JP2002338833A - Composition for optical material, optical material, its manufacturing method, and liquid crystal display device and light-emitting diode obtained using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for an optical material hardly undergoing photodeterioration, having a small linear expansion coefficient and exhibiting a high optical transparency, an optical material, its manufacturing method, and a liquid crystal display device and a light-emitting diode each obtained using the same. SOLUTION: The composition for an optical material comprises as essential ingredients (A) an organic compound bearing in one molecule at least two carbon-carbon double bonds reactive with an SiH group, (B) a silicon compound bearing in one molecule at least two SiH groups, (C) a hydrosilylation catalyst, (D) a compound bearing in one molecule at least two hydrolyzable groups bonded to a metal atom and/or a semi-metal atom, and/or a partial condensate thereof, and (E) water and/or a water-generating compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical material, and more particularly to a composition for an optical material having a small linear expansion coefficient and high optical transparency, an optical material, a method for producing the same, and a method for using the same. The present invention relates to a liquid crystal display device and a light emitting diode.

[0002]

2. Description of the Related Art Materials having a low birefringence, a small photoelastic coefficient and a high optical transparency are used as optical materials for liquid crystal display devices. In the case of a material for a liquid crystal display device or the like, a material used in a manufacturing process needs to have high heat resistance. Conventionally, glass or the like has been used as a material satisfying such requirements.

[0003] Optical materials for liquid crystal display devices and the like are often used in the form of thin films or thin tubes or rods. In accordance with recent market demands, optical materials in the form of thinner films or thinner tubes or rods are used. Use is becoming necessary. However, conventionally used glass has a brittle property in terms of strength, so that the range of use has been limited.

As a tough material, there is a polymer material. For example, in the case of a thermoplastic resin, generally, when an aromatic skeleton is introduced in order to exhibit high heat resistance, the birefringence increases and the photoelastic coefficient increases. Therefore, it is difficult to achieve both high heat resistance and optical performance.

[0005] In the case of thermosetting resins, conventionally known thermosetting resins are generally colored and are not suitable for use in optical materials. Further, they generally have polarity, which is disadvantageous for optical performance. Therefore, for example, in a sealing material application of a light emitting diode, a transparent epoxy resin using an acid anhydride-based curing agent has been widely used as a special thermosetting resin. However, even in such a transparent epoxy resin, the moisture resistance is low due to the high water absorption of the resin, or the light resistance is low due to low light transmittance particularly to low wavelength light, or the resin is colored by light deterioration. Had the disadvantage that On the other hand, a silicone resin is used as a coating material having high light resistance and durability, but since it is generally soft and has a surface tackiness, a foreign matter may adhere to a light emitting surface during mounting, or a mounting device may be used. There is a problem that the light emitting surface is damaged.

In addition, since a polymer material generally has a large linear expansion coefficient and tends to have low dimensional stability during heat molding, various fillers may be added. In this case, a general particulate filler is added. Then, there is a problem that optical transparency is impaired.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to reduce light degradation, to reduce the coefficient of linear expansion, and to further increase optical transparency. An object of the present invention is to provide a composition for an optical material, an optical material, a method for manufacturing the same, and a liquid crystal display device and a light emitting diode using the same, which do not cause a problem that a light emitting surface is damaged by an appliance.

[0008]

Means for Solving the Problems In order to solve the above problems, the present inventors have made intensive studies and found that an organic compound containing at least two carbon-carbon double bonds having a reactivity with a SiH group in one molecule. A compound and at least two S
Produces a silicon compound containing an iH group, a hydrosilylation catalyst, a compound containing at least two hydrolyzable groups bonded to metal atoms and / or metalloid atoms in one molecule, and water and / or water. The inventors have found that the above problems can be solved by using a compound as an essential component in a composition for an optical material, and have accomplished the present invention.

That is, the present invention relates to (A) an organic compound containing at least two carbon-carbon double bonds reactive with a SiH group per molecule, and (B) at least two SiH groups per molecule. Group-containing silicon compound, (C) a hydrosilylation catalyst, (D) a compound containing at least two hydrolyzable groups in one molecule bonded to a metal atom and / or a metalloid atom, and / or a part thereof. An optical material composition (claim 1) comprising a condensate and (E) water and / or a compound that produces water as essential components, wherein the component (A) reacts with a SiH group. The composition for an optical material according to claim 1, which is an organic compound containing at least one vinyl group having a property in one molecule (claim 2), wherein the component (A) is a SiH group. Allyl reactive with The at least one claim 1 composition for optical materials, wherein the organic compounds containing in the molecule (claim 3), component (A),
The composition for an optical material according to claim 1, wherein the composition is 1,2-polybutadiene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, divinylbiphenyl, or bisphenol A diallyl ether (claim 4), The composition (A) according to claim 1, wherein the component (A) is triallyl isocyanurate or trivinylcyclohexane, and further comprises (F) a condensation catalyst as an essential component. The composition for an optical material according to any one of claims 1 to 5 (claim 6),
(F) The composition for an optical material according to claim 6, wherein the condensation catalyst is a Ti-based condensation catalyst (claim 7), wherein the metal atom of the component (D) is Al, Zn, Ga, G
8. One or more atoms selected from the group consisting of e, Sn, Mg, Ca, Ti, and Zr, and the semimetal atom is B and / or Si. The composition for an optical material according to claim 1, wherein the hydrolyzable group of the component (D) is one or more selected from the group consisting of an alkoxy group, a siloxy group, an acyloxy group, and a halogen group. The composition for an optical material according to any one of claims 1 to 8 (claim 9), wherein the optical material is a film for a liquid crystal. The composition for an optical material according to any one of claims 1 to 9, wherein the composition is a plastic cell for a liquid crystal. ) And the optical material is a light emitting diode. The composition for optical materials according to any one of claims 1 to 9, which is a sealing material (claim 12)
Wherein the composition for an optical material according to any one of claims 1 to 12 is previously mixed, and a part of a carbon-carbon double bond and a SiH group reactive with a SiH group in the composition or An optical material (Claim 13), which is obtained by reacting all the materials and curing the hydrolyzable groups bonded to the metal atoms and / or metalloid atoms by hydrolysis and condensation (Claim 13). The composition for an optical material according to claim 1 is mixed in advance, and a carbon-carbon double bond having reactivity with a SiH group in the composition is partially or entirely reacted with the SiH group, and a metal atom and / or a half atom is reacted. 14. A method for producing an optical material according to claim 13 by subjecting a hydrolyzable group bonded to a metal atom to a hydrolysis-condensation reaction (claim 14). A liquid crystal using the optical material according to claim 13. Display device (Request Is 15), a light emitting diode using the optical material according to claim 13 (claim 16).

Further, the light emitting diode of the present invention comprises the following (A)
An organic compound containing at least two carbon-carbon double bonds in one molecule reactive with a SiH group, (B) a silicon compound containing at least two SiH groups in one molecule, and (C) hydrosilylation. Catalyst, (D) metal atom and / or
Or a compound containing at least two hydrolyzable groups bonded to a metalloid atom in one molecule, and / or a partial condensate thereof, and (E) water and / or a compound that generates water as essential components. A light-emitting diode, wherein the light-emitting element is coated with a curable composition that is
The component (A) contains one vinyl group reactive with a SiH group.
18. The light-emitting diode according to claim 17, wherein the light-emitting diode is an organic compound containing at least one compound in a molecule, wherein the component (A) has one molecule of an allyl group reactive with a SiH group. 18. The light-emitting diode according to claim 17, wherein the light-emitting diode is an organic compound containing at least one component (C), wherein the component (A) is 1,2-polybutadiene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, 18. The light emitting diode according to claim 17, wherein the light emitting diode is pentadiene, divinyl biphenyl, or bisphenol A diallyl ether.
Wherein component (A) is triallyl isocyanurate,
Alternatively, the light-emitting diode according to claim 17, which is trivinylcyclohexane (claim 21), wherein the curable composition further contains (F) a condensation catalyst as an essential component. Claims 17 to 2
2. The light-emitting diode according to claim 1 (claim 2).
2) and (F) the condensation catalyst is a Ti-based condensation catalyst, wherein the light-emitting diode according to claim 22 (claim 23), wherein the metal atom of component (D) is A
1, one or more atoms selected from the group consisting of 1, Zn, Ga, Ge, Sn, Mg, Ca, Ti, and Zr, and the semimetal atom is B and / or Si. Item 24. The light emitting diode according to any one of items 17 to 23 (claim 24), wherein the hydrolyzable group of the component (D) is an alkoxy group, a siloxy group, an acyloxy group,
25. The light-emitting diode according to claim 17, wherein the light-emitting diode is one or more groups selected from the group consisting of: and a halogen group.

Further, in the light emitting diode according to the present invention, the curable composition may be mixed before coating the light emitting device, and the curable composition may be mixed with SiH groups in the composition.
26. The method according to claim 17, wherein a part or all of the carbon double bond and the SiH group react, and a hydrolyzable group bonded to a metal atom and / or a metalloid atom undergoes a hydrolysis condensation reaction. The light emitting diode according to claim 1, wherein the light emitting element has an inorganic compound layer containing silicon on a surface thereof, and is obtained from the curable composition in contact with the inorganic compound layer. 27. The light-emitting diode according to claim 17, further comprising a light-transmitting encapsulant, wherein the inorganic compound layer emits light from the light-emitting element. 28. A fluorescent substance capable of absorbing at least a part of light to be emitted and emitting light having another wavelength.
28. A light emitting diode according to claim 28. The method for manufacturing a light emitting diode according to claim 29 is characterized in that (A)
An organic compound containing at least two carbon-carbon double bonds in one molecule reactive with a SiH group, (B) a silicon compound containing at least two SiH groups in one molecule, and (C) hydrosilylation. Catalyst, (D) metal atom and / or
Or a compound containing at least two hydrolyzable groups bonded to a metalloid atom in one molecule, and / or a partial condensate thereof, and (E) water and / or a compound that generates water as essential components. A method for producing a light-emitting diode in which a light-emitting device is coated using a curable composition, wherein the curable composition is mixed in advance before coating the light-emitting device and reacts with SiH groups in the composition. A carbon-carbon double bond having a property and part or all of the SiH group react, and a hydrolyzable group bonded to a metal atom and / or a metalloid atom undergoes a hydrolytic condensation reaction.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

First, the component (A) in the present invention will be described. The component (A) is not particularly limited as long as it is an organic compound containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule. The organic compound does not include a siloxane unit (Si-O-Si) such as a polysiloxane-organic block copolymer or a polysiloxane-organic graft copolymer, and contains only C, H, N, O, S, and halogen as constituent elements. It is preferable that it contains. In the case of those containing a siloxane unit, there are problems of gas permeability and repellency.

The bonding position of the carbon-carbon double bond reactive with the SiH group is not particularly limited, and may be anywhere in the molecule.

The organic compound (A) can be classified into an organic polymer compound and an organic monomer compound.

Examples of the organic polymer type compound include polyether type, polyester type, polyarylate type, polycarbonate type, saturated hydrocarbon type, unsaturated hydrocarbon type, and the like.
Polyacrylate, polyamide, phenol-formaldehyde (phenol resin), and polyimide compounds can be used.

Examples of the organic monomer compound include, for example,
Examples include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene; aliphatic hydrocarbons such as linear and alicyclic; heterocyclic compounds and mixtures thereof.

The carbon-carbon double bond reactive with the SiH group of the component (A) is not particularly limited, but may be represented by the following general formula (I):

[0019]

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A group represented by the formula (wherein R ¹ represents a hydrogen atom or a methyl group) is preferred from the viewpoint of reactivity. Also, from the availability of raw materials,

[0021]

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The group represented by is particularly preferred.

The carbon-carbon double bond reactive with the SiH group of the component (A) is represented by the following general formula (II):

[0024]

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An alicyclic group represented by the formula (wherein R ¹ represents a hydrogen atom or a methyl group) is preferred from the viewpoint that the cured product has high heat resistance. Also, from the availability of raw materials,

[0026]

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The alicyclic group represented by the following is particularly preferred.

The carbon-carbon double bond reactive with the SiH group may be directly bonded to the skeleton of the component (A), or may be covalently bonded via a divalent or higher valent substituent. The divalent or higher substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms.
Those containing only N, O, S, and halogen are preferable. Examples of these substituents include

[0029]

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[0030]

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[0031] Two or more of these divalent or more substituents are connected by a covalent bond to form one
It may constitute a substituent having a valence of at least.

Examples of the group covalently bonded to the above skeleton include vinyl, allyl, methallyl, acryl, methacryl, 2-hydroxy-3- (allyloxy) propyl, and 2-allylphenyl. Group, 3-allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group,
-(Allyloxy) phenyl group, 2- (allyloxy)
Ethyl group, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group,

[0033]

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And the like.

Specific examples of component (A) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetrayl Allyloxyethane, dialylidenepentaerythrit, triallyl cyanurate, triallyl isocyanurate, 1,2,4-
Trivinylcyclohexane, divinylbenzenes (purity 50 to 100%, preferably 80 to 100%
), Divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, 1,2-polybutadiene (1,2-polybutadiene having a 1,2 ratio of 10 to 100%, preferably , 2
Ratio of 50 to 100%), allyl ether of novolak phenol, allylated polyphenylene oxide,

[0036]

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[0037]

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In addition, there may be mentioned a conventionally known epoxy resin in which a glycidyl group is replaced with an allyl group.

As the component (A), a low molecular weight compound, which is difficult to be expressed separately as a skeleton portion and a carbon-carbon double bond as described above, can also be used. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene, and decadiene; and cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene, and norbornadiene. Aliphatic cycloolefin compounds, substituted aliphatic cyclic olefin compounds such as vinylcyclopentene, vinylcyclohexene and the like.

From the viewpoint that the heat resistance can be further improved, the component (A) contains a carbon-carbon double bond reactive with a SiH group in an amount of 0.000 g / g of the component (A).
What is necessary is just to contain 1 mol or more.
Those containing 0.005 mol or more per g are preferable, and those containing 0.008 mol or more are particularly preferable.

The number of carbon-carbon double bonds reactive with the SiH group of the component (A) should be at least two per molecule on average, but if the mechanical strength is desired to be further improved, 2 is required. Preferably, the number is more than three, and more preferably three or more. When the number of carbon-carbon double bonds having reactivity with the SiH group of the component (A) is 1 or less per molecule, the reaction with the component (B) results in only a graft structure and not a crosslinked structure. .

As the component (A), those having fluidity at a temperature of 100 ° C. or less are preferable for obtaining uniform mixing with other components and good workability, and may be linear or branched. Although the molecular weight is not particularly limited, 50
Any of ~ 100,000 can be suitably used. When the molecular weight is 100,000 or more, the raw material generally has a high viscosity and is inferior in workability.
The effect of cross-linking due to reaction with the group is hardly exhibited.

The component (A) preferably has a low content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group from the viewpoint of suppressing coloration, particularly yellowing, and preferably has a low content of a phenolic hydroxyl group and / or Those containing no compound having a derivative of a phenolic hydroxyl group are more preferred. The phenolic hydroxyl group in the present invention refers to a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, a naphthalene ring, an anthracene ring, and the like, and a phenolic hydroxyl group derivative refers to a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted by an alkyl group such as a methyl group and an ethyl group, an alkenyl group such as a vinyl group and an allyl group, and an acyl group such as an acetoxy group.

From the viewpoint of good optical characteristics such as low birefringence and low photoelastic coefficient and good weather resistance, the weight ratio of the aromatic ring to the component (A) is preferably It is preferably 50% by weight or less, more preferably 40% by weight or less, even more preferably 30% by weight or less. Most preferred are those that do not contain an aromatic hydrocarbon ring.

From the coloring properties and optical properties of the obtained cured product, as the component (A), vinyl cyclohexene, dicyclopentadiene, triallyl isocyanurate, 2,2
-Diallyl ether of -bis (4-hydroxycyclohexyl) propane, 1,2,4-trivinylcyclohexane is preferred, triallyl isocyanurate, 2,2-
The diallyl ether of bis (4-hydroxycyclohexyl) propane, 1,2,4-trivinylcyclohexane, is particularly preferred.

Next, the compound (B) having a SiH group will be described.

The compound having a SiH group which can be used in the present invention is not particularly limited.
/ 15194, compounds having at least two SiH groups in one molecule can be used.

Of these, from the viewpoint of availability, a chain and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule is preferable, and has good compatibility with the component (A). From the viewpoint of, the following general formula (III)

[0049]

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(Wherein R ² represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10), and a cyclic group having at least two SiH groups in one molecule. Polyorganosiloxanes are preferred. Note that the substituent R ² in the compound represented by the general formula (III) is preferably composed of C, H, and O, and more preferably a hydrocarbon group.

In addition, from the viewpoint of having good compatibility with the component (A), one selected from a chain and / or cyclic polyorganosiloxane and an organic compound having a carbon-carbon double bond. Reaction products with more than one compound (hereinafter referred to as component (G)) are also preferred. In this case, in order to further increase the compatibility of the reactant with the component (A), a product obtained by removing unreacted siloxanes and the like from the reactant by devolatilization or the like can be used.

The component (G) is an organic compound containing at least one carbon-carbon double bond having a reactivity with a SiH group in one molecule, and those having the same description as the component (A) can also be used. . The organic compound of the component (G) may be the same as or different from the organic compound of the component (A). It is also possible to use one or a mixture of two or more. When it is desired to increase the compatibility of the component (B) with the component (A), the component (G) is preferably the same as the component (A).

The chain and / or cyclic polyorganosiloxane to be reacted with the organic compound (G) is preferably 1,3 from the viewpoint of industrial availability and good reactivity in the case of reaction. , 5,7-Tetramethylcyclotetrasiloxane is preferred.

As the component (B), similarly to the component (A),
From the viewpoint of suppressing coloration, particularly yellowing, those having a low content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group are preferable, and those not containing a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group. Is more preferred. The phenolic hydroxyl group in the present invention is a benzene ring, a naphthalene ring,
A hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by an anthracene ring or the like, and a derivative of a phenolic hydroxyl group means a hydrogen atom of the above-mentioned phenolic hydroxyl group is a methyl group, an alkyl group such as an ethyl group, a vinyl group, an allyl group. And a group substituted by an alkenyl group such as a group or an acyl group such as an acetoxy group.

From the viewpoint of good optical characteristics such as low birefringence and low photoelastic coefficient and good weather resistance, the weight ratio of the aromatic ring to the component (B) is preferably It is preferably 50% by weight or less, more preferably 40% by weight or less, even more preferably 30% by weight or less. Most preferred are those that do not contain an aromatic hydrocarbon ring.

The component (B), which is more preferable from the viewpoint of good optical properties, includes a reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane and vinylcyclohexene, 1,3,5,7-tetra Reaction product of methylcyclotetrasiloxane and dicyclopentadiene,
Reaction product of 5,7-tetramethylcyclotetrasiloxane and triallyl isocyanurate, 1,3,5,7-tetramethylcyclotetrasiloxane and 2,2-bis (4-
(Hydroxycyclohexyl) propane diallyl ether reactant; 1,3,5,7-tetramethylcyclotetrasiloxane and 1,2,4-trivinylcyclohexane reactant; particularly preferred component (B) is A reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane and triallyl isocyanurate,
5,7-tetramethylcyclotetrasiloxane and 2,2
A reaction product of diallyl ether of -bis (4-hydroxycyclohexyl) propane, and a reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane and 1,2,4-trivinylcyclohexane.

The mixing ratio of the components (A) and (B) as described above is not particularly limited as long as the required strength is not lost, but the number (Y) of the number of SiH groups (Y) in the component (B) is (A). )) The ratio of the number of carbon-carbon double bonds (X) in the component is
2.0 ≧ Y / X ≧ 0.9, preferably 1.8
≧ Y / X ≧ 1.0 is more preferable. When 2.0 <Y / X, sufficient curability may not be obtained, and sufficient strength may not be obtained. When Y / X <0.9, the carbon-carbon double bond becomes excessive and It can cause coloring.

Next, the hydrosilylation catalyst as the component (C) will be described.

Hydrosilation catalysts include hydrosilyl
The catalyst is not particularly limited as long as it has catalytic activity for the oxidation reaction.
For example, simple platinum, alumina, silica, carbon black
Solid platinum supported on a carrier such as chloroplatinic acid, salt
Complex of chloroplatinic acid with alcohol, aldehyde, ketone, etc.
, A platinum-olefin complex (for example, Pt (CH₂= C
H ₂)₂(PPh₃)₂, Pt (CH₂= CH₂)₂C
l₂), A platinum-vinylsiloxane complex (for example, Pt
(ViMe₂SiOSiMe₂Vi)_n, Pt [(Me
ViSiO)₄]_m), Platinum-phosphine complexes (eg,
If Pt (PPh₃)₄, Pt (PBu₃)₄),platinum
-Phosphite complex (for example, Pt [P (OPh)₃]
₄, Pt [P (OBu)₃]₄(Where Me is methyl
Group, Bu is butyl group, Vi is vinyl group, Ph is phenyl
Represents a group, and n and m represent integers. ), Dicarbonyldi
Chloroplatinum, Karstedt touch
Medium, also Ashby US Pat.
59601 and 3159662.
Platinum-hydrocarbon complex, as well as Lamorrow
oreaux) in U.S. Pat. No. 3,220,972.
The platinum alcoholate catalyst described in the above. Further
No. 35169 to Modic.
No. 46, a platinum chloride-olefin composite
Bodies are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , and RhAl ₂ O
₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlC
l ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiC
l _4, and the like.

Among these, chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex and the like are preferable from the viewpoint of catalytic activity. These catalysts may be used alone or in combination of two or more.

The amount of the catalyst to be added is not particularly limited. However, in order to have sufficient curability and to keep the cost of the composition relatively low, 10 ⁻⁸ to 10 ⁻¹⁰ to 1 mol of SiH groups are used.
^-1 mol is preferred, more preferably 10 ^-6.
The range is from 10 to 10 ^-2 mol.

Further, a co-catalyst is used in combination with the above-mentioned catalyst.
Is possible, for example, triphenylphosphine
1,2-diester such as dimethyl maleate
Compound, 2-hydroxy-2-methyl-1-butyne
Acetylene alcohol-based compounds such as
Amine compounds such as yellow compounds and triethylamine
No. The amount of the cocatalyst added is not particularly limited.
10 moles per mole of medium ^-2-10²Molar range preferred
And more preferably 10^-1In the range of 10 to 10 moles
You.

Further, a curing retarder can be used for the purpose of improving the storage stability of the composition of the present invention or for controlling the reactivity of the hydrosilylation reaction in the production process. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, and an organic peroxide, and these may be used in combination. As a compound containing an aliphatic unsaturated bond, propargyl alcohols,
Examples include ene-yne compounds, maleic esters and the like. Examples of the organic phosphorus compound include triorganophosphines, diorganophosphines, organophosphones, and triorganophosphites. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide, and the like. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of the tin compound include stannous halide dihydrate, stannous carboxylate, and the like.
As the organic peroxide, di-t-butyl peroxide,
Examples thereof include dicumyl peroxide, benzoyl peroxide, t-butyl perbenzoate and the like.

Among these curing retarders, benzothiazole, thiazole, dimethyl maleate, and 3-hydroxy-3-methyl-1-butyne are preferred from the viewpoint of good retardation activity and good raw material availability.

[0066] The addition amount of the curing retarder, with respect to hydrosilylation catalyst 1mol ^used, and is preferably from 10 -1 to 10 ³ mols, more preferably from 1 to 50 mol.

Next, a compound containing at least two hydrolyzable groups bonded to a metal atom and / or a metalloid atom as the component (D) in one molecule and / or a partial condensate thereof will be described.

As the metal atom of the component (D), any atom located on the left side of the line connecting B and At in the long period table can be used. Among them, in terms of the fact that the raw materials are easily available industrially and have high industrial utility, A
1, Zn, Ga, Ge, Sn, Mg, Ca, Ti, Zr
Is preferable, and Al and Ti are more preferable.

As the metalloid atom of the component (D), any atom located on or adjacent to the line connecting B and At in the long period table can be used. Of these, B and Si are preferred, and Si is more preferred, in that the raw materials are easily available industrially and have high industrial practicality.

These metal atoms and / or metalloid atoms may be of a single type or a combination of a plurality of types.

As the hydrolyzable group bonded to the metal atom and / or metalloid atom of the component (D), various groups can be used as long as they have hydrolytic condensation reactivity. Group, ethoxy group, propoxy group,
Isopropoxy group, butoxy group, t-butoxy group, se
c-butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, cyclohexyloxy group, benzyloxy group, phenoxy group, methoxymethoxy group, 2-methoxyethoxy group,

[0072]

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Siloxy groups such as alkoxy group, trimethylsiloxy group, triphenylsiloxy group, dimethylphenylsiloxy group, methyldiphenylsiloxy group, dimethyl t-butylsiloxy group, etc., formyloxy group, acetyloxy group, ethylcarboxy group, propylcarboxy group Groups, acyloxy groups such as phenylcarboxyl group, methoxycarboxyl group and phenoxycarboxyl group, halogen groups such as chloro group and bromo group, and amino groups such as dimethylamino group and diphenylamino group.

An alkoxy group, a siloxy group, an acyloxy group and a halogen group are preferred from the viewpoint that the reactivity is good and the hydrosilylation reaction is hardly inhibited. Among them, an alkoxy group and a siloxy group are more preferable. In the case of an acyloxy group and a halogen group, there are problems such as corrosion of a mold at the time of curing because they have an acidic volatile component. An alkoxy group is more preferable in that the leaving group is easily removed by volatilization, and a methoxy group, an ethoxy group, an isopropoxy group, and a butoxy group are particularly preferable.

Examples of the component (D) described above include:
Tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraphenoxysilane, methyltriphenoxysilane, dimethyldiphenoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, Alkoxysilanes such as phenyltriethoxysilane, diphenyldiethoxysilane, tetrapropoxysilane and tetrabutoxysilane; acyloxysilanes such as tetraacetoxysilane; siloxysilanes such as tetra (trimethylsiloxy) silane; tetrachlorosilane; Halogenated silanes such as chlorosilane, aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoate Sid, aluminum tributoxide, aluminum sec-butoxydiisopropoxide, aluminum trisec-butoxide, aluminum ethyl acetoacetate diisopropoxide, aluminum trisethyl acetoacetate, aluminum acetylacetonate bisethylacetoacetate, aluminum trisacetylacetate, etc. Aluminum alkoxides, aluminum halides such as aluminum chloride, alkoxymethoxys such as tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, titanium halides such as titanium tetrachloride, boron trimethoxide Alkoxides such as, boron triethoxide, boron triisopropoxide, boron tributoxide , Zirconium alkoxides such as zirconium tetraisopropoxide, magnesium alkoxides such as magnesium methoxide, magnesium ethoxide and magnesium isopropoxide, calcium alkoxides such as calcium methoxide, calcium ethoxide and calcium isopropoxide, dimethoxy zinc , Diethoxy zinc, diisopropoxy zinc, and other alkoxy zincs, and partial condensates thereof.

Tetramethoxysilane and tetraethoxysilane are preferred from the viewpoint of good reactivity and a high effect of reducing the coefficient of linear expansion, and from the viewpoint that the reactivity is good and the toughness of the obtained cured product is not easily impaired. For this reason, methyltrimethoxysilane and methyltriethoxysilane are preferred.

As the component (D), one of the above components may be used, or a plurality of components may be used in combination.

The component (D) can be added in any amount, but the amount obtained by subjecting the component (D) to a hydrolysis-condensation reaction is 5 to 70% by weight of the total composition, preferably It is preferable to add so as to be 10 to 50% by weight. If the amount is too small, the effect of reducing the linear expansion coefficient is small, and if it is too large, the obtained cured product may be brittle.

A compound having one hydrolyzable group bonded to a metal atom and / or a metalloid atom in one molecule may be used in combination with the component (D). Examples of these compounds include monoalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, methyldiphenylmethoxysilane, methyldiphenylethoxysilane, triphenylethoxysilane, and triphenylmethoxysilane. Can be mentioned.

Next, the component (E) will be described.

As the component (E), a compound that produces water can be used in addition to water. Examples of the compound that generates water include compounds having a silanol group such as trimethylsilanol and triphenylsilanol that generate water by condensation, silica adsorbing water, and organic and / or inorganic crystals containing water of crystallization. Can be mentioned.

As the component (E), one of the above-mentioned components may be used, or a plurality of components may be used in combination.

The component (E) may be added in any amount. However, the amount of water generated from the component (E) is less than (D).
The amount is preferably 50 to 200 mol%, more preferably 80 to 120 mol%, based on the theoretical amount of water required for hydrolyzing and condensing all the hydrolyzable groups of the components. Even if the amount is small or large, it may be difficult to obtain the effect of reducing the coefficient of linear expansion.

Next, the component (F) will be described.

The composition of the present invention may optionally contain (F) a condensation catalyst. Examples of the condensation catalyst include hydrochloric acid, p-toluenesulfonic acid, sulfuric acid, acetic acid, phosphoric acid, activated clay, Protic acid catalysts such as boric acid, trifluoroacetic acid, and trifluoromethanesulfonic acid; Lewis acid catalysts such as iron chloride, aluminum chloride, titanium tetrachloride, boron trifluoride, and tin tetrachloride; sodium hydroxide, potassium hydroxide, and sodium Methoxide, alkali metal or alkaline earth metal hydroxide or alkoxide such as potassium t-butoxide and the like, tetraalkylammonium hydroxide, tetraalkylphosphonium hydroxide, alkali catalyst such as potassium carbonate, pyridine, picoline, lutidine, Pyrazine, piperidone, piperidine, Perazine, pyrazole, pyridazine, pyrimidine, pyrrolidine, butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, Diphenylguanidine,
2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-
Amine compounds such as 4-methylimidazole and 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), or salts of these amine compounds with carboxylic acids, etc., obtained from excess polyamines and polybasic acids. Low molecular weight polyamide resin, reaction product of excess polyamine and epoxy compound, silane coupling agent having amino group such as γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, etc. Is mentioned. Further, a fluorine-based compound such as tetrabutylammonium fluoride, potassium fluoride, and sodium fluoride can also be used.
In addition, Sn, Sb, Zn, Fe, Co, Ti, Al,
Conventionally known condensation catalysts (silanol condensation catalysts) such as organic acid salts such as Zr and B, and various metal-based condensation catalysts such as alkoxides and chelates are exemplified. Specific examples of the Sn-based condensation catalyst include tin (II) methoxide, tin (II) ethoxide, tin (II) 2,4-pentanedionate, tin (II) octoate, tin (II) acetate, dibutyltin dilaurate, Dibutyltin malate, dibutyltin diacetate, tin naphthenate, a reaction product of dibutyltin oxide and phthalate, dibutyltin diacetylacetonate, and the like.Specific examples of the Sb-based condensation catalyst include:
Lead (II) hexafluoropentanedionate, lead (I
I) 2,4-pentanedionate, lead (II) 2,2
6,6-tetramethyl-3,5-heptanedionate,
Specific examples of the Zn-based condensation catalyst include dimethoxy zinc, diethoxy zinc, zinc methoxy ethoxide, zinc 2,4-pentanedionate, zinc acetate, zinc 2-ethylhexanoate, and formic acid. Examples include zinc, zinc methacrylate, zinc neodecanoate, zinc undecylenate, and zinc octylate. Specific examples of the Fe-based condensation catalyst include iron (III) benzoylacetonate, iron (III) ethoxide, and iron (III) 2. , 4
-Pentanedionate, iron (III) trifluoropentanedionate, iron octylate and the like. Specific examples of the Co-based condensation catalyst include cobalt (II) 2,4-
Examples include pentanedionate, cobalt (III) 2,4-pentanedionate, and the like. Specific examples of the Ti-based condensation catalyst include diisopropoxybis (ethyl acetoacetate) titanium and diisopropoxybis (methyl acetoacetate). Titanium, diisopropoxybis (acetylacetone) titanium, dibutoxybis (ethyl acetoacetate) titanium and the like are mentioned. Specific examples of the Al-based condensation catalyst include:
Aluminum triisopropoxide, aluminum triisobutoxide, aluminum diisopropoxy second butoxide, aluminum diisopropoxide acetylacetonate, aluminum diisobutoxide acetylacetonate, aluminum diisopropoxide ethyl acetoacetate, aluminum diisopropoxide 2-butoxide ethyl acetoacetate; specific examples of the Zr-based condensation catalyst include zirconium tetrabutoxide, zirconium tetraisopropoxide, zirconium tetramethoxide, zirconium tributoxide monoacetylacetonate, zirconium dibutoxide bisacetylacetonate , Zirconium monobutoxide trisacetylacetonate, zirconium tributoxide monoethylacetoacetate , Zirconium dibutoxide bisethyl acetoacetate, zirconium monobutoxide trisethyl acetoacetate, zirconium tetraacetylacetonate, zirconium tetraethylacetoacetate, and the like. Specific examples of the B-based condensation catalyst include boron methoxide, boron ethoxide, and boron n. −
Butoxide and the like.

Among these, neutral organometallic compounds are preferred from the viewpoint that the hydrosilylation reaction is not easily inhibited, and Ti-based condensation catalysts and Al-based condensation catalysts are more preferred. Particularly preferred catalysts are Ti-based condensation catalysts. It is a catalyst.

As the component (F), one of the above-mentioned components may be used, or a plurality of components may be used in combination.

The component (F) may be added in any amount, but may be added in an amount of 0.01 to 100 parts by weight of the component (D).
The content is preferably from 20 to 20 parts by weight, more preferably from 0.3 to 10 parts by weight. If the amount is too small, it may be difficult to obtain the effect of reducing the linear expansion coefficient in the obtained cured product, and if it is too large, it may be colored.

As the composition of the present invention, various combinations can be used as described above. From the viewpoint of good heat resistance, the cured product obtained by curing the composition has a Tg of 50 ° C. or more. Are preferable, those having a temperature of 100 ° C. or higher are more preferable, and those having a temperature of 150 ° C. or higher are particularly preferable.

The composition of the present invention can be directly formed into a film or the like, but the composition can be dissolved in an organic solvent to form a varnish. Solvents that can be used are not particularly limited, and if specifically exemplified,
Hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane,
Ether solvents such as diethyl ether, acetone, ketone solvents such as methyl ethyl ketone, chloroform,
Halogen solvents such as methylene chloride and 1,2-dichloroethane can be suitably used. The solvent can be used as a mixed solvent of two or more kinds. As the solvent,
Preferred are toluene, tetrahydrofuran and chloroform. The amount of the solvent used is based on 1 g of the component (A) used.
It is preferably used in the range of 0 to 10 mL, and 0.5 to 5 mL.
It is more preferably used in the range of mL, and particularly preferably used in the range of 1-3 mL. If the amount is small, it is difficult to obtain the effect of using a solvent such as a low viscosity,
In addition, when the amount is large, the solvent remains in the material, which tends to cause problems such as thermal cracks. Further, the cost is disadvantageous and the industrial use value is reduced.

The composition of the present invention further comprises an antioxidant, a radical inhibitor, an ultraviolet absorber, an adhesion improver, a flame retardant, a surfactant, a storage stability improver, an ozone deterioration inhibitor, a light stabilizer. , Thickener, plasticizer, coupling agent, antioxidant, heat stabilizer, conductivity imparting agent, antistatic agent, radiation blocking agent, nucleating agent, phosphorus-based peroxide decomposer, lubricant, pigment, metal-free An activator, a physical property modifier and the like can be added as long as the object and effects of the present invention are not impaired. In addition, as a coupling agent, a silane coupling agent is mentioned, for example. The silane coupling agent is not particularly limited as long as it has at least one functional group reactive with an organic group and at least one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acryl group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handleability. From the viewpoints of properties and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity. Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl)
Alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane ,
Examples thereof include alkoxysilanes having a methacryl group or an acryl group such as methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

Further, various additives for improving the characteristics of light emitting diodes may be added to the composition of the present invention. As an additive, for example, a fluorescent substance such as a yttrium aluminum garnet-based fluorescent substance activated with cerium, which absorbs light from a light emitting element and emits longer-wavelength fluorescence,
Coloring agents such as bluing agents that absorb specific wavelengths, silicon oxides such as titanium oxide, aluminum oxide, silica and quartz glass for diffusing light, talc, calcium carbonate, melamine resin, CTU guanamine resin, benzoguanamine resin, etc. And inorganic or organic diffusing materials such as the above, glass, metal oxides such as aluminosilicate, and heat conductive fillers such as metal nitrides such as aluminum nitride and boron nitride.

The additive for improving the characteristics of the light-emitting diode may be contained uniformly or may be contained with a gradient in the content. Such a filler-containing resin portion can be formed as a mold member behind the light emitting surface by flowing the resin containing the filler after flowing the resin for the mold member on the front surface of the light emitting surface into the mold. Also, after forming the mold member, the lead terminals are covered by applying tape from both front and back surfaces, and in this state, the entire lead frame is immersed in the lower half of the light emitting diode mold member in a tank containing a filler-containing resin, and then pulled up. And dried to form a filler-containing resin portion.

The optical material referred to in the present invention generally means a material used for the purpose of transmitting light such as visible light, infrared light, ultraviolet light, X-ray, and laser through the material.

More specifically, a liquid crystal display such as a substrate material in the liquid crystal display field, a light guide plate, a prism sheet, a deflecting plate, a retardation plate, a viewing angle correction film, an adhesive, and a liquid crystal film such as a polarizer protective film. Material around the device. In addition, color PDP (plasma display) encapsulants, anti-reflection films, optical correction films, housing materials, front glass protection films, front glass replacement materials, adhesives expected as next-generation flat panel displays; Light emitting element molding material, light emitting diode sealing material, front glass protection film, front glass substitute material, adhesive used in display devices;
Also, substrate materials for plasma-addressed liquid crystal (PALC) displays, light guide plates, prism sheets, polarizing plates, retardation plates, viewing angle correction films, adhesives, polarizer protective films; and front glass for organic EL (electroluminescence) displays. Protective film, alternative material for front glass, adhesive; various film substrates in field emission display (FED); protective film for front glass, alternative material for front glass, adhesive.

In the field of optical recording, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-
R / DVD-RAM, MO / MD, PD (phase change disk), disk substrate material for optical card, pickup lens, protective film, sealing material, adhesive, etc.

In the field of optical instruments, materials for steel camera lenses, finder prisms, target prisms,
The viewfinder cover and light receiving sensor. Also, it is a shooting lens and a finder of a video camera. Further, it is a projection lens of a projection television, a protective film, a sealing material, an adhesive or the like. Materials for optical sensing devices such as lenses, sealing materials, adhesives, and films.

In the field of optical components, there are fiber materials, lenses, waveguides, sealing materials for elements, adhesives, etc. around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. In the case of an optical passive component or an optical circuit component, it is a lens, a waveguide, a sealing material for a light emitting element, an adhesive or the like. Optoelectronic integrated circuits (OEI
C) Peripheral substrate material, fiber material, element sealing material,
An adhesive or the like.

In the optical fiber field, it is an optical fiber for industrial use such as illumination and light guide for decorative display, display and sign, etc., and for communication infrastructure and for connecting digital equipment in home.

The semiconductor integrated circuit peripheral material is a resist material for microlithography for LSI and super LSI materials.

In the field of automobiles and transportation equipment, lamp reflectors for automobiles, bearing retainers, gears, corrosion-resistant coatings, switches, headlamps, engine parts, electric parts, various interior and exterior parts, drive engines, brake oil tanks, Rustproof steel plates for automobiles, interior panels,
It is an interior material, protection and bundling wire, fuel hose, car lamp, and glass substitute. Further, it is a double glazing for railway vehicles. Also, a toughening agent for aircraft structural materials,
Peripheral components for the engine, wireness for protection and binding, and corrosion-resistant coating.

In the architectural field, there are materials for interior and processing, electric covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a film for house covering.

As next-generation optical / electronic functional organic materials,
Organic EL element peripheral materials, organic photorefractive elements, light-to-light conversion devices such as optical amplifier elements, optical operation elements, substrate materials around organic solar cells, fiber materials, element sealing materials, adhesives, and the like.

The composition for an optical material of the present invention is mixed in advance, and a part or all of the SiH group is reacted with a carbon-carbon double bond having a reactivity with the SiH group in the composition, and the metal atom and / or Alternatively, an optical material can be obtained by curing by subjecting a hydrolyzable group bonded to a metalloid atom to a hydrolysis-condensation reaction.

Various methods can be used for the mixing, but a mixture of the component (A) with the component (C) and the component (E) and a mixture of the component (B) with the component (D). Preferred is a method of mixing them. When the method of mixing the component (C) with the mixture of the component (A), the component (B), the component (D), and the component (E), it is difficult to control the reaction. When the method of mixing the component (B) with the component (C) and the component (D) mixed with the component (A) and the component (E) is mixed, the method of mixing the component (B) in the presence of the component (C) ) The components may react with the moisture in the environment and may deteriorate during storage.
When the components (B) and (E) are mixed and stored,
Since they may deteriorate during storage or the like, they are preferably contained in another component. When the component (F) is used, the component (F) and the component (D) or
Since the component (F) and the component (E) may have high reactivity, it is preferable that these components are separately mixed. Specifically, a method of mixing the component (A) with the components (C) and (F) mixed with the component (B) with the components (D) and (E), and (A) ) Component to component (C),
It is preferable to mix the components (D) and (E) with the components (B) and (F).

In the case where the composition is reacted and cured, the components (A), (B) and (C), or (D)
(E) and (if necessary (F)) the respective necessary amounts of the respective components may be mixed and reacted at once, but after a part of the components is mixed and reacted, the remaining amount is further mixed. By reacting, controlling the reaction conditions after mixing, and utilizing the difference in the reactivity of the substituents, only a part of the functional groups in the composition is reacted (B-staged) and then processed such as molding. A curing method may be used. According to these methods, viscosity adjustment at the time of molding becomes easy.

As a method of curing, the reaction can be carried out simply by mixing, or the reaction can be carried out by heating. From the viewpoint that the reaction is fast and a material having high heat resistance is generally easily obtained, a method of performing the reaction by heating is preferable.

In this case, one of the hydrosilylation reaction of the components (A), (B) and (C) and the hydrolysis and condensation reaction of the components (D), (E) and, if necessary, the component (F) are carried out. Although the reaction can be carried out preferentially, it is preferable to proceed simultaneously and concurrently from the viewpoint that the obtained cured product tends to be more transparent. In order to proceed at the same time in parallel, it is also possible to gradually add the necessary components,
It is also possible by adjusting the content of the component (C), the content of the component (F), and the reaction temperature, respectively, and the latter is simpler.

The reaction temperature can be variously set, for example, a temperature of 30 to 300 ° C. can be applied, and a temperature of 100 to 250 ° C.
Is more preferable, and 150 to 200C is further preferable.
When the reaction temperature is low, the reaction time for causing a sufficient reaction is prolonged, and when the reaction temperature is high, molding tends to be difficult.

The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple stages or continuously as required. It is preferable to carry out the reaction while increasing the temperature stepwise or continuously, rather than performing the reaction at a constant temperature, since a uniform cured product without distortion is easily obtained.

Although the reaction time can be variously set, it is preferable to carry out the reaction at a relatively low temperature for a long time rather than at a high temperature for a short time in that a uniform cured product without distortion is easily obtained.

The pressure during the reaction can also be set variously as required.
The reaction can be performed at normal pressure, high pressure, or reduced pressure. The reaction is preferably carried out under reduced pressure from the viewpoint that volatile components generated by hydrolysis and condensation are easily removed.

The shape of the optical material obtained by curing can be various depending on the application, and is not particularly limited. For example, the optical material is formed into a shape such as a film, a sheet, a tube, a rod, a coating, and a bulk. be able to.

Various molding methods can be employed, including a conventional thermosetting resin molding method. For example, a molding method such as a casting method, a pressing method, a casting method, a transfer molding method, a coating method, and a RIM method can be applied. As the molding die, a polishing glass, a hard stainless steel polishing plate, a polycarbonate plate, a polyethylene terephthalate plate, a polymethyl methacrylate plate, or the like can be used. Further, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film, or the like can be used to improve the releasability from a mold.

Various processes can be performed as necessary at the time of molding. For example, a process of defoaming the composition or a partially reacted composition by centrifugation, decompression, or the like to suppress voids generated during molding, a process of once releasing the pressure during pressing, and the like can be applied.

A liquid crystal display device can be manufactured using the optical material of the present invention.

In this case, the optical material of the present invention may be used as a liquid crystal film such as a plastic cell for a liquid crystal, a polarizing plate, a retardation plate, a protective film for a polarizer, etc., and a liquid crystal display device may be manufactured by an ordinary method.

A light emitting diode can be manufactured using the optical material of the present invention. In this case, the light emitting diode can be manufactured by coating the light emitting element with the composition as described above.

In this case, the light emitting element is not particularly limited, and a light emitting element used for a conventionally known light emitting diode can be used. As such a light emitting element, for example, M
Examples thereof include those formed by laminating a semiconductor material on a substrate provided with a buffer layer such as GaN or AlN as necessary by various methods such as an OCVD method, an HDVPE method, and a liquid phase growth method. Various materials can be used for the substrate in this case, for example, sapphire, spinel,
SiC, Si, ZnO, GaN single crystal and the like can be mentioned.
Of these, sapphire is preferably used from the viewpoint that GaN having good crystallinity can be easily formed and the industrial utility value is high.

The semiconductor material to be laminated is GaAs
s, GaP, GaAlAs, GaAsP, AlGaIn
P, GaN, InN, AlN, InGaN, InGaAs
1N, SiC and the like. Among these, from the viewpoint of obtaining high luminance, a nitride-based compound semiconductor (I
n _x Ga _y Al _z N) are preferred. Such a material may contain an activator or the like.

The structure of the light emitting element includes a MIS junction,
Examples include an n-junction, a homojunction having a PIN junction, a heterojunction, and a double heterostructure. Also, a single or multiple quantum well structure can be used.

The light emitting element may or may not be provided with a passivation layer.

An electrode can be formed on the light emitting element by a conventionally known method.

The electrode on the light emitting element can be electrically connected to a lead terminal or the like by various methods. As the electric connection member, those having good ohmic mechanical connection with the electrode of the light emitting element are preferable, and examples thereof include a bonding wire using gold, silver, copper, platinum, aluminum, or an alloy thereof. . Alternatively, a conductive adhesive or the like in which a conductive filler such as silver or carbon is filled with a resin can be used. Of these, from the viewpoint of good workability, it is preferable to use an aluminum wire or a gold wire.

A light emitting device is obtained as described above.
In the light emitting diode of the present invention, any light emitting element having a vertical luminous intensity of 1 cd or more can be used as the luminous intensity of the light emitting element. Is remarkable, and the effect of the present invention is further remarkable when a light emitting element of 3 cd or more is used.

The light emitting output of the light emitting device can be any one without particular limitation. The effect of the present invention is remarkable when a light emitting device of 1 mW or more at 20 mA is used, and the light emitting output of 4 mW or more at 20 mA is used. The effect of the present invention is more remarkable when a device is used, and the effect of the present invention is more remarkable when a light emitting device of 5 mW or more at 20 mA is used.

The light emitting element can use various emission wavelengths from the ultraviolet region to the infrared region. The effect of the present invention is particularly remarkable when a device having a main emission peak wavelength of 550 nm or less is used.

A single type of light emitting element may be used to emit monochromatic light, or a plurality of light emitting elements may be used to emit monochromatic or multicolor light.

As the lead terminals used in the light emitting diode of the present invention, those having good adhesion to an electric connection member such as a bonding wire and electric conductivity are preferable.
The electrical resistance of the lead terminal is preferably 300 μΩ-cm or less, more preferably 3 μΩ-cm or less.
Examples of these lead terminal materials include iron, copper, copper with iron, copper with tin, and those plated with silver, nickel, or the like. The glossiness of these lead terminals may be appropriately adjusted in order to obtain good light spread.

The light-emitting diode of the present invention can be manufactured by coating a light-emitting element with the composition described above. In this case, the term “coating” is not limited to the method of directly sealing the light-emitting element, but the method of covering the light-emitting element indirectly. This includes the case where the coating is performed. Specifically, the light emitting device may be directly sealed with the composition of the present invention by various methods conventionally used, or a conventionally used epoxy resin, silicone resin, acrylic resin, urea resin, imide resin or the like may be sealed. After sealing the light emitting element with a sealing resin or glass, the light emitting element may be coated on or around it with the composition of the present invention. After the light emitting element is sealed with the composition of the present invention, it may be molded with a conventionally used epoxy resin, silicone resin, acrylic resin, urea resin, imide resin, or the like. By the above-described method, various effects such as a lens effect can be provided by a difference in refractive index and specific gravity.

Various methods can be applied as the sealing method. For example, a liquid composition may be injected into a cup, a cavity, a package recess, or the like in which a light emitting element is disposed at a bottom portion by a dispenser or other method and cured by heating or the like, or may be a solid or high-viscosity liquid composition. The material may be flowed by heating or the like, and may be similarly injected into a concave portion of the package and cured by heating or the like. The package in this case can be made using various materials, and examples thereof include a polycarbonate resin, a polyphenylene sulfide resin, an epoxy resin, an acrylic resin, a silicone resin, and an ABS resin. Further, a method of injecting the composition into the mold in advance, immersing a lead frame or the like in which the light emitting element is fixed there, and then curing the composition can be applied. Alternatively, a dispenser is inserted into the mold in which the light emitting element is inserted. May be molded and cured by injection, transfer molding, injection molding or the like. Further, the composition in a liquid or fluid state may be dropped or coated on the light emitting element and cured. Alternatively, stencil printing on the light emitting element,
The composition can also be molded and cured by screen printing, application through a mask, or the like.
In addition, a method in which a composition partially cured or cured in advance into a plate shape, a lens shape, or the like may be fixed on a light emitting element. Further, the light-emitting element can be used as a die bonding agent for fixing to a lead terminal or a package, or can be used as a passivation film on the light-emitting element. Further, it can be used as a package substrate.

The shape of the covering portion is not particularly limited, and can take various shapes. For example, a lens shape, a plate shape, a thin film shape, a shape described in JP-A-6-244458, and the like can be mentioned. These shapes may be formed by molding and curing the composition, or may be formed by post-processing after curing the composition.

The light emitting diode of the present invention can be of various types, for example, any type such as a lamp type, an SMD type and a chip type. Various types of SMD type and chip type package substrates are used, for example, epoxy resin, BT resin,
Ceramics and the like can be mentioned.

In addition, various conventionally known methods can be applied to the light emitting diode of the present invention. For example, a method of providing a layer for reflecting or condensing light on the back of the light emitting element, a method of forming a complementary colored portion on the bottom corresponding to yellowing of the sealing resin,
A method in which a thin film that absorbs light having a wavelength shorter than the main emission peak is provided on the light emitting element, a method in which the light emitting element is sealed with a soft or liquid sealing material, and then the surroundings are molded with a hard material, and light from the light emitting element is removed. A method in which a light-emitting element is sealed with a material containing a phosphor that emits longer-wavelength fluorescent light by absorption and then molding is performed around the light-emitting element; a method in which a material containing the phosphor is molded in advance and then molded together with the light-emitting element; As described in −244458, a method of increasing the luminous efficiency by using a molding material in a special shape, a method of forming a two-step recessed package to reduce uneven brightness, a method of inserting and fixing a light emitting diode in a through hole, and light emission A method of forming a thin film on the element surface that absorbs light having a wavelength shorter than the main emission wavelength, and connecting the light emitting element by flip chip connection using solder bumps etc. Method in which light is taken out from the substrate direction by connecting the lead member or the like Te, and the like.

The light emitting diode of the present invention can be used for various known applications. Specifically, for example, a backlight, an illumination, a sensor light source, an instrument light source for a vehicle, a signal light, an indicator light, a display device, a light source of a planar light emitter, a display, a decoration, various lights, and the like can be given.

[0136]

EXAMPLES Examples and comparative examples of the present invention will be shown below, but the present invention is not limited by the following.
(Synthesis Example 1) A stirrer and a condenser were set in a 1 L three-necked flask. In this flask, add bisphenol A1
14 g, potassium carbonate 145 g, allyl bromide 14
0 g and acetone (250 mL) were added, and the mixture was stirred at 60 ° C. for 12 hours. The supernatant was taken, washed with an aqueous sodium hydroxide solution using a separating funnel, and then washed with water. After the oil layer was dried over sodium sulfate, the solvent was distilled off using an evaporator, and 126 g of a pale yellow liquid was obtained. ¹ H-
NMR revealed that bisphenol A was diallyl ether in which the OH group of bisphenol A was allyl etherified. The yield was 82% and the purity was 95% or more.

(Synthesis Example 2) A stirrer, a condenser, and a dropping funnel were set in a 1 L four-necked flask. In this flask, 150 g of toluene, 15.6 μL of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum),
500 g of 1,3,5,7-tetramethylcyclotetrasiloxane was added, and the mixture was heated to 70 ° C. and stirred in an oil bath. 64 g of bisphenol A diallyl ether produced in Synthesis Example 1 was diluted with 40 g of toluene and added dropwise from a dropping funnel. After stirring at the same temperature for 60 minutes, the mixture was allowed to cool, and 4.74 mg of benzothiazole was added. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a slightly viscous liquid. ^{According to 1} H-NMR, this was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with bisphenol A diallyl ether (referred to as a partial reactant A)
It turned out to be.

(Synthesis Example 3) A magnetic stirrer and a condenser were set in a 200 mL two-necked flask. 50 g of toluene, 11.3 μL of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum), 5.0 g of triallyl isocyanurate, 37.04 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added to the flask. Then, the mixture was heated and stirred in a 90 ° C. oil bath for 30 minutes. Further, the mixture was heated and refluxed for 2 hours in a 130 ° C. oil bath.
176 mg of 1-ethynyl-1-cyclohexanol was added. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ¹ H-
NMR revealed that this was a product in which part of the SiH groups of 1,3,5,7-tetramethylcyclotetrasiloxane had reacted with triallyl isocyanurate (referred to as partial reactant B).

(Example 1) 16.1 g of bisphenol A diallyl ether produced in Synthesis Example 1, 15.4 g of the partially reacted product A produced in Synthesis Example 2, 3.1 g of tetramethoxysilane, and 1.0 g of water 0.5 g of diisopropoxybis (methyl acetoacetate) titanium and 3 ml of THF
Were mixed in a cup. As shown in Synthesis Example 2, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention. This was poured into an ointment can covered with a polyimide film, and 50 ° C./15 hours.
80 ° C / 7 hours, 100 ° C / 17 hours, and 150 ° C
Heating was performed for 24 hours to obtain a colorless, almost transparent, film-like cured product that was slightly cloudy visually. The obtained cured product was hard and had no surface tack.

Example 2 16.1 g of bisphenol A diallyl ether produced in Synthesis Example 1, 15.4 g of the partially reacted product A produced in Synthesis Example 2, 15.8 g of tetramethoxysilane, and 2.7 g of water , 2.0 g of diisopropoxybis (methyl acetoacetate) titanium and 3 ml of THF
Were mixed in a cup. As shown in Synthesis Example 2, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention. This was poured into an ointment can covered with a polyimide film, and 50 ° C./15 hours.
80 ° C / 7 hours, 100 ° C / 17 hours, and 150 ° C
Heating was performed for 24 hours to obtain a colorless cured film which was slightly cloudy visually. The obtained cured product was hard and had no surface tack.

Example 3 16.1 g of bisphenol A diallyl ether prepared in Synthesis Example 1, 15.4 g of the partially reacted product A prepared in Synthesis Example 2, 3.1 g of tetraethoxysilane, and 1.0 g of water 0.5 g of diisopropoxybis (methyl acetoacetate) titanium and 3 ml of THF
Were mixed in a cup. As shown in Synthesis Example 2, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention. This was poured into an ointment can covered with a polyimide film, and 50 ° C./15 hours.
80 ° C / 7 hours, 100 ° C / 17 hours, and 150 ° C
/ 24 hours to obtain a slightly yellow but transparent cured film. The obtained cured product was hard and had no surface tack.

Example 4 16.1 g of bisphenol A diallyl ether produced in Synthesis Example 1, 15.4 g of partially reacted product A produced in Synthesis Example 2, 15.8 g of tetraethoxysilane, and 2.7 g of water , 2.0 g of diisopropoxybis (methyl acetoacetate) titanium and 3 ml of THF
Were mixed in a cup. As shown in Synthesis Example 2, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention. This was poured into an ointment can covered with a polyimide film, and 50 ° C./15 hours.
80 ° C / 7 hours, 100 ° C / 17 hours, and 150 ° C
/ 24 hours to obtain a slightly yellow but transparent cured film. The obtained cured product was hard and had no surface tack.

Example 5 16.1 g of bisphenol A diallyl ether prepared in Synthesis Example 1, 15.4 g of partially reacted product A prepared in Synthesis Example 2, 15.8 g of boron trimethoxide, and 2.7 g of water 2.0 g of titanium diisopropoxybis (methyl acetoacetate) and 2 ml of THF
Were mixed in a cup. As shown in Synthesis Example 2, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention. This was poured into an ointment can covered with a polyimide film, and 50 ° C./15 hours.
80 ° C / 7 hours, 100 ° C / 17 hours, and 150 ° C
/ 24 hours to obtain a slightly brown but transparent cured film. The obtained cured product was hard and had no surface tack.

Example 6 16.1 g of bisphenol A diallyl ether prepared in Synthesis Example 1, 15.4 g of the partially reacted product A prepared in Synthesis Example 2, 15.8 g of boron triethoxide, and 2.7 g of water 2.0 g of titanium diisopropoxybis (methyl acetoacetate) and 2 ml of THF
Were mixed in a cup. As shown in Synthesis Example 2, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention. This was poured into an ointment can covered with a polyimide film, and 50 ° C./15 hours.
80 ° C / 7 hours, 100 ° C / 17 hours, and 150 ° C
/ 24 hours to obtain a slightly brown but transparent cured film. The obtained cured product was hard and had no surface tack.

Example 7 16.1 g of bisphenol A diallyl ether prepared in Synthesis Example 1, 15.4 g of partially reacted product A prepared in Synthesis Example 2, and a partial condensate of tetramethoxysilane (methyl silicate manufactured by Colcoat Co., Ltd.) 5
1) 15.8 g, 4.4 g of water, 3.5 g of diisopropoxybis (methyl acetoacetate) titanium, and 2 m of THF
were mixed in a cup. As shown in Synthesis Example 2, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention. The mixture was poured into an ointment can covered with a polyimide film, and was heated at 50 ° C. for 15 hours, at 80 ° C. for 7 hours, at 100 ° C. for 17 hours, and further for 15 hours.
Heating was performed at 0 ° C. for 24 hours to obtain a slightly yellow but transparent cured film. The obtained cured product was hard and had no surface tack.

Example 8 16.1 g of bisphenol A diallyl ether produced in Synthesis Example 1, 15.4 g of partially reacted product A produced in Synthesis Example 2, and a partial condensate of methyltrimethoxysilane (manufactured by Owens Illinois) GR65
0) 3.2 g, water 1.2 g, diisopropoxybis (methyl acetoacetate) titanium 1.8 g, THF 2 ml
Were mixed in a cup. As shown in Synthesis Example 2, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention. This was poured into an ointment can covered with a polyimide film, and 50 ° C./15 hours.
80 ° C / 7 hours, 100 ° C / 17 hours, and 150 ° C
Heating was performed for 24 hours to obtain a colorless cured film which was slightly cloudy visually. The obtained cured product was hard and had no surface tack.

Comparative Example 1 16.1 g of bisphenol A diallyl ether produced in Synthesis Example 1, 15.4 g of the partially reacted product A produced in Synthesis Example 2, and particulate silica (Fuselex E-1 manufactured by Tatsumori Co., Ltd.) ) 15.7g, THF2m
were mixed in a cup. As shown in Synthesis Example 2, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention. The mixture was poured into an ointment can covered with a polyimide film, and was heated at 50 ° C. for 15 hours, at 80 ° C. for 7 hours, at 100 ° C. for 17 hours, and further for 15 hours.
Heating was performed at 0 ° C. for 24 hours to obtain a white opaque cured film. The obtained cured product was hard and had no surface tack.

Comparative Example 2 16.1 g of bisphenol A diallyl ether produced in Synthesis Example 1, 15.4 g of the partially reacted product A produced in Synthesis Example 2, and 2 ml of THF were mixed in a cup. As shown in Synthesis Example 2, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention. This was poured into an ointment can covered with a polyimide film, and was heated at 50 ° C for 15 hours at 80 ° C.
/ 7 hours, 100 ° C / 17 hours, and 150 ° C / 24 hours
Heating was performed for a time to obtain a transparent cured film. The obtained cured product was hard and had no surface tack.

(Measurement Example 1) The cured products prepared in Examples 3, 5, 8 and Comparative Example 2 were measured for linear expansion coefficient. The coefficient of linear expansion was measured using a thermomechanical analyzer. The measurement conditions were as follows: a film sample was cut into a strip having a size of 3 × 15 mm, and measured at a temperature rising rate of 10 ° C./min under a nitrogen stream in a tensile mode with a chuck of 10 mm and a load of 3 g. The average coefficient of linear expansion in was used as a measured value. The results are shown in Table 1.

[0150]

[Table 1]

As shown in Table 1, in Examples of the present invention, the coefficient of linear expansion is reduced.

Example 9 2.5 g of triallyl isocyanurate and 3.0 g of the partially reacted product B synthesized in Synthesis Example 3
3.1 g of tetramethoxysilane, 1.0 g of water,
Diisopropoxybis (methyl acetoacetate) titanium
3 g and 3 ml of THF were mixed in a cup to obtain a composition. As shown in Synthesis Example 3, partial reactant B contains a platinum vinyl siloxane complex as component (C) of the present invention. This was flowed through a cell formed by inserting a 0.5 mm thick silicone rubber sheet as a spacer between two glass plates, and was heated at 80 ° C./60 minutes and 100 ° C./6.
Heating was performed at 120 ° C./60 minutes for 0 minutes to obtain a substantially colorless and transparent sheet-like cured product. The obtained cured product was hard and had no surface tack.

(Measurement Example 2) The cured product prepared in Example 9 was subjected to a SX120 type xenon weather meter (black panel temperature: 63 ° C., irradiation for 2 hours, rainfall: 1) manufactured by Suga Test Instruments.
(8 minutes) for 70 hours to examine whether or not the cured product was colored. As a result, no color was observed and the colorless and transparent state was maintained. The composition of the present invention has excellent light fastness.

(Example 10) The sheet-like cured product prepared as in Example 9 is cut into an appropriate shape and fixed to a light-transmitting window provided on a metal cap for a can type. On the other hand, a light emitting device having a double hetero structure in which an InGaN active layer doped with Si and Zn formed on a sapphire substrate by MOCVD (metal organic chemical vapor deposition) is sandwiched between n-type and p-type AlGaN cladding layers. Prepare Subsequently, after mounting this light emitting element on a metal stem for a can type, a p-electrode and an n-electrode are connected to respective leads by Au.
Wire bonding with wire. This is hermetically sealed with the above-mentioned metal cap for can type. In this manner, a can-type light emitting diode can be manufactured.

(Example 11) An n-type GaN layer, which is an undoped nitride semiconductor, and a Si-doped n-type layer were formed on a cleaned sapphire substrate by MOCVD (metal organic chemical vapor deposition).
GaN layer serving as an n-type contact layer formed with a type electrode, an n-type GaN layer serving as an undoped nitride semiconductor, a GaN layer serving as a barrier layer forming a light emitting layer, an InGaN layer forming a well layer, and a barrier layer A GaN layer (quantum well structure), an AlGaN layer as a Mg-doped p-type cladding layer, and a GaN layer as a Mg-doped p-type contact layer are sequentially laminated on the light emitting layer. The surface of each pn contact layer is exposed on the same side of the nitride semiconductor on the sapphire substrate by etching. On each contact layer,
Al is deposited using a sputtering method to form positive and negative electrodes. After a scribe line is drawn on the completed semiconductor wafer, the semiconductor wafer is divided by an external force to form light emitting elements.

The light emitting device is die-bonded on the bottom surface of a cup of a mount lead made of iron-containing copper plated with silver on the surface by using an epoxy resin composition as a die-bonding resin. This is heated at 170 ° C. for 75 minutes to cure the epoxy resin composition and fix the light emitting element. Next, the positive and negative electrodes of the light emitting element are wire-bonded to the mount lead and the inner lead with an Au wire to establish electrical continuity.

The composition prepared in the same manner as in Example 9 is poured into a casting case which is a shell-shaped mold. A part of the mount lead and the inner lead in which the light emitting element is arranged in the cup is inserted into a casting case, and initial curing is performed at 100 ° C. for 1 hour. The light emitting diode is extracted from the casting case and cured at 120 ° C. for 1 hour in a nitrogen atmosphere. Thereby, a lamp type light emitting diode such as a shell type can be produced.

(Example 12) A composition and a light emitting device were prepared by the method described in Example 11.

A substrate having lead electrodes is formed by forming a pair of copper foil patterns on a glass epoxy resin by etching. The light emitting element is die-bonded on a glass epoxy resin using an epoxy resin. Each electrode of the light emitting element and each lead electrode are wire-bonded with an Au wire, respectively, to establish electrical continuity. A glass epoxy resin having a through hole as a mask and a side wall is fixedly arranged on the substrate with the epoxy resin. In this state, the composition is dispensed on a glass epoxy resin substrate on which the light emitting elements are arranged, and the composition is filled in a cavity using a through hole. In this state, 1
Cure at 00 ° C for 1 hour and then at 150 ° C for 1 hour. By dividing each light emitting diode chip, a chip type light emitting diode can be produced.

(Example 13) A composition and a light emitting device were prepared by the method described in Example 11.

A chip type light emitting diode package is formed by insert molding using PPS resin. The inside of the package has an opening in which the light emitting element is arranged, and a silver-plated copper plate is arranged as an external electrode. A light emitting element is fixed inside the package by die bonding using an epoxy resin. An Au wire, which is a conductive wire, is wire-bonded to each electrode of the light-emitting element and each external electrode provided on the package to be electrically connected.
The composition is filled in the package opening as a mold member. In this state, 100 ° C. for 1 hour and 150 ° C. for 1 hour
Allow time to cure. Thus, a chip type light emitting diode can be manufactured.

(Example 14) A composition and a light emitting device were prepared by the method described in Example 11.

The composition is heated to 90 ° C. for 30 minutes to be B-staged.

A substrate having lead electrodes is formed by forming a pair of copper foil patterns on a glass epoxy resin by etching. The light emitting element is die-bonded on a glass epoxy resin using an epoxy resin. Each electrode of the light emitting element and each lead electrode are wire-bonded with an Au wire, respectively, to establish electrical continuity. The light emitting element and a part of the lead electrode are sealed by transfer molding using the composition in the B stage. An SMD type light emitting diode can be manufactured.

(Embodiment 15) A nitride semiconductor is sequentially etched from the p-type nitride semiconductor layer side by a RIE (Reactive Ion Etching) apparatus to form a negative electrode in the same manner as in Embodiment 10. The surface of the n-type contact layer is exposed. Next, Ni / Au is applied to a film thickness of 60 over almost the entire surface of the uppermost p-type contact layer by a lift-off method.
/ 200 ° to form a first positive electrode having good ohmic contact and excellent transparency. Further, Au is laminated on a part of the translucent first positive electrode to a thickness of 1 μm to form a second positive electrode to be a positive electrode side bonding portion.

On the other hand, W / Al / W / Au was deposited on the surface of the n-type contact layer exposed by etching to a film thickness of 200.degree.
000Å / 2000Å / 3000Å
An unnecessary resist film is removed to form a negative electrode, thereby forming an LED element. As a result, a negative electrode having good ohmic contact without performing annealing is formed. Further, although the negative electrode serves as a bonding portion, the above-described configuration has high mechanical strength, and thus an LED element that can be driven stably can be obtained.

Next, the bonding of each electrode is performed by patterning.
Only the exposed portion is exposed to contact the entire surface of the device.
₂An insulating inorganic compound layer made of
D element. The insulating inorganic compound layer is at least short.
It is only necessary that the positive electrode be formed so as to prevent entanglement.
If provided on the upper surface of the semiconductor layer between the pole and the negative electrode
Good. Providing the insulating inorganic compound layer in this manner,
When mounting miniaturized light emitting devices with high reliability,
Always important. The material of the insulating inorganic compound layer is small.
Both may be insulating, for example, SiO 2₂, TiO₂,
Al₂O₃, Si ₃N₄Single layer or multiple layers consisting of
Can be.

In this embodiment, the insulating inorganic compound layer is provided continuously up to the end face of the light emitting element. Thereby, the shaved end surface and the exposed surface of the substrate can be protected from high temperature and high humidity, and a light emitting element capable of maintaining high reliability even when used for a long time under severe environmental conditions can be obtained. Further, the insulating inorganic compound layer provided in direct contact with the sapphire substrate or gallium nitride preferably has a thermal expansion coefficient close to that of the member in contact therewith, whereby reliability can be further improved. Incidentally, the thermal expansion coefficient of each material is 7.5 to 8.5 for the sapphire substrate.
× 10 ⁻⁶ / k, gallium nitride is 3.2 to 5.6 × 10
⁻⁶ / k, silicon dioxide 0.3 to 0.5 × 10 ⁻⁶ /
k, silicon nitride is 2.5 to 3.0 × 10 ⁻⁶ / k.

In the light emitting element used in this embodiment, most of the light emitted from the light emitting layer is totally reflected at the interface between the upper and lower layers, and tends to emit light from the light emitting end with a high light density. When such a light emitting element is directly covered with a resin, light and heat from the light emitting element concentrate on the light emitting element, so that an adjacent resin portion is significantly deteriorated locally. It is considered that this causes a change in color tone and a decrease in reliability of the light emitting diode. Therefore, in this example, a light-emitting element having an insulating inorganic compound layer on the surface thereof has a relatively high adhesion to the insulating inorganic compound layer and a composition of the present invention having excellent light resistance and heat resistance. By directly covering the light emitting region, light emitted from the end of the light emitting region is efficiently extracted to the outside, deterioration at the interface is suppressed, and a highly reliable light emitting device is provided.

The above-mentioned light-emitting end means the end of the light-emitting layer and the n-type contact layer. Therefore, it is preferable that the insulating inorganic compound layer provided at these ends is made of an inorganic substance having a smaller refractive index than GaN, which is often used as an n-type contact layer. Thereby, deterioration of the composition can be suppressed. Further, the insulating inorganic compound is, for example, SiO ₂ as a first layer directly in contact with a light emitting end of a light emitting element, and a _second layer having a higher refractive index than the first layer in contact with the first layer. T with TiO ₂ laminated as a layer of
and iO ₂ / SiO _2, and a two-layer structure such as TiO 2 / MgF _2, by providing the optical multilayer film having a three-layer structure formed by laminating the insulating film and the metal as SiO 2 / Al / SiO ₂ , Can also be reflective. In the case of a plurality of layers, the film thickness is preferably 5000 to 5 μm, more preferably 1 to 3 μm.

In the case where an inorganic compound layer is provided on the surface of a light emitting element and a sealing material is formed with the composition of the present invention in contact with the inorganic compound layer as in this embodiment, the inorganic compound layer The inorganic compound layer is formed of a metal atom, which is a part of the essential component (D) of the composition of the present invention, in consideration of the difference in the optical refractive index, the difference in the thermal expansion coefficient, and the adhesiveness of each interface between the inorganic compound and the sealing material. And / or has a common atom with a metalloid atom. Thereby, light extraction efficiency and reliability can be improved. Furthermore, when silicon is selected as the common atom, compared to a case where other atoms are selected as the common atom, high reliability and optical characteristics tend to be maintained even under environmental conditions such as high temperature and high humidity. is there. Although the reason for this is not clear, the essential component (A) of the composition of the present invention and the substance containing silicon have a good affinity due to some action, and it is considered that their interface has high adhesion, and as a result, moisture and It is considered that the invasion of outside air was suppressed. The inorganic compound layer containing silicon is not particularly limited as long as at least silicon is contained in the inorganic compound, and specifically, SiO ₂ , SiN, SiON, and S
inorganic compound layer consisting iH ₄ etc. can be mentioned.

The wafer having the LED elements formed as described above is shaved by a polishing process to a substrate thickness capable of being scribed, placed on an adhesive sheet so that the substrate surface is in contact with the adhesive sheet, and formed into chips by the scribe process. Divided into The divided LED chips are fixed inside the same package as in Example 13 by the same method, and are electrically connected by wire bonding with Au wire.

Next, the composition prepared in the same manner as in Example 9 is injected into the package. After injection, 10
After curing at 0 ° C. for 1 hour and 150 ° C. for 1 hour to form a sealing material, a chip type light emitting diode is formed.

Since the light emitting diode thus formed is made of a sealing material having excellent heat resistance and toughness, cracks in the resin and the light emitting element due to thermal stress during mounting or lighting are generated. And wire breakage can be prevented.

Further, the encapsulant thus obtained is subjected to the hydrolysis-condensation reaction of the component (D) to obtain an amorphous metal oxide and / or an amorphous semimetal oxide formed of an aggregate of fine particles. Things are dispersed. Since the fine particle aggregate has high purity and high transparency, the linear expansion coefficient of the sealing material can be reduced without hindering the light extraction efficiency. Thus, it is possible to obtain a light emitting diode capable of realizing both improvement in reliability and maintenance of optical performance.

As described above, since the light emitting diode of the present invention has excellent heat resistance, even if the light emitting diode is mounted on a conductive member having no Pb and having a high melting point, chromaticity fluctuation and reliability can be improved. It is possible to realize an environment-friendly display device that does not cause deterioration in performance.

The sealing material of the present invention is a cured product having flexibility in thermal stress. Conventionally, rubber-like elastic resins, gel resins, and the like are known as resins having flexibility in thermal stress, but these resins have low mechanical strength because they have a low crosslinking density or do not have a crosslinking structure, and Due to the tackiness, there are problems such as foreign matter easily adhering,
It was not suitable for forming a light emitting surface to be the outermost surface. On the other hand, the composition of the present invention has no risk of attaching foreign matter or being damaged by the mounting device. As described above, according to the present invention, by using the composition of the present invention, a member for covering a light emitting element and a wire portion and a member for a light emitting surface serving as a surface portion of a light emitting device can be integrally formed, and mass productivity and workability can be improved. Thus, a light emitting diode having excellent characteristics can be obtained. Further, since it has excellent light resistance to sunlight, the light emitting surface is not discolored even when mounted on an outdoor display substrate, and good reliability can be maintained.

In the present invention, various fluorescent substances such as an inorganic fluorescent substance and an organic fluorescent substance can be contained in each constituent member. As an example of such a fluorescent substance, there is a fluorescent substance containing a rare earth element which is an inorganic fluorescent substance. As the rare earth element-containing phosphor, specifically, Y, Lu, Sc, La,
A garnet-type phosphor having at least one element selected from the group of Gd and Sm and at least one element selected from the group of Al, Ga, and In is given. In particular, a yttrium / aluminum oxide-based phosphor activated with cerium is preferable. In addition to Ce, Tb, Cu, Ag, Au, Fe, Cr, Nd, Dy,
Ni, Ti, Eu, Pr and the like can be contained. Further, the composition of the present invention is capable of absorbing a part of light of the light emitting element and emitting light of another wavelength, and has a surface coated with a substance containing an inorganic element common to the composition. When an inorganic fluorescent substance is added, these interfaces tend to have good adhesion due to chemical bonding or the like. Moreover, the above-mentioned fluorescent substance is fixed in the above-mentioned composition in a state of being well dispersed in the above-mentioned composition. As a result, a color conversion type light-emitting diode capable of uniformly emitting light with high luminance by improving the light absorption rate and light extraction efficiency of the inorganic fluorescent substance is obtained.

(Embodiment 16) In the same manner as in Embodiment 13, a light emitting element is mounted in a package and is electrically connected by wires. Here, a resist film is formed on the surface excluding the opening of the package. The package on which the LED chips are placed is placed in a container containing pure water.

On the other hand, in the case of the particulate phosphor, a solution obtained by dissolving rare earth elements of Y, Gd, and Ce in an stoichiometric ratio in an acid is coprecipitated with oxalic acid. This is mixed with a coprecipitated oxide obtained by calcination and aluminum oxide to obtain a mixed raw material. This was mixed with aluminum fluoride as a flux, packed in a crucible, and heated at 1400 ° C. in a weak reducing atmosphere and a reducing atmosphere.
For 3 hours to obtain a fired product. The fired product is ball-milled in water, washed, separated, dried, and finally passed through a sieve to form a (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce phosphor. A mixed solution obtained by dispersing the fluorescent substance thus obtained in a SiO ₂ sol is formed.

Next, after adjusting the pH to 5.0 with acetic acid,
Immediately pour the mixed solution into the container in which the package is placed. After standing (Y _0.8 Gd _0.2 ) ₃ Al
₅ O _{1 2:} Ce phosphor is settling in the package opening and the light emitting element. The package in which the waste liquid in the container is removed and the particulate phosphor is deposited on the LED chip is dried at 120 ° C.

Next, the light emitting diode is taken out of the container, and the particulate phosphor adhered to the non-light emitting portion of the light emitting diode is removed together with the resist mask. The light emitting diode thus obtained has an inorganic compound layer in which the thickness of both the LED chip and the package bottom is substantially equal to about 40 μm. Further, a composition prepared in the same manner as in Example 9 as a mold member in a package having an inorganic compound layer formed thereon for the purpose of protecting the LED chip and the particulate phosphor from external stress, sunlight, moisture, dust and the like. To form a sealing member.

The light-emitting diode thus obtained is composed of a sealing member having excellent durability and having a reduced linear expansion coefficient difference from other members. It has excellent reliability without color shift and color unevenness during use.

Example 17 A light emitting diode was formed in the same manner as in Example 10, except that the composition of the present invention was used as a die bond resin. With such a structure, all of the members around the light emitting element can be made of a composition having excellent heat resistance and light resistance, and a light emitting diode with higher reliability can be obtained.

[0185]

The material produced from the composition of the present invention has low light degradation, low linear expansion coefficient, high optical transparency, and is hard and has no surface tackiness. It is a material suitable for.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 33/00 H01L 33/00 N (72) Inventor Manabu Tsumura 5-23-23 Torikai Nishi, Settsu-shi, Osaka Hironori Dormitory A 101 (72) Inventor Harumi Sakamoto 1-28-28 Torikai Wado, Settsu-shi, Osaka Sunny Court Room 401 (72) Inventor Masayuki Fujita 5-5-2-102, Torikai-Nishi, Settsu-shi, Osaka (72) Inventor Masafumi Kuramoto 491 Kaminakacho Oka, Anan City, Tokushima Prefecture, within Nichia Chemical Industry Co., Ltd. (72) Inventor Michihide Miki 491 Kaminakamachi Oka, Anan City, Tokushima Prefecture, 100 Nichia Chemical Industry Co., Ltd. 4J002 BG041 BL011 CC041 CF001 CF161 CG001 CH001 CL001 CM041 DA117 DD078 DE197 EC078 EX006 EX038 EX049 FD157 GP00 5F041 AA34 AA44 CA04 CA05 CA34 CA40 CA46 CA65 DA16 DA19 DA33 DA34 DA45 DA73 DA76 DB01 DB06 DB09

Claims (29)

[Claims] (A) a carbon having a reactivity with a SiH group;
An organic compound containing at least two carbon double bonds in one molecule, (B) a silicon compound containing at least two SiH groups in one molecule, (C) a hydrosilylation catalyst,
(D) a compound containing at least two hydrolyzable groups bonded to a metal atom and / or a metalloid atom per molecule, and / or a partial condensate thereof, and (E) water and / or water A composition for an optical material, comprising a compound as an essential component. 2. The composition for an optical material according to claim 1, wherein the component (A) is an organic compound containing at least one vinyl group reactive with a SiH group in one molecule. 3. The composition for an optical material according to claim 1, wherein the component (A) is an organic compound containing at least one allyl group reactive with a SiH group in one molecule. 4. The optical material according to claim 1, wherein the component (A) is 1,2-polybutadiene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, divinylbiphenyl, or bisphenol A diallyl ether. Composition. 5. The composition for an optical material according to claim 1, wherein the component (A) is triallyl isocyanurate or trivinylcyclohexane. 6. The composition for an optical material according to claim 1, further comprising (F) a condensation catalyst as an essential component. 7. The composition for an optical material according to claim 6, wherein (F) the condensation catalyst is a Ti-based condensation catalyst. 8. The metal atom of the component (D) is Al, Zn,
8. The semiconductor device according to claim 1, which is one or more atoms selected from the group consisting of Ga, Ge, Sn, Mg, Ca, Ti, and Zr, and wherein the metalloid atom is B and / or Si. The composition for an optical material according to any one of the preceding claims. 9. The method according to claim 1, wherein the hydrolyzable group of the component (D) is one or more groups selected from the group consisting of an alkoxy group, a siloxy group, an acyloxy group, and a halogen group. 9. The composition for an optical material according to any one of 8. 10. The composition for an optical material according to claim 1, wherein the optical material is a liquid crystal film. 11. The composition for an optical material according to claim 1, wherein the optical material is a plastic cell for a liquid crystal. 12. The composition for an optical material according to claim 1, wherein the optical material is a sealing material for a light emitting diode. 13. A composition for an optical material according to claim 1, which is mixed in advance, and a carbon-carbon double bond having a reactivity with a SiH group in the composition and SiH
An optical material obtained by reacting a part or all of the groups and subjecting the hydrolyzable group bonded to a metal atom and / or a metalloid atom to a hydrolysis-condensation reaction to cure the material. 14. The composition for an optical material according to claim 1, which is previously mixed, and a carbon-carbon double bond having a reactivity with a SiH group in the composition and SiH
14. The method for producing an optical material according to claim 13, wherein a part or all of the groups are reacted to cause a hydrolytic condensation reaction of a hydrolyzable group bonded to a metal atom and / or a metalloid atom. 15. A liquid crystal display device using the optical material according to claim 13. 16. A light-emitting diode using the optical material according to claim 13. 17. An organic compound containing (A) at least two carbon-carbon double bonds reactive with a SiH group in one molecule, and (B) an organic compound containing at least two SiH groups in one molecule. A silicon compound, (C) a hydrosilylation catalyst,
(D) a compound containing at least two hydrolyzable groups bonded to a metal atom and / or a metalloid atom per molecule, and / or a partial condensate thereof, and (E) water and / or water A light-emitting diode in which a light-emitting element is coated with a curable composition containing a compound as an essential component. 18. The light emitting diode according to claim 17, wherein the component (A) is an organic compound containing at least one vinyl group reactive with a SiH group in one molecule. 19. The light emitting diode according to claim 17, wherein the component (A) is an organic compound containing at least one allyl group reactive with a SiH group in one molecule. 20. The light emitting diode according to claim 17, wherein the component (A) is 1,2-polybutadiene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, divinylbiphenyl, or bisphenol A diallyl ether. 21. The light emitting diode according to claim 17, wherein the component (A) is triallyl isocyanurate or trivinylcyclohexane. 22. The light emitting diode according to claim 17, wherein the curable composition further contains (F) a condensation catalyst as an essential component. 23. The light emitting diode according to claim 22, wherein the (F) condensation catalyst is a Ti-based condensation catalyst. 24. The metal atom of the component (D) is Al, Z
one or more atoms selected from the group consisting of n, Ga, Ge, Sn, Mg, Ca, Ti, and Zr;
The light emitting diode according to any one of claims 17 to 23, wherein the metalloid atoms are B and / or Si. 25. The hydrolyzable group of the component (D) is one or more groups selected from the group consisting of an alkoxy group, a siloxy group, an acyloxy group, and a halogen group. The light emitting diode according to any one of the above. 26. The curable composition is pre-mixed before coating the light emitting device so that a part or all of a carbon-carbon double bond and a SiH group reactive with a SiH group in the composition are mixed. The light emitting diode according to any one of claims 17 to 25, wherein the hydrolyzable group which has reacted and bonded to the metal atom and / or the metalloid atom has undergone a hydrolysis condensation reaction. 27. The light-emitting element has an inorganic compound layer containing silicon on its surface, and a light-transmitting sealing material obtained from the curable composition is provided in contact with the inorganic compound layer. The light emitting diode according to any one of claims 17 to 26, characterized in that: 28. The inorganic compound layer includes a fluorescent substance capable of absorbing at least a part of light emitted from the light emitting element and emitting light having another wavelength. Item 29. The light emitting diode according to Item 27. 29. (A) an organic compound containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule, and (B) an organic compound containing at least two SiH groups in one molecule. A silicon compound, (C) a hydrosilylation catalyst,
(D) a compound containing at least two hydrolyzable groups bonded to a metal atom and / or a metalloid atom per molecule, and / or a partial condensate thereof, and (E) water and / or water A method for producing a light-emitting diode in which a light-emitting element is coated using a curable composition containing a compound as an essential component, wherein the curable composition is pre-mixed before coating the light-emitting element. Part or all of the SiH group reacts with the carbon-carbon double bond reactive with the SiH group in the product, and the hydrolyzable group bonded to the metal atom and / or the metalloid atom undergoes a hydrolytic condensation reaction. A method for manufacturing a light emitting diode, comprising: