阅读说明：本技术 固体有机硅材料、使用其而成的层积体和发光器件 (Solid organosilicon material, and laminate and light-emitting device using same ) 是由 尼子雅章 水上真弓 赤坂昌保 津田武明 于 2018-05-02 设计创作，主要内容包括：课题：本发明提供固体有机硅材料、使用其的层积体等,容易以均匀的纳米级的膜厚进行薄膜化,通过配置在作为发光器件的层积体与空气的界面,能够改善光取出效率等。解决方案：该固体有机硅材料含有：(A)数均粒径1～100nm的中空或多孔质的无机微粒、和(B)在分子内具有由R<Sup>A</Sup>SiO<Sub>3/2</Sub>(式中,R<Sup>A</Sup>为碳原子数6～14的芳基)表示的芳基硅氧烷单元和由(R<Sub>2</Sub>SiO<Sub>2/2</Sub>)n(式中,R为可以被卤原子取代的碳原子数1～20的烷基或碳原子数6～14的芳基、n为3～1000的范围的数)表示的聚二有机硅氧烷结构的有机聚硅氧烷,成分(A)的含量为10～95质量％的范围。(The subject is as follows: the invention provides a solid organosilicon material, a laminated body using the same, and the like, which can be easily thinned with a uniform nano-scale film thickness, and can improve light extraction efficiency and the like by being arranged at an interface between the laminated body as a light emitting device and air. The solution is as follows: the solid organosilicon material contains: (A) number average particle diameter of 1 to 100nmHollow or porous inorganic fine particles, and (B) having R in the molecule A SiO 3/2 (in the formula, R A Aryl siloxane unit represented by aryl group having 6 to 14 carbon atoms) and a siloxane compound represented by (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, and n is a number in the range of 3 to 1000), and the content of the component (A) is in the range of 10 to 95 mass%.)

1. A solid silicone material comprising: (A) hollow or porous inorganic fine particles having a number average particle diameter of 1 to 100nm, and

(B) having in the molecule a structure represented by R^ASiO_3/2(in the formula, R^AAryl siloxane unit represented by aryl group having 6 to 14 carbon atoms) and a siloxane compound represented by (R)₂SiO_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, and n is a number in the range of 3 to 1000)The organopolysiloxane having a siloxane structure contains 10-95 mass% of component (A).

2. The solid silicone material according to claim 1, wherein the component (A) is an inorganic fine particle having a hollow silica fine particle with a number average particle diameter of 40 to 70nm as a main component, and the content of the component (A) is in a range of 40 to 95 mass%.

3. The solid silicone material according to claim 1, wherein the component (B) is 20 to 80 mass% of R in the entire organopolysiloxane^ASiO_3/2(in the formula, R^AThe same groups as described above) are used.

4. A solid silicone material as claimed in claim 1 or 3 wherein component (B) is a silicone resin composition consisting of { (R)₂SiO_2/2)}_a{R^ASiO_3/2)_1-a(wherein R, R^AAn organopolysiloxane represented by the above-mentioned group, wherein a is a number in the range of 0.8 to 0.2).

5. The solid silicone material of claim 1, 3 or 4, wherein ingredient (B) is an organopolysiloxane having a hot melt property.

6. The solid silicone material described in any one of claims 1 to 5, which is film-like or film-like.

7. The solid silicone material according to claim 6, wherein the film thickness is 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 member composed of the solid silicone material described in 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 comprising the solid silicone material according to any one of claims 1 to 8 is disposed on the 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 containing at least one phosphor.

13. The laminate according to claim 10 or 12, which has the following structure: the structure has a solid layer composed of the solid silicone material described in any one of claims 1 to 8 and a layer containing at least one phosphor, and the solid layer composed of the solid silicone material described above is disposed at an interface with air.

14. A light emitting device having at least one light source, a layer comprising at least one phosphor formed thereon, and a solid layer of the solid silicone material of any one of claims 1 to 8 disposed at an interface with air.

15. A method for producing a laminate according to any one of claims 10 to 13, which comprises the following steps (i) to (iii):

(i) a step of forming the solid silicone material according to any one of claims 1 to 5 into a film or a film on another structure;

(ii) a step of dispersing the solid silicone material according to any one of claims 1 to 5 in an organic solvent, coating the other structure in the form of a film or a thin film, and then removing the organic solvent;

(iii) a step of laminating another structure on a film-like or film-like member made of the solid silicone material according to any one of claims 1 to 5.

16. A method for producing a laminate according to claim 10, 12 or 13, which comprises the following steps.

(a) A step of dispersing the solid silicone material according to any one of claims 1 to 5 in an organic solvent on a release layer, applying the solid silicone material to another structure in a film or film form, and then removing the organic solvent;

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

(c) A step of separating the silicone layer laminated with the film-like or film-like solid silicone material obtained in the step (b) from the release layer as a unit,

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

17. The method of manufacturing a laminate according to claim 15 or 16, wherein the laminate is a light-emitting device, and the film-like or film-like member made of a solid silicone material is disposed at an interface with air.

Technical Field

The present invention relates to a solid silicone material, and a laminate and a light-emitting device using the same, and particularly to a solid silicone material comprising: the light-emitting device can be easily made into a thin film with a uniform thickness of nanometer order, and can be arranged at the interface between the laminate as the light-emitting device and the air, thereby improving the light extraction efficiency. The present invention also relates to a method for producing a laminate and an optical device using the solid silicone material.

Background

Solid silicone materials are used in a wide range of industrial fields because of their excellent moldability, heat resistance, cold resistance, electrical insulation, weather resistance, hydrophobicity, and transparency. The cured product of the curable silicone composition is less likely to be discolored than other organic materials and is less likely to have a decrease in physical properties, and therefore, is also suitable as an optical material, particularly a sealant for a light-emitting device (inorganic or organic light-emitting diode).

In recent years, for the production of a new light-emitting device, a silicone-containing material has been proposed which is hot-melt, is solid or semisolid at room temperature, and is heated and melted at a high temperature. Unlike a general liquid material, a silicone-containing material having a hot-melt property is excellent in handling workability and uniform coating property, and for example, the present applicant and the like have proposed in patent document 1 an optical device in which a reactive or non-reactive silicone-containing hot-melt composition having a resin-like siloxane structure and a linear siloxane structure in a molecule is used for a sealing material film. The sealing material has a high refractive index, and can be used in combination with a sealing material film (phosphor layer) having a phosphor material that converts a wavelength from a light source, thereby providing a light-emitting device excellent in productivity and light emission efficiency. However, in the field of light emitting devices, particularly when the phosphor layer is used, higher light extraction efficiency is required, and there is still room for improvement in the light emitting device. Patent document 1 does not disclose the incorporation of specific hollow or porous inorganic fine particles and the use of a thin film, particularly a nano-sized thin film, for improving light extraction efficiency.

On the other hand, hollow or porous inorganic fine particles having a small particle diameter have a structure containing air in the inside or pores, and are used as an antireflection layer of an antireflection film because they have a low refractive index with respect to an air layer when blended into a resin as a binder. Specifically, incident light (incident light from an external light source) is reflected at an interface of the antireflection layer having a low refractive index with respect to the base material layer, and the antireflection is realized by interference between the incident light and the reflected light. For example, patent documents 2 to 4 disclose an antireflection film 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 having a high refractive index and having a hot melt property, particularly a silicone material having a resin-like siloxane structure and a linear siloxane structure in a molecule, and do not disclose the use of a film for improving light extraction efficiency in a light-emitting device having a light source therein. Patent document 5 proposes a cured product in which spherical hollow silica bead particles are mixed in a silicone resin matrix as a matrix resin in a resin casting material for electronic components, but the use of a silicone material having a resinous siloxane structure and a linear siloxane structure in the molecule is not disclosed at all, and the use of a thin film in which the hollow silica bead particles are extremely coarse at 5 to 15 μm is not disclosed at all.

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made to solve the above problems, and an object thereof is to provide a silicone material which can improve light extraction efficiency without impairing workability and sealing performance particularly in the case of preparing a laminate for a light-emitting device which is uniformly thinned to a thickness of nanometers, and a laminate and a light-emitting device using the silicone material. Further, the present invention aims to provide a method for producing a laminate and a light-emitting device using the silicone material.

Means for solving the problems

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a solid silicone material containing: (A) hollow or porous inorganic fine particles having a number average particle diameter of 1 to 100nm, and

(B) having in the molecule a structure represented by R^ASiO_3/2(in the formula, R^AAryl siloxane unit represented by aryl group having 6 to 14 carbon atoms) and a siloxane compound represented by (R)₂SiO_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, and n is a number in the range of 3 to 1000), and the content of the component (A) is in the range of 10 to 95 mass%. The solid silicone material is hot-melt, and particularly can be easily formed into a thin film of nanometer order, and can be applied to a light-emitting device as an optical member to improve the light extraction efficiency.

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

The present inventors have also found that the above problems can be solved by a light-emitting device having at least one light source, a layer containing at least one phosphor formed thereon, and a solid layer made of the above solid silicone material disposed at an interface with air, and have achieved the present invention.

The present inventors have also found that the above problems can be solved by a method for manufacturing a laminate or a light-emitting device having a step of molding the solid silicone material into a film or film form, and have achieved the present invention.

Advantageous effects

By using the solid silicone material of the present invention, a silicone material, a laminate using the same, and a light-emitting device can be provided, which can improve light extraction efficiency without impairing workability and sealing performance particularly in the case of preparing a laminate for light-emitting devices that is uniformly thinned to a thickness of nanometers. Further, a method for manufacturing a laminate or a light-emitting device having a step of molding the solid silicone material into a film or a film can be provided.

Detailed Description

Solid organosilicon materials

First, the solid silicone material of the present invention will be explained. The solid organosilicon material is characterized by having a structure containing air in the interior or pores thereof, and dispersing a predetermined amount of hollow or porous inorganic fine particles having a small particle diameter (nano-order) in a polymer matrix having R in the molecule^ASiO_3/2An arylsiloxane unit (T branched unit or resin structure) and a siloxane unit represented by (R)₂SiO_2/2) And n represents a polydiorganosiloxane structure (a siloxane linear structure).

More specifically, the solid silicone material of the present invention is a solid silicone material containing:

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

(B) having in the molecule a structure represented by R^ASiO_3/2(in the formula, R^AAryl siloxane unit represented by aryl group having 6 to 14 carbon atoms) and a siloxane compound represented by (R)₂SiO_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, and n is a number in the range of 3 to 1000), and the content of the component (A) is in the range of 10 to 95 mass%. The following description is made in detail.

(A) Composition (I)

(A) The component (B) is a hollow or porous inorganic fine particle having an average particle diameter of 1 to 100nm, has a structure containing air in the inside or pores, and can reduce the refractive index of the polymer matrix to realize a low-refractive-index solid layer. When such hollow or porous inorganic fine particles having a small particle diameter are formed in a nano-order thin film, the light extraction efficiency can be improved by the light source/phosphor layer while achieving low refractive index of the film.

Here, the hollow inorganic fine particles are substantially spherical fine particles having a cavity inside, and are spherical to elliptical fine particles having a smooth surface or having a concave-convex shape. The hollow inorganic fine particles themselves have a low refractive index (for example, a refractive index: 1.20 to 1.45). Specific examples thereof include hollow silica fine particles. Similarly, the porous inorganic fine particles are inorganic fine particles having a structure in which a plurality of cavities are provided in one fine particle. The kind of the inorganic fine particles is not particularly limited, and inorganic fine particles such as colloidal silica, porous silica sol, hollow silica sol, MgF2 sol and the like are preferable, and inorganic fine particles containing hollow silica fine particles as a main component of colloidal silica are particularly preferable. The silica fine particles may be subjected to a known surface modification such as acrylic modification, and the surface of the inorganic fine particles may be treated with silazane or a known silane coupling agent in order to improve dispersibility. These inorganic fine particles may be used alone in 1 kind, or may be used in combination in 2 or more kinds different in kind or average particle diameter. The hollow inorganic fine particles of the present invention are preferably substantially spherical as described above, and particularly preferably plate-like particles, needle-like particles, tubular particles, and the like, which do not contain non-spherical particles, i.e., particles having a long and short diameter.

(A) The average particle diameter of the component is the number average particle diameter of the 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 measuring apparatus or the like. The number average particle diameter is in the range of 1 to 100nm, and particularly preferably inorganic particles containing hollow silica particles having an average particle diameter of 40 to 70nm as a main component. When the average particle size of the inorganic fine particles is larger than the upper limit, the particles may be larger than the nano-scale film thickness, and in addition, light may be diffusely reflected by rayleigh scattering in the produced thin film, so that the solid layer may be whitened and the transmittance thereof may be lowered. On the other hand, when the average particle size of the inorganic fine particles is smaller than the lower limit, the inorganic fine particles may cause aggregation, which reduces dispersibility of the inorganic fine particles, and in addition, the light extraction efficiency of the film-like member described later may not be improved by the light source/phosphor layer.

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, a component having a refractive index in the range of 1.20 to 1.45 is preferably used, and 1.25 to 1.37 is preferable. (A) The lower the refractive index of the component, the more preferable, but in the hollow silica fine particles, 1.20 is a substantial lower limit, and if it exceeds 1.45, the refractive index approaches a sufficiently high refractive index, and therefore a sufficient effect of improving the light extraction efficiency may not be obtained.

(B) Composition (I)

(B) The component (a) is a resin-linear polymer type organopolysiloxane containing T units having aryl groups as a binder of the component (a), and has a high refractive index and is hot-melt, so that a thin film-like solid layer having a uniform film thickness of the order of nanometers can be easily formed.

Such a component (B) has a structure represented by the formula R in the molecule^ASiO_3/2(in the formula, R^AAryl siloxane represented by aryl group having 6 to 14 carbon atoms)Unit and unit of₂SiO_2/2) And 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, and n is a number in the range of 3 to 1000).

The aryl group having 6 to 14 carbon atoms is a phenyl group, tolyl group, xylyl group, naphthyl group or anthracenyl group, and a phenyl group is preferable from the viewpoint of industrial production. R is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, or a dodecyl group; aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthracenyl; and groups in which some or all of the hydrogen atoms bonded to these groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or the like, and methyl or phenyl is preferable from the viewpoint of industrial production.

More specifically, the component (B) has T unit: r¹SiO_3/2(R¹Is a monovalent organic group, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, and all R in the molecule¹At least 1 or more aryl groups having 6 to 14 carbon atoms), an optional Q unit: with SiO_4/2A resin structural block of the siloxane unit represented by (R)₂SiO_2/2) Wherein the linear blocks represented by n (wherein n is the same number and R is the same group) are linked by a silyl group bond or a Si-O-Si bond, and have a structure in which R is a linear block linked by a silyl group bond or a Si-O-Si bond^ASiO_3/2In the resin-linear organopolysiloxane block copolymer of units, in the silyl group linkage or Si-O-Si linkage linking the resin structural block and the linear structural block in the polymer, it is preferable that the Si atom bonded to the resin structure constitutes R^ASiO_3/2And (4) units.

(B) The resin block of component (B) is a partial structure which imparts hot-melt property to the whole of component (B), and is a resinous organopolysiloxane structure. This structure forms part of a structure composed of a resinous organopolysiloxane which will be R^ASiO_3/2The aryl siloxane units represented as necessary and bonding a large number of T units or Q units. Especially containing a large amount of the compound in the moleculeIn the case of an aryl group such as a phenyl group, the refractive index of the component (B) can be increased. Preferably, the component (B) is 20 to 80 mass% of the total organopolysiloxane-containing component (R)^ASiO_3/2(wherein RA represents the same group as above) and a resin structure substantially consisting of only R^ASiO_3/2The aryl siloxane unit represented is formed, which is particularly preferable from the viewpoint of the above-mentioned hot melt property and refractive index.

The linear structure is (R)₂SiO_2/2) The non-reactive block represented by n is R₂SiO_2/2The diorganosiloxy unit represented by the formula has a structure in which at least 3 units or more, preferably 5 units or more are chain-connected. The linear structural block is a partial structure that imparts appropriate flexibility to a solid layer formed from the present copolymer. Wherein n is the polymerization degree of the diorganosiloxy unit constituting the partial structure, and is 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 upper limit, the property of linear molecules derived from the linear structure is strongly exhibited, and the film formability may be reduced. On the other hand, when n is less than the lower limit, the properties as linear molecules are insufficient, and particularly when the film is made thin, repulsion and the like are likely to occur, and uniform coating and the like cannot be achieved, and the characteristic physical properties of the component (B) may not be achieved.

The functional group R of the diorganosiloxy unit constituting the linear structure is an alkyl group or an aryl group, and these groups are required to be non-reactive with respect to the resin structure and the functional group thereof in the same molecule, and to maintain the linear structure without causing polymerization such as condensation reaction in the molecule. These alkyl groups and aryl groups are the same groups as described above, and from the industrial viewpoint, methyl groups or phenyl groups are preferred.

(B) The resin structural block and the linear structural block in the component (a) are preferably linked by a silyl group bond derived from a hydrosilylation reaction between an alkenyl group and a silicon atom-bonded hydrogen atom, or a Si-O-Si bond derived from a condensation reactive group at the terminal of the resin structure or the linear structure. In particular, in the present invention, Si atoms bonded to the resin structure are particularly preferableForm R¹SiO_3/2The unit particularly preferably has the following partial structure (T-Dn). From an industrial point of view, R is preferable¹Is phenyl, preferably R is methyl or phenyl.

Partial structure (T-Dn)

In the above partial structure, the terminal of the Si — O-bond constituting the left side of the T unit is preferably bonded to a hydrogen atom or another siloxane unit constituting the resin structure, preferably another T unit, respectively. On the other hand, the Si-O-bonded end 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. When a hydrogen atom is bonded to the Si-O-bonded terminal, a silanol group (Si-OH) is formed.

From the viewpoints of hot-melt property of the component (B), improvement of refractive index required for light extraction efficiency, and uniform coating property particularly in the case of forming a thin film, it is preferable that the component (B) consists of only R^ASiO_3/2Aryl siloxane units represented by the formula and R₂SiO_2/2The diorganosiloxane units represented constitute a non-reactive organopolysiloxane. More specifically, the component (B) is preferably { (R)₂SiO_2/2))_a{R^ASiO_3/2)_1-a

An organopolysiloxane represented. In the formula, R, R^AA 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, for the same group.

Hot melt

(B) The component (B) is preferably a hot melt, more specifically, it is non-flowable at 25 ℃ and preferably has a melt viscosity of 200,000 pas or less at 100 ℃. The term "non-fluidity" means a state in which the hot melt adhesive does not flow under no load, and for example, means a state in which the softening point is lower than that measured by the softening point test method based on the ring and ball method of hot melt adhesive specified in JIS K6863-1994 "softening point test method of hot melt adhesive". That is, the softening point is required to be higher than 25 ℃ in order to be non-flowable at 25 ℃. The component (B) preferably has a melt viscosity at 100 ℃ 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 · s. When the melt viscosity at 100 ℃ is within the above range, the adhesiveness of a film or the like after hot melting and cooling at 25 ℃ is good. Further, the use of the component (B) having a melt viscosity of 100 to 15,000 pas may suppress deformation or peeling of a film or the like after molding.

Mixing 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 in the case where the component (B) is an inorganic fine particle having the above-described preferable hollow silica fine particle as a main component, the content of the component (a) is particularly preferably in the range of 40 to 95% by mass.

Optional ingredients

The solid silicone material of the present invention may contain any additives such as adhesion improving agents such as organic functional alkoxysilane compounds such as vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-methacryloxypropyltrimethoxysilane, and may contain, as other optional components, any of the following additives as long as the technical effects of the present invention are not impaired: phenol, quinone, amine, phosphorus, phosphite, sulfur, thioether and other antioxidants; triazole-based and benzophenone-based light stabilizers; phosphoric ester, halogen, phosphorus, antimony flame retardants; 1 or more kinds of antistatic agents including cationic surfactants, anionic surfactants, nonionic surfactants, and the like; dyes, pigments, and the like. However, when the film is made thinner, it is preferable that solid particles other than the component (A), particularly a particle component having an average primary particle diameter of more than 100nm, are not added.

The solid silicone material of the present invention may be applied by dispersing in an organic solvent in order to form a film, a thin film, or the like, which will be described later. The type of the organic solvent used is not particularly limited as long as it is a compound capable of dissolving all or a part of the constituent components in the composition, and an organic solvent having a boiling point of 80 ℃ or more and less than 200 ℃ is preferably used. Examples thereof include: non-halogenated solvents such as isopropyl alcohol, tert-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 dimethyl ether, ethylene glycol diethyl ether, 2-methoxyethanol (ethylene glycol monomethyl ether), diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, 1-methoxy-2-propyl acetate, 1-ethoxy-2-propyl acetate, octamethylcyclotetrasiloxane, and hexamethyldisiloxane, trifluoromethylbenzene, 1, 2-bis (trifluoromethyl) benzene, 1, 3-bis (trifluoromethyl) benzene, 1, 4-bis (trifluoromethyl) benzene, trifluoromethylchlorobenzene, trifluoromethylfluorobenzene, and the like, Halogenated solvents such as hydrofluoroethers. These organic solvents may be used alone or in combination of two or more. In view of improving workability in handling the solid silicone material of the present invention, uniformity of the solid layer, and heat resistance, isopropyl alcohol, methyl isobutyl ketone, and the like are preferable.

Use as films or membranes

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

Here, the film thickness of the film-like or film-like solid silicone material can be designed as desired, but in order to improve the light extraction efficiency by the light source/phosphor layer, the film thickness is preferably in the range of L to 4L (nm), particularly preferably in the range of 1.5L to 2.5L (nm), with respect to the average primary particle diameter L (nm) of the component (a). In this range, since a structure in which 1 to 4 inorganic fine particles of the component (a) supported by the solid silicone material are stacked in the layer on average, preferably about 2 inorganic fine particles are stacked in the thickness direction of the film, there is a practical advantage that the light extraction efficiency can be improved by the light source/phosphor layer most. For example, when inorganic fine particles containing hollow silica fine particles having an average primary particle diameter (L) of 50nm as a main component are used, the range of 1.5L to 2.5L (nm) means a range of 75 to 125nm of the thickness of the film to be formed. However, in addition to the above-described film thickness, even if the film thickness is, for example, about 50 to 150nm, the light extraction efficiency can be improved by the light source/phosphor layer. The thickness of the laminate (as a solid layer, as a solid silicone material of the present invention) is preferably within the above range.

The hardness of the film-or film-like solid silicone material is also dependent on the substrate, and is not particularly limited, and practically preferably 2B or more in pencil hardness.

The use of the solid silicone material as described above is not particularly limited, and particularly, a film-like or film-like solid silicone material having a film thickness in the range of 50 to 300nm improves light extraction efficiency by the light source/phosphor layer, and is therefore useful as a single solid silicone material or a laminate containing the material as an optical member.

Method for forming film into film or film

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

(i) Film formation based on forming process

The solid silicone material of the present invention is hot-melt, and therefore can be formed into a film on a desired substrate by a known molding method such as integral molding. Examples of the general molding method 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 slip form molding machine, a double press molding machine, and a low-pressure encapsulation molding machine may be used.

(ii) Film-like coating using solvent and film formation based on solvent removal

The solid silicone material of the present invention can be uniformly dispersed in an organic solvent such as isopropyl alcohol or methyl isobutyl ketone, and thus can be applied to a desired substrate in the form of a film, and the organic solvent is removed by means of drying or the like, thereby obtaining a film-like or film-like member. When the coating is performed in the form of a film, the viscosity is preferably adjusted to a range of 100 to 10,000mPa · s using a solvent, and when the coating is diluted with a solvent, the coating can be used in a range of 0 to 2000 parts by mass relative to the sum (100 parts by mass) of the solid components. As the coating method, the following methods can be used without limitation: roll coating using gravure coating, offset gravure printing, offset transfer roll coater, curtain coating using reverse roll coating, air knife coating, curtain coating, comma coating, Mayer bar coating, spin coating, and other known methods for forming a cured layer. The amount of coating is arbitrary, but it is preferable to coat the coating so that the solid content removed as an organic solvent has the above-mentioned film thickness. As described later, by using a laminate in which a film-like or film-like member of the solid silicone material of the present invention is formed on a release coating layer, the film-like or film-like member, or a laminate including the film-like or film-like member, can be separated from the release layer and disposed on another substrate.

Laminate body

The solid silicone material of the present invention is particularly preferably usable as a solid layer constituting a layered structure such as an optical package proposed by the present applicant in patent document 1 and the like, and is particularly preferably disposed at an interface with air as a solid layer constituting a light-emitting device or a laminate member used in the light-emitting device. In this case, if the laminate is a light-emitting device, it is particularly preferable to have a layer containing at least one kind of phosphor (hereinafter referred to as "phosphor layer") between the light source and the solid silicone material of the present invention, from the viewpoint of the technical effect of the present invention.

Peelable layered body

First, a laminate in which a film-like or film-like member of the solid silicone material of the present invention is disposed on a release layer will be described. The film-like or film-like member made of the solid silicone material of the present invention and a laminated member (for example, a laminated sheet further having a phosphor layer) including the same are handled as separate members as required. When the solid layer composed of the solid silicone material of the present invention is disposed on the release layer, the film-like or film-like member composed of the solid silicone material of the present invention, and the laminated member including the same, can be easily separated from the release layer constituting the laminated body 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 have another release layer. In the following examples, "/" means that the layers face each other in the stacking direction of the multilayer body (generally, the thickness direction perpendicular to the substrate). The substrate and the release layer may be integrated or formed in one layer (a substrate having releasability provided with material or physical irregularities).

Example 1: substrate/release layer/solid layer comprising the solid silicone material of the invention/optional layer (which may be 1 or 2 or more layers)

Example 2: substrate/release layer/solid layer comprising the solid silicone material of the present invention/optional layer (which may be 1 or 2 or more layers)/release layer/substrate

In particular, as in example 2, in the case of a structure having a film-like or film-like member made of the solid silicone material of the present invention and a laminated member including the same sandwiched between two release layers, the member having the solid layer made of the solid silicone material of the present invention can be transported (including transportation to foreign countries) while being protected by a base material, and the base material having the release layers can be separated from both surfaces of the laminated body at a desired timing and place, whereby only the film-like or film-like member made of the solid silicone material of the present invention and the laminated member including the same can be disposed or laminated on a desired structure, for example, a light source of a light-emitting device. In particular, in the case where the laminate is a laminate sheet or the like having a laminate member including a solid layer made of the solid silicone material of the present invention and a phosphor layer, the laminate sheet is useful in that the workability can be improved.

The above-mentioned substrate is not particularly limited, and there may be exemplified paperboard, cardboard, clay-coated paper, polyolefin laminated paper, particularly polyethylene laminated paper, synthetic resin film/sheet, natural fiber fabric, synthetic fiber fabric, artificial leather fabric, metal foil. Particularly preferred are synthetic resin films/sheets, and examples of the synthetic resin include: polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, cyclic polyolefin, nylon. The substrate is preferably in the form of a film or sheet. The thickness thereof is not particularly limited and may be set according to the intended thickness according to the use. As described later, the material of the substrate itself that functions as a release layer or the structure having a release property in which fine irregularities are physically formed on the surface of the substrate may be used.

The release layer may be referred to as a release liner, a release layer, or a release coating layer, and may be a release layer having release coating ability such as a silicone-based release agent, a fluorine-based release agent, an alkyd-based release agent, or a fluorine silicone-based release agent, or a substrate itself in which fine irregularities are physically formed on the surface of the substrate and which is insoluble in the solid silicone material attached to the present invention.

The solid layer composed of the solid silicone material of the present invention can be disposed by forming a film on the release layer by the same method as described in the above "method for forming a film into a film or a thin film". In particular, it is preferable that a solid layer of a film-like or film-like solid silicone material is formed on the release layer of the film-like substrate or sheet-like substrate by uniformly dispersing the solid silicone material in an organic solvent such as isopropyl alcohol or methyl isobutyl ketone by the above-mentioned method, coating the coating layer, and removing the organic solvent by drying or the like. The film thickness of the film-like or 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, 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 member is preferably a cured layer or a solid organopolysiloxane (silicone layer) obtained by curing an organopolysiloxane having a curing reactive functional group, and is preferably a cured silicone layer obtained by curing an organopolysiloxane having a hydrosilylation reactive group and/or a radical reactive group, a condensation or dealcoholization reactive group in the presence of a catalyst, or a resin-linear polymer type organopolysiloxane similar to the component (B). The organopolysiloxane having a curing reactive group may be linear, branched, cyclic, or resinous, or may be used in combination with two or more curing reactions.

In particular, it is preferable that the other silicone layer disposed on the solid layer made of the solid silicone material of the present invention is a resin-linear polymer type solid organopolysiloxane similar to the component (B), and it is preferable that a phosphor described later is dispersed in the solid organopolysiloxane.

The other layers in the laminated member may be 1 or more layers or 2 or more layers having different functions. 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, but is preferably 1 μm or more, and may be 50 to 10,000 μm, and is particularly preferably 100 to 1,000 μm in view of workability.

The phosphor layer in which 1 or more layers, particularly the organic silicon layer different from the solid layer, are laminated on the solid layer made of the solid organosilicon material of the present invention preferably contains at least one or more kinds of phosphors. The phosphor layer functions particularly as a wavelength conversion material, and when it is disposed on a light source, it can convert the emission wavelength thereof. The phosphor is not particularly limited, and examples thereof include oxide-based phosphors, oxynitride-based phosphors, and nitride-based phosphors widely used in Light Emitting Diodes (LEDs) and organic electroluminescence elements (OLEDs)Yellow, red, green and blue light emitting phosphors comprising a phosphor, a sulfide-based phosphor, a sulfur oxide-based phosphor, and the like. Examples of the oxide-based phosphor include: yttrium, aluminum, garnet-based YAG-based green to yellow light-emitting phosphors containing cerium ions; a TAG yellow phosphor of terbium, aluminum, or garnet type containing cerium ion; silicate green to yellow light-emitting phosphors containing cerium and europium ions. Examples of the oxynitride-based phosphor include sialon-based red to green light-emitting phosphors containing europium ions and containing silicon, aluminum, oxygen, and nitrogen. The nitride-based phosphor may be, for example, a Cousin-based red-emitting phosphor of calcium, strontium, aluminum, silicon, and nitrogen-based containing europium ion. As the sulfide-based phosphor, a ZnS-based green emitting phosphor containing copper ions or aluminum ions can be exemplified. As the oxysulfide phosphor, Y containing europium ion can be exemplified₂O₂S is a red-emitting phosphor. 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 containing a reinforcing filler may be used for the purpose of imparting mechanical strength to a cured product and improving the protection or adhesion of the cured product, which is different from the solid layer. The silicone layer may contain a thermally conductive filler or an electrically conductive filler so as to impart thermal conductivity or electrical conductivity to the cured product, which is different from the solid layer. The phosphor may be used in combination with these fillers, and the surface of these particulate components may be surface-treated with alkoxysilane, organohalosilane, organosilazane, siloxane oligomer, or the like in order to improve dispersibility in the silicone layer.

The laminate has a structure in which a solid layer made of the solid silicone material of the present invention is disposed on the release layer, and particularly preferably further has a phosphor layer containing a phosphor or the like and a silicone layer different from the solid layer. In the case where the solid layer composed of the solid silicone material of the present invention is disposed on the release layer, the laminated member itself, in which the solid layer composed of the solid silicone material of the present invention is separated easily from the release layer constituting the laminated body, can be used as an optical member or the like for the production of another structure.

Laminate having light source and phosphor, and light-emitting device

When the solid layer made of the solid silicone material of the present invention can be disposed at the interface with air and on the light source of a Light Emitting Diode (LED) or an organic electroluminescence device (OLED), the solid layer made of the solid silicone material of the present invention is disposed at the interface with air, and 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 of a light source, and particularly preferably has a phosphor-containing silicone layer. 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, and the solid layer made of the solid silicone material of the present invention may be formed so as to cover a part or the whole of the phosphor layer, or may be disposed outside the phosphor layer with the functional layer of another layered body interposed therebetween. The thickness of the whole 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, the thickness may be 50 to 10,000 μm, particularly preferably 100 to 1,000 μm, in addition to the thickness of the light source portion.

Improvement of light extraction efficiency and improvement of heat resistance

The layered body having the light source and the phosphor layer is a light-emitting device such as a light-emitting diode (LED) or an organic electroluminescent element (OLED), and the light extraction efficiency of the light-emitting device can be improved by obtaining the arrangement of the light source, the phosphor layer, and the solid layer composed of the solid silicone material of the present invention. In addition, by selecting a solid layer composed of a solid silicone material, coloring or the like associated with heat generation of the light-emitting device can be prevented in some cases, and particularly, heat resistance of the light-emitting device can be improved in some cases.

Method for producing laminate

The method for producing the laminate of the present invention is not particularly limited, and a method for producing a laminate having any of the following steps (i) to (iii) is preferable in terms of forming the solid silicone material of the present invention into a film or film and arranging the same. The coating method in this step can be exemplified by the same method as described above.

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

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

(iii) A step of laminating another structure on a film-like or 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 as a peelable laminate, and the solid layer composed of the solid silicone material of the present invention or a laminate including the solid silicone material can be easily separated from the peeling layer and used. The solid layer composed of the solid silicone material of the present invention separated from the release layer or the laminated member itself including the same is preferably used for the production of another structure as an optical member or the like, and therefore a method for producing a laminated body having the following steps is particularly preferred. In particular, the other structure is preferably a precursor of a light-emitting device having a light source or the like, and the method for manufacturing a light-emitting device having a solid layer made of the solid silicone material of the present invention disposed at an interface with air is particularly preferred.

Characterized by using a layered member (silicone layer) comprising a peelable layered body/the solid silicone material (thin layer) of the present invention, and a method for producing a layered body, comprising the steps of:

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

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

(c) A step of separating the silicone layer laminated with the film-like or film-like solid silicone material obtained in the step (b) from the release layer as a unit,

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