JP7173689B2 - Solid silicone material, laminate and light-emitting device using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a solid silicone material, a laminate and a light-emitting device using the same, and in particular, it is easily thinned with a uniform nanometer-scale film thickness, and is arranged at the interface with the air of the laminate, which is a light-emitting device. The present invention relates to a solid silicone material capable of improving light extraction efficiency and the like by The present invention also relates to a method for manufacturing laminates and optical devices using the solid silicone material.

Solid silicone materials have excellent moldability, heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency, and are therefore used in a wide range of industrial fields. In particular, the cured product of the curable silicone composition is resistant to discoloration compared to other organic materials, and has less deterioration in physical properties. Also suitable as an agent.

In recent years, hot-melt silicone-containing materials that are solid or semi-solid at room temperature and are melted by heating at high temperatures have been proposed for new manufacturing processes of light-emitting devices. Silicone-containing materials with hot-melt properties, unlike ordinary liquid materials, are excellent in handling workability and uniform coating properties. It proposes an optical assembly using a reactive or non-reactive silicone-containing hot-melt composition having a chain siloxane structure as a sealing material film. The sealing material has a particularly high refractive index and is used in combination with a sealing material film (phosphor layer) having a fluorescent material that converts the wavelength of light emitted from the light source. device can be provided. However, in the field of light-emitting devices, there is a demand for higher light extraction efficiency, particularly when the phosphor layer described above is used. Note that Patent Document 1 does not disclose any use of a thin film, particularly a nanometer-scale thin film, for improving light extraction efficiency, or blending specific hollow or porous inorganic fine particles.

On the other hand, hollow or porous inorganic fine particles with a small particle diameter have a structure containing air inside or in pores, and when blended with a binder resin, they give a low refractive index to the air layer. , and is used as an antireflection layer in antireflection films. Specifically, incident light (incident light from an external light source) is reflected at the interface of the antireflection layer, which has a low refractive index with respect to the base layer, and antireflection is achieved by interference between the incident light and the reflected light. is. For example, Patent Documents 2 to 4 disclose antireflection films containing hollow or porous inorganic fine particles using silicone as a binder resin. However, these patent documents do not disclose the use of a silicone material that provides a high refractive index and has hot-melt properties, in particular, a silicone material that has a resinous siloxane structure and a linear siloxane structure in its molecule. There is no disclosure of the use of thin films to improve light extraction efficiency in light emitting devices having light sources therein. In addition, Patent Document 5 proposes a cured product in which spherical silica hollow bead particles are blended into a silicone resin matrix as a base resin in a resin casting material for electronic parts. No use of a silicone material having a linear siloxane structure is disclosed, silica hollow bead particles are extremely coarse at 5-15 μm, and no use of a thin film is disclosed.

Japanese Patent Publication No. 2016-508290 International Patent Publication No. 2009-001723 International Patent Publication No. 2008-117652 JP 2004-258267 A JP-A-06-84642

The present invention has been made to solve the above problems. An object of the present invention is to provide a silicone material capable of improving light extraction efficiency without impairing its sealing performance, and a laminate and a light-emitting device using the same. Another object of the present invention is to provide a method for manufacturing a laminate and a light-emitting device using the silicone material.

As a result of intensive studies, the present inventors found (A) hollow or porous inorganic fine particles having a number average particle size of 1 to 100 nm, and (B) R ^A SiO _3/2 in the molecule (wherein R ^A is an arylsiloxane unit represented by aryl group having 6 to 14 carbon atoms) and (R ₂ SiO _2/2 )n (wherein R is an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom) or an aryl group having 6 to 14 carbon atoms, n is a number in the range of 3 to 1000), and the content of component (A) is 10 to The inventors have found that the above problems can be solved by using a solid silicone material in the range of 95% by mass, and have arrived at the present invention. The solid silicone material has hot-melt properties, and is particularly easy to form into a nanometer-scale thin film. By applying it as an optical member to a light-emitting device, the light extraction efficiency can be improved.

Furthermore, the present inventors have found that the above problems can be solved by a laminate having a solid layer made of the above solid silicone material, and have completed the present invention.

Similarly, the inventors have provided at least one light source, a layer containing at least one phosphor formed thereon, and a solid layer of the above solid silicone material disposed at the interface with air. Furthermore, the inventors have found that the above problems can be solved by a light-emitting device, and have arrived at the present invention.

In addition, the present inventors have found that the above problems can be solved by a method for manufacturing a laminate or a light-emitting device, which includes a step of molding the solid silicone material into a film or thin film, and have completed the present invention. .

By using the solid silicone material of the present invention, handling workability and uniform thinning of the film thickness of nanometers are readily available. It is possible to provide a silicone material capable of improving light extraction efficiency, a laminate using the same, and a light-emitting device without impairing anything. Moreover, it is possible to provide a method for manufacturing a laminate or a light-emitting device, which comprises a step of molding the above-described solid silicone material into a film or thin film.

[Solid silicone material]
First, the solid silicone material of the present invention will be described. The solid silicone material has a structure in which air is contained inside or in the pores, and hollow or porous inorganic fine particles with a small particle size (nanometer scale) are represented by R ^A SiO _3/2 in the molecule. from a resin-linear block copolymer type organopolysiloxane having both an arylsiloxane unit (T-branching unit or resin structure) and a polydiorganosiloxane structure (siloxane linear structure) represented by (R ₂ SiO _2/2 )n It is characterized by dispersing a certain amount in a polymer matrix.

More specifically, the solid silicone material of the present invention is
(A) Hollow or porous inorganic fine particles having a number average particle diameter of 1 to 100 nm, and (B) R ^A SiO _3/2 (wherein R ^A is an aryl group having 6 to 14 carbon atoms) in the molecule. the represented arylsiloxane unit 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 with a halogen atom; A solid silicone material containing an organopolysiloxane having a polydiorganosiloxane structure represented by (n is a number in the range of 3 to 1000), wherein the content of component (A) is in the range of 10 to 95% by mass. , which will be described in detail below.

[(A) Component]
Component (A) is hollow or porous inorganic fine particles having an average particle size of 1 to 100 nm, having a structure containing air inside or in pores, and reducing the refractive index of the polymer matrix to achieve a low refractive index. A solid layer of a rate can be realized. When such hollow or porous inorganic fine particles having a small particle diameter are formed into a nanometer-scale thin film, they realize a low refractive index property of the thin film and increase the light extraction efficiency through the light source/phosphor layer. It is an ingredient that improves

Here, the hollow inorganic microparticles are substantially spherical microparticles having cavities inside, and are spherical to ellipsoidal microparticles whose surfaces may be smooth or uneven. The hollow inorganic fine particles themselves have a low refractive index (for example, refractive index: 1.20 to 1.45). Specific examples include hollow silica fine particles. Similarly, porous inorganic fine particles are inorganic fine particles having a structure in which a plurality of cavities are provided in one fine particle. The type of inorganic fine particles is not particularly limited, but inorganic fine particles such as colloidal silica, porous silica sol, hollow silica sol, MgF2 sol, etc. are preferable. Inorganic fine particles are preferably exemplified. These silica fine particles may be subjected to known surface modification such as acrylic modification, and furthermore, from the viewpoint of improving dispersibility, the surface of inorganic fine particles is treated with silazane or a known silane coupling agent. may be Furthermore, these inorganic fine particles may be used singly or in combination of two or more kinds having different types or different average particle sizes. The hollow inorganic fine particles of the present invention preferably have a substantially spherical shape as described above, and do not include non-spherical particles, that is, plate-like particles, needle-like particles, tube-like particles, etc. having long and short diameters. is particularly preferred.

The average particle size of component (A) is the number average particle size of individual inorganic fine particles that are not agglomerated, and is the average primary particle size 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 it is particularly preferable that the inorganic fine particles are composed mainly of hollow silica fine particles having an average particle diameter of 40 to 70 nm. If the average particle diameter of the inorganic fine particles is larger than the upper limit, the particles may become larger than the nanometer-scale film thickness, and the solid layer may appear whitish due to the diffuse reflection of light due to Rayleigh scattering in the thin film produced. , its transmittance may decrease. On the other hand, if the average particle diameter of the inorganic fine particles is smaller than the above lower limit, the dispersibility of the inorganic fine particles decreases and causes aggregation. may not be able to improve

The refractive index of component (A) is not particularly limited and varies depending on the manufacturing method, but from the viewpoint of the technical effect of the present invention, the refractive index is in the range of 1.20 to 1.45. It is preferable to use 1.25 to 1.37. The lower the refractive index of component (A), the better. In some cases, the effect of improving the light extraction efficiency cannot be obtained.

[(B) Component]
Component (B) is a resin-linear polymer type organopolysiloxane containing T units having an aryl group, which serves as a binder for component (A) above, and has a high refractive index and hot-melt properties. Therefore, it is possible to easily form a thin film-like solid layer that is uniform and has a film thickness on the nanometer scale.

Such component (B) contains an arylsiloxane unit represented by R ^A SiO _3/2 (wherein R ^A is an aryl group having 6 to 14 carbon atoms) 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 with a halogen atom, n is a number in the range of 3 to 1000) It is an organopolysiloxane having a polydiorganosiloxane structure.

Here, the aryl group having 6 to 14 carbon atoms is a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, and preferably a phenyl group from the viewpoint of industrial production. R is a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, alkyl group such as dodecyl group; phenyl group, tolyl group, Aryl groups such as xylyl groups, naphthyl groups and anthracenyl groups; A methyl group or a phenyl group is preferred from the standpoint of production.

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 having 1 to 6 carbon atoms, and all R at least ^one of 1 is an aryl group having 6 to 14 carbon atoms), optionally a Q unit: a resin structural block having a siloxane unit represented by SiO _4/2 and (R ₂ SiO _2/2 ) and a linear structural block represented by n (wherein n is the same number as described above and R is the same group as described above), and a structure in which a silalkylene bond or a Si—O—Si bond is connected, and a resin-linear organopolysiloxane block copolymer having R ^A SiO _3/2 units, wherein the silalkylene bond or Si—O—Si bond connecting the resin structural block and the linear structural block in the polymer is in the resin structure. It is preferred that the linking Si atoms constitute R ^A SiO _3/2 units.

The resin structural block in component (B) is a partial structure that imparts hot-melt properties to component (B) as a whole, and is a resinous organopolysiloxane structure. Such a structure essentially comprises an arylsiloxane unit represented by R ^A SiO _3/2 and forms a partial structure composed of a resin-like organopolysiloxane in which a large number of T units or Q units are bonded. In particular, when a large number of aryl groups such as phenyl groups are contained in the molecule, the refractive index of component (B) can be increased. Preferably, component (B) is an organopolysiloxane containing 20 to 80% by mass of the total organopolysiloxane of arylsiloxane units represented by R ^A SiO _3/2 (wherein R ^A is the same group as above). From the standpoints of the above hot-melt properties and refractive index, it is particularly preferred that it is siloxane and the resin structure is formed substantially only from arylsiloxane units represented by R ^A SiO _3/2 .

The linear structure is a non-reactive block represented by (R ₂ SiO _2/2 )n, and the diorganosiloxy units represented by R ₂ SiO _2/2 are at least 3 units or more, preferably 5 units. The structure described above is connected in a chain. Such linear building blocks are substructures that give the solid layer formed by the copolymer a moderate degree of flexibility. 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 upper limit, the property as a linear molecule derived from the linear structure is strongly exhibited, and the thin film formability may be deteriorated. On the other hand, if n is less than the above lower limit, the property as a linear molecule is not sufficient, and characteristic physical properties of the component (B) such as repelling and the like being likely to occur when the film is made thin and uniform coating cannot be achieved. It may not be possible.

The functional group R on the diorganosiloxy unit that constitutes the linear structure is an alkyl group or an aryl group, which are non-reactive to the resin structure and its functional groups in the same molecule and undergo intramolecular condensation. It is necessary to maintain the linear structure without causing a polymerization reaction such as reaction. These alkyl groups and aryl groups are the same groups as described above, and from an industrial point of view, a methyl group or a phenyl group is preferred.

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

（Ｔ－Ｄｎ）Partial structure (TDn)

(TDn)

Preferably, in the above partial structure, the ends of the Si—O—bonds on the left side constituting the T unit are each bonded to a hydrogen atom or another siloxane unit constituting the resin structure, preferably another T unit. do. On the other hand, the end of the Si—O—bond on the right is bonded to another siloxane unit, triorganosiloxy unit (M unit) or hydrogen atom forming a linear structure or resin structure. Needless to say, when a hydrogen atom bonds to the end of the Si--O--bond, a silanol group (Si--OH) is formed.

From the viewpoint of the hot-melt property of component (B), the refractive index required to improve the light extraction efficiency, and the uniform coating property especially when thinned, component (B) is R ^A SiO _3/2 . A non-reactive organopolysiloxane consisting solely of arylsiloxane units represented by R ₂ SiO _2/2 and diorganosiloxane units represented by R 2 SiO 2/2 is preferred. More specifically, component (B) is
{(R ₂ SiO _2/2 )} _a {R ^A SiO _3/2 } _1-a
Organopolysiloxane represented by is preferred. In the formula, R and ^RA are the same groups as described above, and a is a number within the range of 0.8 to 0.2, more preferably a number within the range of 0.80 to 0.40.

[Hot melt property]
Component (B) preferably exhibits hot-melt properties, specifically, it is non-flowable at 25°C and preferably has a melt viscosity of 200,000 Pa·s or less at 100°C. Non-fluid means that it does not flow under no load. Indicates the state below the softening point measured by the test method. That is, in order to be non-flowable at 25°C, the softening point must be higher than 25°C. Preferably, component (B) has a melt viscosity at 100° C. of 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 10 to 20,000 Pa・It is within the range of s. When the melt viscosity at 100°C is within the above range, adhesion of a thin film or the like after cooling to 25°C after hot-melting is good. Further, by using the component (B) having a melt viscosity of 100 to 15,000 Pa·s, it may be possible to suppress deformation and peeling of the thin film after molding.

[Combination amount]
In the solid silicone material of the present invention, when the content of component (A) is in the range of 10 to 95% by mass, and component (B) is inorganic fine particles containing the preferred hollow silica fine particles as a main component, ( It is particularly preferred that the content of component A) is in the range of 40 to 95% by mass.

[Optional component]
The solid silicone material of the present invention includes vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldisilane, so long as the objects of the present invention are not hindered. Optional additives such as adhesion improvers such as organic functional alkoxysilane compounds such as ethoxysilane and 3-methacryloxypropyltrimethoxysilane. Phenolic, quinone, amine, phosphorus, phosphite, sulfur, thioether, etc. antioxidants; triazole, benzophenone, etc. light stabilizers; phosphate, halogen, phosphorus, antimony flame retardants such as system; one or more antistatic agents such as cationic surfactants, anionic surfactants and nonionic surfactants; dyes, pigments and the like may be added. However, when thinning, it is preferable not to add solid particles other than the component (A), particularly particle components having an average primary particle size exceeding 100 nm.

The solid silicone material of the present invention can be dispersed in an organic solvent and applied for the purpose of forming a film or thin film, which will be described later. The type of organic solvent to be used is not particularly limited as long as it is a compound capable of dissolving all or part of the constituent components in the composition, and those having a boiling point of 80° C. or more and less than 200° C. are preferably used. be done. For example, i-propyl alcohol, t-butyl alcohol, cyclohexanol, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, mesitylene, 1,4-dioxane, dibutyl ether, anisole, 4-methylanisole, ethylbenzene, ethoxybenzene, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 2-methoxyethanol (ethylene glycol monomethyl ether), diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, propyl propionate, 1-methoxy-2-propyl acetate, Non-halogen solvents such as 1-ethoxy-2-propyl acetate, octamethylcyclotetrasiloxane, and hexamethyldisiloxane, trifluoromethylbenzene, 1,2-bis(trifluoromethyl)benzene, 1,3-bis( halogen-based 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. From the standpoints of workability in handling the solid silicone material of the present invention, uniformity of the solid layer and improvement in heat resistance, i-propyl alcohol, methyl isobutyl ketone and the like are preferably used.

[Use as film or thin film]
The solid silicone material of the present invention can be used as a member in any desired form. is preferred. In particular, the solid silicone material of the present invention can be designed into a uniform thin film having a thickness on the nanometer scale, preferably a film or thin film having a thickness in the range of 50 to 300 nm. can provide a solid silicone material in the form of a

Here, the thickness of the film-like or thin-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, ) with respect to the average primary particle diameter L (nm) of the component, the film thickness is preferably in the range of L to 4L (nm), and the film thickness is in the range of 1.5L to 2.5L (nm) is particularly preferred. Within this range, the inorganic fine particles of component (A) supported on the solid silicone material should have a structure in which 1 to 4 particles on average in the layer, preferably about 2 particles in the thickness direction of the film are stacked. Therefore, there is a practical benefit that the light extraction efficiency is most improved through the light source/phosphor layer. As an example, when using inorganic fine particles mainly composed of hollow silica fine particles having an average primary particle diameter (L) of 50 nm, the range of 1.5 L to 2.5 L (nm) means that the film thickness is 75 to 125 nm range. However, it is possible to improve the light extraction efficiency through the light source/phosphor layer even with a thickness other than the above thickness, for example, a thickness of about 50 to 150 nm. It should be noted that the film thickness of the solid silicone material of the present invention is preferably within the above range even in the layered product (solid layer) described later.

Since the hardness of the film-like or thin-film-like solid silicone material depends on the base material, it is not particularly limited, but from a practical standpoint, it preferably has a pencil hardness of 2B or more.

Applications of the solid silicone material as described above are not particularly limited. In order to improve the light extraction efficiency, the solid silicone material alone or a laminate containing the material is useful as an optical member.

[Method of Forming a Film or Thin Film]
The method for forming a film or thin film of the solid silicone material according to the present invention is not particularly limited, and the film can be formed by the following methods.

(i) Film formation by molding process Since the solid silicone material according to the present invention has hot-melt properties, it can be formed into a film on a desired substrate by a known molding technique such as integral molding. Common molding techniques include transfer molding, injection molding, and compression molding. For example, in transfer molding, the plunger of a molding machine is filled with the solid silicone material of the present invention, and automatic molding is performed to obtain a film-like or thin-film-like member as a molding. As the molding machine, any of an auxiliary ram type molding machine, a slide type molding machine, a double ram type molding machine and a low pressure encapsulation molding machine can be used.

(ii) Thin film coating using a solvent and film formation by removing the solvent The solid silicone material according to the present invention can be uniformly dispersed in organic solvents such as i-propyl alcohol and methyl isobutyl ketone. A film-like or thin-film-like member can be obtained by coating a thin film on the base material to be used and removing the organic solvent by means such as drying. When coating in the form of a film, it is preferable to adjust the viscosity using a solvent so that the overall viscosity is in the range of 100 to 10,000 mPa s. parts), it can be used in the range of 0 to 2000 parts by mass. Coating methods include gravure coating, offset coating, offset gravure, roll coating using an offset transfer roll coater, reverse roll coating, air knife coating, curtain coating using a curtain flow coater, comma coating, Meyer bar, and spin coating. A method used for the purpose of forming a coat or other known cured layers can be used without limitation. Although the coating amount is arbitrary, it is preferable to apply the coating so as to obtain the above film thickness as a solid content after removal of the organic solvent. As will be described later, by using a laminate in which a film-like or thin-film-like member of the solid silicone material according to the present invention is formed on a release coating layer, the film-like or thin-film-like member, or a laminate containing the same can be obtained. The member can be separated from the release layer and placed on another substrate.

[Laminate]
The solid silicone material of the present invention can be particularly suitably used as a solid layer constituting a laminate structure such as an optical assembly as proposed by the present applicant in Patent Document 1 and the like. As a solid layer constituting the laminated member used for the above, it is preferably arranged at the interface with the air. At that time, if the laminate is a light emitting device, it is necessary to have a layer containing at least one phosphor (hereinafter referred to as "phosphor layer") between the light source and the solid silicone material of the present invention. It is particularly preferable from the viewpoint of the technical effects of the present invention.

[Peelable laminate]
First, a laminate in which a film-like or thin-film-like member of a solid silicone material according to the present invention is arranged on a release layer will be described. A film-like or thin-film-like member made of the solid silicone material of the present invention, and a laminated member including the same (for example, a laminated sheet further provided with a phosphor layer) are required to be handled individually as desired. When a solid layer made of the solid silicone material according to the present invention is disposed on the release layer, a film-like or thin-film member made of the solid silicone material of the present invention from the release layer constituting the laminate, and a laminated member including the same. can be easily separated and handled. Such a laminate has a release layer facing the solid layer made of the solid silicone material of the present invention, and may optionally further include other release layers. can. In the following examples, "/" means that each layer is opposed to each other in the stacking direction of the laminate (generally the thickness direction perpendicular to the substrate). Further, the base material and the release layer may be integral or the same layer (a base material having releasability by providing material or physical unevenness).

Example 1: Substrate/Release Layer/Solid Layer Consisting of Solid Silicone Material of the Present Invention/Other Optional Layers (Can Be One Layer or Two or More Layers)

Example 2: Substrate/Release Layer/Solid Layer Consisting of the Solid Silicone Material of the Present Invention/Other Optional Layers (May Be One Layer or Two or More Layers)/Release Layer/Substrate

In particular, as in Example 2, when a film-like or thin-film-like member made of the solid silicone material of the present invention and a laminate member including the same are sandwiched between two release layers, the solid silicone material of the present invention is used. A component with a solid layer can be transported (including exported internationally) while protected by the substrate, and the substrate with the release layer can be separated from both sides of the laminate at the desired time and place. Then, a film-like or thin-film-like member made of the solid silicone material of the present invention, or a lamination member containing the same can be placed or laminated on a desired structure such as a light source of a light-emitting device. In particular, when the laminate member is a laminate sheet or the like having a solid layer made of the solid silicone material of the present invention and a phosphor layer, such a laminate is useful in that it can improve the handling workability.

The above base material is not particularly limited, but paperboard, corrugated cardboard, clay coated paper, polyolefin laminated paper, especially polyethylene laminated paper, synthetic resin film/sheet, natural fiber cloth, synthetic fiber cloth, artificial leather cloth , metal foil are exemplified. In particular, synthetic resin films and sheets are preferred, and examples of synthetic resins include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, cyclopolyolefin, and nylon. The substrate is preferably film-like or sheet-like. The thickness is not particularly limited, and can be designed to have a desired thickness depending on the application. As will be described later, the base material itself may be made of a material that functions as a peeling layer, or may have a structure in which peelability is imparted by physically forming fine unevenness on the surface of the base material. .

The release layer is sometimes called a release liner, a release layer, or a release coating layer, and preferably has a release coating capability such as a silicone-based release agent, a fluorine-based release agent, an alkyd-based release agent, or a fluorosilicone-based release agent. It may be a release layer, a base material having fine physical irregularities formed on the surface of the base material, or a base material itself that is difficult to adhere to the solid silicone material of the present invention.

The solid layer made of the solid silicone material of the present invention can be disposed on the release layer by forming a film in the same manner as described in the above "Method of forming a film or thin film". be. In particular, the solid silicone material is uniformly dispersed in an organic solvent such as i-propyl alcohol or methyl isobutyl ketone by the method described above and then applied onto the release layer of a film-like substrate or sheet-like substrate, followed by drying or the like. Preferably, a solid layer of solid silicone material in film or thin film form is deposited on the release layer by removing the organic solvent by means. The film thickness of the film-like or thin-film-like solid silicone material is the same as described above.

The solid layer made of the solid silicone material of the present invention may be used alone, but is more preferably a laminated member in which the same or different layers are laminated on the solid layer. In particular, another layer in the laminated member is preferably a cured layer obtained by curing an organopolysiloxane having a curing reactive functional group or a solid organopolysiloxane (silicone layer). A cured silicone layer obtained by curing an organopolysiloxane having a reactive group and/or a radically reactive group, a condensation- or dealcohol-reactive group in the presence of a catalyst, or a resin-linear polymer type similar to component (B). Organopolysiloxanes are preferred. Here, the organopolysiloxane having curing reactive groups may be linear, branched, cyclic, or resinous, and two or more curing reactions may be used in combination.

Particularly preferably, the other silicone layer placed on the solid layer made of the solid silicone material of the present invention is a resin-linear polymer type solid organopolysiloxane similar to component (B) above, The silicone layer is preferably formed by dispersing a phosphor, which will be described later, in the solid organopolysiloxane.

The other layers in the laminated member may be one or more layers, or may be multiple layers having two or more layers with different functions. Although the thickness of the entire laminated member laminated on the solid layer made of the solid silicone material of the present invention is not particularly limited, it is preferably 1 μm or more. It may be up to 10,000 μm, with a range of 100-1,000 μm being particularly preferred.

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

In the laminate described above, the silicone layer different from the solid layer may be a silicone layer containing a reinforcing filler because it imparts mechanical strength to the cured product and improves protective properties or adhesive properties. Moreover, 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. The above phosphors and these fillers may be used in combination, and in order to improve the dispersibility in the silicone layer, the surface of these particulate components may be coated with alkoxysilane, organohalosilane, organosilazane, or siloxane oligomer. You may surface-treat by etc.

The above laminate has a structure in which a solid layer made of the solid silicone material of the present invention is disposed on a release layer, and particularly preferably, a silicone layer different from the solid layer and containing a phosphor or the like. It has a phosphor layer. When the solid layer made of the solid silicone material according to the present invention is disposed on the release layer, the solid layer made of the solid silicone material of the present invention or a laminated member containing the same can be easily removed from the release layer constituting the laminate. The separated laminate member itself can be used as an optical member or the like for manufacturing other structures.

[Laminate with Light Source and Phosphor, Light Emitting Device]
A solid layer of the solid silicone material of the present invention can be placed at an interface with air, and when placed on a light emitting diode (LED) or organic electroluminescent device (OLED) light source, the solid layer of the present invention A solid layer of silicone material can be placed at the air interface to improve the light extraction efficiency of the entire stack including the light source. It is particularly preferable that such a laminate have a phosphor layer containing the same phosphor as the wavelength conversion material for the light source, particularly a silicone layer containing the phosphor. Here, the light emitted from the light source is preferably wavelength-converted by the phosphor layer and reaches the solid layer made of the solid silicone material of the present invention disposed at the interface with the air. The solid layer made of material may be formed so as to partially or entirely cover the phosphor layer, or may be arranged outside the phosphor layer via another functional layer of the laminate. Although the total thickness of these laminates is not particularly limited, it is preferably 1 μm or more. , 100 to 1,000 μm is particularly preferred.

[Improvement of light extraction efficiency and improvement of heat resistance]
A laminate comprising such a light source and a phosphor layer is a light emitting device such as a light emitting diode (LED) or an organic electroluminescent device (OLED), and a solid body comprising the light source, the phosphor layer and the solid silicone material of the present invention. The arrangement of layers can improve the light extraction efficiency of the light emitting device. Furthermore, by selecting a solid layer made of a solid silicone material, it may be possible to prevent coloration or the like due to heat generation of the light-emitting device, and in particular, it may be possible to improve the heat resistance of the light-emitting device.

[Laminate production method]
The method for producing the laminate according to the present invention is not particularly limited, but from the standpoint of depositing and disposing the solid silicone material of the present invention in the form of a thin film or film, the following steps (i) to (iii) ), it is preferably a method for manufacturing a laminate. In addition, the method similar to the above is illustrated as the coating method etc. concerning the said process.
(i) forming the solid silicone material of the present invention into a film or thin film on another structure; (ii) dispersing the solid silicone material of the present invention in an organic solvent; Alternatively, the step of removing the organic solvent after coating in the form of a thin film (iii) the step of laminating another structure on the film-like or thin-film-like member made of the solid silicone material of the present invention.

In particular, the solid silicone material of the present invention can be handled in the form of a peelable laminate, and a solid layer made of the solid silicone material of the present invention or a laminate member containing the solid layer can be easily separated from the release layer for use. can do. Since the solid layer made of the solid silicone material of the invention separated from the release layer or the laminated member containing the solid layer is preferably used as an optical member or the like for the production of other structures, the following steps are performed. is particularly preferred. In particular, the other structure is preferably a precursor of a light-emitting device equipped with a light source or the like, and the manufacturing method includes a solid layer made of the solid silicone material of the present invention placed at an interface with air. Particularly preferred is a method for manufacturing a light emitting device.

Steps of a method for manufacturing a peelable laminate, characterized in that a laminate member (silicone layer) containing the solid silicone material (thin layer) of the present invention is used:
(a): A step of dispersing the solid silicone material of the present invention in an organic solvent on the release layer, coating it on another structure in the form of a film or thin film, and then removing the organic solvent;
(b): a step of laminating the same or different silicone layer on the film-like or thin-film-like solid silicone material obtained in step (a);
(C): Step (D): The step (D) of separating the silicone layer obtained in the step (B), in which the film-like or thin film-like solid silicone material is laminated, from the release layer (D): laminating the obtained laminate on another structure

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these. As for the number average particle diameter of the hollow silica fine particles, the average particle diameter described in each company's catalog is described.

(Synthesis example 1)
A 1 L four-necked round bottom flask was charged with phenylsilsesquioxane hydrolyzate (135.00 g, 0.99 mol Si) and toluene (135.00 g). The mixture was heated to reflux under a nitrogen atmosphere 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. Methyltriacetoxysilane (20.23 g, 0.09 mol Si) was then 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 twice to lower the acetic acid concentration, and a part of the toluene was distilled off to obtain a transparent resin-toluene solution of organopolysiloxane having a 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 Si) and toluene (235.00 g). Under this 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. The reaction mixture was heated at reflux for 2 hours, then 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 removed by azeotropic distillation. This procedure was repeated four more times to lower the acetic acid concentration, and a part of the toluene was distilled off to obtain a toluene solution of organopolysiloxane having a transparent resin-linear polymer structure (weight average molecular weight = 93500, solid content concentration). 66.73%) was obtained.

(Synthesis example 3)
A 1 L four-necked round bottom flask was charged with phenylsilsesquioxane hydrolyzate (135.00 g, 0.99 mol Si) and toluene (360.00 g). The mixture was heated to reflux under a nitrogen atmosphere for 30 minutes. After cooling the reaction mixture to 100° C., a solution of diacetoxy-terminated polydimethylsiloxane (siloxane degree of polymerization 105) was added. The reaction mixture was heated at reflux for 2 hours, then methyltriacetoxysilane (13.48 g, 0.06 mol Si) was added and the mixture was refluxed for 2.5 hours. Vinylmethyldiacetoxysilane (12.65 g, 0.07 mol of Si) was added and the mixture was refluxed for 2 hours before adding water (76 mL) and azeotroping for 30 minutes, waiting for the organic layer to separate. The aqueous layer was removed from the bottom. The water was then replaced with saturated saline and the same procedure was repeated two more times to reduce the acetic acid concentration, followed by two more times with water. By partially distilling off the toluene, a toluene solution of organopolysiloxane having a transparent resin-linear polymer structure (weight average molecular weight=72000, solid content concentration 61.23%) was obtained.

[Examples 1-3, Comparative Examples 1-2]
(Example 1)
Hollow silica fine particles (Sururia 4320 manufactured by Nikki Shokubai Kasei Co., Ltd., silica solid content 20.5% by weight, hollow silica fine particles, number average particle diameter 60 nm, 0.258 g) and methyl isobutyl ketone (6.30 g) were placed in a container and stirred. , the 66.73% by weight organopolysiloxane-toluene solution (0.020 g) obtained in Synthesis Example 2 was added to obtain a 1% by weight adjustment solution 1A. Using a coating machine (PI-1210 FILM COATER) and a bar (RDS Webster, NY No. 3), a release sheet (T788 manufactured by Daicel) was coated with Preparation Solution 1A. After being left at room temperature for about 30 minutes, it was dried in an oven at 40°C for 1 hour to obtain Film 1. When the thickness of the coat layer was measured with a film thickness measuring device (F20 thin film analyzer manufactured by Filmetrics), it was 188.2 nm.

The organosiloxane-toluene solution (66.7 g) obtained in Synthesis Example 1 was added with diazabicycloundecene (20 ppm relative to organosiloxane) and a phosphor (NYAG 4454-L, manufactured by Intematix, 10.1 g). was added, and the mixture was uniformly stirred using a rotation-revolution stirrer (ARV-310LED manufactured by Thinky Co., Ltd.) equipped with a vacuum degassing mechanism to obtain adjustment liquid 1B. This adjustment liquid 1B was cast onto the coated side of film 1 with a gap of 925 μm using a coating machine (PI-1210 FILM COATER). This sheet was dried in an oven at 40C overnight and then dried in a vacuum oven at 50C for 2 hours to obtain a phosphor sheet 1.

The resulting phosphor sheet 1 was cut into a circle with a diameter of 36 mm, peeled off from the release sheet, placed on the LED chip with the coated surface facing up, and sealed using a vacuum laminator (Nisshinbo Laminator 0505S). did.

(Example 2)
Hollow silica fine particles (Sururia 4320 manufactured by Nikki Shokubai Kasei Co., Ltd., silica solid content 20.5% by weight, hollow silica fine particles, number average particle diameter 60 nm, 0.068 g) and methyl isobutyl ketone (3.46 g) were placed in a container and stirred. , and the 66.73% by weight organopolysiloxane-toluene solution (0.005 g) obtained in Synthesis Example 2 was added to obtain a 0.5% by weight adjustment solution 2A. Using a coating machine (PI-1210 FILM COATER) and a bar (RDS Webster, NY No.3), a release sheet (T788 manufactured by Daicel) was coated with adjustment solution 2A. After being left at room temperature for about 30 minutes, it was dried in an oven at 40°C for 1 hour to obtain Film 2. When the thickness of the coating layer was measured with a film thickness measuring device (F20 thin film analyzer manufactured by Filmetrics), it was 113.1 nm.

The same adjustment liquid 1B as in Example 1 was cast on the coated side of film 2 with a gap of 925 μm using a coating machine (PI-1210 FILM COATER). This sheet was dried in an oven at 40C overnight and then dried in a vacuum oven at 50C for 2 hours to obtain a phosphor sheet 2. The resulting phosphor sheet 2 was placed on an LED chip in the same manner as in Example 1, and sealed using a vacuum laminator.

(Example 3)
Methyl isobutyl ketone (2.75 g) was added to dilute adjusted solution 1A (0.30 g) of Example 1 to prepare 0.1% by weight adjusted solution 3A. Using a coating machine (PI-1210 FILM COATER) and a bar (RDS Webster, NY No. 3), a release sheet (T788 manufactured by Daicel) was coated with adjustment solution 3. After being left at room temperature for about 30 minutes, it was dried in an oven at 40°C for 1 hour to obtain Film 3. When the thickness of the coating layer was measured with a film thickness measuring device (F20 thin film analyzer manufactured by Filmetrics), it was 213 nm.

The same adjustment liquid 1B as in Example 1 was cast on the coated side of film 3 with a gap of 925 μm using a coating machine (PI-1210 FILM COATER). After drying this sheet in an oven at 40C overnight, it was further dried in a vacuum oven at 50C for 2 hours to obtain a phosphor sheet 3. The resulting phosphor sheet 3 was placed on an LED chip in the same manner as in Example 1, and sealed using a vacuum laminator.

(Comparative example 1)
The same adjustment liquid 1B as in Example 1 was coated on a release sheet (T788 manufactured by Daicel) with a gap of 925 μm using a coating machine (PI-1210 FILM COATER). After drying this sheet in an oven at 40C overnight, it was further dried in a vacuum oven at 50C for 2 hours to obtain a phosphor sheet 4. The resulting phosphor sheet 4 was placed on an LED chip in the same manner as in Example 1, and sealed using a vacuum laminator.

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

Using a coating machine (PI-1210 FILM COATER) and a bar (R.D.S. Webster, N.Y. No. 3), a release sheet (T788 manufactured by Daicel) was coated with adjustment solution 4A. After being left at room temperature for about 30 minutes, it was dried in an oven at 40°C for 1 hour to obtain Film 4. When the thickness of the coating layer was measured with a film thickness measuring device (F20 thin film analyzer manufactured by Filmetrics), it was 110 nm.

The same adjustment liquid 1B as in Example 1 was cast on the coated side of film 4 with a gap of 925 μm using a coating machine (PI-1210 FILM COATER). This sheet was dried in an oven at 40C overnight and then dried in a vacuum oven at 50C for 2 hours to obtain a phosphor sheet 5. The resulting phosphor sheet 5 was placed on an LED chip in the same manner as in Example 1, and sealed using a vacuum laminator.

[Evaluation method]
Measurement of total radiant flux Light-emitting semiconductor devices (Examples 1 to 3, Comparative Examples 1 and 2) obtained by encapsulating LED chips by the above process were measured using a total luminous flux measurement device (manufactured by Otsuka Electronics Co., Ltd.). , the total radiant flux (mW) was measured. The results are shown in Table 1 below.

[Examples 5-6, Comparative Example 3]
In Examples 5 and 6 and Comparative Example 7 below, light-emitting semiconductor devices obtained by the following method were used. In the examples, the thickness of the thin film layer (coating layer) containing the hollow silica fine particles obtained by spin coating indicates a value obtained by separately spin coating the same amount of the solution alone.
(Fabrication of optical semiconductor package)
As an optical semiconductor element, a light-emitting semiconductor device with an MA5050 package (W*N-045) having a light-emitting layer made of InGaN and an LED chip having a main emission peak of 454.7-460 nm was used.

As the encapsulating resin, the organosiloxane-toluene solution (105.4 g) obtained in Synthesis Example 1 was added with diazabicycloundecene (0.01 g, 100 ppm relative to organosiloxane) and a phosphor (manufactured by Intematics, Inc.). NYAG 4454-L, 17.348 g), adhesion promoter (Shin-Etsu Chemical Co., Ltd. KBE-402, 0.433 g), and silanol-terminated polyphenylmethylsiloxane (siloxane polymerization degree 4-5, 11.22 g) were added, and the vacuum degassing mechanism was added. A rotation-revolution stirrer (ARV-310LED manufactured by Thinky Co., Ltd.) was used to stir uniformly to obtain adjustment liquid 1C.

Conditioning liquid 1C was cast on a release film (SPPET5003BU manufactured by Mitsui Tocello) with a gap of 925 μm using a coating machine (PI-1210 FILM COATER). The sheet was dried overnight in a nitrogen circulating oven set at 40 degrees, followed by an additional 2 hours in a vacuum oven at 50 degrees.

A circular shape with a diameter of 32 mm was cut from the obtained phosphor sheet, and sealed on an LED chip using a vacuum laminator (Laminator 0505S manufactured by Nisshinbo Co., Ltd.). The obtained light-emitting semiconductor device was placed on a stainless steel (SUS) plate with a spacer of 1.4 mm in height, and a release film and a SUS plate were placed on top in that order. Cured. After that, it was completely cured in a programmed oven set at 100 degrees/1 hour, 120 degrees/1 hour, 140 degrees/1 hour, 150 degrees/1 hour, and 160 degrees/3 hours.

(Example 5)
Hollow silica fine particles (Sururia 4320 manufactured by Nikki Shokubai Kasei Co., Ltd., silica solid content 20.5% by weight, hollow silica fine particles, number average particle diameter 60 nm, 0.378 g) and methyl isobutyl ketone (9.3 g) were placed in a container and stirred. , the 66.73 wt% organopolysiloxane-toluene solution (0.029 g) obtained in Synthesis Example 2 was added to prepare a 1 wt% solution 1.

This solution 1 was dropped on the encapsulation layer of the obtained light-emitting semiconductor device, and was spun at 300 rpm for 15 seconds using a spin coater (Mikasa spin coater 1H-DXII), and then increased to 1500 rpm and spun for 30 seconds. and coated on the upper surface. Separately, the thickness of the coating layer alone using the same amount of solution was measured with a film thickness measuring device (F20 thin film analyzer manufactured by Filmetrics), and it was 113 nm. The thickness of the entire layer including the coat layer and the cured layer formed by curing the phosphor sheet was about 400 μm. The light-emitting semiconductor device was dried in a programmed oven set at 70 degrees/20 minutes and 150 degrees/1 hour.

(Example 6)
Hollow silica fine particles (Sururia 4320 manufactured by Nikki Shokubai Kasei Co., Ltd., silica solid content 20.5% by weight, hollow silica fine particles, number average particle diameter 60 nm, 0.2084 g) and methyl isobutyl ketone (5.00 g) were placed in a container and stirred. , 61.23% by weight organopolysiloxane-toluene solution (0.017 g) obtained in Synthesis Example 3, hydrosilyl group-terminated polyorganosiloxane (0.0004 g) and 0.1% by weight platinum complex-toluene solution (0.0003 g) were further added. A 1% by weight solution 2 was prepared.

This solution 2 was dropped on the encapsulation layer of the obtained light-emitting semiconductor device, and was spun at 300 rpm for 15 seconds using a spin coater (Mikasa spin coater 1H-DXII), then increased to 1500 rpm and spun for 30 seconds. and coated on the upper surface. The light-emitting semiconductor device was dried in a programmed oven set at 70 degrees/20 minutes and 150 degrees/1 hour. Separately, the thickness of the coating layer alone using the same amount of solution was measured with a film thickness measuring device (F20 thin film analyzer manufactured by Filmetrics), and it was 113 nm. The thickness of the entire layer including the coat layer and the cured layer formed by curing the phosphor sheet was about 400 μm.

(Comparative Example 3)
Aerosil (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 mixed by stirring for 20 seconds using a dental mixer. A solution 1 was obtained. A 1% by weight solution 3 was prepared by diluting the obtained mixed solution 1 (0.05 g) with methyl isobutyl ketone (2.56 g).

This solution 1 was dropped on the encapsulation layer of the obtained light-emitting semiconductor device, and was spun at 300 rpm for 15 seconds using a spin coater (Mikasa spin coater 1H-DXII), and then increased to 1500 rpm and spun for 30 seconds. and coated on the upper surface. The light-emitting semiconductor device was dried in a programmed oven set at 70 degrees/20 minutes and 150 degrees/1 hour. Separately, the thickness of the coating layer alone using the same amount of solution was measured with a film thickness measuring device (F20 thin film analyzer manufactured by Filmetrics), and it was 110 nm. The thickness of the entire layer including the coat layer and the cured layer formed by curing the phosphor sheet was about 400 μm.

[Evaluation method]
Measurement of total radiant flux Using a total luminous flux measurement device (manufactured by Otsuka Electronics Co., Ltd.), measure the total radiant flux (mW) of the light-emitting semiconductor device obtained in the above process before and after applying the adjustment solution. did.

In the examples of the present invention, the change rate of the total radiant flux before and after coating was improved in the light-emitting semiconductor device, and the light extraction efficiency from the LED chip was improved. In particular, the light extraction efficiency was most improved 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 fine particles.

Claims (16)

(A) Hollow or porous inorganic fine particles having a number average particle diameter of 1 to 100 nm, and (B) R ^A SiO _3/2 (wherein R ^A is an aryl group having 6 to 14 carbon atoms) in the molecule. the represented arylsiloxane unit 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 with a halogen atom; n is a number in the range of 3 to 1000) and contains an organopolysiloxane having hot-melt properties, and the content of component (A) is 10 to 95% by mass. range, a solid silicone material. 2. The solid silicone material according to claim 1, wherein component (A) is inorganic fine particles that are hollow silica fine particles having a number average particle diameter of 40 to 70 nm, and the content of component (A) is in the range of 40 to 95% by mass. . Component (B) is an organopolysiloxane containing 20 to 80% by mass of the total organopolysiloxane of arylsiloxane units represented by R ^A SiO _3/2 (wherein R ^A is the same group as above). A solid silicone material according to claim 1 . Component (B) is {(R ₂ SiO _2/2 )} _a {R ^A SiO _3/2 } _1-a (wherein R and R ^A are the same groups as above and a is 0.8 to 0 4. The solid silicone material of claim 1 or claim 3, which is an organopolysiloxane represented by a number in the range of .2. The solid silicone material according to any one of claims 1 to 4, which is in the form of a film or a thin film. 6. The solid silicone material according to claim 5, wherein the film thickness is in the range of 50-300 nm. 7. The solid silicone material according to claim 5, wherein the film thickness is in the range of L to 4L (nm) with respect to the average particle size L (nm) of component (A). An optical member comprising the solid silicone material according to any one of claims 1 to 7. A laminate comprising a solid layer of the solid silicone material according to any one of claims 1-7. The laminate according to claim 9, having a structure in which a solid layer made of the solid silicone material according to any one of claims 1 to 7 is arranged on the release layer. 10. Laminate according to claim 9, comprising a solid layer of the solid silicone material according to any one of claims 1 to 7 and a layer containing at least one phosphor. A solid layer made of the solid silicone material according to any one of claims 1 to 7, and a layer containing at least one phosphor, wherein the solid layer made of the solid silicone material is air and 12. The laminate according to claim 9 or 11, having a structure arranged at the interface of the At least one light source, a layer containing at least one phosphor formed thereon, and a solid layer made of the solid silicone material according to any one of claims 1 to 7 disposed at an interface with air. A light-emitting device with The method for producing a laminate according to any one of claims 9 to 12, comprising any one of the following steps (i) to (iii).
(i) molding the solid silicone material according to any one of claims 1 to 4 into a film or thin film on another structure; (ii) any of claims 1 to 4; Step (iii) removing the organic solvent after dispersing the solid silicone material according to any one of claims 1 to 4 in an organic solvent and coating it on another structure in the form of a film or thin film. A step of laminating another structure on a film-like or thin-film-like member made of the solid silicone material according to any one of the above items. 13. The method for producing a laminate according to claim 9, 11 or 12, comprising the following steps.
(B): After dispersing the solid silicone material according to any one of claims 1 to 4 in an organic solvent on the release layer and coating it on another structure in the form of a film or thin film. , removing the organic solvent;
(b): a step of laminating the same or different silicone layer on the film-like or thin-film-like solid silicone material obtained in step (a);
(C): Step (D): The step (D) of separating the silicone layer obtained in the step (B), in which the film-like or thin film-like solid silicone material is laminated, from the release layer (D): laminating the obtained laminate on another structure 16. The method for manufacturing a laminate according to claim 14 or 15, wherein the laminate is a light-emitting device, and a film-like or thin-film-like member made of a solid silicone material is arranged at an interface with air.