CN110603295A - Solid organosilicon material, and laminate and light-emitting device using same - Google Patents

Abstract

Problem: The present invention provides a solid silicone material, a laminate using it, etc., which can be easily thinned with a uniform nanometer-order film thickness, and can improve light extraction by disposing it at the interface between the laminate as a light-emitting device and air efficiency etc. Solution: The solid organosilicon material contains: (A) hollow or porous inorganic particles with a number average particle diameter of 1-100nm, and (B) having R ^A SiO _3/2 (wherein, R ^A An arylsiloxane unit represented by an aryl group having 6 to 14 carbon atoms) and (R ₂ SiO _2/2 )n (wherein, R is an alkane having 1 to 20 carbon atoms that may be substituted by a halogen atom) group or an aryl group with 6 to 14 carbon atoms, and n is a number in the range of 3 to 1,000), the organopolysiloxane of the polydiorganosiloxane structure represented by the content of the component (A) is 10 to 95% by mass range.

Description

Solid silicone material, laminate and light-emitting device using same

technical field

The present invention relates to a solid silicone material, a laminate using the same, and a light-emitting device, and particularly to a solid silicone material that can be easily thinned with a uniform nanometer-order film thickness, and can be used as a light-emitting device by disposing The interface between the laminate and the air can improve light extraction efficiency and the like. In addition, the present invention relates to a method for producing a laminate and an optical device using the solid silicone material.

Background technique

Solid silicone materials have excellent moldability, heat resistance, cold resistance, electrical insulation, weather resistance, hydrophobicity, and transparency, and are therefore used in a wide range of industrial fields. The cured product of the curable silicone composition is less prone to discoloration than other organic materials and has less degradation in physical properties, so it is also suitable as an optical material, especially a sealing agent for light-emitting devices (inorganic or organic light-emitting diodes).

In recent years, for the new manufacturing process of light-emitting devices, a material containing silicone has been proposed, which has thermal fusibility, is solid or semi-solid at room temperature, and undergoes heating and melting at high temperature. Silicone-containing materials having hot-melt properties are different from ordinary liquid materials, and are excellent in operability and uniform coating. Reactive or non-reactive silicone-containing hot melt compositions of linear siloxane structure and linear siloxane structure are used for sealing material films. This sealing material has a high refractive index, and when used in combination with a sealing material film (phosphor layer) having a fluorescent material that converts wavelengths from a light source, it is possible to provide a light-emitting device excellent in productivity and luminous efficiency. However, in the field of light-emitting devices, especially when the above-mentioned phosphor layers are used, higher light extraction efficiency is required, and there is still room for improvement in the above-mentioned light-emitting devices. It should be noted that Patent Document 1 does not disclose anything about mixing specific hollow or porous inorganic fine particles or using a thin film for improving light extraction efficiency, especially a nanoscale thin film.

On the other hand, small-diameter hollow or porous inorganic fine particles have a structure containing air inside or in pores, and when mixed into a resin as a binder, bring a low refractive index to the air layer, so It is used as an anti-reflection layer of an anti-reflection film. Specifically, incident light (incident light from an external light source) is reflected on the interface of the antireflection layer having a low refractive index with respect to the substrate layer, and antireflection is achieved by interference between incident light and reflected light. For example, Patent Documents 2 to 4 disclose antireflection films that use silicone as a binder resin and contain hollow or porous inorganic fine particles. However, in these patent documents, the use of a silicone material having a high refractive index and heat-fusibility, particularly a silicone material having a resinous siloxane structure and a linear siloxane structure in the molecule There is no disclosure, nothing about the use of thin films for improving the light extraction efficiency in light emitting devices having a light source inside. In addition, Patent Document 5 proposes a cured product in which spherical silica hollow bead particles are mixed in a silicone resin matrix as a matrix resin in resin injection molding materials for electronic components. There is no disclosure about the use of organosilicon materials having a resinous siloxane structure and a linear siloxane structure, and there is no disclosure about the use of silica hollow bead particles with an extremely coarse particle size of 5-15 μm and a thin film.

prior art literature

patent documents

Patent Document 1: Japanese Patent Application Publication No. 2016-508290

Patent Document 2: International Patent Publication No. 2009-001723

Patent Document 3: International Patent Publication No. 2008-117652

Patent Document 4: Japanese Patent Laid-Open No. 2004-258267

Patent Document 5: Japanese Patent Laid-Open No. 06-84642

Contents of the invention

The problem to be solved by the invention

The present invention was made in order to solve the above-mentioned problems, and its object is to provide a sealant that does not impair workability, and is intended to be uniformly thinned with a film thickness of nanometers and applied to a laminated body as a light-emitting device. A silicone material capable of improving light extraction efficiency due to its performance, a laminate and a light-emitting device using the same. Another object of the present invention is to provide a method for producing a laminate and a light-emitting device using the silicone material.

means to solve the problem

As a result of intensive research, the present inventors found that the above-mentioned problems can be solved by using a solid silicone material comprising (A) a hollow or porous silicone material having a number average particle diameter of 1 to 100 nm. Inorganic particles, and

(B) having an arylsiloxane unit represented by ^RA SiO _3/2 (wherein, ^RA is an aryl group having 6 to 14 carbon atoms) in the molecule and (R ₂ SiO _2/2 )n (wherein, R is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 carbon atoms which may be substituted by a halogen atom, and n is a number in the range of 3 to 1000) Polydiorganosiloxane In the organopolysiloxane of the structure, the content of the component (A) is in the range of 10 to 95% by mass. The solid organosilicon material has thermal fusibility, and is particularly easy to be thinned at the nanometer level, and can be used as an optical component in a light-emitting device to improve its light extraction efficiency.

In addition, the inventors of the present invention have found that the above-mentioned problems can be solved by a laminate having a solid layer composed of the above-mentioned solid silicone material, and have achieved the present invention.

Likewise, the present inventors have found that by having at least one light source, a layer comprising at least one phosphor formed thereon, and a solid layer composed of the above-mentioned solid silicone material arranged at an interface with air, it is possible to The present invention has been achieved by solving the above-mentioned problems.

In addition, the present inventors have found that the above-mentioned problems can be solved by a method of manufacturing a laminate or a light-emitting device having a step of forming the above-mentioned solid silicone material into a film or thin film, and have accomplished the present invention.

Beneficial effect

By using the solid silicone material of the present invention, it is possible to provide its sealing performance without impairing workability and especially when it is prepared to be uniformly thinned with a film thickness of nanometers and applied to a laminated body as a light-emitting device. A silicone material improving light extraction efficiency, a laminate and a light emitting device using the same. In addition, it is possible to provide a method for producing a laminate or a light-emitting device having the step of forming the solid silicone material into a film or thin film.

Detailed ways

Solid silicone material

First, the solid silicone material of the present invention will be described. The solid silicone material is characterized in that it has a structure containing air inside or in pores, and a certain amount of hollow or porous inorganic particles with small particle diameters (nanoscale) are dispersed in the polymer matrix. A polydiorganosiloxane having both an arylsiloxane unit represented by R ^A SiO _3/2 (T branched unit or resin structure) and (R ₂ SiO _2/2 )n in the molecule Structure (siloxane linear structure) resin-linear block copolymer type organopolysiloxane composition.

More specifically, the solid silicone material of the present invention is the following solid silicone material, and contains:

(A) hollow or porous inorganic fine particles with a number average particle diameter of 1 to 100 nm, and

(B) having an arylsiloxane unit represented by ^RA SiO _3/2 (wherein, ^RA is an aryl group having 6 to 14 carbon atoms) in the molecule and (R ₂ SiO _2/2 )n (wherein, R is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 carbon atoms which may be substituted by a halogen atom, and n is a number in the range of 3 to 1000) Polydiorganosiloxane In the organopolysiloxane of the structure, the content of the component (A) is in the range of 10 to 95% by mass. Hereinafter, it will describe in detail.

(A) Ingredients

Component (A) is hollow or porous inorganic fine particles with an average particle diameter of 1 to 100 nm, has a structure containing air inside or in the pores, can lower the refractive index of the polymer matrix, and realizes a solid layer with a low refractive index. When such small-diameter hollow or porous inorganic particles are formed into a nanoscale thin film, the low refractive index of the thin film can be achieved and the light extraction efficiency can be improved by the light source/phosphor layer.

Here, the hollow inorganic fine particles refer to substantially spherical fine particles having cavities inside, and are true spherical to ellipsoidal fine particles whose surface is smooth or may have unevenness. The hollow inorganic particles themselves have a low refractive index (for example, refractive index: 1.20-1.45). Specific examples include hollow silica fine particles and the like. Similarly, porous inorganic fine particles refer to inorganic fine particles having a structure in which a single particle has a plurality of cavities. The type of inorganic fine particles is not particularly limited, and inorganic fine particles such as colloidal silica, porous silica sol, hollow silica sol, MgF2 sol, etc. are preferred, and hollow silica as colloidal silica is particularly preferably exemplified. Inorganic fine particles with silicon oxide fine particles as the main component. It should be noted that these silica particles can be subjected to known surface modification such as acrylic modification, and from the aspect of improving dispersibility, the surface of the inorganic particles can also be treated with silazane or a known silane coupling agent. . In addition, these inorganic fine particles may be used alone or in combination of two or more different types or average particle diameters. It should be noted that the hollow inorganic fine particles of the present invention are preferably approximately spherical as described above, and particularly preferably do not contain non-spherical, that is, plate-shaped particles, needle-shaped particles, tubular particles, etc. having a long and short diameter of the particles.

The average particle diameter of the component (A) is the number average particle diameter of individual inorganic fine particles that are not aggregated, and is an average primary particle diameter that can be measured using a laser diffraction scattering method particle size distribution analyzer or the like. The number average particle diameter is in the range of 1 to 100 nm, and inorganic fine particles mainly composed of hollow silica fine particles having an average particle diameter of 40 to 70 nm are preferable. When the average particle diameter of the inorganic fine particles is larger than the upper limit, the particles may become larger than the film thickness of the nanometer order. In addition, light may be diffusely reflected due to Rayleigh scattering in the manufactured thin film, and the solid layer may be whitish. , and its transmittance decreases. On the other hand, when the average particle diameter of the inorganic fine particles is less than the above-mentioned lower limit, it becomes the cause of aggregation that reduces the dispersibility of the inorganic fine particles. In addition, for the film-shaped members described later, sometimes the light source/phosphor layer cannot be used. light extraction efficiency.

The refractive index of the component (A) is not particularly limited and varies depending on the production method, but from the viewpoint of the technical effect of the present invention, it is preferable to use a component having a refractive index in the range of 1.20 to 1.45, preferably 1.25 to 1.37. The lower the refractive index of the component (A), the better. However, in the case of hollow silica fine particles, 1.20 is a substantial lower limit, and when it exceeds 1.45, it approaches a sufficiently high refractive index, so that a sufficient improvement in light extraction efficiency may not be obtained. Effect.

(B) Ingredients

The (B) component is a resin-linear polymer type organopolysiloxane containing a T unit having an aryl group, which is a binder of the above-mentioned (A) component, and has a high refractive index and thermal fusibility, so it can be easily Form a uniform film-like solid layer with a film thickness on the order of nanometers.

Such (B) component has an arylsiloxane unit represented by R ^A SiO _3/2 (wherein, R ^A is an aryl group having 6 to 14 carbon atoms) and a compound represented by (R ₂ SiO ₂ ) in the molecule. _/2 ) n (in the formula, R is an alkyl group with 1 to 20 carbon atoms or an aryl group with 6 to 14 carbon atoms that may be substituted by a halogen atom, and n is a number in the range of 3 to 1000) Organopolysiloxane of organosiloxane structure.

Here, the aryl group having 6 to 14 carbon atoms is phenyl, tolyl, xylyl, naphthyl, or anthracenyl, and phenyl is preferable from the viewpoint of industrial production. In addition, R is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and other alkyl groups; phenyl, toluene aryl groups such as radicals, xylyl groups, naphthyl groups, and anthracenyl groups; and groups that replace part or all of the hydrogen atoms bonded to these groups with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, etc., from industrial production From the above aspect, methyl or phenyl is preferred.

More specifically, the component (B) has a T unit: R ¹ SiO _3/2 (R ¹ is a monovalent organic group, a hydroxyl group, or an alkoxy group with 1 to 6 carbon atoms, and all R ¹ in the molecule at least one aryl group with 6 to 14 carbon atoms), any Q unit: a resin structural block having a siloxane unit represented by SiO _4/2 and (R ₂ SiO _2/2 )n (formula Among them, n is the same number, R is the same group), the linear structural block represented by silyl bond or Si-O-Si bond link structure, and has R ^A SiO _3/ A ₂ -unit resin-linear organopolysiloxane block copolymer, preferably with The Si atoms bonded to the resin structure constitute the ^RA SiO _3/2 unit.

The resin structural block in the component (B) is a partial structure that imparts heat-fusibility as a whole of the component (B), and is a resinous organopolysiloxane structure. This structure forms a partial structure composed of a resinous organopolysiloxane having an arylsiloxane unit represented by R ^A SiO _3/2 as an essential and bonded large number of T units or Q units . Especially when many aryl groups, such as a phenyl group, are contained in a molecule|numerator, the refractive index of (B) component can be raised. Preferably, the component (B) is an organopolysiloxane containing an arylsiloxane unit represented by ^RA SiO _3/2 (where RA is the same group) in an amount of 20 to 80% by mass of the entire organopolysiloxane. The resin structure of polysiloxane is substantially formed only by aryl siloxane units represented by R ^A SiO _3/2 , which is particularly preferable from the above-mentioned points of thermal meltability and refractive index.

The linear structure is a non-reactive block represented by (R ₂ SiO _2/2 )n, and the diorganosiloxy unit represented by R ₂ SiO _2/2 is connected in a chain with at least 3 units, preferably 5+ unit structure. The linear structural block is a partial structure that imparts appropriate flexibility to the solid layer formed from the present copolymer. In the formula, n is the degree of polymerization of the diorganosiloxy units constituting the partial structure, preferably in the range of 3 to 250, more preferably in the range of 5 to 250, 50 to 250, 100 to 250, and 200 to 250 . When n in the partial structure exceeds the above-mentioned upper limit, the property as a linear molecule derived from a linear structure appears strong, and thin film formability may decrease. On the other hand, when n is less than the above-mentioned lower limit, the properties as a linear molecule are insufficient, especially when thinned, repulsion and the like are likely to occur, and uniform coating cannot be achieved, and the characteristic properties of the (B) component may not be realized.

The functional group R on the diorganosiloxy unit constituting the linear structure is an alkyl group or an aryl group, and they need to be non-reactive to the resin structure and its functional groups in the same molecule, and do not cause polymerization reactions such as condensation reactions in the molecule , maintaining a linear structure. These alkyl and aryl groups are the same groups as above, and are preferably methyl or phenyl from an industrial point of view.

(B) The resin structural block and the linear structural block in the component are preferably bonded by a silyl group derived from a hydrosilylation reaction between an alkenyl group and a silicon atom-bonded hydrogen atom, or derived from a resin structure or a linear structure. Si-O-Si bond connection of the condensable reactive group at the terminal. In particular, in the present invention, it is particularly preferable that the Si atoms bonded to the resin structure constitute the R ¹ SiO _3/2 unit, and it is particularly preferable to have the following partial structure (T-Dn). From an industrial point of view, R ¹ is preferably phenyl, and R is preferably methyl or phenyl.

Partial structure (T-Dn)

Preferably, in the partial structure described above, the ends of the Si—O—bonds on the left side of the T unit are bonded to hydrogen atoms or other siloxane units constituting the resin structure, preferably other T units. On the other hand, the Si—O—bonded terminal on the right side is bonded to other siloxane units, triorganosiloxy units (M units), or hydrogen atoms forming a linear structure or a resin structure. In addition, when a hydrogen atom is bonded to the terminal of Si-O- bond, it will naturally form a silanol group (Si-OH).

From the viewpoint of the heat-fusibility of the component (B), the refractive index required to improve the light extraction efficiency, and the uniform coating property in the case of thinning in particular, it is preferable that the component (B) is composed of only R ^A SiO _{3 /} A non-reactive organopolysiloxane composed of an arylsiloxane unit represented by ₂ and a diorganosiloxane unit represented by R ₂ SiO _2/2 . More specifically, the preferred component (B) is {(R ₂ SiO _2/2 )) _a {R ^A SiO _3/2 ) _1-a

Represented organopolysiloxane. In the formula, R and R ^A are the same groups as described above, and a is a number in the range of 0.8 to 0.2, more preferably a number in the range of 0.80 to 0.40.

hot melt

The component (B) preferably exhibits hot-melt property, specifically, non-fluidity at 25°C, and preferably has a melt viscosity of 200,000 Pa·s or less at 100°C. Non-fluidity means that it does not flow under no load, for example, it means that it is lower than the softening point of the hot-melt adhesive according to the ring and ball method specified in JIS K6863-1994 "Test method for softening point of hot-melt adhesive" The state of the softening point determined in the test method. That is, in order to be non-fluid at 25°C, the softening point needs to be higher than 25°C. Preferably, the melt viscosity of component (B) at 100°C is 200,000 Pa·s or less, 100,000 Pa·s or less, 50,000 Pa·s or less, 20,000 Pa·s or less, or a range of 10 to 20,000 Pa·s Inside. When the melt viscosity at 100° C. is within the above range, the adhesiveness of a film or the like after cooling at 25° C. after thermal melting is favorable. In addition, by using the above-mentioned component (B) having a melt viscosity of 100 to 15,000 Pa·s, deformation or peeling of a film or the like after molding may be suppressed.

Compounding amount

In the solid silicone material of the present invention, the content of the component (A) is in the range of 10 to 95% by mass, and when the component (B) is an inorganic fine particle mainly composed of the above-mentioned preferable hollow silica fine particles, especially It is preferable that content of (A) component is the range of 40-95 mass %.

any ingredient

As long as the solid silicone material of the present invention does not hinder the purpose of the present invention, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane and other organic functional alkoxysilane compounds, etc. Any additives such as property enhancers, and as other arbitrary components, as long as the technical effect of the present invention is not impaired, you can add: phenolic, quinone, amine, phosphorus, phosphite, sulfur, sulfide, etc. Antioxidants; light stabilizers such as triazole series and benzophenone series; flame retardants such as phosphate ester series, halogen series, phosphorus series and antimony series; cationic surfactants, anionic surfactants, nonionic surfactants One or more antistatic agents composed of surfactants, etc.; dyes, pigments, etc. However, in the case of thinning, it is preferable not to add solid particles other than the (A) component, particularly particle components having an average primary particle diameter of more than 100 nm.

The solid silicone material of the present invention can be dispersed in an organic solvent for coating in order to form a film or thin film described later. The organic solvent used is not particularly limited as long as it is a compound capable of dissolving all or a part of the constituents in the composition, but an organic solvent with a boiling point of 80° C. or higher and less than 200° C. is preferably used. Examples include: isopropyl alcohol, t-butyl alcohol, cyclohexanol, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, mesitylene, 1,4-dioxane , dibutyl ether, anisole, 4-methyl anisole, ethylbenzene, ethoxybenzene, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 2-methoxyethanol (ethyl Glycol monomethyl ether), diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, 1-methoxy-2-propyl acetate, 1-ethoxy-2-propyl acetic acid Non-halogenated solvents such as esters, octamethylcyclotetrasiloxane, and hexamethyldisiloxane, trifluoromethylbenzene, 1,2-bis(trifluoromethyl)benzene, 1,3-bis( Halogenated solvents such as trifluoromethyl)benzene, 1,4-bis(trifluoromethyl)benzene, trifluoromethylchlorobenzene, trifluoromethylfluorobenzene, and hydrofluoroether. These organic solvents may be used alone or in combination of two or more. Isopropyl alcohol, methyl isobutyl ketone, and the like are preferable from the viewpoint of improving the workability of the solid silicone material of the present invention, the uniformity of the solid layer, and the heat resistance.

Use as membrane or thin film

The solid silicone material of the present invention can be used as a member in a desired form, but it is preferably in the form of a film or a thin film when used for the purpose of improving light extraction efficiency through the light source/phosphor layer. In particular, the solid silicone material of the present invention has a nanoscale film thickness and can be designed as a uniform thin film, preferably a film or thin film solid silicone material with a film thickness in the range of 50 to 300 nm.

Here, the film thickness of the film-like or film-like solid silicone material can be designed as desired, but for the purpose of improving the light extraction efficiency through the light source/phosphor layer, it is preferable to use diameter L (nm), film thickness in the range of L to 4L (nm), particularly preferably film thickness in the range of 1.5L to 2.5L (nm). In this range, the inorganic fine particles of the (A) component supported by the solid silicone material can be obtained in a layer in which an average of 1 to 4, preferably about 2 layers are stacked with respect to the thickness direction of the film. The practical benefit of improving light extraction efficiency is the light source/phosphor layer. As an example, when using inorganic fine particles mainly composed of hollow silica fine particles with an average primary particle diameter (L) of 50 nm, the range of 1.5L to 2.5L (nm) refers to the film thickness of 75 to 125nm range. However, in addition to the above-mentioned film thickness, even if the film thickness is about 50 to 150 nm, the light extraction efficiency can be improved by the light source/phosphor layer. In addition, it is preferable that the film thickness of the laminated body mentioned later (as a solid layer, the solid silicone material of this invention falls within the said range.

The hardness of the film-like or film-like solid silicone material also depends on the base material, so it is not particularly limited, but practically, it is preferably 2B or more in terms of pencil hardness.

There are no particular limitations on the use of the solid silicone material as above. In particular, film-like or thin-film solid silicone materials with a film thickness in the range of 50 to 300 nm improve light extraction efficiency through the light source/phosphor layer, so as solid A silicone material alone or a laminate containing the material is useful as an optical component.

Method of forming a film into a film or thin film

The method of forming the solid silicone material of the present invention into a film or film is not particularly limited, and the following methods can be used for film formation.

(i) Film formation by forming process

The solid silicone material of the present invention has thermal fusibility, so it can be formed into a film on a desired substrate by a known molding method such as integral molding. Typical molding methods include transfer molding, injection molding, and compression molding. For example, in transfer molding, the solid silicone material of the present invention is filled into a plunger of a molding machine and automatically molded to obtain a film-like or film-like member as a molded product. As the molding machine, any one of an auxiliary press molding machine, a slide molding machine, a double press molding machine, and a low-pressure encapsulation molding machine can be used.

(ii) Thin film coating using solvent and film formation by solvent removal

The solid silicone material of the present invention can be uniformly dispersed in organic solvents such as isopropyl alcohol and methyl isobutyl ketone, so it is coated on a desired substrate in a thin film, and the organic solvent is removed by means of drying, etc. This results in membrane-like or film-like parts. In the case of coating in the form of a film, it is preferable to use a solvent to adjust the viscosity so that the overall viscosity is in the range of 100 to 10,000 mPa·s. parts) can be used in the range of 0 to 2000 parts by mass. As the coating method, the following methods can be used without limitation: roll coating using gravure coating, offset coating, offset gravure printing, offset transfer roll coater, etc., using reverse roll coating, air knife coating Curtain coating such as curtain coating, comma coating, Mayer bar coating, spin coating, and other known methods used to form a cured layer. In addition, the amount of application is arbitrary, but it is preferable to apply so that the solid content after removal of the organic solvent becomes the above-mentioned film thickness. It should be noted that, as will be described later, the film-like or film-like member, or A laminated member including these is separated from the release layer and placed on another base material.

laminated body

The solid silicone material of the present invention is particularly preferably used as a solid layer constituting a laminate structure such as an optical assembly proposed by the applicant of the present application in Patent Document 1, etc. The solid layer of the part is placed at the interface with the air. At this time, as long as the laminate is a light-emitting device, from the aspect of the technical effect of the present invention, it is particularly preferable to have a layer containing at least one phosphor (hereinafter referred to as " phosphor layer").

exfoliative layer body

First, a laminate of a film-shaped or film-shaped member in which the solid silicone material of the present invention is disposed on a release layer will be described. Membrane-like or film-like parts made of the solid silicone material of the present invention, laminated parts containing them (for example laminated sheets also having a phosphor layer) are handled as individual parts according to desired requirements. In the case where the solid layer composed of the solid silicone material of the present invention is disposed on the release layer, it is possible to easily separate the film-shaped or film-shaped member composed of the solid silicone material of the present invention, including them, from the release layer constituting the laminate. The laminated parts are operated. Such a laminate has a release layer facing the solid layer made of the solid silicone material of the present invention, and may optionally have another release layer, and the following laminate structures can be exemplified. In addition, in the following examples, "/" means that each layer faces each other in the lamination direction (generally, the thickness direction perpendicular|vertical to a base material) of a laminated body. In addition, the substrate and the release layer may be integrated or in the same layer (substrate provided with material or physical unevenness and provided with release properties).

Example 1: substrate/peeling layer/solid layer made of the solid silicone material of the present invention/other arbitrary layers (can be 1 layer or 2 or more layers)

Example 2: substrate/peeling layer/solid layer made of the solid silicone material of the present invention/other arbitrary layers (can be 1 layer or more than 2 layers)/peeling layer/substrate

In particular, as in Example 2, in the case of a structure in which a film-like or film-like member made of the solid silicone material of the present invention, or a laminated member comprising them is sandwiched between two peeling layers, it is possible to combine the Parts with a solid layer made of a solid silicone material are transported (including transport to foreign countries) while being protected by the base material, and the base material with the release layer is separated from both sides of the laminate at the desired time and place, Therefore, only film-like or thin-film members made of the solid silicone material of the present invention, and laminated members including them can be arranged or laminated on a desired structure such as a light source of a light-emitting device. In particular, when the laminated body is a laminated sheet or the like having a solid layer made of the solid silicone material of the present invention and a phosphor layer, the laminated body is useful in that its handling can be improved.

There are no particular limitations on the aforementioned base material, and cardboard, cardboard, clay-coated paper, polyolefin-laminated paper, especially polyethylene-laminated paper, synthetic resin film/sheet, natural fiber fabric, synthetic fiber fabric, artificial leather cloth are exemplified , metal foil. Synthetic resin films/sheets are particularly preferred. Examples of synthetic resins include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, and polyethylene terephthalate. Ester, cyclopolyolefin, nylon. Preferably, the substrate is in the form of a film or a sheet. There is no particular limitation on its thickness, and it can be set to a desired thickness according to the application. In addition, as mentioned later, the material which functions as a peeling layer of the said base material itself, or the structure which has peelability by physically forming fine unevenness|corrugation on the surface of a base material may be sufficient.

The release layer is sometimes also called a release liner, a release layer or a release coating layer. The peeling layer of the release coating and the surface of the substrate physically form fine irregularities and are insoluble in the substrate itself adhered to the solid silicone material of the present invention.

The solid layer made of the solid silicone material of the present invention can be formed on the release layer by the same method as described in the above "Method of forming a film or film". It is particularly preferred to apply the solid silicone material uniformly dispersed in organic solvents such as isopropyl alcohol and methyl isobutyl ketone by the above-mentioned method on the release layer of a film-shaped substrate or a sheet-shaped substrate, and then dry etc. to remove the organic solvent, thereby forming a solid layer of a film-like or film-like solid silicone material on the release layer. The film thickness of the film-like or thin-film solid silicone material is the same as above.

The solid layer composed of the solid silicone material of the present invention can be used alone, and a laminated member in which the same or different layers are laminated on the solid layer is more preferable. In particular, the other layer in the laminated part is preferably a cured layer or a solid organopolysiloxane (organosilicon layer) obtained by curing an organopolysiloxane having a curing-reactive functional group, preferably a hydrogenated A silicone cured layer obtained by curing an organopolysiloxane with a silylation reactive group and/or a free radical reactive group, a condensation or a dealcoholization reactive group in the presence of a catalyst or the same as (B) component Resin-linear polymer type organopolysiloxane. Here, the organopolysiloxane having a curing reactive group may be linear, branched, cyclic, or resinous, and may be used in combination of two or more curing reactions.

It is particularly preferable that the other silicone layer arranged on the solid layer composed of the solid silicone material of the present invention is a resin-linear polymer type solid organopolysiloxane similar to the above-mentioned component (B), preferably in this A silicone layer in which a phosphor described later is dispersed in a solid organopolysiloxane.

The other layers in the above-mentioned laminated member may be one or more layers, or two or more layers having different functions. In addition, the thickness of the entire laminated member laminated on the solid layer composed of the solid silicone material of the present invention is not particularly limited, but is preferably 1 μm or more, and may be 50 to 10,000 μm from the viewpoint of workability. , particularly preferably in the range of 100 to 1,000 μm.

One or more layers laminated on the solid layer made of the solid silicone material of the present invention, particularly a silicone layer different from the solid layer, is preferably a phosphor layer containing at least one or more phosphors. In particular, the phosphor layer functions as a wavelength conversion material, and when placed on a light source, can convert the emission wavelength thereof. The phosphor is not particularly limited, and examples of phosphors widely used in light-emitting diodes (LEDs) and organic electroluminescent devices (OLEDs) are made of oxide-based phosphors, oxynitride-based phosphors, nitride-based phosphors, sulfur Yellow, red, green and blue light-emitting phosphors composed of substance-based phosphors, sulfur oxide-based phosphors, etc. Examples of oxide-based phosphors include: yttrium, aluminum, and garnet-based YAG-based green to yellow light-emitting phosphors containing cerium ions; terbium-, aluminum-, and garnet-based TAG-based yellow light-emitting phosphors containing cerium ions; A silicate-based green-yellow light-emitting phosphor containing cerium and europium ions. In addition, examples of oxynitride-based phosphors include silicon-, aluminum-, oxygen-, and nitrogen-based sialon-based red to green light-emitting phosphors containing europium ions. In addition, examples of nitride-based phosphors include calcium, strontium, aluminum, silicon, and nitrogen-based Cousin-based red light-emitting phosphors containing europium ions. As the sulfide-based phosphor, a ZnS-based green light-emitting phosphor containing copper ions or aluminum ions can be exemplified. As the sulfur oxide-based phosphor, a Y ₂ O ₂ S-based red light-emitting phosphor containing europium ions can be exemplified. In the laminate of the present invention, two or more of these phosphors may be used in combination.

In the above-mentioned laminate, the silicone layer different from the solid layer may be a silicone layer containing a reinforcing filler in order to impart mechanical strength to the cured product and improve protection or adhesiveness. In addition, the silicone layer different from the solid layer may be a silicone layer containing a thermally conductive filler or an electrically conductive filler in order to impart thermal conductivity or electrical conductivity to the cured product. It should be noted that the above-mentioned phosphors can be used in combination with these fillers. In order to improve the dispersibility of the silicone layer, alkoxysilanes, organohalosilanes, organosilazanes, siloxane oligomers, etc. The surfaces of these particulate components are surface-treated.

The above-mentioned laminate has a structure in which a solid layer composed of the solid silicone material of the present invention is disposed on a release layer, and is particularly preferably a phosphor layer containing a phosphor or the like further comprising a silicone layer different from the solid layer. When the solid layer composed of the solid silicone material of the present invention is disposed on the release layer, the laminate itself of the solid layer composed of the solid silicone material of the present invention can be easily separated from the release layer constituting the laminate as an optical component. Parts, etc. are used in the manufacture of other structures.

Laminated body and light emitting device having light source and phosphor

The solid layer made of the solid organosilicon material of the present invention can be arranged at the interface with air, and when it is arranged on the light source of a light-emitting diode (LED) or an organic electroluminescent element (OLED), the solid layer composed of the solid organosilicon material of the present invention The solid layer is arranged at the interface with the air, so that the light extraction efficiency of the entire laminate including the light source can be improved. The laminate particularly preferably has a phosphor layer containing the same phosphor as described above as a wavelength conversion material for a light source, and particularly preferably has a silicone layer containing a phosphor. Here, it is preferable that the light emitted from the light source undergo wavelength conversion through the phosphor layer and reach the solid layer composed of the solid silicone material of the present invention disposed at the interface with the air, and the solid layer composed of the solid silicone material of the present invention It may be formed to cover a part or the whole of the phosphor layer, or may be arranged outside the phosphor layer via a functional layer of another laminate. The overall thickness of these laminates is not particularly limited, but is preferably 1 μm or more, and in the case of a light emitting device or the like, may be 50 to 10,000 μm, particularly preferably 100 to 1,000 μm, except for the thickness of the light source.

Improvement of light extraction efficiency and improvement of heat resistance

The laminated body having a light source and a phosphor layer is a light-emitting device such as a light-emitting diode (LED) or an organic electroluminescent element (OLED), and is obtained by obtaining the above-mentioned light source, a phosphor layer, and a solid layer made of the solid organic silicon material of the present invention. configuration, it is possible to improve the light extraction efficiency of the light emitting device. In addition, by selecting a solid layer made of a solid silicone material, it may be possible to prevent coloring or the like accompanying heat generation of the light emitting device, and in particular, the heat resistance of the light emitting device may be improved.

Manufacturing method of laminated body

The method for producing the laminate of the present invention is not particularly limited, but from the viewpoint of forming and disposing the solid silicone material of the present invention into a thin film or film, it is preferable to include the following steps (i) to (iii): The production method of the laminated body of any process. In addition, the coating method etc. of this process can illustrate the method similar to the above.

(i) The step of forming the solid silicone material of the present invention into a film or thin film on another structure

(ii) The process of dispersing the solid silicone material of the present invention in an organic solvent and coating it in the form of a film or thin film on another structure, and then removing the organic solvent

(iii) The step of laminating other structures on the film-shaped or film-shaped member made of the solid silicone material of the present invention

In particular, the solid silicone material of the present invention can be handled as a peelable laminate, and the solid layer composed of the solid silicone material of the present invention, or a laminated member containing it, can be easily separated from the peelable layer. And make use of. It is preferable that the solid layer composed of the solid silicone material of the present invention separated from the peeling layer or the laminated member containing it be used as an optical member itself in the manufacture of other structures, and therefore a laminated body having the following steps is particularly preferable: Manufacturing method. In particular, the other structure is preferably a precursor of a light-emitting device such as a light source, and the manufacturing method is particularly preferably a method of manufacturing a light-emitting device having a solid layer composed of the solid silicone material of the present invention disposed at the interface with air.

The process of the production method of the laminate is characterized by using a laminate member (organosilicon layer) comprising a peelable laminate/solid silicone material (thin layer) of the present invention:

(a) A step of dispersing the solid silicone material of the present invention in an organic solvent on the release layer, and coating it in a film or film form on another structure, and then removing the organic solvent,

(b) a step of laminating the same or different silicone layers on the film-like or thin-film solid silicone material obtained in the step (a),

(c) a step of integrally separating the silicone layer obtained in the step (b) on which the film-like or thin-film solid silicone material is laminated from the peeling layer,

(d) A step of laminating the laminate obtained in the step (c) on another structure

Example

Hereinafter, although an Example is given and demonstrated about this invention, this invention is not limited to this. In addition, the number-average particle diameter of hollow silica fine particle is the average particle diameter described in the catalog of each company.

Synthesis Example 1

A 1 L four-necked round bottom flask was filled with phenylsilsesquioxane hydrolyzate (135.00 g, 0.99 mol of Si) and toluene (135.00 g). Under a nitrogen atmosphere, the mixture was heated at reflux for 30 minutes. After cooling the reaction mixture to 100° C., a solution of diacetoxy-terminated polyphenylmethylsiloxane (siloxane degree of polymerization 186) was added. The reaction mixture was heated at reflux for 2 hours. Then, methyltriacetoxysilane (20.23 g, 0.09 mol of Si) was added, and the mixture was refluxed for 1 hour. Water (30 mL) was added and the aqueous phase was removed by azeotropic distillation. This procedure was repeated two more times to reduce the concentration of acetic acid, and further distill off a part of the toluene, thereby obtaining a toluene solution of an organopolysiloxane having a transparent resin-linear polymer structure (weight average molecular weight=70300, solid content Concentration 79.12%).

Synthesis example 2

A 1 L four-necked round bottom flask was charged with phenylsilsesquioxane hydrolyzate (80.00 g, 0.59 mol of Si) and toluene (235.00 g). Under a nitrogen atmosphere, the mixture was heated at reflux for 30 minutes. After cooling the reaction mixture to 100° C., a solution of diacetoxy-terminated polydimethylsiloxane (siloxane degree of polymerization 105) was added. After heating the reaction mixture for 2 hours under reflux, methyltriacetoxysilane (5.35 g, 0.02 mol of Si) was added, and the mixture was refluxed for 1 hour. Water (45 mL) was added and the aqueous phase was removed by azeotropic distillation. This procedure was repeated four more times to reduce the concentration of acetic acid, and further distill off a part of the toluene, thereby obtaining a toluene solution of an organopolysiloxane having a transparent resin-linear polymer structure (weight average molecular weight=93500, solid content Concentration 66.73%).

Synthesis example 3

A 1-L four-necked round-bottomed flask was filled with phenylsilsesquioxane hydrolyzate (135.00 g, 0.99 mol of Si) and toluene (360.00 g). Under a nitrogen atmosphere, the mixture was heated at reflux for 30 minutes. After cooling the reaction mixture to 100° C., a solution of diacetoxy-terminated polydimethylsiloxane (siloxane degree of polymerization 105) was added. After heating the reaction mixture for 2 hours under reflux, methyltriacetoxysilane (13.48 g, 0.06 mol of Si) was added, and the mixture was refluxed for 2.5 hours. Then, vinylmethyldiacetoxysilane (12.65 g, 0.07 mol of Si) was added, the mixture was refluxed for 2 hours, then water (76 mL) was added, azeotroped for 30 minutes, and after the separation of the organic layer, the water was removed from below Floor. Next, the water was replaced with saturated saline, and the same procedure was repeated two more times to lower the concentration of acetic acid, and then it was repeated two more times with water. Part of the toluene was distilled off to obtain a toluene solution of an organopolysiloxane having a transparent resin-linear polymer structure (weight average molecular weight = 72000, solid content concentration 61.23%).

Examples 1-3 and Comparative Examples 1-2

Example 1

Hollow silica microparticles (Surria 4320 manufactured by Nikke Catalyst Chemicals Co., Ltd., silica solid content 20.5% by weight, hollow silica microparticles, number average particle diameter 60 nm, 0.258 g) and methyl isobutyl ketone (6.30g) was put into a container, it stirred, and the 66.73 weight% organopolysiloxane-toluene solution (0.020g) obtained in the synthesis example 2 was added, and 1 weight% of adjustment solution 1A was obtained. Adjustment solution 1A was coated on a release sheet (T788 manufactured by Daicel Corporation) using a coater (PI-1210 film coater) and a rod (R.D.S. Webster, N.Y. No. 3). After standing at room temperature for about 30 minutes, it was dried in a 40 degree oven for 1 hour to obtain a film 1 . The thickness of the coating layer was measured with a film thickness measuring machine (F20thin film analyzer manufactured by Filmetricks Co., Ltd.), and it was 188.2 nm.

To the organosiloxane-toluene solution (66.7 g) obtained in Synthesis Example 1, diazabicycloundecene (20 ppm relative to the organosiloxane) and a phosphor (manufactured by Intematex Co., Ltd.) were added. , NYAG 4454-L, 10.1 g) was stirred so as to become uniform using a self-revolving stirrer (ARV-310LED manufactured by Shiheki Corporation) having a vacuum degassing mechanism to obtain an adjustment liquid 1B. This adjustment solution 1B was poured on the coating surface side of the film 1 with a gap of 925 μm using a coater (PI-1210 FILM COATER). This sheet was dried overnight in an oven at 40C, and then further dried in a vacuum oven at 50C for 2 hours to obtain a phosphor sheet 1 .

After punching the obtained phosphor sheet 1 into a circle with a diameter of 36 mm, it was peeled off from the peeling sheet, placed on the LED chip so that the coated surface was on top, and was vacuum coated using a vacuum coating machine (Nisshinbo Coating Machine 0505S ) for sealing.

Example 2

Hollow silica microparticles (Surria 4320 manufactured by Nikke Catalyst Chemicals Co., Ltd., 20.5% by weight of silica solid content, hollow silica microparticles, number average particle diameter 60 nm, 0.068 g) and methyl isobutyl ketone (3.46g) was put into a container, it stirred, and the organopolysiloxane-toluene solution (0.005g) of 66.73 weight% obtained in the synthesis example 2 was added, and the adjustment solution 2A of 0.5 weight% was obtained. Adjustment solution 2A was coated on a release sheet (T788 manufactured by Daicel Corporation) using a coater (PI-1210 film coater) and a rod (R.D.S. Webster, N.Y. No. 3). After standing at room temperature for about 30 minutes, it was dried in a 40-degree oven for 1 hour to obtain a film 2 . The thickness of the coating layer was measured with a film thickness measuring machine (F20thin film analyzer manufactured by Filmetricks Co., Ltd.), and it was 113.1 nm.

The same adjustment solution 1B as in Example 1 was poured on the coating surface side of the film 2 with a gap of 925 μm using a coater (PI-1210 FILM COATER). This sheet was dried overnight in an oven at 40C, and then further dried in a vacuum oven at 50C for 2 hours to obtain a phosphor sheet 2 . The obtained phosphor sheet 2 was placed on the LED chip by the same method as in Example 1, and sealed using a vacuum laminating machine.

Example 3

To adjustment solution 1A (0.30 g) of Example 1, methyl isobutyl ketone (2.75 g) was added and diluted, and 0.1% by weight of adjustment solution 3A was adjusted. Adjustment solution 3A was coated on a release sheet (T788 manufactured by Daicel Corporation) using a coater (PI-1210 film coater) and a rod (R.D.S. Webster, N.Y. No. 3). After standing at room temperature for about 30 minutes, it was dried in a 40 degree oven for 1 hour to obtain a film 3 . The thickness of the coating layer was measured with a film thickness measuring machine (F20thin film analyzer manufactured by Filmetricks Co., Ltd.), and it was 213 nm.

The same adjustment solution 1B as in Example 1 was poured on the coated surface side of the film 3 with a gap of 925 μm using a coater (PI-1210 FILM COATER). This sheet was dried overnight in an oven at 40C, and then further dried in a vacuum oven at 50C for 2 hours to obtain a phosphor sheet 3 . The phosphor sheet 3 thus obtained was placed on the LED chip by the same method as in Example 1, and sealed using a vacuum laminating machine.

Comparative example 1

The same adjustment solution 1B as in Example 1 was poured on a release sheet (T788 manufactured by Daicel Corporation) with a gap of 925 μm using a coater (PI-1210 FILM COATER). This sheet was dried overnight in an oven at 40C, and then further dried in a vacuum oven at 50C for 2 hours to obtain a phosphor sheet 4 . The phosphor sheet 4 obtained was placed on the LED chip by the same method as in Example 1, and sealed using a vacuum laminating machine.

Comparative example 2

Reinforcing silica (Aerosil 200S, 0.107 g) and methyl isobutyl ketone (1.00 g) were added to the 66.73% by weight organosiloxane-toluene solution (3.29 g) obtained in Synthesis Example 2, and used A dental mixer was used to stir for 20 seconds to obtain a mixed solution 1. The obtained mixed solution (0.05 g) was diluted with methyl isobutyl ketone (2.56 g), and 1 weight% solution 4A was adjusted.

The adjustment solution 4A was coated on a release sheet (T788 manufactured by Daicel Corporation) using a coater (PI-1210 film coater) and a rod (R.D.S. Webster, N.Y. No. 3). After standing at room temperature for about 30 minutes, it was dried in a 40-degree oven for 1 hour to obtain a film 4 . The thickness of the coating layer was measured with a film thickness measuring machine (F20 thin film analyzer manufactured by Filmetricks Co., Ltd.), and it was 110 nm.

The same adjustment solution 1B as in Example 1 was poured on the coated surface side of the film 4 with a gap of 925 μm using a coater (PI-1210 FILM COATER). This sheet was dried overnight in an oven at 40C, and then further dried in a vacuum oven at 50C for 2 hours to obtain a phosphor sheet 5 . The obtained phosphor sheet 5 was placed on the LED chip by the same method as in Example 1, and sealed using a vacuum laminating machine.

Evaluation method

Determination of full radiation beam

Regarding the light-emitting semiconductor devices (Examples 1-3, Comparative Examples 1-2) obtained by sealing the LED chip through the above steps, the total radiation beam (mW) was measured using a total beam measuring device (manufactured by Otsuka Electronics Co., Ltd.). . The results are shown in Table 1 below.

Table 1

Embodiment 5～6, comparative example 3

In the following Examples 5 to 6 and Comparative Example 7, light-emitting semiconductor devices obtained by the following methods were used. In addition, in the examples, the thickness of the thin film layer (coating layer) containing hollow silica particles obtained by spin coating represents the value measured separately by spin coating the same amount of solution.

Fabrication of optical semiconductor packages

A light-emitting semiconductor device in an MA5050 package (W*N-045) mounted with an LED chip having a light-emitting layer made of InGaN and a main light-emitting peak of 454.7-460 nm as an optical semiconductor element was used.

As a sealing resin, to the organosiloxane-toluene solution (105.4 g) obtained in Synthesis Example 1 were added diazabicycloundecene (0.01 g, an amount of 100 ppm relative to organosiloxane) and fluorescent Body (Iyetematetsu Co., Ltd., NYAG 4454-L, 17.348g), adhesion imparting agent (Shin-Etsu Chemical Co., Ltd. KBE-402, /0433g) and silanol-terminated polyphenylmethylsiloxane Polymerization degree 4-5, 11.22g), using a self-revolving stirrer with a vacuum degassing mechanism (ARV-310LED manufactured by Shiheki Co., Ltd.), stirred so as to become uniform, and obtained adjustment liquid 1C.

The adjustment solution 1C was poured on a release film (SPPET5003BU manufactured by Mitsui Tosero) with a gap of 925 μm using a coater (PI-1210 FILM COATER). After drying the sheet overnight in an oven set at 40 degrees, it was further dried in a vacuum oven at 50 degrees for 2 hours.

The obtained phosphor sheet was punched out into a circular shape with a diameter of 32 mm, and sealed on the LED chip using a vacuum laminating machine (Laminating machine 0505S manufactured by Nisshinbo Co., Ltd.). The obtained light-emitting semiconductor device was placed on a stainless steel (SUS) plate provided with a spacer with a height of 1.4mm, and the release film and the SUS plate were placed on it from the previous time, and it was heated and cured by compressing at 135 degrees for 30 minutes using a heat press machine. . It was then allowed to fully cure in a programmed oven set at 100 degrees/1 hour, 120 degrees/1 hour, 140 degrees/1 hour, 150 degrees/1 hour, 160 degrees/3 hours.

Example 5

Hollow silica microparticles (Surria 4320 manufactured by Nikke Catalyst Chemicals Co., Ltd., silica solid content 20.5% by weight, hollow silica microparticles, number average particle diameter 60 nm, 0.378 g) and methyl isobutyl ketone (9.3 g) was put into a container, stirred, and the 66.73 weight% organopolysiloxane-toluene solution (0.029g) obtained in the synthesis example 2 was added, and the solution 1 of 1 weight% was obtained.

This solution 1 was hung on the sealing layer of the obtained light-emitting semiconductor device, using a spin coater (Mikasa supine coater 1H-DXII), started to rotate at 300 rpm for 15 seconds, then increased to 1500 rpm, rotated for 30 seconds, and coated on upper surface. When the thickness of the coating layer alone using the same amount of solution was measured with a film thickness measuring machine (F20 thin film analyzer manufactured by Filmetricks Co., Ltd.), it was 113 nm. In addition, the film thickness of the entire layer including the cured layer obtained by curing the coating layer and the phosphor layer was about 400 μm. The light-emitting semiconductor devices were dried in a programmed oven set at 70 degrees/20 minutes and 150 degrees/1 hour.

Example 6

Hollow silica microparticles (Surria 4320 manufactured by Nikke Catalyst Chemicals Co., Ltd., silica solid content 20.5% by weight, hollow silica microparticles, number average particle diameter 60 nm, 0.2084 g) and methyl isobutyl ketone (5.00 g) was placed in a container, stirred, and the 61.23% by weight organopolysiloxane-toluene solution (0.017 g) obtained in Synthesis Example 3, hydrosilyl-terminated polyorganosiloxane (0.0004 g) were added. and a 0.1% by weight platinum complex-toluene solution (0.0003 g), resulting in a 1% by weight solution 2.

Hang this solution 2 on the sealing layer of the obtained light-emitting semiconductor device, use a spin coater (Mika Suspin Coter 1H-DXII), start spinning at 300 rpm for 15 seconds, increase to 1500 rpm, spin for 30 seconds, and coat the surface upper part. The light emitting semiconductor devices were dried in a programmed oven set at 70 degrees/20 minutes and 150 degrees/1 hour. When the thickness of the coating layer alone using the same amount of solution was measured with a film thickness measuring machine (F20 thin film analyzer manufactured by Filmetricks Co., Ltd.), it was 113 nm. In addition, the film thickness of the entire layer including the cured layer obtained by curing the coating layer and the phosphor layer was about 400 μm.

Comparative example 3

Aerosol (200S, 0.107 g) and methyl isobutyl ketone (1.00 g) were added to the 66.73% by weight organopolysiloxane-toluene solution (3.29 g) obtained in Synthesis Example 2, and stirred for 20 minutes using a dental mixer. seconds, a mixed solution 1 is obtained. The obtained mixed solution 1 (0.05 g) was diluted with methyl isobutyl ketone (2.56 g), and the solution 3 of 1 weight% was adjusted.

Hang this solution 1 on the sealing layer of the obtained light-emitting semiconductor device, use a spin coater (Mika Suspin Coter 1H-DXII), start spinning at 300 rpm for 15 seconds, increase to 1500 rpm, spin for 30 seconds, and coat the surface upper part. The light emitting semiconductor devices were dried in a programmed oven set at 70 degrees/20 minutes and 150 degrees/1 hour. The thickness of the coating layer alone using the same amount of solution was measured with a film thickness measuring machine (F20 thin film analyzer manufactured by Filmetricks Co., Ltd.), and it was 110 nm. In addition, the film thickness of the entire layer including the cured layer formed by curing the coating layer and the phosphor layer was about 400 μm.

Evaluation method

Determination of full radiation beam

For the light-emitting semiconductor device obtained by the above process, the total beam (mW) before and after coating the adjustment solution was measured using a total beam measuring device (manufactured by Otsuka Electronics Co., Ltd.).

Table 2

In the embodiments of the present invention, regarding the light emitting semiconductor device, the change rate of the total radiation beam before and after coating is improved, and the light extraction efficiency from the LED chip can be improved. In particular, in Example 2 in which the film thickness of the solid silicone material of the present invention was designed to be about 113 nm, which is about twice the average particle diameter (60 nm) of the hollow silica particles, the light extraction efficiency was most improved.

Claims (17)

1. A solid organosilicon material, which contains: (A) hollow or porous inorganic particles with a number average particle diameter of 1 to 100 nm, and (B) having an arylsiloxane unit represented by ^RA SiO _3/2 (wherein, ^RA is an aryl group having 6 to 14 carbon atoms) in the molecule and (R ₂ SiO _2/2 )n (wherein, R is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 carbon atoms which may be substituted by a halogen atom, and n is a number in the range of 3 to 1000) Polydiorganosiloxane In the organopolysiloxane of the structure, the content of the component (A) is in the range of 10 to 95% by mass. 2. The solid organosilicon material according to claim 1, wherein the component (A) is an inorganic particle having a number-average particle diameter of 40 to 70 nm as a main component of hollow silica particles, and the content of the component (A) is 40 to 70 nm. 95% by mass. 3. The solid organosilicon material according to claim 1, wherein the component (B) is composed of ^RA SiO _3/2 (wherein, ^RA is the The same group) is an organopolysiloxane represented by an arylsiloxane unit. 4. The solid organosilicon material according to claim 1 or 3, wherein component (B) is composed of {(R ₂ SiO _2/2 )} _a { ^RA SiO _3/2 ) _1-a (wherein, R , ^RA is the same group as above, and a is an organopolysiloxane represented by a number in the range of 0.8 to 0.2). 5. The solid silicone material according to claim 1, 3 or 4, wherein the component (B) is a heat-fusible organopolysiloxane. 6. The solid silicone material according to any one of claims 1 to 5, which is in the form of a film or a thin film. 7. The solid silicone material according to claim 6, which has a film thickness in the range of 50 to 300 nm. 8. The solid silicone material according to claim 6 or 7, wherein the film thickness is in the range of L to 4L (nm) relative to the average particle diameter L (nm) of the component (A). 9. An optical component composed of the solid silicone material according to any one of claims 1 to 8. 10. A laminate having a solid layer composed of the solid silicone material according to any one of claims 1 to 8. 11. The laminate according to claim 9, which has a structure in which a solid layer made of the solid silicone material according to any one of claims 1 to 8 is arranged on a release layer. 12. The laminate according to claim 10, which has a solid layer composed of the solid silicone material according to any one of claims 1 to 8 and a layer comprising at least one phosphor. 13. The laminate according to claim 10 or 12, which has a structure having a solid layer made of the solid silicone material according to any one of claims 1 to 8 and comprising at least one Phosphor layer, and a solid layer made of the above-mentioned solid silicone material is arranged at the interface with air. 14. A light-emitting device having at least one light source, a layer comprising at least one phosphor formed thereon, and the solid organic compound according to any one of claims 1 to 8 disposed at an interface with air. A solid layer of silicon material. 15. A method for producing a laminate, which is a method for producing the laminate according to any one of claims 10 to 13, comprising any one of the following steps (i) to (iii): (i) the process of forming the solid silicone material described in any one of claims 1 to 5 into a film or film on other structures; (ii) dispersing the solid organosilicon material according to any one of claims 1 to 5 in an organic solvent, coating other structures in the form of a film or film, and then removing the organic solvent; (iii) A step of laminating another structure on the film-shaped or film-shaped member made of the solid silicone material according to any one of claims 1 to 5. The manufacturing method of the laminated body which is the manufacturing method of the laminated body of Claim 10, 12 or 13 which has the following process. (a) On the release layer, the solid silicone material according to any one of claims 1 to 5 is dispersed in an organic solvent, and after being coated in a film or thin film on other structures, the organic solvent is removed process; (b) a step of laminating the same or different silicone layers on the film-like or thin-film solid silicone material obtained in the step (a), (c) a step of integrally separating the silicone layer obtained in the step (b) on which the film-like or thin-film solid silicone material is laminated from the peeling layer, (d) A step of laminating the laminate obtained in the step (c) on another structure 17. The method for manufacturing a laminated body according to claim 15 or 16, wherein the laminated body is a light-emitting device, and a film-shaped or thin-film member made of a solid silicone material is arranged at an interface with air.