] [A 1 2] Analysis of each layer and evaluation method of light guide plate

[A- 1-2-1] Solid Si—NMR spectrum measurement and silanol content calculation Example A— 1 Each layer of the light guide plate of 1! /, Solid Si-NMR spectrum under the following conditions Measurement and waveform separation analysis. From the obtained waveform data, the half width of each peak was determined for each layer of the light guide plate of Example A-11. In addition, the ratio (%) of the silanol-derived silicon atoms in all the silicon atoms is calculated from the ratio of the silanol-derived peak area to the total peak area, and is compared with the separately analyzed content of silicon. The silanol content was determined by

[0501] <Device conditions>

Equipment: Chemagnetics Infinity CMX-400 Nuclear Magnetic Resonance Spectrometer

²⁹ Si resonance frequency: 79. 436MHz

Probe: 7.5mm φ CP / MAS probe

Measurement temperature: room temperature

Sample rotation speed: 4kHz

Measurement method: Single pulse method

^^ 1 decoupling frequency: 50kHz

²⁹ Si flip angle: 90 ° ²⁹ Si90 ° pulse width: 5. O ^ s

Repeat time: 600s

Integration count: 128 times

Observation width: 30kHz

Broad Jung factor: 20Hz

Reference sample: Solid Si—dimethylsilicone rubber for NMR reference material (polydimethylsiloxane)

[0502] <Data processing method>

512 points were taken as measurement data, and zero-filled to 8192 points and Fourier transformed.

[0503] <Waveform separation analysis method>

For each peak of the spectrum after Fourier transform, optimization calculation is performed by nonlinear least square method with the center position, height, and half width of the peak shape created by Lorentz waveform and Gaussian waveform or a mixture of both as variable parameters. I did it.

The peak was identified with reference to AIChE Journal, 44 (5), p. 1141, 1998, etc.

[0504] [A— 1 2— 2] Measurement of the C content

Example A-1 A single hardened material of each layer (low refractive index layer, high refractive index layer, light scattering layer) of the light guide plate of 1 was pulverized to about 100 m, and in a platinum crucible in air at 450 ° C. 1 hour, then 7 hours at 550 ° C and 1.5 hours at 950 ° C. After calcination to remove the carbon component, add more than 10 times the amount of sodium carbonate to the resulting residue and burner. Heat and melt it, cool it, add demineralized water, adjust the pH to a neutral level with hydrochloric acid while adjusting the pH to about several ppm, and use `` SPS1700HVR '' manufactured by Seiko Denshi. ICP analysis became fi.

[0505] [A— 1 2— 3] Hardness measurement

Example A— For each layer of the light guide plate of 1 (low refractive index layer, high refractive index layer, light scattering layer), A type (Duguchi meter type A) rubber hardness tester manufactured by Furusato Seiki Seisakusho was used, and JIS K6253 The hardness (Shore A) was measured according to the above. [0506] [A— 1 2— 4] Refractive index measurement

Example A—11 For each layer of the light guide plate (low refractive index layer, high refractive index layer, light scattering layer) in 1! /, Using a Abbe refractometer at 25 ° C, the refractive index was measured. It was measured.

[0507] [A— 1 2— 5] Adhesion evaluation method

Example A—1 When the end of the coating layer (upper layer) of the light guide plate in 1 is pinched with tweezers and slowly peeled off in the right-angle direction, the film does not peel off easily, but breaks partly. Those that can be easily peeled are defined as “bad”.

[0508] [A— 1 2— 6] Light extraction effect

Observe the state of light emission of the light guide plate of Example A-1 1 by visual inspection and / or photograph, and determine that the light is uniformly extracted from the entire desired location of the desired location. What was recognized that light was not extracted uniformly was defined as “defective”.

[0509] [Table 2]

[A—2. Examples and comparative examples in the case where a boundary is provided] [A-2-1. Preparation of formation liquid for each layer]

[A— 2 1— 1] Synthesis of specific layer (low refractive index layer) forming solution Momentive 'Performance''Materials' Japan GK Co., Ltd. Both-end silanol Dimethenoresiri 1-year-old Inore XC96— 723 1450. 190g prepared. This was placed in a 2 L three-necked Kolben equipped with a stirring blade and a condenser, and stirred at room temperature until the zirconium tetraacetylacetylate powder was sufficiently dissolved. This dissolved in about 15 minutes. The liquid was heated to 120 ° C and stirred while refluxing for 30 minutes.

Yes

[0511] Subsequently, a gas blowing tube was connected to the Kolben port, and stirring was continued at 120 ° C for 5 hours while nitrogen was blown into the reaction solution with SV20. Here, “SV” is an abbreviation for “Space Velocity” and indicates the amount of blowing per unit time. Therefore, SV20 means blowing N of 20 times the volume of the reaction solution in one hour.

2

After the nitrogen blowing was stopped and the Kolben was cooled to room temperature, the reaction solution was transferred to an eggplant-shaped flask and distilled under reduced pressure on an oil bath at 120 ° C and lkPa for 20 minutes using a rotary evaporator. Refractive index layer) forming liquid (viscosity 282 mPa * s; hereinafter referred to as “low refractive index binder” as appropriate) was obtained.

[0512] [A- 2 1 2] Synthesis of specific layer (high refractive index layer) forming solution A

Momentive 'Performance' Materials' Japan GK Co., Ltd. Both End Silanol Dimethylol Silicone Oile XC96-723 42g, Both End Silanol Methyl Phenyl Silcon Corn Oil 98g, Phenyltrimethoxysilane 14g, and Catalyst 0.308 g of zirconium tetracetylacetonate powder was prepared and weighed into a 200 ml three-necked Kolben equipped with a stirring blade and a condenser. The mixture was stirred at room temperature until the zirconium tetracetylacetonate powder was sufficiently dissolved. This dissolved in about 15 minutes. The liquid was heated to 120 ° C. and stirred while refluxing for 30 minutes.

[0513] Subsequently, a gas blowing tube was connected to the mouth of Kolben, and stirring was continued at 120 ° C for 6 hours while nitrogen was blown into the reaction solution with SV20.

After the nitrogen blowing was stopped and the Kolben was cooled to room temperature, the reaction solution was transferred to an eggplant-shaped flask and distilled off under reduced pressure at 120 ° C. and lkPa for 20 minutes on an oil bath using a rotary evaporator. [0514] Ultrafine silica (trade name: AEROSIL # RX200, manufactured by Nippon Aerosil Co., Ltd.) 0. lg, and 1 · Og of the reaction solution after distillation under reduced pressure, were mixed in the container as inorganic particles. , Centrifugal defoaming was performed using a rotation / revolution mixer defoamer. Thereafter, the container was placed in a vacuum chamber and a defoaming operation was further performed to obtain a specific layer (high refractive index layer) forming liquid A (hereinafter referred to as “high refractive index binder 8” as appropriate).

[0515] [A— 2-1 1 3] Synthesis of specific layer (high refractive index layer) forming solution B

Momentive 'Performance' Materials' Japan GK Co., Ltd. Both Ends Silanol Dimethylol Silicone Oile XC96-723 105g, Both Ends Silanol Methyl Phenyl Silcon Corn Oil YF3804, Phenyltrimethoxysilane 14g, and Catalyst 0.308 g of zirconium tetracetylacetonate powder was prepared and weighed into a 200 ml three-necked Kolben equipped with a stirring blade and a condenser. The mixture was stirred at room temperature until the zirconium tetracetylacetonate powder was sufficiently dissolved. This dissolved in about 15 minutes. The liquid was heated to 120 ° C. and stirred while refluxing for 30 minutes.

[0516] Subsequently, a gas blowing tube was connected to the Kolben port, and stirring was continued at 120 ° C for 6.5 hours while nitrogen was blown into the reaction solution with SV20.

Nitrogen blowing was stopped and Kolben was cooled to room temperature.After that, the reaction solution was transferred to an eggplant-shaped flask and distilled under reduced pressure on an oil bath at 120 ° C and lkPa for 20 minutes using a rotary evaporator. l. A high refractive index binder of 43 was obtained.

Ultrafine silica particles (made by Nippon Aerosil Co., Ltd., trade name: A EROSIL # RX200) 0. lg and the above high refractive index binder 1 · Og are mixed in the container and mixed to remove the rotating / revolving mixer. Centrifugal defoaming was performed using a foaming device. Thereafter, the container was placed in a vacuum chamber and further defoamed to obtain a specific layer (high refractive index) forming liquid B (hereinafter referred to as “high refractive index binder” where n = 1.43).

[0517] [A— 2 — 1 4] Synthesis of specific layer (weir) formation liquid B

Ultrafine silica particles (made by Nippon Aerosil Co., Ltd., trade name: AEROSIL # 130) 0.78 g, epoxy resin (made by Japan Epoxy Resin, trade name: Epicoat 828US) 4. 98 g, epoxy resin as inorganic particles in the container Curing agent (made by Japan Epoxy Resin, trade name: J ER Epicure YLH1230) 4. Add 24g, mix and rotate. Centrifugal defoaming was performed using the apparatus. Thereafter, the container was evacuated and further defoaming was performed to obtain a specific layer (weir) forming liquid B.

[0518] [A-2-1-5] Synthesis of specific layer (weir) forming liquid C

As the inorganic particles in the container, 0.55 g of ultrafine silica (made by Nippon Aerosil Co., Ltd., trade name: AEROSIL # 130), non-aggregated type alumina (made by Baikowski, trade name: CR1, median particle size 0.95 microns) 2.0 g, Epoxy resin (made by Japan Epoxy Resin, product name: Epicoat 828US) 4.03g, epoxy resin curing agent (made by Japan Epoxy Resin, product name: JER Epicure YLH1230) 3.42g are mixed and mixed. Was used for centrifugal defoaming. Thereafter, the container was evacuated and further defoaming was performed to obtain a specific layer (weir) forming liquid C.

[0519] [A-2-1-6] Preparation of specific layer (high refractive light scattering layer / low scattering type) forming solution

Al O fine powder “CR1 (median particle size 400nm)” 0.lg as light scattering particles [A— 1— 1— 2]

twenty three

The mixture was mixed with 9.9 g of the specific layer (high refractive index layer) forming liquid (n = l.46) described above in, and centrifugal defoaming and mixing were performed using a rotation / revolution system mixer defoaming device. Thereafter, the container was further evacuated and mixed under vacuum to obtain a liquid for forming a specific layer (high refractive light scattering layer / low scattering type).

[0520] [A— 2— 1 7] Preparation of specific layer (high refractive light scattering layer / medium scattering type) forming solution

As a light scattering particle, “Tospearl 145 (median particle size 5 m)” manufactured by Momentive 'Performance' Materials' Japan G.K. l. Og and Al O fine powder “CR1 (median particle size 400η)

twenty three

m) jO.lg is mixed with 8.9g of the specific layer (high refractive index layer) forming liquid (n = l.46) described in [A- 1 1 2], and a rotating / revolving mixer deaerator is used. Then, centrifugal defoaming and mixing were performed. Thereafter, the container was evacuated and further defoamed and mixed to obtain a specific layer (high refractive light scattering layer / medium scattering type) forming liquid.

[0521] [A-2-1-8] Preparation of specific layer (high refractive light scattering layer / strong scattering type) forming solution

As a light scattering particle, “Tospearl 145 (median particle size 5 m)” manufactured by Momentive “Performance” Materials “Japan GK” 2. Og and Al O fine powder “CR1 (median particle size 400η)

twenty three

m) ”0.2 g is mixed with 7.8 g of the specific layer (high refractive index layer) formation liquid (n = l.46) described above in [A-1 1-2], and a rotating / revolving mixer deaerator , Centrifugal defoaming and mixing were performed. After that, the container is evacuated and further defoamed and mixed to a specific layer (high refractive light scattering layer / strong A scattering type) forming liquid was obtained.

[0522] [A- 2- 1-9] Preparation of specific layer (low refractive light scattering layer) forming solution

As light scattering particles, 2 m spherical silica 2. Og and specific layer (low refractive index layer) formation liquid (n = l. 42) synthesized with [A-1 1-1-1] 8. Og is mixed and rotated. · Centrifugal defoaming and mixing were performed using a revolving mixer defoamer. Thereafter, the container was further evacuated and mixed under vacuum to obtain a liquid for forming a specific layer (low refractive light scattering layer).

[0523] [Example A— 2-1]

[Manufacture of light guide plates]

Drill a 2mmφ hole in a 0.43mm thick glass fiber reinforced epoxy laminate with a drill, seal the hole with chemical-resistant tape from the back side of this hole, and then insert a high refractive index binder into the hole from the front side. A sputum was injected and held at 150 ° C for 1 hour to cure and close the hole. Then, the chemical resistant tape was peeled off.

In addition, a blue LED was installed directly under the hole, and the light emitted from the blue LED was transmitted to the upper part of the substrate through a high refractive index binder A that closed the hole. Specifically, a lamp with a C46 0MB chip manufactured by Tully Corp. die-bonded with epoxy silver paste on a surface mount package made of polyphthalamide (3.4 mm x 2.8 mm) and wire bonded with a gold wire. A cured blue LED was used, which was sealed with a low refractive index binder and held at 90 ° C for 1 hour, 110 ° C for 2 hours, and 150 ° C for 3 hours and cured.

[0524] A boundary portion was drawn on the substrate using the specific layer (weir) forming liquid B. The boundary was drawn to be a weir surrounding the blue LED. The boundary portion was drawn using a syringe with a nozzle diameter of 290 m. At this time, the distance from the syringe nozzle to the substrate surface was set to 500 m. The drawing speed was 10 cm / sec. Furthermore, the pressure when extruding the specific layer (weir) forming solution B from the syringe was set to 1.5 MPa.

Thereafter, this was held in an air atmosphere at 150 ° C. and atmospheric pressure for 0.5 hour to cure the boundary. As a result, a boundary portion having a height of 500 111 and a width of 1 mm and having no ridgeline was obtained.

[0525] In the next step, a low refractive index binder was applied to the inner portion of the boundary on the substrate. At this time, the boundary portion acted as a weir to dam the low refractive index binder, and the low refractive index binder was applied only inside the boundary portion, and the leakage force was applied to the outside of the boundary portion. Also low bending The refractive index binder is applied so as not to cover the upper part of the high refractive index binder A that closes the hole, and the low refractive index layer formed by the low refractive index binder does not hinder the transmission of light transmitted through the hole. I did it.

Then, this was held in an air atmosphere at 150 ° C. and atmospheric pressure for 1 hour, and the low refractive index binder was cured to form a low refractive index layer having a thickness of 35 m.

[0526] Further, a high refractive index binder A was applied to the inner part of the boundary portion on the low refractive index layer. Also at this time, the boundary portion acted as a weir to block the high refractive index binder A, and the high refractive index binder A was applied only to the inside of the boundary portion, and the leakage force was applied to the outside of the boundary portion. Then, this was held in an air atmosphere at 150 ° C. and atmospheric pressure for 1 hour to cure the high refractive index binder A, thereby forming a high refractive index layer A having a thickness of 415 m.

[0527] Further, a low refractive index binder was applied to the inside portion of the boundary portion on the high refractive index layer A. Also at this time, the boundary portion acted as a weir to block the low refractive index binder, and the low refractive index binder was applied only to the inside of the boundary portion, and the leakage force was applied to the outside of the boundary portion. Then, this was held in an air atmosphere at 150 ° C. and atmospheric pressure for 1 hour, and the low refractive index binder was cured to form a low refractive index layer having a thickness of 30 m.

The light guide plate was manufactured as described above.

[0528] [Evaluation]

The blue LED with an emission wavelength of 460 nm was emitted from under the hole of the obtained light guide plate, and the state was observed.

Further, in the same manner as in the above “[A-1-2-5] Adhesion evaluation method”, the adhesion of each layer of the obtained light guide plate was evaluated. In Table 3 and Tables 4 and 5, which will be described later, “Good” indicates that the adhesiveness is “good”.

In addition, in the same manner as “[A-1-2-2-1] Solid Si-NMR spectrum measurement and silanol content calculation” described above, solid Si-NMR spectrum measurement was performed on each layer of the obtained light guide plate. And the silanol content was measured.

Further, in the same manner as in the above-mentioned “Measurement of [A-12-2] Caydenium Content”, the Cay content was measured for each layer of the obtained light guide plate.

In addition, in the same manner as the “[A-1 2 3] hardness measurement” described above, each layer of the obtained light guide plate The hardness (Shore A) was measured.

Further, the refractive index of each layer of the obtained light guide plate was measured in the same manner as in the above “[A-1-2-4] refractive index measurement”.

Using a lmm-thick cured product prepared in the same way as the transmittance measurement, using the air layer as a reference, measure the ^^ values with COH-300A manufactured by Nippon Denshoku Industries Co., Ltd. I did.

The results are shown in Table 3.

[0529] In addition, in the section of the light extraction property in Table 3, if the field power S is “O”, it means that the light emitting surface has reached the vicinity of the weir! “X” means that light is emitted only directly above the chip.

In addition, in the light extraction property section of Table 3, if the field power S “◯” of “the entire surface shines”, it means that the entire surface divided by the weir emits light, and “△” If it is, it means that it emits light to the middle between the LED and the boundary. If “X”, it means that only the surface near the chip emits light.

Furthermore, in the section of light extraction property in Table 3, if the column “Light shielding at boundary” is “◯”, it means that only the surface inside the boundary emits light, and “X” If this is the case, it means that the light reaches the adjacent surface beyond the boundary.

[0530] [Example A— 2-2]

A light guide plate was produced in the same manner as in Example A-2-1 except that the low refractive index layer was not formed on the high refractive index layer A. The obtained light guide plate was evaluated in the same manner as in Example A-2-1. The results are shown in Table 3.

[0531] [Comparative Example A— 2-1]

A light guide plate was produced in the same manner as in Example A-2-1 except that the high refractive index layer A and the low refractive index layer on the high refractive index layer A were not formed. The obtained light guide plate was evaluated in the same manner as in Example A-2-1. The results are shown in Table 3.

[0532] [Example A-2-3]

The boundary layer is formed using the specific layer (weir) forming liquid C instead of the specific layer (weir) forming liquid B, and the force that does not form the low refractive index layer on the high refractive index layer A. Example A—2 except for A light guide plate was manufactured in the same manner as -1. The obtained light guide plate was evaluated in the same manner as in Example A-21. The results are shown in Table 3.

[0533] [Comparative Example A— 2— 2]

A light guide plate was produced in the same manner as in Example A-2-3, except that the high refractive index layer A and the low refractive index layer on the high refractive index layer A were not formed. The obtained light guide plate was evaluated in the same manner as in Example A-2-1. The results are shown in Table 3.

[0534] [Table 3]

[0535] [Comparative Example A—2-3]

[Manufacture of light guide plates]

A blue LED chip (clamp) is applied to the electrode on a 0.43 mm thick glass fiber reinforced epoxy laminate. Lee Co., Ltd., product name: C460MB290) was attached by die bonding with epoxy silver paste and wire bonding with Au wire. A high refractive index binder A was raised and applied onto this LED chip, and was cured by holding at 150 ° C. for 1 hour, and the LED chip was sealed with a high refractive index layer A.

[0536] A boundary portion was drawn on the substrate using the specific layer (weir) forming liquid B. The boundary was drawn to be a weir surrounding the blue LED. The boundary portion was drawn using a syringe having a nozzle diameter of 570 m. At this time, the distance from the syringe nozzle to the substrate surface was set to 650 m. The drawing speed was 10 cm / sec. Furthermore, the pressure when extruding the specific layer (weir) forming liquid B from the syringe was set to 2 MPa.

[0537] Next, a high refractive index binder A was applied to an inner portion of the boundary portion on the substrate.

At this time, the boundary portion acted as a weir to block the high refractive index binder A, and the high refractive index binder A was applied only to the inside of the boundary portion, and the leakage force was applied to the outside of the boundary portion.

Then, this was held in an air atmosphere at 150 ° C. and atmospheric pressure for 1 hour to cure the high refractive index binder A to form a high refractive index layer having a thickness of 500 μm.

[0538] The obtained light guide plate was evaluated in the same manner as in Example A-2-1 by turning on the LED on the substrate. The results are shown in Table 4.

In addition, in the light extraction property section of Table 4, if the field power S “○” of “power to shine far away”, it means that the light emitting surface has reached the vicinity of the weir, and if it is “△”. This means that the LED emits light to the middle of the LED and the boundary. If “X”, it means that it emits light just above the chip! /.

Also, in the light extraction property section of Table 4, if the field power S “○” of “the whole surface shines,” it means that the entire surface separated by the weir is emitting light, and “△” If it is, it means that it emits light to the middle between the LED and the boundary. If “X”, it means that only the surface near the chip emits light.

Furthermore, in the light extraction property section of Table 4, if the “Light shielding at the boundary” column is “◯”, it means that only the surface inside the boundary emits light. If so It means that the light emission reaches the surface.

[0539] [Example A— 2— 4]

The LED chip is sealed with a low refractive index layer, and instead of the high refractive index layer A, a low refractive index layer is formed in the same manner as in Example A 21 on the substrate, and on the low refractive index layer, A light guide plate was produced in the same manner as in Comparative Example A-2-3, except that the light scattering layer was formed as follows. For the light scattering layer, a specific layer (low refractive light scattering layer) forming solution is applied to the inner part of the boundary portion on the low refractive index layer, and this is applied in an air atmosphere at 150 ° C and atmospheric pressure. It was formed by holding for a time and curing. At this time, the thickness of the light scattering layer was 470 πι. In this case as well, the boundary part acts as a weir to dam the specific layer (low refractive light scattering layer) forming liquid, and the specific layer (low refractive light scattering layer) forming liquid is applied only inside the boundary part. There was no leakage outside the section.

The obtained light guide plate was evaluated in the same manner as in Example V2-1. The results are shown in Table 4.

[0540] [Example Α— 2-5]

The height of the weir is 500 inches, and instead of the high refractive index layer A, a low refractive index layer having a thickness of 30 m is formed on the substrate in the same manner as in Example A-2-1. A light guide plate was produced in the same manner as in Comparative Example A-2-3, except that the high refractive index layer B was formed on the refractive index layer as follows.

For the high refractive index layer B, a high refractive index binder B is applied to the inner part of the boundary portion on the low refractive index layer, and this is held in an air atmosphere at 150 ° C. and atmospheric pressure for 1 hour. Hardened to form. At this time, the thickness of the high refractive index layer B was 470 m. In this case as well, the boundary acts as a weir to block the high refractive index binder B, and the high refractive index binder B is applied only to the inside of the boundary, and the leakage force is applied to the outside of the boundary. .

The obtained light guide plate was evaluated in the same manner as in Example A-2-1. The results are shown in Table 4.

[0541] [Example A— 2-6]

The specific layer (weir) forming liquid C was used in place of the specific layer (weir) forming liquid B, and the low refractive index layer was formed in the same manner as in Example A-21 in place of the high refractive index layer A. Its low refractive index The high refractive index layer A was formed on the layer in the same manner as in Example A-2-1, and the specific layer (low refractive light scattering layer) forming liquid was replaced on the high refractive index layer A. Comparative Example A-2-3 except that a light scattering layer was formed in the same manner as Example A-2-4, except that a specific layer (high refractive light scattering layer / low scattering type) forming solution was used. A light guide plate was manufactured in the same manner as described above. The obtained light guide plate was evaluated in the same manner as in Example A-2-1. The results are shown in Table 4.

[0542] [Example A— 2-7]

Specified layer (weir) forming solution C is used instead of specified layer (weir) forming solution B, and specified layer (high refractive light scattering layer / strong scattering type) is used instead of the specified layer (low refractive light scattering layer) forming solution. A light guide plate was produced in the same manner as in Example A-2-6 except that the forming liquid was used.

[0543] [Example A— 2-8]

Except that the specific layer (high refractive light scattering layer / medium scattering type) forming liquid was used instead of the specific layer (high refractive light scattering layer / strong scattering type) forming liquid, the same as in Example A-2-7 Make a light guide plate.

[0544] [Table 4]

[0545] [Example A— 2-9]

[Manufacture of light guide plates]

A blue LED (CREE, trade name: C460MB290) was attached to an electrode on a 0.43 mm thick glass fiber reinforced epoxy laminated substrate by die bonding with epoxy silver paste and wire bonding with Au wire. This LED was sealed in a dome shape with a high refractive index binder A, and cured by holding at 150 ° C. for 1 hour.

[0546] A boundary portion was drawn on the substrate using the specific layer (weir) forming liquid C. The boundary is Drawing was made to be a weir surrounding the blue LED. The boundary portion was drawn using a syringe with a nozzle diameter of 290 m. At this time, the distance from the nozzle of the syringe to the substrate surface was 350 111. The drawing speed was 15 cm / sec. Furthermore, the pressure when extruding the specific layer (weir) forming liquid C from the syringe was set to 4 MPa.

Thereafter, this was held in an air atmosphere at 150 ° C. and atmospheric pressure for 0.5 hour to cure the boundary. As a result, a boundary part with a height of 300 111 and a width of 1.3 mm and no ridgeline was obtained.

[0547] Next, a low refractive index layer and a high refractive index layer A were formed in the inner part of the boundary portion on the substrate in the same manner as in Example A-2-1. Example A-2 except that the specific layer (high refractive light scattering layer / strong scattering type) forming liquid was used on the high refractive index layer A instead of the specific layer (low refractive light scattering layer) forming liquid. — A light-scattering layer was formed in the same manner as in 4 to produce a light guide plate.

The obtained light guide plate was evaluated in the same manner as in Example A-2-1. The results are shown in Table 5.

[0548] In addition, in the section of the light extraction property in Table 5, if the field power S "〇" of "power that shines far away", it means that the light emitting surface reaches the weir! “X” means that light is emitted only directly above the chip.

In addition, in the light extraction property section of Table 5, if the field power S “○” of “the whole surface is shining,” it means that the entire surface separated by the weir is emitting light, and “X” If there is, it means that only the surface near the chip emits light! /.

Furthermore, in the light extraction property section of Table 5, if the column “Light shielding at boundary” is “◯”, it means that only the surface inside the boundary emits light, and “X” If this is the case, it means that the light reaches the adjacent surface beyond the boundary.

[0549] [Example A— 2-10]

A light guide plate was manufactured in the same manner as in Example A-2-9 except that the drawing speed when forming the boundary portion was 24 cm / sec. As a result, a light guide plate having a boundary portion having a height of 150 m and a width of 0.6 mm and having no ridgeline was obtained.

The obtained light guide plate was evaluated in the same manner as in Example A-2-1. The results are shown in Table 5. [0550] [Example A-2-11]

A light guide plate was produced in the same manner as in Example A-29 except that the boundary portion was formed using the specific layer (weir) forming liquid C instead of the specific layer (weir) forming liquid B.

[0551] [Example A— 2-12]

Example A-2—Except that the specific layer (weir) forming liquid B was used instead of the specific layer (weir) forming liquid C, and that the drawing speed when forming the boundary was 9 cm / second. In the same manner as in 9, a light guide plate was produced.

[0552] [Example A— 2-13]

A light guide plate was produced in the same manner as Example A-2-9 except that the high refractive index layer A was formed directly on the substrate without forming the low refractive index layer, and the light scattering layer was formed thereon. did.

[0553] [Example A—2-14]

A light guide plate was made in the same manner as in Example A-2-9 except that the light scattering layer was not formed.

The obtained light guide plate was evaluated in the same manner as in Example V2-1. The results are shown in Table 5.

[0554] [Table 5]

[Summary]

From Table 35, a layer with a different refractive index that enhances light guiding is superior in the ability to guide light far away, and a light extraction surface with a scattering layer provides uniform light emission (light extraction). ). Further, by providing a boundary portion, even if light guide layers having different light emission colors are adjacent to each other, the color is shielded and the colors are not mixed. Reflection inward occurred and the LED power was able to improve the light emission uniformity near the boundary, which tends to be the darkest farthest. Total thickness of specific layers stacked 1 Even in the case of a 20 μm thin film, it was possible to form a very thin light guide layer with no deterioration in the in-plane light emission uniformity. In this way, a light guide layer capable of uniformly emitting light with a simple structure can be formed by using a stack of layers having different refractive indexes and a combination of a scattering layer and a boundary layer.

[0556] [B. Virtual model mainly related to fifth to eighth light guide members, examples and comparative examples]

[Virtual model 1]

The virtual model 1 shown below is a virtual model that will have the same functions and effects as those of Example B-1 and Example 2 described later when the light guide plate is manufactured as follows.

[0557] [B- 1 1] Preparation of low refractive index layer forming solution

Toray Dow Cowing Co., Ltd. ¾ICR6101UP, a low-refractive index resin that does not contain a polar group and is a rubber-like one-part dimethyl silicone resin (refractive index η = 1 · 41), is stirred with a centrifugal defoaming type stirring device Defoaming to obtain a low refractive index layer forming liquid.

[0558] [B- 1-2] Preparation of high refractive index layer forming solution

Momentum Performance Materials Japan GK I VS5022, which is a rubber-like two-component phenylmethyl silicone resin (η = 1 · 53) that does not contain polar groups as a high-refractive index resin, is centrifuged using a centrifugal defoaming stirrer. By stirring and degassing, a high refractive index layer forming liquid is obtained.

[0559] [Β— 1 3] Preparation of light scattering layer forming solution

As light scattering particles, 0.75g of Tospearl 145 (median particle size 5 111) manufactured by Momentive Noformance Materials Japan G.K. and Al O fine powder CR1 (median particle size 400η

twenty three

m) 0.076g was mixed with 11.3g of the rubber-like two-component phenylmethyl silicone resin and 2.5g of heptane described in [B-1 -2] and stirred and defoamed with a centrifugal defoaming stirrer. Thus, a light scattering layer forming liquid is obtained.

[0560] [B— 1 4] Primer solution

As the primer solution, for example, the primer solution “Primer C” manufactured by Shin-Etsu Chemical Co., Ltd. (which is considered to contain polar groups such as amino groups and methacryl groups) is used as it is. In addition, it is preferable to use a primer solution dedicated for optical use because it causes little yellowing during heat curing!

[0561] [B-1 5] Application of optical material forming liquid

Pour 2 g of low refractive index layer forming liquid [B—11] into a 5 cm diameter Teflon (registered trademark) petri dish, level it, and cure for 1 hour in a 150 ° C ventilator. The An lmm transparent cured film is obtained.

With the cured film in a Teflon petri dish, apply [B-1-4] Primer C thinly on the low refractive index layer, air-dry the primer solvent, and then set [B-1 2] high Pour 2 g of the refractive index layer forming solution, level it, cure for 1 hour in a 150 ° C ventilator, and stack a transparent high refractive index layer with a thickness of 1 mm on the low refractive index layer. .

Furthermore, apply [B-1-4] Primer C thinly on this layered cured product, air-dry the primer solvent, and pour the [B-13] light scattering layer forming solution to level it. Curing for 1 hour in a ventilator at ° C, and a third film with a thickness of 0.8 mm is deposited.

[0562] The obtained light guide plate having a three-layer structure was taken out of the petri dish, and sealed with the above-mentioned high refractive index resin Toray Dow Corning CR6175 from one end on the circumference to the central high refractive index layer. Press the LED to emit light. As a result, it is considered that blue light propagates in the high refractive index layer and the entire surface of the light scattering layer shines.

[0563] When sharp tweezers are inserted between the low-refractive index layer and the high-refractive index layer, the light guide plate of virtual model 1 does not spontaneously expand the peeling between the layers starting from the tweezers. It does not happen and is expected to be in close contact. Similarly, when an external force is applied between the high-refractive index layer and the light scattering layer, this also is expected to be in close contact without causing spontaneous expansion of peeling.

[0564] [Example B-1]

A high-refractive index layer using LPS2410 made by Shin-Etsu Chemical Co., Ltd., which is a two-part dimethyl silicone resin that has an epoxy group as a polar group in the low-refractive index layer, with a force S that is the same as the virtual model 1. In addition, Toray Dow Cowing Co., Ltd. ¾JCR6175, which is a two-component phenylmethyl silicone resin having an epoxy group “methoxy group” as a polar group, was used to prepare a light guide plate in which three layers were directly laminated without applying a primer.

[0565] This light guide plate was taken out of the petri dish, and in the same manner as in the virtual model 1, from the one end on the circumference to the central high refractive index layer was sealed with the same high refractive index resin as that of the high refractive index layer. When a blue LED was pressed to emit light, it was observed that blue light propagated through the high refractive index layer and the entire light scattering layer shined.

[0566] A sharp tweezer was inserted between the low refractive index layer and the high refractive index layer. The light guide plate of Example B-1 was in close contact with each other, with no spontaneous expansion of peeling from the tweezers. Similarly, when an external force was applied between the high-refractive index layer and the light scattering layer, it was also in close contact without causing spontaneous expansion of the peeling starting from the tweezers.

[0567] [Example B-2]

Example B-1 The force of a three-layer structure having the same low-refractive index layer, high-refractive index layer, and light scattering layer as in Example 1. Primer C used in virtual model 1 is thinly applied between each layer, and the primer solvent is used. After air drying, the next layer was poured and leveled and cured to produce a light guide plate with three layers laminated.

[0568] As in the virtual model 1, a blue LED with a wavelength of 460 nm sealed with a high refractive index resin similar to that in Example B-1 was pressed from one end of the circumference to the central high refractive index layer. When the light was emitted, it was observed that blue light propagated through the high refractive index layer and the entire light scattering layer was shining.

[0569] When sharp tweezers were inserted between the low-refractive index layer and the high-refractive index layer, the light guide plate of Example B-2 expanded spontaneous peeling between the layers starting from the tweezers. Did not happen and was in close contact. Similarly, when an external force was applied between the high-refractive index layer and the light scattering layer, this also did not expand spontaneously starting from the tweezers, and was in close contact.

[0570] [Comparison virtual model 1]

It has a three-layer structure using the same resin as the virtual model 1, but if a light guide plate is produced in which three layers are laminated directly without applying a primer between each layer, the light guide plate will be removed from the petri dish. Since peeling easily occurs and separates from the boundary surface of each layer, it cannot be used as a light guide plate due to insufficient adhesion.

[0571] [Comparative Example B-1]

[B-2-1] Preparation of low refractive index layer forming liquid

Methinosilicate (MKC Siliquette MS51 made by Mitsubishi Chemical Co., Ltd. MS51) 30. 80 g, methanole 56. 53 g, water 6.51 g, and 6.16 g of 5% by weight acetylacetone aluminum salt methanol solution as a catalyst were sealed. Mix in a container, seal tightly, and stir with a stirrer, heat in a 50 ° C hot water bath for 8 hours, return to room temperature, and prepare hydrolysis' polycondensation liquid . The refractive index of the cured product of this liquid is 1.44.

[0572] [B—2-2] Preparation of high refractive index layer forming solution

Methinoresilicate (MKC Siliquette MS51 from Mitsubishi Chemical Co., Ltd. MS51) 30.80g, methanole 56.53g, water 6.51g, titania sol with silica zirconia-coating with a particle size of 5nm as a refractive index modifier (solid content 20 19.6 g of methanol dispersion (weight%) and 6.16 g of 5 wt% acetylethylacetone aluminum salt methanol solution as a catalyst are mixed in a container that can be sealed, sealed, stirred with a stirrer, and heated at 50 ° C. After heating in a bath for 8 hours, the temperature was returned to room temperature, and a hydrolysis / polycondensation solution was prepared. The refractive index of the cured product of this liquid is 1.52.

[0573] [B— 2-3] Preparation of light scattering layer forming solution

twenty three

m) 0.076 g was mixed with 30 g of the high refractive index layer forming solution described above in [B-2-2] and stirred with a stirrer to obtain a light scattering layer forming solution.

[0574] [B— 2-4] Application of optical material forming liquid

Pour 1 Og of the low refractive index layer-forming solution obtained in [B-2-1] into a 5 cm diameter Teflon (registered trademark) Shear, hold at 35 ° C for 30 minutes, and then hold at 50 ° C for 1 hour. After removing the film, it was heated and cured at 150 ° C. for 3 hours to obtain a hard glass film having a thickness of about 0.3 mm. However, many cracks were generated in this film during the drying process, and it was impossible to take out as a complete circular transparent glass film.

[0575] Further, using the high refractive index layer forming liquid obtained in [B2-2-2] and the light scattering layer forming liquid of [B2-2-3], the same formulation as the low refractive index layer forming liquid is used. Attempts to create a single film at the time Many warps and cracks occurred, and it was impossible to take out as a complete circular glassy film.

[0576] Thus, each layer is in a state where it is difficult to form a single layer film, and it was not possible to form a light guide plate in which three layers were stacked as in virtual model 1. In addition, these films could not obtain a sufficient area and film thickness for measuring the film hardness using the Shore A and Shore D hardness meters, and could not obtain a hardness measurement value. The general glass plate hardness represented by Shore D

2

Since it was 100, it is estimated that it has the same degree of hardness. Therefore, Siloxa Power of having silanol structure and silanol or alkoxy group as a polar group No degree of cross-linking adjustment V, the hard siloxane compound of Comparative Example B-1 has chemical adhesion between each layer! / However, due to insufficient flexibility, the shrinkage stress generated during curing cannot be relieved, and it is considered that the light guide plate cannot be formed due to breakage.

The results of the above examples and comparative examples are summarized in Table 6. In the adhesion column, D / H represents the adhesion between the low refractive index layer and the high refractive index layer, and H / L represents the adhesion between the high refractive index layer and the light scattering layer. . Also, in the Adhesion column, ◎ indicates that when tweezers are inserted between layers, it is difficult to insert tweezers due to lack of spontaneous separation starting from the tweezers and strong adhesion. 〇 means that when tweezers are inserted between the layers, there is no spontaneous separation starting from the tweezers, but tweezers are easy to insert, and X indicates that the tweezers are removed from the petri dish. Indicates that two-layer separation or damage has occurred. Furthermore, in the column of the light extraction effect, ◯ indicates that the whole light scattering layer is shining, and X indicates that it is not observed.

[Table 6]

[¾ 6 and O: Comparison ^ Results]

'

1::? · 5 · ί ■? ■■■ ¾ ； ..

.; i, ϋ

;;.

!

ί'.ί o

- ^; La--Later; V: Set-'' Shi T; ·> :::: '; Q ¾i; s::' Manipulated.

[C. Examples and comparative examples mainly related to ninth light guide member]

[c-i. Preparation of forming solution for each layer]

[C 1 1] Synthesis of specific layer (low refractive index layer) forming solution

Momentive 'Performance''Materials' Japan GK Co., Ltd. Both-end silanol Dimethenoresiri = i 1-year-old Inore XC96— 723 1450. 3. 190g was prepared. This was placed in a 2 L three-necked Kolben equipped with a stirring blade and a condenser, and stirred at room temperature until the zirconate powder was sufficiently dissolved. This will allow 15 minutes It dissolved in about. The liquid was heated to 120 ° C and stirred while refluxing for 30 minutes.

Yes

[0579] Subsequently, a gas blowing tube was connected to the mouth of Kolben, and stirring was continued at 120 ° C for 5 hours while nitrogen was blown into the reaction solution with SV20. Here, “SV” is an abbreviation for “Space Velocity” and indicates the amount of blowing per unit time. Therefore, SV20 means blowing N of 20 times the volume of the reaction solution in one hour.

2

[0580] [C-1-2] Synthesis of specific layer (high refractive index layer) forming solution A

Momentive 'Performance' Materials' Japan GK Co., Ltd. both-end silanol Dimethylol silicone oil XC96-723 42g, Both-end silanol methylphenol corn oil YF3804 98g, Phenyltrimethoxysilane 14g, and catalyst 0.308 g of zirconium tetracetylacetonate powder was prepared and weighed into a 200 mL three-necked Kolben equipped with a stirring blade and a condenser. The mixture was stirred at room temperature until the zirconium tetracetylacetonate powder was sufficiently dissolved. This dissolved in about 15 minutes. The liquid was heated to 120 ° C. and stirred while refluxing for 30 minutes.

[0581] Subsequently, a gas blowing tube was connected to the mouth of Kolben, and stirring was continued at 120 ° C for 6 hours while nitrogen was blown into the reaction solution with SV20.

After the nitrogen blowing was stopped and the Kolben was cooled to room temperature, the reaction solution was transferred to an eggplant-shaped flask and distilled off under reduced pressure at 120 ° C. and lkPa for 20 minutes on an oil bath using a rotary evaporator.

[0582] Ultrafine silica (trade name: AEROSIL # RX200) manufactured by Nippon Aerosil Co., Ltd. as an inorganic particle, 0.1 lg, and 1.0 g of the reaction solution after distillation under reduced pressure were mixed in a container. , Centrifugal defoaming was performed using a rotation / revolution mixer defoamer. Thereafter, the container was placed in a vacuum chamber and a defoaming operation was further performed to obtain a specific layer (high refractive index layer) forming liquid A (hereinafter referred to as “high refractive index binder 8” as appropriate). [0583] [C 1 3] Synthesis of specific layer (weir) forming liquid B

Ultrafine silica particles (made by Nippon Aerosil Co., Ltd., trade name: AEROSIL # 130) 0.78 g, epoxy resin (made by Japan Epoxy Resin, trade name: Epicoat 828US) 4. 98 g, epoxy resin as inorganic particles in the container Curing agent (made by Japan Epoxy Resin, trade name: J ER Epicure YLH1230) 4. 24 g was added and mixed, and centrifugal defoaming was performed using a rotating / revolving mixer defoaming device. Thereafter, the container was evacuated and further defoaming was performed to obtain a specific layer (weir) forming liquid B.

[0584] [C 14] Synthesis of specific layer (weir) forming liquid C

Ultrafine silica particles (made by Nippon Aerosil Co., Ltd., trade name: AEROSIL # 130) 0.55 g, non-agglomerated type alumina (made by Baikowski, trade name: CR1, median particle size 0.95 microns) as inorganic particles in the container 2. 0g, epoxy resin (made by Japan Epoxy Resin, trade name: Epicoat 828US) 4. 03g, epoxy resin curing agent (made by Japan Epoxy Resin, trade name: JER Epicure YLH1230) Centrifugal defoaming was performed using a revolving mixer defoaming device. Thereafter, the container was evacuated and further defoaming was performed to obtain a specific layer (weir) forming liquid C.

[0585] [C- 1-5] Preparation of specific layer (high refractive light scattering layer / low scattering type) forming solution

After stopping the nitrogen blowing and cooling the reaction solution to room temperature, transfer the reaction solution to an eggplant-shaped flask and use a rotary evaporator on the oil bath for 120 minutes at 120 ° C and lkPa for 20 minutes. Distills off moisture and low boiling carbon components, and eliminates solvent-free A high refractive index binder (η = 1 · 46) was obtained.

[0586] Al Ο fine powder "CR1 (median particle size 400nm)" 0.lg as light scattering particles, the above high refraction

twenty three

Binder (n = l. 46) 9. Mix with 9g and perform centrifugal defoaming and mixing using a rotating / revolving mixer defoaming device. Thereafter, the container was evacuated and further defoamed and mixed to obtain a liquid for forming a specific layer (high refractive light scattering layer / low scattering type).

[0587] [C-1-6] Preparation of specific layer (high refractive light scattering layer / medium scattering type) forming solution

As light-scattering particles, Motosive 'Performance' Materials' Japan Tospearl 145 (median particle size 5 m) 'l.Og and Al O fine powder' CR1 (median particle size 400η

twenty three

m) j O. lg was mixed with 8.9 g of the above high refractive index binder (n = l. 46) and subjected to centrifugal defoaming and mixing using a rotation / revolution system mixer defoaming device. Thereafter, the container was further evacuated and mixed under vacuum to obtain a specific layer (high refractive light scattering layer / medium scattering type) forming liquid.

[0588] [C- 1-7] Preparation of specific layer (high refractive light scattering layer / strong scattering type) forming solution

twenty three

m) 0.2 g of j was mixed with 7.8 g of the above-described high refractive index binder (n = l. 46), and centrifugal defoaming and mixing were performed using a rotation / revolution system mixer defoaming device. Thereafter, the container was further evacuated and mixed under vacuum to obtain a liquid for forming a specific layer (high refractive light scattering layer / strong scattering type).

[0589] [C- 1-8] Preparation of specific layer (low refractive light scattering layer) forming solution

Momentive 'Performance' 'Materials' Japan GK Co., Ltd. Both-end silanol Dimethenoresiri 1-year-old Inore XC96— 723 1450.82g, Phenyloloxysilane 145g 3 · 190 g was prepared, weighed into a 2 L three-necked Kolben equipped with a stirring blade and a condenser, and stirred at room temperature for 15 minutes until the catalyst was sufficiently dissolved. Thereafter, the temperature of the reaction solution was raised to 120 ° C., and initial hydrolysis was performed while stirring at 120 ° C. under total reflux for 30 minutes.

[0590] Subsequently, nitrogen was blown in with SV20, and the resulting methanol, water, and low-boiling components of by-products were distilled off and stirred at 120 ° C, and the polymerization reaction was further continued for 5 hours.

Nitrogen blowing was stopped and the reaction solution was cooled down to room temperature. After that, the reaction solution was transferred to an eggplant-shaped flask, and the rotary evaporator was used on an oil bath at 120 ° C and lkPa at 20 ° C. Methanol, water, and low-boiling carbon components remaining in minute amounts were distilled off to obtain a solvent-free low refractive index binder (η = 1 · 42) (282 mPa's).

[0591] As light scattering particles, 2 m spherical silica 2. Og and the low refractive index binder (n = 1)

42) 8. Og was mixed, and centrifugal defoaming and mixing were performed using a rotation / revolution mixer defoaming device. Thereafter, the container was evacuated and further defoamed and mixed to obtain a specific layer (low refractive light scattering layer) forming liquid.

[0592] [C-2. Description of operation and evaluation of specific examples]

[Example C 1]

[Manufacture of light guide plates]

[0593] A boundary portion was drawn on the substrate using the specific layer (weir) forming liquid B. The boundary was drawn to be a weir surrounding the blue LED. The boundary portion was drawn using a syringe with a nozzle diameter of 290 m. At this time, the distance from the syringe nozzle to the substrate surface was set to 500 m. The drawing speed was 10 cm / sec. Furthermore, the pressure when extruding the specific layer (weir) forming solution B from the syringe was set to 1.5 MPa.

In the next step, a low refractive index binder was applied to the inner part of the boundary portion on the substrate. At this time, the boundary portion acts as a weir for blocking the low refractive index binder, Only a low refractive index binder was applied, and it did not leak outside the boundary. Further, the low refractive index binder is applied so as not to cover the upper portion of the high refractive index binder A that closes the hole, and the low refractive index layer formed by the low refractive index binder allows the light transmitted through the hole to be transmitted. The transmission was not hindered.

[0595] Further, a high refractive index binder A was applied to the inner portion of the boundary portion on the low refractive index layer. Also at this time, the boundary portion acted as a weir for blocking the high refractive index binder A, and the high refractive index binder A was applied only to the inside of the boundary portion, and did not leak to the outside of the boundary portion. Then, this was held in an air atmosphere at 150 ° C. and atmospheric pressure for 1 hour to cure the high refractive index binder A, thereby forming a high refractive index layer A having a thickness of 415 m.

[0596] Further, a low refractive index binder was applied to the inner part of the boundary portion on the high refractive index layer A. Also at this time, the boundary portion acted as a weir for blocking the low refractive index binder, and the low refractive index binder was applied only to the inside of the boundary portion and did not leak to the outside of the boundary portion. Then, this was held in an air atmosphere at 150 ° C. and atmospheric pressure for 1 hour, and the low refractive index binder was cured to form a low refractive index layer having a thickness of 30 m.

The light guide plate was manufactured as described above.

[0597] [Evaluation]

Further, for each layer of the obtained light guide plate as described below, adhesion evaluation, solid-state Si-NMR spectrum measurement, silanol content, key content, hardness (Shore A), refractive index, and haze Was measured.

The results are shown in Table 7.

[0598] [Analysis of each layer and evaluation method of light guide plate]

[Solid Si—NMR spectrum measurement and silanol content calculation]

For each layer of the light guide plate of Example C1, solid Si-NMR spectrum measurement and waveform separation analysis were performed under the following conditions. From the obtained waveform data, the light guide of Example C 1 For each layer of the plate, the half width of each peak was determined. In addition, the ratio (%) of silanol-derived silicon atoms to the total peak area is calculated from the ratio of silanol-derived peak area to the total peak area and compared with the separately analyzed content of silicon. The silanol content was determined.

[0599] <Device conditions>

²⁹ Si resonance frequency: 79. 436MHz

Probe: 7.5mm φ CP / MAS probe

Measurement temperature: room temperature

Sample rotation speed: 4kHz

Measurement method: Single pulse method

^^ 1 decoupling frequency: 50kHz

²⁹ Si flip angle: 90 °

²⁹ Si90 ° pulse width: 5. O ^ s

Repeat time: 600s

Integration count: 128 times

Observation width: 30kHz

Broad Jung factor: 20Hz

[0600] <Data processing method>

[0601] <Waveform separation analysis method>

[0602] [Measurement of key content] Example C 1 A single hardened material of each layer (low refractive index layer, high refractive index layer, low refractive index layer) of the light guide plate was pulverized to about 100 m, and 1 hour at 450 ° C in a platinum crucible. After baking for 7 hours at 550 ° C for 1 hour and at 950 ° C for 1.5 hours to remove the carbon component, add 10 times or more of sodium carbonate to a small amount of the resulting residue and heat with a burner Then melt it, add demineralized water, adjust the pH to a neutral level with hydrochloric acid while adjusting the pH to about several ppm, and use `` SPS1700HVR '' manufactured by Seiko Denshi. ICP analysis became fi.

[0603] [Hardness measurement]

For each layer of the light guide plate of Example C 1 (low refractive index layer, high refractive index layer, low refractive index layer), use A type (Duguchi meter type A) rubber hardness tester manufactured by Furusato Seiki Seisakusho and comply with JIS K6253 The hardness (Shore A) was measured according to the standard.

[Refractive index measurement]

Example C 1 A single hardened material of each layer (low refractive index layer, high refractive index layer, low refractive index layer) of the light guide plate is pulverized into a powder of about several tens of meters, and the refractive index in the vicinity of the predicted refractive index is obtained. Refractive index standard liquid (refractive liquid) having a refractive index of a binder that is dispersed at several points and observed under natural light, and the floating powder becomes transparent without light scattering and cannot be confirmed by visual observation. Immersion method).

[0604] [Adhesion evaluation method]

Example C 1 When the light guide plate coating layer (upper layer) on one end of the light guide plate is pinched with tweezers and slowly peeled off in the right-angle direction, the film does not easily peel off, but breaks partially. In Fig. 9, it is represented by “◯”), and those that can be easily peeled are defined as “bad”.

[0605] [-^ Values evaluation method]

A single cured film with a smooth surface of about lmm thick that is free from scattering due to scratches and unevenness of optical materials is prepared. Using this single cured film, the air layer is used as a reference and manufactured by Nippon Denshoku Industries Co., Ltd. The ^^ values were measured with COH-300A.

[0606] In addition, in the section of the light extraction property in Table 7, if the field power S "○" of "power that shines far away", it means that the light emitting surface reaches the weir! “X” means that light is emitted only directly above the chip. Also, in the light extraction property section of Table 7, if the field power S “◯” of “the whole surface shines,” it means that the entire surface separated by the weir is emitting light, and “△” If it is, it means that it emits light to the middle between the LED and the boundary. If “X”, it means that only the surface near the chip emits light.

Furthermore, in the light extraction property section of Table 7, if the “Light shielding at the boundary” column is “◯”, it means that only the surface inside the boundary emits light, and “X” If this is the case, it means that the light reaches the adjacent surface beyond the boundary.

[0607] [Example C 2]

A light guide plate was produced in the same manner as in Example C 1 except that the low refractive index layer was not formed on the high refractive index layer A. The obtained light guide plate was evaluated in the same manner as in Example C-1. The results are shown in Table 7.

[0608] [Example C 3]

The boundary layer was formed using the specific layer (weir) forming liquid C instead of the specific layer (weir) forming liquid B, and the low refractive index layer was not formed on the high refractive index layer A. A light guide plate was produced in the same manner as in Example C 1 except that. The obtained light guide plate was evaluated in the same manner as in Example C-1. The results are shown in Table 7.

[0609] [Table 7]

[Example C 4]

[Manufacture of light guide plates]

A blue LED chip (product name: C460MB290) was attached to the electrode on the 0.43 mm thick glass fiber reinforced epoxy laminate by die bonding with epoxy silver paste and wire bonding with Au wire. A high refractive index binder A was raised and applied onto this LED chip, and was cured by holding at 150 ° C. for 1 hour, and the LED chip was sealed with a high refractive index layer A. [0611] A boundary portion was drawn on the substrate using the specific layer (weir) forming liquid B. The boundary was drawn to be a weir surrounding the blue LED. The boundary portion was drawn using a syringe having a nozzle diameter of 570 m. At this time, the distance from the syringe nozzle to the substrate surface was set to 650 m. The drawing speed was 10 cm / sec. Furthermore, the pressure when extruding the specific layer (weir) forming liquid B from the syringe was set to 2 MPa.

[0612] Next, a high refractive index binder A was applied to an inner portion of the boundary portion on the substrate.

[0613] The obtained light guide plate was evaluated in the same manner as in Example C 1 by turning on the LED on the substrate. The results are shown in Table 8.

In addition, in the section of light extraction property in Table 8, if the field power S “◯” of “power that shines far away”, it means that the light emitting surface has reached the vicinity of the weir, and if “△”, This means that the LED emits light to the middle of the LED and the boundary. If “X”, it means that it emits light just above the chip! /.

Also, in the light extraction property section of Table 8, if the field power S “◯” of “the whole surface shines,” it means that the entire surface divided by the weir is emitting light, and “△” If it is, it means that it emits light to the middle between the LED and the boundary. If “X”, it means that only the surface near the chip emits light.

Furthermore, in the section of light extraction property in Table 8, if the field power S of “shielding light at the boundary” S “◯”, it means that only the surface inside the boundary emits light, and “X "Means that the light reaches the adjacent surface beyond the boundary.

[0614] [Example C 5]

The LED chip is sealed with a low refractive index layer, and instead of the high refractive index layer A, a low refractive index layer is formed in the same manner as in Example C 1 on the substrate. In the way A light guide plate was produced in the same manner as in Example C4 except that the disordered layer was formed.

For the light scattering layer, a specific layer (low refractive light scattering layer) forming solution is applied to the inner part of the boundary portion on the low refractive index layer, and this is applied in an air atmosphere at 150 ° C and atmospheric pressure. It was formed by holding for a time and curing. At this time, the thickness of the light scattering layer was 470 πι. In this case as well, the boundary part acts as a weir to dam the specific layer (low refractive light scattering layer) forming liquid, and the specific layer (low refractive light scattering layer) forming liquid is applied only inside the boundary part. There was no leakage outside the section.

The obtained light guide plate was evaluated in the same manner as in Example C-1. The results are shown in Table 8.

[0615] [Example C 6]

Specific layer (weir) formation liquid The specific layer (weir) formation liquid C was used instead of the soot, and the low refractive index layer was formed in the same manner as in Example C 1 instead of the high refractive index layer A. The high refractive index layer A was formed on the low refractive index layer in the same manner as in Example C 1, and the specific layer (low refractive light scattering layer) forming liquid was replaced on the high refractive index layer A. In the same manner as in Example C4, except that a specific layer (high refractive light scattering layer / low scattering type) forming liquid was used, a light scattering layer was formed in the same manner as in Example C5. Manufactured.

[0616] [Example C 7]

Specified layer (weir) forming solution C is used instead of specified layer (weir) forming solution B, and specified layer (high refractive light scattering layer / strong scattering type) is used instead of the specified layer (low refractive light scattering layer) forming solution. A light guide plate was produced in the same manner as in Example C-6 except that the forming solution was used.

[0617] [Example C 8]

In the same manner as in Example C-7, except that the specific layer (high refractive light scattering layer / medium scattering type) forming liquid was used instead of the specific layer (high refractive light scattering layer / strong scattering type) forming liquid. A light plate was manufactured. The obtained light guide plate was evaluated in the same manner as in Example C1. The results are shown in Table 8.

[Table 8]

[0619] [Example C 9]

[Manufacture of light guide plates]

A blue LED (product name: C460MB290, manufactured by Tari Co., Ltd.) was attached to the electrode on the 0.43-mm thick glass fiber reinforced epoxy laminated substrate by die bonding with epoxy silver paste and wire bonding with Au wire. This LED was sealed in a dome shape with a high refractive index binder A, and cured by holding at 150 ° C. for 1 hour.

[06201] A boundary layer was drawn on the substrate using the specific layer (weir) forming liquid C. The boundary is Drawing was made to be a weir surrounding the blue LED. The boundary portion was drawn using a syringe with a nozzle diameter of 290 m. At this time, the distance from the nozzle of the syringe to the substrate surface was 350 111. The drawing speed was 15 cm / sec. Furthermore, the pressure when extruding the specific layer (weir) forming liquid C from the syringe was set to 4 MPa.

[0621] Next, a low-refractive index layer and a high-refractive index layer A were formed in the inner part of the boundary portion on the substrate in the same manner as in Example C1. In addition to Example C 5 except that the specific layer (low refractive light scattering layer) forming liquid was used on the high refractive index layer A instead of the specific layer (low refractive light scattering layer) forming liquid. Similarly, a light scattering layer was formed to produce a light guide plate.

The obtained light guide plate was evaluated in the same manner as in Example C-1. The results are shown in Table 9.

[0622] In addition, in the section of light extraction property in Table 9, if the field power S "〇" of "power that shines far," it means that the light emitting surface has reached the vicinity of the weir! “X” means that light is emitted only directly above the chip.

Also, in the light extraction property section of Table 9, if the field power S “○” of “the whole surface shines,” it means that the entire surface separated by the weir is emitting light, and “X” If there is, it means that only the surface near the chip emits light! /.

Furthermore, in the light extraction property section of Table 9, if the column “Light shielding at boundary” is “◯”, it means that only the surface inside the boundary emits light, and “X” If this is the case, it means that the light reaches the adjacent surface beyond the boundary.

[0623] [Example C 10]

A light guide plate was produced in the same manner as in Example C 9 except that the drawing speed when forming the boundary was 24 cm / sec. As a result, a light guide plate having a boundary portion having a height of 150 m and a width of 0.6 mm and having no ridgeline was obtained.

The obtained light guide plate was evaluated in the same manner as in Example C-1. The results are shown in Table 9. [0624] [Example C 11]

A light guide plate was produced in the same manner as in Example C-9 except that the boundary layer was formed using the specific layer (weir) forming liquid C instead of the specific layer (weir) forming liquid B.

[0625] [Example C 12]

Same as Example C 9 except that the specific layer (weir) forming liquid B was used instead of the specific layer (weir) forming liquid C and that the drawing speed when forming the boundary was 9 cm / sec. Thus, a light guide plate was manufactured.

[0626] [Example C 13]

A light guide plate was produced in the same manner as in Example C-9 except that the high refractive index layer A was formed directly on the substrate without forming the low refractive index layer, and the light scattering layer was formed thereon.

[0627] [Example C 14]

A light guide plate was produced in the same manner as in Example C-9 except that the light scattering layer was not formed.

[0628] [Table 9]

[Summary]

From Table 79, a layer with different refractive indexes that enhances the light guide is superior in the ability to guide light far away, and a light-extracting surface with a scattering layer provides uniform light emission (light capture). It can be seen that it is excellent in In addition, by providing a boundary portion, even if the light-guiding layers having different emission colors are adjacent to each other, the color is shielded and there is no color mixing. As a result, the light emission uniformity near the boundary, which tends to be the darkest farthest from the LED, was improved. Total number of specific layers stacked Even in the case of a 120 m thick thin film, the in-plane light emission uniformity was not degraded, and an extremely thin light guide layer could be formed. In this way, a light guide layer capable of uniformly emitting light with a simple structure can be formed by using a stack of layers having different refractive indexes and a combined use of a scattering layer and a boundary layer.

[0630] [C 3] Manufacture of light guide plate

[C 3—1] Preparation of forming solution for each layer

[C 3-1 1] Preparation of specific layer (low refractive index layer) A (low refractive index; n = 1. 41) Momentive 'Performance' Materials' Japan GK Co., Ltd. Inore XC96-723 (390g), methynoleylmethoxysilane (10.41g), and zirconium tetraacetylacetonate powder (0.280g) as a catalyst, stirring blade, fractionating tube, Dimroth condenser and Liebig condenser Weighed into the attached 500 ml three-necked Kolben and stirred at room temperature for 15 minutes until the coarse particles of the catalyst were dissolved. Thereafter, the temperature of the reaction solution was raised to 100 ° C. to completely dissolve the catalyst, and initial hydrolysis was performed while stirring at 500 rpm for 30 minutes under 100 ° C. total reflux.

[0631] Subsequently, the distillate was connected to the Liebig condenser side, and nitrogen was blown into the liquid with SV20, and the methanol, water, and low-boiling carbon components of by-products were distilled off accompanied with nitrogen. C, and stirred at 500 rpm for 1 hour. Subsequently, the nitrogen flow rate was increased to SV40 and the polymerization reaction was continued for 4.7 hours while the temperature was further raised to 130 ° C while being blown into the solution, and a reaction solution having a viscosity of 158.7 mPa's was obtained. “SV” is an abbreviation of “Space Velocity” and refers to the volume of blown volume per unit time. Therefore, SV20 means blowing N of 20 times the volume of the reaction solution per hour. .

2

[0632] After stopping nitrogen blowing and cooling the reaction solution to room temperature, transfer the reaction solution to an eggplant-shaped flask and leave it in a minute amount at 120 ° C and lkPa for 20 minutes on an oil bath using a rotary evaporator. The methanol, water, and low boiling point carbon components were distilled off to obtain a solvent-free solution having a viscosity of 260 mPa's.

[0633] 10 g of this solution and zirconium tetraacetyl acetate powder 0 · 04 g were weighed in a glass screw tube bottle, and stirred and dissolved in an oil bath at 100 ° C for 5 minutes (hereinafter referred to as “low refractive index binder” as appropriate). Eight "! /, U). Low-refractive index binder A solution 2g after transparent dissolution, Nippon Aerosil Co., Ltd. Hydrophobic fumed silica RX200 was weighed to 0.194g ointment, and the rotation Using a Xerer deaerator, the mixture was stirred for 3 minutes in the mixing mode and for 1 minute in the defoaming mode to obtain a specific layer (low refractive index layer) forming liquid A (low refractive index; n = 1 · 41).

[0634] [C 3-1 2] Preparation liquid of specific layer (low refractive index layer) formation liquid B (low refractive index; n = l. 42)

Momentive 'Performance' 'Materials' Japan GK Co., Ltd. Both-end Silanol Dimethinoresiri 1-year-old Inore XC96— 723 1450.82g, Phenylolinoxysilane 14.5 g 190g prepared. This was placed in a 2 L three-necked Kolben equipped with a stirring blade and a condenser, and stirred at room temperature until the zirconium tetraacetylacetylate powder was sufficiently dissolved. This dissolved in about 15 minutes. The liquid was heated to 120 ° C and stirred while refluxing for 30 minutes.

Yes

[0635] Subsequently, a gas blowing tube was connected to the mouth of Kolben, and stirring was continued at 120 ° C for 5 hours while nitrogen was blown into the reaction solution with SV20. After stopping the nitrogen blowing and cooling the Kolben to room temperature, the reaction solution was transferred to an eggplant-shaped flask and distilled under reduced pressure on an oil bath at 120 ° C and lkPa for 20 minutes using a rotary evaporator. 's solvent-free liquid was obtained.

[0636] 10 g of this liquid and zirconium tetraacetylacetonate powder 0 · 06 g were weighed in a glass screw tube bottle and stirred and dissolved in an oil bath at 100 ° C for 5 minutes (hereinafter referred to as “low refractive index binder” 2) 2g of low-refractive index binder B after transparent dissolution, weigh hydrophobic fumed silica RX200 made by Nippon Aerosil Co., Ltd. into 0.196g ointment jar, The mixture was stirred for 3 minutes in the mixed mode and 1 minute in the defoaming mode to obtain a specific layer (low refractive index layer) forming liquid B (low refractive index; n = 1.42).

[0637] [C—3-1—3] Preparation of specific layer (high refractive index layer) forming liquid C (high refractive index; n = l. 46)

Momentive 'Performance'Materials' Japan GK Co., Ltd. Both End Silanol Dimethylol Silicone Oile XC96-723 42g, Both End Silanol Methyl Phenyl Silcon Corn Oil 98g, Phenyltrimethoxysilane 14g, and Catalyst Prepare 0.308 g of zirconium tetracetylacetonate powder, weigh it into a three-necked Kolben equipped with a stirring blade and a condenser, and stir at room temperature for 15 minutes until the catalyst is sufficiently dissolved. did. After this, the temperature of the reaction solution was raised to 120 ° C and stirred for 2 hours at 120 ° C total reflux. Initial hydrolysis was carried out.

After stopping the nitrogen blowing and cooling the reaction solution to room temperature, transfer the reaction solution to an eggplant-shaped flask and use a rotary evaporator on the oil bath for 120 minutes at 120 ° C and lkPa for 20 minutes. Water and low boiling water components were distilled off to obtain a solvent-free liquid having a viscosity of 150 mPa's.

[0638] 10 g of this solution and zirconium tetraacetylacetonate powder 0 · 08 g were weighed in a glass screw tube bottle and stirred and dissolved in an oil bath at 100 ° C for 5 minutes (hereinafter referred to as “high refractive index binder” "!" High-refractive-index binder solution C 2g after clear dissolution, Nippon Aerosil Co., Ltd. Hydrophobic fumed silica RX200 was weighed to 0.175g ointment jar, using a rotating / revolving mixer deaerator 3 The mixture was stirred in the defoaming mode for 1 minute to obtain a specific layer (high refractive index layer) forming liquid C (high refractive index; n = 1.46).

[0639] [C 3-1 4] Preparation of specific layer (high refractive index light scattering layer) forming solution D

Specific layer (high refractive index layer) formation liquid of [C—3—1—3] 5 g of liquid C, and light scattering particles, A1 O fine powder “CR-1 (median particle size 400 nm)” is 0.1 l lg , Momentive 'Performance'

twenty three

Reals' Japan GK “Tospearl 145 (median particle size 5 m)” is weighed in a 1.09 g mixing container, and is subjected to centrifugal defoaming and mixing using a rotating / revolving mixer defoaming device. (High refractive index light scattering layer) Formation liquid D was obtained.

[0640] [C 3-2] Preparation of weir formation liquid

Preparation of [C 3-2-1] weir formation solution A (white condensation silicone resin)

[C 3—1-2] Low refractive index binder B liquid 4.2g, Al O fine powder “

twenty three

Measure CR-1 (median particle size 400nm) 1 · 407g, Nippon Aerosil Co., Ltd. Hydrophobic Humid Silica Aerosil RX200 1.302g into a mixing container, and use a rotating / revolving mixer deaerator. Centrifugal defoaming and mixing were performed. A white weir formation liquid A was obtained.

[0641] Preparation of [C 3-2-2] weir formation liquid B (white addition type silicone resin)

Silicone resin OE6336 manufactured by Toray Dow Cowing Co., Ltd. OE6336—A solution 2.0g, B solution 2.0g, Al O fine powder “CR-1 (median particle size 400nm)” 0.8g as light scattering particles, Japan Erosil Hydrophobic Fumed Silica Aerosil RX200 was weighed in a 0.7g mixing container, and centrifugal defoaming and mixing were performed using a rotating / revolving mixer defoaming device to obtain white weir forming liquid B It was.

[0642] [C 3-2 3] Preparation of weir formation liquid C (black addition type silicone resin)

Silicone resin OE6336 manufactured by Toray Dow Cowing Co., Ltd.

Measure 5g of black pigment BM-C made by Mitsubishi Materials as a black pigment in a 1.5g mixing container, and perform centrifugal defoaming and mixing using a rotating / revolving mixer defoaming device. Forming liquid C was obtained.

[0643] [C-4. Description of operation and evaluation of specific examples]

[Example C 15]

An example of manufacturing a light-emitting device having a weir and having a coating-type light guide layer is described below.

[Manufacture of light guide plates]

We prepared a wiring board with a recess for installing the LED in the center and a white solder paste applied to the area other than the recess. In addition, a reflector is attached to the recess.

Yes

A green LED was mounted in the recess. Next, a boundary portion was drawn on this substrate using the weir forming liquid A obtained in [C-3 2 1]. The boundary was drawn to be a weir surrounding the green LED. In addition, drawing of the boundary part was performed by using a pneumatic nozzle dispenser manufactured by Musashi Engineering Co., Ltd., and a taper nozzle TPN-22G (inner diameter: 0.4 mm) manufactured by the same company. The drawing speed at this time was 2 mm / sec. Furthermore, the pressure when pushing out the weir forming liquid A from the syringe was set to 0.364 MPa.

Thereafter, this was held in an air atmosphere at 150 ° C. and atmospheric pressure for 1.0 hour to cure the boundary. As a result, a boundary with a height of about 300 m and no ridgeline was obtained.

[0644] Next, the specific layer (low refractive index layer) forming liquid A was applied to the inner part of the boundary portion on the substrate using a dispenser. Here, the boundary acts as a weir to dam the specific layer (low refractive index layer) forming liquid A, and the specific layer (low refractive index layer) forming liquid A is applied only inside the boundary and the outside of the boundary There was no leaking power. In addition, the specific layer (low refractive index layer) forming liquid A does not penetrate into the recesses on the wiring board! /, And is applied to the specific layer (low refractive index layer) forming liquid A. The low refractive index layer formed in such a manner was made not to disturb the transmission of light transmitted through the recess.

This was held in an air atmosphere at 150 ° C. and atmospheric pressure for 1 hour to cure the specific layer (low refractive index layer) forming liquid A to form a low refractive index layer having a thickness of about 50 m.

[0645] Further, the specific layer (low refractive index layer) forming liquid B was applied onto the low refractive index layer inside the boundary using a dispenser. Also at this time, the boundary part acts as a weir to dam the specific layer (low refractive index layer) forming liquid B, and the specific layer (low refractive index layer) forming liquid B is applied only inside the boundary part. Did not leak outside.

Then, this was held in an air atmosphere at 150 ° C. and atmospheric pressure for 1 hour, and the specific layer (low refractive index layer) forming liquid B was cured to form a high refractive index layer having a thickness of about 200 m.

[0646] Further, the specific layer (high refractive index light scattering layer) forming liquid D was applied onto the high refractive index layer inside the boundary using a dispenser. Also at this time, the boundary part acts as a weir to dam the specific layer (high refractive index light scattering layer) forming liquid D, and the specific layer (high refractive index light scattering layer) forming liquid D is applied only inside the boundary part. There was a leaking force outside the boundary.

Then, this is held in an air atmosphere at 150 ° C. and atmospheric pressure for 1 hour, and the specific layer (high refractive index light scattering layer) forming liquid D is cured to give a high refractive index light scattering layer having a thickness of about 50 m. Formed. As described above, a light emitting device having a coating type light guide layer as schematically shown in FIG. 29 was manufactured.

[0647] [Evaluation]

The light emitting device having the obtained coating type light guide layer was energized to emit the green LED, and the state was observed.

Further, in the same manner as in Example C1, for each layer of the obtained light guide plate, evaluation of adhesion, solid-state Si-NMR spectrum measurement, silanol content, key content, hardness (Shore A), and ^^ Measured values.

[0648] Further, the refractive index of each layer of the light guide plate was measured in the following manner.

[Refractive index measurement]

The refractive index of each layer can be measured using known methods such as immersion method (solid object), Pulflich refractometer, Abbe refractometer, prism coupler method, interferometry, and minimum declination method. come. Each layer of this example has very little change in refractive index before and after curing. Therefore, each layer of the light guide plate of Example C-15 was measured with an Abbe refractometer (sodium D line (589 nm)) in the liquid state before curing. The forming liquid refractive index of (low refractive index layer, high refractive index layer, light scattering layer) was measured.

[0649] The results are shown in Table 10.

In Table 10, those with good adhesion in the results of evaluation of adhesion are indicated by “◯”.

Also, in the light extraction property section of Table 10, if the field power s “◯” of “power to shine far away,” it means that the light emitting surface has reached the vicinity of the weir, and if “△”. This means that the light emitting surface reaches the middle of the LED and weir, and “X” means that it emits light just above the chip! /.

Also, in the light extraction property section of Table 10, if the field power S “◯” of “the whole surface shines”, it means that the entire surface separated by the weir emits light, and “△” If there is, it means that the LED emits light to the middle of the boundary and “X” means that only the surface near the chip emits light.

Furthermore, in the light extraction property section of Table 10, if the “Light shielding at the boundary” column is “◯”, it means that only the surface inside the boundary emits light. If there is, it means that the light reaches the adjacent surface beyond the boundary and is emitted.

[0650] [Example C 16]

The light emitting device of Example C-16 was manufactured in the same manner as Example C-15 except that the specific layer (low refractive index layer) forming liquid B was used as the low refractive index layer forming liquid. Evaluation similar to 15 was performed. The results are shown in Table 10.

[0651] [Table 10]

[0652] [What can be seen from Examples C 15 and C 16]

Even if the weir material was made of silicone resin, the ability to form the light guide layer suitably without the weir and the light guide layer being peeled off. In addition, the difference in refractive index between the high-refractive index layer and the low-refractive index layer is larger than that of Example C-16. Example C-15 has a light propagation efficiency higher than that of Example C-16 and is more uniform than the LED. I was able to emit light.

[0653] [C 5] Other examples of production and evaluation of weirs

[C 5—1] Drawing and hardening of weir

[C- 5- 1-1] White weir (additional silicone resin) A square weir with a side of 1 cm was drawn on the slide glass using the white weir formation liquid B obtained in [C 3-2-2]. The weir was drawn using a pneumatic air dispenser made by Musashi Engineering Co., Ltd., and a taper nozzle TPN-22G (inner diameter 0.4 mm) made by the company. The drawing speed at this time was 3 mm / sec. Furthermore, the pressure when extruding the weir forming liquid B from the syringe was set to 150 kPa.

Thereafter, this was maintained in an air atmosphere at 150 ° C. and atmospheric pressure for 1.0 hour to cure the weir. As a result, a white weir with a height of about 300 μm and no ridgeline! / Was obtained.

[0654] [C 5— 1 2] Black weir (addition type silicone resin)

The weir was drawn in the same manner as in [C-5-1-1-1] except that the black weir formation liquid C obtained in [C3-2-3] was used on the slide glass. . This resulted in a black weir with a height of about 300 μm and no edge! /.

[0655] [C 5-2] Weir evaluation

Drawing the weir 'We applied stress to the hardened glass slide and divided it into two. We observed the shape of the fractured surface of the weir with a stereomicroscope, and investigated the height and cross-sectional structure of the weir. For the weir [C 5-11], a low refractive index layer, a high refractive index layer, and a light scattering layer are laminated and cured in the same manner as in Example C 15 inside the weir to break it and The fracture surface was observed with a microscope, and the adhesion and wettability between the weir and the light guide layer material were examined.

[0656] [C 5-3] Functions of various weirs

From the experimental examples of Example C 15 and [C 5-11], [C 5-12], it was found that both the condensation type silicone resin and the addition type silicone resin can form the weir suitably. In addition, the weir formed with any resin did not peel off the interface between the weir and the specific layer with good adhesion to the specific layer forming the light guide layer, and no cissing occurred when applying the specific layer. . It was also found that the weir can be colored white or black.

[0657] When two light guide layer areas that propagate different colors are separated by a weir, if the weir is white, the white weir reflects the light in each area and the light leaks to the adjacent area This has the effect of preventing color mixing. However, if the white weir is very thin or thin, the light shielding effect may be insufficient. In this case, it is considered that the use of the black weir can surely prevent the light mixing loss due to light absorption S and the color mixing of light to the adjacent area. It is.

Industrial applicability

[0658] The light guide member of the present invention can usually be made thicker, cracks are prevented from occurring in the thick film part, peeling from the substrate and peeling on the laminated surface are suppressed, and heat resistance is further improved. Excellent effects on light and light resistance. In addition, the light guide member of the present invention is usually flexible, has excellent adhesion during lamination, suppresses the generation of cracks even during long-term use, and suppresses peeling from the substrate and peeling on the laminated surface. Is done.

In the optical waveguide and the light guide plate formed using the light guide member of the present invention, the occurrence of cracks is suppressed even in the thick film portion where the degree of freedom in the film thickness design is high. Peeling is suppressed, and further excellent effects of heat resistance and light resistance are exhibited.

Therefore, the light guide member, the light guide, and the light guide plate of the present invention have extremely high industrial applicability in the respective fields. In particular, it is suitable for use in applications such as optical waveguides, illumination, electrical decoration, and displays.

[0660] Although the present invention has been described in detail using specific embodiments, it is obvious to those skilled in the art that various modifications can be made without departing from the spirit and scope of the present invention.

In addition, this application is a Japanese patent application filed on November 22, 2006 (Japanese Patent Application 2006-3 15765), a Japanese patent application filed March 30, 2007 (Japanese Patent Application 2007-093686), Japanese patent application filed on March 30, 2007 (Japanese Patent Application No. 2007-093687) and Japanese patent application filed on March 30, 2007 dated 30 March 2007 (Japanese Patent Application No. 2007-093688) Which is incorporated by reference in its entirety.

Claims

Claims [1] A light guide member in which two or more layers having different refractive indexes are laminated, wherein at least two layers of the layers are in contact with each other and satisfy the following conditions: . (1) In the solid Si-nuclear magnetic resonance spectrum, (i) the peak top position is in the chemical shift region of 40 ppm or more and Oppm or less, and the peak half-value width is 0.3 ppm or more and 3. Oppm or less. A peak selected from the group that also has a peak force, and (ii) the peak top position is in the region of chemical shift—80 ppm or more—less than 40 ppm, and the peak half-value width is 0.3 ppm or more and 5. Oppm or less, Have at least one. (2) The content of silicon is 10% by weight or more. (3) The content of silanol is 0.01% by weight or more and 10% by weight or less. (4) Hardness measured by Durometer Type A (Shore A) is 5 or more and 90 or less. [2] A light guide member formed by laminating two or more layers having different refractive indexes, wherein at least two layer forces of the layers are in contact with each other. (5) In the solid Si-nuclear magnetic resonance spectrum, (i) The peak top position is in the region of chemical shift-40 ppm or more and Oppm or less, and the peak half-value width is 0.5 ppm or more and 3. Oppm or less. And (ii) the peak selected at the peak top position is in the region of chemical shift — 80 ppm or more — less than 40 ppm, and the peak half-value width is 1. Oppm or more and 5. Oppm or less. Have at least one. (2) The content of silicon is 10% by weight or more. (3) The content of silanol is 0.01% by weight or more and 10% by weight or less. [3] The light guide member according to claim 1 or 2, wherein a refractive index of at least one of the layers in contact with each other is 1.45 or more. [4] The refractive index of at least one of the layers in contact with each other is 1.45 or more, and the refractive index of at least one other layer is less than 1.45. Item 3. The light guide member according to Item 2. [5]-^ Light guide member in which two or more layers having different values are laminated, and at least two-layer force of the layers in contact with each other satisfying the following conditions: .

(1) In the solid Si-nuclear magnetic resonance spectrum,

Has at least one peak selected from the group that also has force.

(2) The content of silicon is 10% by weight or more.

[6]-^ A light guide member in which two or more layers having different values are laminated,

At least two layer forces that touch each other among the layers satisfy the following conditions:

A light guide member.

(5) In the solid Si-nuclear magnetic resonance spectrum,

(ii) The peak top position is in the region of chemical shift—80 ppm or more—less than 40 ppm, and the peak half-value width is 1. Oppm or more and 5. Oppm or less.

Has at least one peak selected from the group that also has force.

(2) The content of silicon is 10% by weight or more.

[7] A light guide member in which two or more layers having different refractive indexes are laminated,

And at least one of the layers has the following characteristics:

Equipped with a light source whose main wavelength of emission peak is 500nm or less

A light guide member. (6) Contain polar groups at the interface with other layers.

(8) Having a siloxane bond.

[8] A light guide member in which two or more layers having different refractive indexes are laminated,

A light guide member.

(6) Contain polar groups at the interface with other layers.

(8) Having a siloxane bond.

[9]-^ A light guide member in which two or more layers having different values are laminated,

At least one layer force S of the layer, having the following characteristics, and

A light guide member.

(6) Contain polar groups at the interface with other layers.

(8) Having a siloxane bond.

[10]-^ A light guide member in which two or more layers having different values are laminated,

A light guide member.

(6) Contain polar groups at the interface with other layers.

(8) Having a siloxane bond.

[11] The light guide member according to any one of [7] to [10], wherein the layer satisfying the above conditions (6) to (8) contains a bull group and / or a hydrosilyl group.

[12] At least one layer force of the layer-^ 50

The light guide member according to any one of claims 5, 6, 9 and 10.

[13] At least one of the layers contains inorganic particles

The light guide member according to any one of claims 1 to 12, wherein the force is any one of the above.

[14] The median particle size of the inorganic particles is;! ~ LOnm

The light guide member according to claim 13.

[15] At least one of the layers contains inorganic particles having a median particle size of 0.05-50 Hm, and the layer and / or at least one other layer has a median particle size of 1 to; Contains inorganic particles

The light guide member according to any one of claims 1 to 14, wherein the force is any one of the above items.

[16] At least one of the layers contains a phosphor

The light guide member according to any one of claims 1 to 15, wherein:

[17] The angle formed between the side surface of the member and the laminated surface is not less than 30 degrees and not more than 80 degrees

The light guide member according to any one of claims 1 to 16, wherein the force is any one of the above items.

[18] Provided with a boundary portion penetrating at least two of the layers

The light guide member according to any one of claims 1 to 17, wherein the force is any one of the above.

[19] A method of manufacturing a light guide member comprising a light guide layer obtained by curing a fluid curable material on a substrate,

Providing a weir for partitioning the light guide layer on the substrate;

Coating the curable material on the substrate;

Curing the curable material.

A method for manufacturing a light guide member.

[20] providing the weir with a dispenser

The method for manufacturing a light guide member according to claim 19.

[21] A light guide member comprising a substrate, a light guide layer, and a weir that partitions the light guide layer,

The light guide layer has a high refractive index layer and a low refractive index layer;

The weir does not have a ridgeline

A light guide member.

[22] The light guide layer is formed by curing a curable material.

22. The light guide member according to claim 21, wherein:

[23] The light guide layer has a scattering layer

23. The light guide member according to claim 21 or claim 22, wherein

[24] The light guide layer has a phosphor-containing layer

24. The light guide member according to any one of claims 21 to 23, wherein:

[25] An optical waveguide, characterized by being formed using the light guide member according to any one of [1] to [18] and [18] to [21].

[26] A light guide plate formed using the light guide member according to any one of claims 1 to 18 and 21 to 24.