TW201906932A - Solid organic germanium material, laminated body using the same, and light-emitting element - Google Patents

Abstract

The present invention provides a solid organosilicon material, a laminate using the same, etc. The solid organosilicon material is easily thinned with a uniform nanometer-thick film thickness, and is arranged at the interface between the laminate as a light emitting element and air Can improve light extraction efficiency. The solid organosilicon material of the present invention contains (A) hollow or porous inorganic fine particles with a number average particle size of 1 to 100 nm, and (B) a molecule having R ^A SiO _3/2 (where R ^A is carbon Aromatic siloxane units represented by aryl groups with 6 to 14 atoms and (R ₂ SiO _2/2 ) n (where R is an alkyl group or carbon with 1 to 20 carbon atoms that can be substituted by halogen atoms Aryl group with 6 to 14 atoms, n is a number in the range of 3 to 1000), an organic polysiloxane with a polydiorganosiloxane structure, and the content of component (A) is in the range of 10 to 95% by mass .

Description

Solid organic silicon material, laminated body using the same, and light-emitting element

The present invention relates to a solid organic silicon material, a laminated body using the same, and a light-emitting element, and more particularly, to a solid organic silicon material described below, that is, it is easy to realize a thin film with a uniform nano-scale film thickness, and is arranged as a light-emitting element At the interface of the laminate and air, the light extraction efficiency can be improved. The present invention also relates to a method for manufacturing a multilayer body and an optical element using the solid silicone material.

The solid silicone material has excellent moldability, heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency, so it can be used in many industrial fields. Compared with other organic materials, the cured product of the curable silicone composition is less likely to change color, and has less reduction in physical properties. Therefore, it is also suitable as an optical material, especially a light-emitting element (inorganic or organic light-emitting diode). Of sealant.

In recent years, with regard to the manufacturing process of new light-emitting elements, it has been proposed to include a solid or semi-solid state at room temperature, heat-melt at high temperature, and have a heat-fusible silicone-containing material. The hot-melt-containing silicone-containing material is different from the conventional liquid material and has excellent workability and uniform coating properties. For example, the applicant has proposed an optical component in Patent Document 1 which uses a reaction in a sealing material film. The hot-melt composition containing organic or non-reactive organosilicon, and the hot-melt composition has a resinous siloxane structure and a linear siloxane structure in the molecule. This sealing material is used in combination with a sealing material film (phosphor layer) having a fluorescent material that has a high refractive index and converts the wavelength from a light source, and can provide a light-emitting element excellent in productivity and luminous efficiency. However, in the field of light-emitting elements, especially in the case where the above-mentioned phosphor layer is used, higher light extraction efficiency is required, and the above-mentioned light-emitting element has room for improvement. In addition, in Patent Document 1, there is no related disclosure regarding the formulation of specific hollow or porous inorganic fine particles or the use of a film, especially a nano-scale film, for improving light extraction efficiency.

On the other hand, hollow or porous inorganic fine particles with a small particle size have a structure that contains air in the inside or in the pores. When formulated into a resin as a binder, it imparts a low refractive index to the air layer, so it is used as an antireflective sheet. Its anti-reflection layer. Specifically, incident light (incident light from an external light source) is reflected at the interface of the anti-reflection layer having a low refractive index with respect to the substrate layer, and reflection is prevented by interference of the incident light and the reflected light. For example, Patent Documents 2 to 4 disclose antireflection films using silicone as a binder resin and containing hollow or porous inorganic fine particles. However, these patent documents do not contain any information on the use of silicone materials that can impart high refractive index and have hot melt properties, especially those with resinous siloxane structure and linear siloxane structure in the molecule. There is also no related disclosure regarding the use of a thin film for improving light extraction efficiency in a light-emitting element having a light source inside. Furthermore, Patent Document 5 proposes that a cured product of spherical silica hollow beads be formulated for a silicone resin matrix as a matrix resin in a resin casting material for use in electronic parts, but there is nothing about the use of a resin having an internal resin. Relevant disclosures of organosilicon materials with a linear siloxane structure and a linear siloxane structure, and the hollow silica beads are very coarse, with a particle size of 5 to 15 µm, and there is no disclosure of the use of thin films. [Known Technical Literature] [Patent Literature]

[Patent Literature 1] Japanese Patent Publication No. 2016-508290 [Patent Literature 2] International Patent Publication No. 2009-001723 [Patent Literature 3] International Patent Publication No. 2008-117652 [Patent Literature 4] Japanese Patent Laid-Open No. 2004 -258267 [Patent Document 5] Japanese Patent Laid-Open No. 06-84642

[Problems to be Solved by the Invention] The present invention was developed to solve the above-mentioned problems, and an object of the present invention is to provide an organic silicon material, a laminated body using the same, and a light-emitting element. The nano-film thickness is uniformly thinned, and when applied to a laminated body as a light-emitting element, the sealing performance is not impaired, and the light extraction efficiency can be improved. Another object of the present invention is to provide a method for manufacturing a multilayer body and an optical element using the silicone material. [Technical means to solve the problem]

After intensive research, the inventors discovered that by using hollow or porous inorganic particles containing (A) a number average particle diameter of 1 to 100 nm, and (B) having R ^A SiO _3/2 ( In the formula, R ^A is an aryl siloxane unit represented by an aryl group having 6 to 14 carbon atoms, and (R ₂ SiO _2/2 ) n (where R is a carbon atom number 1 which may be substituted by a halogen atom). An alkyl group of ~ 20 or an aryl group of 6 to 14 carbon atoms, n is a number in the range of 3 to 1000), and the organopolysiloxane having a polydiorganosiloxane structure is expressed, and the content of component (A) is The solid organic silicon material in the range of 10 to 95% by mass can solve the above problems and complete the present invention. The solid organic silicon material has hot-melt property, and is particularly easy to realize nano-scale thin film. When used as an optical component for a light-emitting element, its light extraction efficiency can be improved.

Furthermore, the present inventors have found that the above-mentioned problems can be solved by a laminated body containing a solid layer composed of the above-mentioned solid silicone material, and the present invention has been completed.

Similarly, the present inventors have found that light emission is provided by having at least one light source, a layer including at least one phosphor formed thereon, and a solid layer made of the above-mentioned solid organic silicon material disposed on an interface with air. Element, which can solve the above problems, thereby completing the present invention.

In addition, the present inventors have found that the above-mentioned problems can be solved by a method of manufacturing a laminated body or a light-emitting device having a process for molding the solid silicone material into a sheet shape or a thin film shape, thereby completing the present invention. [Inventive effect]

By using the solid silicone material of the present invention, it is easy to use, and it is particularly easy to achieve uniform thin film with a nanometer film thickness, and when it is used as a laminated body of a light-emitting device, there is no damage to its sealing performance. Organic silicon material capable of improving light extraction efficiency, laminated body using the same, and light emitting element. In addition, a method for manufacturing a laminated body or a light-emitting device having a process for molding the solid silicone material into a sheet shape or a film shape can be provided.

[Solid Silicone Material] First, the solid silicone material of the present invention will be described. The solid silicone material is characterized in that a fixed amount of small-diameter (nano-scale) hollow or porous inorganic particles having a structure containing air inside or in pores are dispersed in a resin-linear block copolymer type organic In a polymer matrix composed of polysiloxane, the organic polysiloxane has both an _arylsiloxane unit (T branch unit or resin structure) represented by R ^A SiO _3/2 in the molecule and ( R ₂ SiO _2/2 ) n is a polydiorganosiloxane structure (silane linear structure).

More specifically, the solid organosilicon material of the present invention contains (A) hollow or porous inorganic fine particles having a number average particle diameter of 1 to 100 nm; and (B) having R ^A SiO _{3/2 in the} molecule (where , R ^A is an aryl siloxane unit represented by 6 to 14 carbon atoms) and (R ₂ SiO _2/2 ) n (where R is a carbon atom number 1 to 20 which may be substituted by a halogen atom) An alkyl group or an aryl group having 6 to 14 carbon atoms, and n is a number in the range of 3 to 1000), and the polydiorganosiloxane structure is an organopolysiloxane having a content of 10 to 10 95% by mass. The solid silicone material is described in detail below. [(A) Ingredient]

(A) The component is hollow or porous inorganic fine particles with an average particle diameter of 1 to 100 nm. It has a structure containing air inside or in the pores, which can reduce the refractive index of the polymer matrix and realize a solid layer with a low refractive index. Such small-diameter hollow or porous inorganic fine particles are as described below. When the nano-sized thin film is designed, the low refractive index of the thin film can be realized, and the light extraction rate can be improved through the light source / fluorescent layer.

Here, the hollow inorganic fine particles refer to generally spherical fine particles having voids inside, and are spherical or ellipsoidal fine particles having smooth or uneven surfaces. 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 and the like. Similarly, porous inorganic fine particles refer to inorganic fine particles having a structure in which a plurality of voids are provided in one fine particle. The type of the inorganic fine particles is not particularly limited. Inorganic fine particles such as silica gel, porous silica sol, hollow silica sol, MgF2 sol, and the like are preferred. Inorganic fine particles containing silica hollow silica particles as a main component are particularly exemplified. In addition, these silicon oxide fine particles may be subjected to well-known surface modification such as acrylic modification. From the viewpoint of improving dispersibility, the surface of the inorganic fine particles may also be treated with silazane or a well-known silane coupling agent. Furthermore, these inorganic fine particles may be used individually by 1 type, and may be used in combination of 2 or more types whose types or average particle diameters differ. In addition, as described above, the hollow inorganic fine particles of the present invention preferably have a substantially spherical shape, and particularly preferably do not contain non-spherical, that is, plate-like particles, needle-like particles, tubular particles, and the like having particle diameters.

(A) The average particle diameter of a component is the number average particle diameter of each inorganic fine particle which is not aggregated, and is an average primary particle diameter which can be measured using a laser diffraction scattering particle size analyzer and the like. The number average particle diameter is in a range of 1 to 100 nm, and inorganic particles containing hollow silica particles having an average particle diameter of 40 to 70 nm as a main component are particularly preferred. If the average particle diameter of the inorganic fine particles is larger than the upper limit, the particles may be larger than the nanometer-thick film thickness. In addition, in the manufactured thin film, light is diffusely reflected by Rayleigh scattering. The solid layer becomes white, resulting in a decrease in its transmittance. On the other hand, if the average particle diameter of the inorganic fine particles is smaller than the lower limit, the dispersibility of the inorganic fine particles is reduced and aggregation is caused. In addition, for a thin film member described later, the light extraction efficiency may not be improved through the light source / fluorescent layer.

The refractive index of the component (A) is not particularly limited and varies depending on the manufacturing method, but from the viewpoint of the technical effects of the present invention, it is preferable to use a refractive index in the range of 1.20 to 1.45, and preferably 1.25 to 1.37. The lower the refractive index of the component (A), the better, but among hollow silica particles, 1.20 is the actual lower limit, and if it exceeds 1.45, it will approach a very high refractive index, and the effect of sufficiently improving the light extraction efficiency may not be obtained. [(B) Ingredient]

The (B) component is a resin-linear polymer-type organic polysiloxane containing a T unit having an aryl group as a binder of the component (A), and has a high refractive index and hot-melt properties, so it is easy to form a uniform and A film-like solid layer with a nanometer thickness.

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

Here, aryl-based phenyl, tolyl, xylyl, naphthyl, and anthracenyl having 6 to 14 carbon atoms are preferably phenyl from the viewpoint of industrial production. In addition, R is an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl; phenyl, toluene Aryl groups such as methyl, xylyl, naphthyl, anthracenyl, etc .; replace some or all of the hydrogen atoms bonded to these groups with halogen atoms such as fluorine, chlorine, and bromine atoms; From a viewpoint, a methyl group or a phenyl group is preferable.

More specifically, (B) component has a T-cell line: R ¹ SiO _3/2 the (R ¹ is a monovalent organic group, a hydroxyl group or an alkoxy group having a carbon number of 1 to 6, at least ¹ molecule of all R More than one aryl group having 6 to 14 carbon atoms), arbitrary Q unit: resin structure block of siloxane unit represented by SiO _4/2 and (R ₂ SiO _2/2 ) n (where n is the above Same number, R is the same group as above) Structure of linear structure block represented by silicon alkyl bond or Si-O-Si bond, and resin-linear organic having R ^A SiO _3/2 unit A polysiloxane block copolymer, in which the Si atom or Si-O-Si bond connecting the resin structure block and the linear structure block in the polymer, preferably the Si atom bonded to the resin structure constitutes R ^A SiO _3/2 unit.

The resin structure block in the component (B) is a partial structure that imparts hot-melt properties to the entire component (B), and is a resinous organic polysiloxane structure. The relevant structure forms a partial structure composed of a resin-like organic polysiloxane containing an arylsiloxane unit represented by R ^A SiO _3/2 as an essential component and a large number of T units or Q units bonded. In particular, when a large amount of an aryl group such as a phenyl group is contained in the molecule, the refractive index of the component (B) can be increased. The component (B) is preferably an organic polysiloxane containing 20 to 80% by mass of the arylsiloxane unit represented by R ^A SiO _3/2 (where R ^A is the same group as above), since From the viewpoint of the above-mentioned hot-melt property and refractive index, it is particularly preferable that the resin structure is substantially formed of only an _{arylsiloxane unit} 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 two organic silanol units represented by R ₂ SiO _2/2 are connected by at least 3 units, preferably 5 units or more It is a chain-like structure. The related linear structure block is a partial structure that imparts moderate softness to a solid layer formed from the copolymer. In the formula, n is the polymerization degree of the two organosilyloxy units constituting the partial structure, and is preferably in a range of 3 to 250, more preferably in a range of 5 to 250, 50 to 250, 100 to 250, and 200 to 250. If n in a part of the structure exceeds the above upper limit, the properties of the linear molecules derived from the linear structure will be strongly manifested, resulting in a decrease in film moldability. On the other hand, if n is lower than the lower limit described above, the properties of the linear molecules are insufficient, especially the cissing phenomenon is likely to occur during thin film formation, uniform coating cannot be achieved, and the characteristics of the component (B) may not be achieved. Sexuality.

The functional group R in the two organic silanol units constituting the linear structure is an alkyl group or an aryl group. These groups are not reactive to the resin structure and its functional groups in the same molecule, and no condensation reaction will occur in the molecule. The polymerization reaction needs to maintain a linear structure. The alkyl group and the aryl group are the same groups as described above, and are preferably a methyl group or a phenyl group from the industrial viewpoint.

The resin structure block and the linear structure block in the component (B) are preferably derived from a silylene bond derived from a silylation reaction between an alkenyl group and a silicon atom bonded hydrogen atom, or derived from a resin structure or a linear structure end The Si-O-Si bond of the condensation-reactive group is linked. In the present invention, it is particularly preferred that the Si atom bonded to the resin structure constitutes an R ¹ SiO _3/2 unit, and particularly preferably has the following partial structure (T-Dn). From an industrial standpoint, R ¹ is preferably phenyl, and R is preferably methyl or phenyl. Partial structure (T-Dn) [Chemical Formula 1] (T-Dn)

In the above partial structure, the left Si-O-bond end constituting the T unit is preferably bonded to a hydrogen atom or other siloxane units constituting the resin structure, and preferably other T units. On the other hand, the end of the right Si-O-bond is bonded to other siloxane units, triorganosiloxy units (M units) or hydrogen atoms forming a linear structure or a resin structure. In addition, when a hydrogen atom is bonded to the Si-O- bond terminal, a silanol group (Si-OH) is naturally formed.

From the viewpoint of improving the hot-melt property of the component (B), the refractive index required for the light extraction efficiency, and especially the uniform coatability during thinning, the component (B) is preferably represented by only R ^A SiO _3/2 Non-reactive organic polysiloxane composed of an arylsiloxane unit and two organic siloxane units represented by R ₂ SiO _2/2 . More specifically, the component (B) is preferably an organopolysiloxane represented by {(R ₂ SiO _2/2 )} _a {R ^A SiO _3/2 } _1-a . In the formula, R and R ^A are the same groups as described above, and a is a number in a range of 0.8 to 0.2, and more preferably a number in a range of 0.80 to 0.40. [Hot meltability]

The component (B) preferably has hot-melt properties, specifically, preferably non-fluidity at 25 ° C, and a melt viscosity at 100 ° C of 200,000 Pa · s or less. Non-flowability refers to the non-flowing state under no load. For example, it indicates that the softening is lower than the ring and ball method using hot-melt adhesives specified by JIS K 6863-1994 "Test Method for Softening Point of Hot-melt Adhesives". The state of the softening point measured by the point test method. That is, in order to have non-flowability at 25 ° C, the softening point must be higher than 25 ° C. The component (B) preferably 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 a range of 10 to 20,000 Pa · s. When the melt viscosity at 100 ° C is within the above range, the adhesiveness of the film or the like is good after cooling to 25 ° C after hot melting. In addition, by using the component (B) having a melt viscosity of 100 to 15,000 Pa · s, it is possible to suppress deformation and peeling of a film or the like after molding. [Mixed amount]

The content of the component (A) in the solid silicone material of the present invention is in the range of 10 to 95% by mass, and the content of the component (A) when the component (B) is an inorganic fine particle containing the above-mentioned preferred hollow silica fine particles as a main component. The range of 40 to 95 mass% is especially preferable. [Optional component]

The solid organosilicon material of the present invention may be added within a range that does not hinder the object of the present invention. Vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyl Organic functional alkoxysilane compounds such as trimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, etc. Anti-oxidants such as phenols, quinones, amines, phosphorus, phosphorous acid, sulfur, thioethers, etc. can be added as other optional ingredients within the range that does not impair the technical effects of the present invention. ; Light stabilizers such as triazoles and benzophenones; flame retardants such as phosphates, halogens, phosphorus, antimony; etc .; cationic surfactants, anionic surfactants, nonionic surfactants Antistatic agents composed of one or more agents; dyes, pigments, etc. However, in order to achieve a thin film, it is preferable not to add solid particles other than the component (A), and in particular, particle components having an average primary particle diameter exceeding 100 nm.

The solid silicone material of the present invention may be dispersed in an organic solvent and applied for the purpose of forming a film or a thin film to be described later. The organic solvent to be used may be any compound that can dissolve all or a part of the constituents in the composition, and its type is not particularly limited, and a boiling point of 80 ° C. or higher and less than 200 ° C. is preferably used. Examples include isopropanol, tert-butanol, cyclohexanol, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, mesitylene, and 1,4-dioxane. Alkane, dibutyl ether, anisole, 4-methylanisole, ethylbenzene, ethoxybenzene, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 2-methoxy Ethyl alcohol (ethylene glycol monomethyl ether), diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, propyl propionate, 1-methoxy-2-propane Halogen-free solvents such as methyl acetate, 1-ethoxy-2-propyl acetate, octamethylcyclotetrasiloxane, and hexamethyldisilazane; trifluoromethylbenzene, 1, 2-bis (trifluoromethyl) benzene, 1,3-bis (trifluoromethyl) benzene, 1,4-bis (trifluoromethyl) benzene, trifluoromethylchlorobenzene, trifluoromethylfluorobenzene , Hydrofluoric ether and other halogen solvents. These organic solvents may be used alone or in combination of two or more. From the viewpoint of improving the workability of the solid silicone material of the present invention, the uniformity of the solid layer, and heat resistance, isopropyl alcohol, methyl isobutyl ketone, and the like are preferably used. [Use as a sheet or film]

The solid silicone material of the present invention can be used as a member in a desired form, but when it is used for the purpose of improving light extraction efficiency through a light source / phosphor layer, it is preferably a sheet or film. In particular, the solid silicone material of the present invention can be designed to have a uniform thin film shape with a nano-scale film thickness, and it is preferable to provide a thin sheet or thin film solid silicone material with a film thickness ranging from 50 to 300 nm.

Here, the film thickness of the flaky or thin-film solid silicone material can be designed as desired, but for the purpose of improving the light extraction efficiency through the light source / phosphor layer, the average primary particle diameter L (nm) of the component (A) ), The film thickness is preferably in the range of L to 4L (nm), and the film thickness is particularly preferably in the range of 1.5L to 2.5L (nm). Within this range, the inorganic fine particles of component (A) supported by the solid organosilicon material can average 1 to 4 in the layer, and preferably has a structure of about 2 overlaps with respect to the film thickness direction, so it is most suitable to pass the light source / The phosphor layer improves light extraction efficiency. As an example, when inorganic fine particles containing hollow silica particles having an average primary particle size (L) of 50 nm are used as the main component, the range of 1.5 L to 2.5 L (nm) is converted to a film thickness of 75 to 125 nm. range. However, in addition to the above-mentioned film thickness, for example, when the film thickness is about 50 to 150 nm, the light extraction efficiency can be improved through the light source / fluorescent layer. In addition, in the laminated body described later (as a solid layer), the film thickness of the solid silicone material of the present invention is also preferably within the above range.

The hardness of the flake-shaped or thin-film solid silicone material also depends on the base material, so it is not particularly limited, but it is preferably a pencil hardness of 2B or more in actual use.

There are no particular restrictions on the use of the solid silicone materials described above, but in order to improve the light extraction efficiency through the light source / fluorescent layer, a thin or thin film solid silicone material with a film thickness in the range of 50 to 300 nm is used as the solid silicone material. A single body or a laminated body containing the material is particularly suitable for use as an optical member. [Method for forming film into sheet shape or film shape]

The method for forming the solid silicone material according to the present invention into a thin sheet or a thin film is not particularly limited, and the film can be formed by the following method. (Ⅰ) Film formed by molding

The solid organic silicon material according to the present invention has hot-melt properties, so it can be formed on a desired substrate by a well-known molding method such as integral molding. Examples of the conventional molding method include transfer molding, injection molding, and compression molding. For example, in the injection molding, the solid silicone material according to the present invention is filled into a plunger of a molding machine, and the molding is performed automatically to obtain a sheet-shaped or film-shaped member, which is a molding. As for the molding machine, any one of an auxiliary piston type molding machine, a slider type molding machine, a double piston type molding machine, and a low pressure injection molding machine can be used. (Ⅱ) Thin film coating with solvent and removal of solvent to form a film

The solid organic silicon material according to the present invention can be uniformly dispersed in organic solvents such as isopropanol and methyl isobutyl ketone, so it can be coated on a desired substrate into a thin film and then removed by methods such as drying. An organic solvent, thereby obtaining a sheet-like or film-like member. When coating in a thin sheet, it is preferable to adjust the viscosity with a solvent so that the overall viscosity is in the range of 100 to 10,000 mPa · s. When diluted with a solvent, it can be 0 to A solvent is used in the range of 2000 parts by mass. The coating method is not particularly limited, and roll coating, gravure offset printing, gravure offset printing, offset printing using roll transfer coating, reverse roll coating, air knife coating, and curtain flow coating can be used. Etc. Curtain coating, comma blade coating, Meyer bar coating, spin coating, and other well-known methods for the purpose of forming a cured layer. In addition, although the coating amount is arbitrary, it is preferable to apply so that it may become the said film thickness as a solid part after removal of an organic solvent. In addition, as described later, by using a laminated body of a sheet-like or film-like member having the solid silicone material according to the present invention formed on a release coating layer, the sheet-like or film-like member or a laminate including the same can be used. The laminated member is separated from the release layer and is arranged on another substrate. [Laminated body]

The solid organosilicon material of the present invention is particularly suitable for use as a solid layer constituting a laminated body structure such as an optical component proposed by the applicant of the present application, such as Patent Document 1, and particularly as a solid layer constituting a light-emitting element or a laminated member used for the light-emitting element. Placed on the interface with air. At that time, if the multilayer body is a light-emitting element, from the viewpoint of the technical effects of the present invention, it is particularly preferable to have a layer containing at least one kind of phosphor between the light source and the solid silicone material of the present invention (hereinafter referred to as "fluorescent layer"). . [Peelable laminate]

First, a laminated body of a sheet-like or film-like member in which the solid silicone material according to the present invention is disposed on the release layer will be described. According to requirements, the sheet-like or film-like member composed of the solid silicone material of the present invention, and a laminated member including the same (for example, a laminated sheet having a phosphor layer) are required to be used alone as a member. When a solid layer composed of the solid silicone material according to the present invention is disposed on the release layer, it is easy to separate the sheet-like or film-like member composed of the solid silicone material of the present invention from the release layer constituting the laminated body, and the laminate including the same. Build and use. Such a laminate has a release layer facing the solid layer composed of the solid silicone material of the present invention, and may further include other release layers as desired, and the following laminate structure can be exemplified. In addition, in the following examples, "/" means that the lamination direction (generally perpendicular to the thickness direction of the substrate) of each layer and the laminated body is opposite. In addition, the base material and the release layer may be integral or the same layer (material or a base material provided with physical unevenness so as to have release properties). Example 1: Substrate / Release layer / Solid layer composed of the solid silicone material of the present invention / any other layer (may be 1 or more layers) Example 2: Substrate / Release layer / Solid silicone material from the present invention Structured solid layer / any other layer (can be 1 layer or more) / release layer / base material

In particular, as shown in Example 2, when a sheet-like or film-like member made of the solid silicone material of the present invention and a base member including the same are sandwiched by two release layers, the base member can be protected in a state The components with a solid layer composed of the solid silicone material of the present invention are transported (including export to foreign countries). The substrate with the release layer can be separated from both sides of the laminated body at the desired time and place. Only the present invention will be used. A sheet-like or film-like member made of a solid organic silicon material, and a laminated member including it are arranged or laminated to a desired structure, such as a light source of a light-emitting element. When the laminated member of the related laminated body is a laminated sheet including a solid layer composed of the solid silicone material of the present invention and a phosphor layer, etc., it is very useful in improving the workability.

The above substrate is not particularly limited, and examples thereof include board paper, corrugated paper, clay coated paper, polyolefin laminated paper, especially polyethylene laminated paper, synthetic resin sheet / board, natural fiber cloth, synthetic fiber cloth, and artificial leather cloth. And metal foil. Particularly preferred are synthetic resin films and sheets. Examples of the synthetic resin include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, and polyethylene terephthalate. Esters, cyclic polyolefins, and nylon. The substrate is preferably in the form of a sheet or a sheet. The thickness is not particularly limited and can be designed to a desired thickness according to the application. In addition, as described later, the substrate itself may function as a material that functions as a release layer or a structure in which fine irregularities are physically formed on the surface of the substrate so as to have a release property.

The release layer is also called a release liner, a release layer or a release coating, and preferably has a release coating performance of a silicone-based release agent, a fluorine-based release agent, an alkyd-based release agent, or a fluoropolysiloxane-based release agent. The release layer can also form fine irregularities on the surface of the substrate physically, or it can be the substrate itself that is not easy to adhere to the solid silicone material of the present invention.

The solid layer composed of the solid organosilicon material of the present invention can be formed into a film according to the method described in the above-mentioned "Method for Forming Film into Sheet or Film Form", and can be disposed on the release layer. It is particularly preferred that the solid silicone material is uniformly dispersed in an organic solvent such as isopropyl alcohol, methyl isobutyl ketone, etc. according to the above method, and then coated on a peeling layer of a sheet-shaped substrate or a sheet-shaped substrate, and dried, etc. The method removes the organic solvent, thereby forming a solid layer of a thin sheet or thin film of a solid silicone material on the release layer. The film thickness of the flaky or thin-film solid silicone material is the same as above.

The solid layer composed of the solid organosilicon material of the present invention can be used alone, and it is more preferable that the solid layer is a laminated member having the same or different layers laminated on the solid layer. The other layers in the laminated member are particularly preferably a cured layer or a solid organic polysiloxane (organic silicon layer) obtained by curing an organic polysiloxane having a curing-reactive functional group, and preferably a hydrosilation reaction. The organic silicon curing layer formed by curing reaction of organic groups and / or radical reactive groups, condensation or dealcohol-reactive groups in the presence of a catalyst, or the same as component (B) Resin-linear polymer-type organic polysiloxane. Here, the organopolysiloxane having a curing-reactive group may be linear, branched, cyclic, or resinous, or two or more curing reactions may be used in combination.

The other organic silicon layer disposed on the solid layer composed of the solid organic silicon material of the present invention is particularly preferably a resin-linear polymer-type solid organic polysiloxane having the same component as the above (B), and is preferably the solid organic silicon. An organosilicon layer formed by dispersing a phosphor described later on polysiloxane.

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

One or more layers laminated on the solid layer composed of the solid organosilicon material of the present invention, especially an organosilicon layer different from the solid layer, is preferably a phosphor layer containing at least one or more phosphors. The relevant phosphor layer can particularly function as a wavelength conversion material, and when placed on a light source, it can convert its emission wavelength. The phosphor is not particularly limited, and examples thereof include oxide-based phosphors, nitrogen oxide-based phosphors, and the like, which are widely used in light-emitting diodes (LEDs) or organic light-emitting diodes (OLEDs). Yellow, red, green, and blue light-emitting phosphors composed of nitride-based phosphors, sulfide-based phosphors, and sulfur-oxide-based phosphors. Examples of the oxide-based phosphor include yttrium, aluminum, and garnet-based YAG green to yellow light-emitting phosphors containing cerium ions; TAG-based yellow light-emitting phosphors containing erbium, aluminum, and garnet cerium ions Body; and silicate green to yellow light-emitting phosphors containing cerium and europium ions. Examples of the nitrogen oxide-based phosphor include silicon, aluminum, oxygen, and nitrogen-containing SiAlON-based red to green light-emitting phosphors including thallium ions. Examples of the nitride-based phosphor include CASN-based red light-emitting phosphors containing calcium, strontium, aluminum, silicon, and nitrogen of thallium ions. Examples of the sulfide-based phosphor include a ZnS-based green color-emitting phosphor containing copper ions and aluminum ions. Examples of the sulfur oxide-based phosphor include a Y ₂ O ₂ S-based red light-emitting phosphor containing europium ions. In the multilayer body according to the present invention, these phosphors may be used in combination of two or more kinds.

In the above-mentioned laminated body, the organic silicon layer different from the solid layer may be an organic silicon layer containing a reinforcing filler in order to impart mechanical strength to the cured product and provide protection or adhesion. In addition, in order to make the cured product have thermal conductivity or electrical conductivity, the organic silicon layer different from the solid layer may also be an organic silicon layer containing a thermally conductive filler or a conductive filler. In addition, the above phosphors can be used in combination with these fillers. In order to improve their dispersibility in the organic silicon layer, alkoxysilanes, organic halogenated silanes, organic silazanes, and siloxane oligomers can be used. The surface of these particulate components is surface-treated.

The structure in which the above-mentioned laminated system is configured by disposing the solid layer composed of the solid silicone material of the present invention on the release layer is particularly preferable to further include a silicone layer different from the solid layer and a phosphor layer containing a phosphor or the like. When the solid layer composed of the solid silicone material according to the present invention is disposed on the release layer, the solid layer composed of the solid silicone material of the present invention or a laminated member including the solid layer can be easily separated from the release layer constituting the laminate. The laminated member itself is used as an optical member or the like to manufacture other structures. [Laminated body with light source and phosphor, light-emitting element]

The solid layer composed of the solid organosilicon material of the present invention can be disposed on the interface with air, and when disposed on a light emitting diode (LED) or organic light emitting diode (OLED) light source, the solid layer is composed of the solid organosilicon material of the present invention. The solid layer can be arranged on the interface with the air to improve the light extraction efficiency of the entire multilayer body including the light source. The related multilayer body preferably has a phosphor layer containing the same phosphor as described above, especially a wavelength conversion material containing an organic silicon layer containing phosphor as a light source. Here, it is preferable that the light emitted from the light source is converted into a wavelength by the phosphor layer to reach a solid layer composed of the solid silicone material of the present invention disposed on the interface with the air, and a solid composed of the solid silicone material of the present invention. The layer can be formed to cover a part or the entire phosphor layer, and can also be arranged on the outside of the phosphor layer through the functional layers of other laminates. The overall thickness of the laminated body is not particularly limited, but it is preferably 1 µm or more. When used as a light-emitting element, the thickness may be 50 to 10,000 µm, and more preferably 100 to 1,000 µm, in addition to the thickness of the light source portion. [Improved light extraction efficiency and heat resistance]

The laminated body provided with the relevant light source and phosphor layer is a light emitting element such as a light emitting diode (LED) or an organic light emitting diode (OLED). The light source, the phosphor layer, and the solid organic silicon material of the present invention are adopted. The arrangement of the solid layer can improve the light extraction efficiency of the light-emitting element. Furthermore, by selecting a solid layer composed of a solid silicone material, it is possible to prevent the phenomenon of coloring and the like accompanying the heat generation of the light emitting element, and particularly to improve the heat resistance of the light emitting element. [Manufacturing method of laminated body]

The manufacturing method of the laminated body according to the present invention is not particularly limited, but from the viewpoint of forming the solid silicone material of the present invention into a thin film or a thin sheet and arranging it, it is preferable to have the following processes (ⅰ) to (ⅲ A method for manufacturing a laminated body in any of the processes). Examples of the coating method and the like related to this process include the same methods described above. (Ii) The process of molding the solid silicone material of the present invention into a sheet or film shape on other structures (i) Dispersing the solid silicone material of the present invention in an organic solvent and coating it on other structures Process of lamellar or thin film and then removing organic solvent (ⅲ) Process of laminating other structures on a lamellar or thin film member made of the solid silicone material of the present invention

The solid silicone material of the present invention can be used in particular in the form of a peelable laminate, and it is easy to separate and use a solid layer composed of the solid silicone material of the present invention or a laminated member including the same from the peeling layer. The solid layer composed of the solid organosilicon material of the present invention or the laminated member containing the separated layer is suitable as an optical member and the like for producing other structures. Therefore, a method for producing a laminated body having the following processes is particularly preferred. . The other structure is particularly preferably a light-emitting element precursor provided with a light source or the like, and the manufacturing method is particularly preferably a light-emitting element manufacturing method including a solid layer composed of the solid silicone material of the present invention disposed on an interface with air.

A manufacturing method of a laminated body characterized by using a laminated member (organic silicon layer) including a peelable laminated body / the solid organic silicon material (thin layer) of the present invention includes: (a): on the peeled layer, The process of inventing the solid organic silicon material dispersed in an organic solvent, coating it on other structures as a flake or film, and then removing the organic solvent; (b): the flake or obtained in the process (a) The process of laminating the same or different organic silicon layers on a thin film solid organic silicon material; (c): integrating the organic silicon layer obtained by the process (b) and laminating a thin or thin film solid organic silicon material as a whole; , A process of separating from the peeling layer; and (d): a process of laminating the laminated body obtained by the process (c) on another structure. [Example]

The following examples illustrate the invention, but the invention is not limited thereto. The number average particle diameter of the hollow silica particles is described as the average particle diameter described in the catalog of each company. (Synthesis example 1)

A 1 L four-mill-mouth round bottom flask was filled with phenylsilsesquioxane hydrolysate (135.00 g, 0.99 mol of Si) and toluene (135.00 g). The mixture was heated under reflux under a nitrogen atmosphere for 30 minutes. After the reaction mixture was cooled to 100 ° C, a solution of diethoxyl-terminated polyphenylmethylsiloxane (siloxane polymerization degree 186) was added. The reaction mixture was heated while refluxing for 2 hours. After that, methyltriethoxysilane (20.23 g, 0.09 mol of Si) was added, and the mixture was refluxed for 1 hour. Water (30 mL) was added and the aqueous phase was removed by azeotropic distillation. This step was repeated twice more to reduce the acetic acid concentration, and then a part of toluene was distilled off, so as to obtain a toluene solution of an organopolysiloxane having a transparent resin-linear polymer structure (weight average molecular weight = 70300, solid content concentration 79.12%). (Synthesis example 2)

A 1 L four-mill-mouth round bottom flask was filled with phenylsilsesquioxane hydrolysate (80.00 g, 0.59 mol of Si) and toluene (235.00 g). The mixture was heated under reflux under a nitrogen atmosphere for 30 minutes. After the reaction mixture was cooled to 100 ° C, a solution of diethoxyl-terminated polydimethylsiloxane (siloxane polymerization degree 105) was added. The reaction mixture was heated for 2 hours while refluxing, and then methyltriethoxysilane (5.35 g, 0.02 mol of Si) was added, and the mixture was refluxed for 1 hour. Water (45 mL) was added and the aqueous phase was removed by azeotropic distillation. This step was repeated 4 more times to reduce the acetic acid concentration, and then a part of toluene was distilled off, so as to obtain a toluene solution of organopolysiloxane having a transparent resin-linear polymer structure (weight average molecular weight = 93500, solid part concentration 66.73%). (Synthesis example 3)

A 1 L four-mill-mouth round bottom flask was filled with phenylsilsesquioxane hydrolysate (135.00 g, 0.99 mol of Si) and toluene (360.00 g). The mixture was heated under reflux under a nitrogen atmosphere for 30 minutes. After the reaction mixture was cooled to 100 ° C, a solution of diethoxyl-terminated polydimethylsiloxane (siloxane polymerization degree 105) was added. The reaction mixture was heated while refluxing for 2 hours, and then methyltriethoxysilane (13.48 g, 0.06 mol of Si) was added, and the mixture was refluxed for 2.5 hours. Add vinylmethyldiethoxysilane (12.65 g, 0.07 mol of Si), reflux the mixture for 2 hours, and then add water (76 mL) to azeotropize for 30 minutes. After the organic layer is separated, remove it from the bottom Water layer. Next, the water was replaced with saturated saline, and the same procedure was repeated twice more to reduce the acetic acid concentration, and then repeated twice more with water. Part of the toluene was distilled off to obtain a toluene solution of an organopolysiloxane having a transparent resin-linear polymer structure (weight-average molecular weight = 72000, solid content concentration of 61.23%). [Examples 1 to 3, Comparative Examples 1 to 2] (Example 1)

Hollow silica fine particles (Surria 4320 manufactured by Nippon Hitsuke Chemical Co., Ltd., 20.5% by weight of silica solids, hollow silica fine particles, number average particle size 60 nm, 0.258 g) and methyl isobutyl ketone (6.30 g) Stir in a container, and then add 66.73% by weight of the organopolysiloxane-toluene solution (0.020 g) obtained in Synthesis Example 2 to obtain a 1% by weight adjustment solution 1A. Using a coater (PI-1210 FILM COATER) and a rod (R.D.S. Webster, N.Y. No. 3), an adjustment solution 1A was applied to a release sheet (T788 manufactured by DAICEL). After being left at room temperature for about 30 minutes, it was dried in an oven at 40 ° C for 1 hour to obtain sheet 1. The thickness of the coating layer was measured with a thickness gauge (F20 thin film analyzer manufactured by FILMETRICS), and the result was 188.2 nm.

To the organosiloxane-toluene solution (66.7 g) obtained in Synthesis Example 1, 1,8-diazabicyclo [5.4.0] undec-7-ene (20 ppm relative to the organosiloxane (Quantity) and phosphor (INTEMATIX, NYAG 4454-L, 10.1 g), using a rotary revolution mixer with vacuum degassing mechanism (THINKY company ARV-310LED) to stir uniformly to obtain the adjustment liquid 1B. Using a coater (PI-1210 FILM COATER), the conditioning liquid 1B was cast on the coated surface side of the sheet 1 with a gap of 925 µm. The sheet was dried in an oven at 40 ° C. overnight, and then dried in a vacuum oven at 50 ° C. for 2 hours to obtain a phosphor sheet 1.

The obtained phosphor sheet 1 was cut into a circular shape having a diameter of 36 mm, and then it was torn from the peeling sheet and set on the LED wafer with the coating side facing up, and a vacuum laminator (Nissin spinning laminator 0505S) was used. ) Sealed. (Example 2)

Hollow silica fine particles (Surria 4320 manufactured by Nippon Hitsuke Chemical Co., Ltd., 20.5 wt% of silica solids, hollow silica fine particles, number average particle size 60 nm, 0.068 g) and methyl isobutyl ketone (3.46 g) Stir in a container, and then add 66.73% by weight of the organopolysiloxane-toluene solution (0.005 g) obtained in Synthesis Example 2 to obtain 0.5% by weight of the adjusted solution 2A. Using a coater (PI-1210 FILM COATER) and a rod (R.D.S. Webster, N.Y. No. 3), an adjustment solution 2A was applied to a release sheet (T788 manufactured by DAICEL). After being left at room temperature for about 30 minutes, it was dried in an oven at 40 ° C for 1 hour to obtain sheet 2. The thickness of the coating layer was measured with a thickness gauge (F20 thin film analyzer manufactured by FILMETRICS), and the result was 113.1 nm.

Using a coater (PI-1210 FILM COATER), the same adjustment liquid 1B as in Example 1 was cast on the coated surface side of the sheet 2 with a gap of 925 µm. The sheet was dried in an oven at 40 ° C. overnight, and then dried in a vacuum oven at 50 ° C. for 2 hours to obtain a phosphor sheet 2. The obtained phosphor sheet 2 was set on an LED wafer 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 the adjustment solution 1A (0.30 g) of Example 1 to be diluted, and the adjustment solution 3A was adjusted to 0.1% by weight. Using a coater (PI-1210 FILM COATER) and a rod (R.D.S. Webster, N.Y. No. 3), the adjustment solution 3A was applied to a release sheet (T788 manufactured by DAICEL). After being left at room temperature for about 30 minutes, it was dried in an oven at 40 degrees for 1 hour to obtain sheet 3. The thickness of the coating layer was measured with a thickness gauge (F20 thin film analyzer manufactured by FILMETRICS), and it was 213 nm.

Using a coater (PI-1210 FILM COATER), the same adjustment liquid 1B as in Example 1 was cast on the coated surface side of the sheet 3 with a gap of 925 µm. The sheet was dried in an oven at 40 ° C. overnight, and then dried in a vacuum oven at 50 ° C. for 2 hours to obtain a phosphor sheet 3. The obtained phosphor sheet 3 was set on an LED wafer in the same manner as in Example 1 and sealed using a vacuum laminator. (Comparative Example 1)

Using a coater (PI-1210 FILM COATER), the same adjustment liquid 1B as in Example 1 was applied to a release sheet (DAICEL Corporation T788) with a gap of 925 µm. The sheet was dried in an oven at 40 ° C. overnight, and then dried in a vacuum oven at 50 ° C. for 2 hours to obtain a phosphor sheet 4. The obtained phosphor sheet 4 was set on an LED wafer in the same manner as in Example 1 and sealed using a vacuum laminator. (Comparative Example 2)

To 66.73% by weight of the organosiloxane-toluene solution (3.29 g) obtained in Synthesis Example 2 was added reinforced silica (Aerosil 200S, 0.107 g) and methyl isobutyl ketone (1.00 g), and the mixture was stirred with a Dental mixer. In 20 seconds, a mixed solution 1 was obtained. The obtained mixed solution (0.05 g) was diluted with methyl isobutyl ketone (2.56 g) to prepare a 1% by weight solution 4A.

Using a coater (PI-1210 FILM COATER) and a rod (R.D.S. Webster, N.Y. No. 3), an adjustment solution 4A was applied to a release sheet (T788 manufactured by DAICEL). After being left at room temperature for about 30 minutes, it was dried in an oven at 40 ° C for 1 hour to obtain sheet 4. The thickness of the coating layer was measured with a thickness gauge (F20 thin film analyzer manufactured by FILMETRICS), and the result was 110 nm.

Using a coater (PI-1210 FILM COATER), the same adjustment liquid 1B as in Example 1 was cast on the coated surface side of the sheet 4 with a gap of 925 µm. The sheet was dried in an oven at 40 ° C. overnight, and then dried in a vacuum oven at 50 ° C. for 2 hours to obtain a phosphor sheet 5. The obtained phosphor sheet 5 was set on an LED wafer in the same manner as in Example 1 and sealed using a vacuum laminator. [Evaluation method] Measurement of total radiation beam

For the light-emitting semiconductor devices (Examples 1 to 3 and Comparative Examples 1 to 2) obtained by sealing the LED wafer by the above-mentioned process, the total radiation beam (mW) was measured using a total beam measuring device (manufactured by Otsuka Electronics Co., Ltd.). The results are shown in Table 1 below. [Table 1] [Examples 5 to 6, Comparative Example 3]

In the following Examples 5 to 6, and Comparative Example 7, a light-emitting semiconductor device obtained by the following method was used. In addition, in the examples, the thickness of a thin film layer (coating layer) containing hollow silica particles obtained by spin coating is a value separately measured by spin coating the same amount of solution separately. (Production of Optical Semiconductor Packaging)

As the optical semiconductor device, a MA5050 package (W * N-045) light-emitting semiconductor device was used. The light-emitting semiconductor device was mounted with an LED wafer having a light-emitting layer made of InGaN and a main light-emitting peak of 454.7-460 nm.

As a sealing resin, 1,8-diazabicyclo [5.4.0] undec-7-ene (0.01 g) was added to the organosiloxane-toluene solution (105.4 g) obtained in Synthesis Example 1. The amount of the organosiloxane is 100 ppm), the phosphor (manufactured by INTEMATIX, NYAG 4454-L, 17.348 g), the thickener (KBE-402, manufactured by Shin-Etsu Chemical Co., Ltd., 0.433 g), and silanol-terminated polybenzene The methyl methyl siloxane (the degree of polymerization of the siloxane is 4 to 5, 11.22 g) was stirred with a rotation revolution mixer (ARV-310LED, manufactured by THINKY) with a vacuum degassing mechanism, and the adjustment solution 1C was obtained.

Using a coater (PI-1210 FILM COATER), a conditioning solution 1C was cast on a release sheet (SPPET5003BU manufactured by Mitsui Tohcello) with a gap of 925 µm. The sheet was dried in a nitrogen circulation oven set at 40 degrees overnight, and then dried in a vacuum oven at 50 degrees for 2 hours.

The obtained phosphor sheet was cut into a circular shape having a diameter of 32 mm, and sealed on an LED wafer using a vacuum laminator (a laminator 0505S manufactured by Nisshinbo Co., Ltd.). The obtained light-emitting semiconductor device was placed on a stainless steel (SUS) plate provided with a spacer having a height of 1.4 mm, and a release sheet and a SUS plate were sequentially placed thereon, and compressed with a hot press at 135 degrees for 30 minutes to perform heat curing. After that, they were completely cured in a programmable 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 (Surria 4320 manufactured by Nippon Hitsuke Chemical Co., Ltd., 20.5 wt% of silica solids, hollow silica fine particles, number average particle size 60 nm, 0.378 g) and methyl isobutyl ketone (9.3 g) Stir in a container, and then add 66.73% by weight of the organopolysiloxane-toluene solution (0.029 g) obtained in Synthesis Example 2 to prepare 1% by weight of solution 1.

This solution 1 was dropped on the sealing layer of the obtained light-emitting semiconductor device, and a spin coater (MIKASA spin coater 1H-DXII) was used to start spinning at 300 rpm for 15 seconds, and then the speed was increased to 1500 rpm and rotated. Apply to upper part of surface for 30 seconds. The thickness of only the coating layer using the same amount of solution was measured with a thickness gauge (F20 thin film analyzer manufactured by FILMETRICS), and the result was 113 nm. In addition, the total thickness of the layer including the coating layer and the cured layer obtained by curing the phosphor sheet is approximately 400 µm. The light-emitting semiconductor device was dried in a programmable oven set at 70 degrees / 20 minutes and 150 degrees / 1 hour. (Example 6)

Hollow silica fine particles (Surria 4320 manufactured by Nippon Shokin Chemical Co., Ltd., 20.5% by weight of silica solids, hollow silica fine particles, number average particle size 60 nm, 0.2084 g) and methyl isobutyl ketone (5.00 g) Stir in a container, and then add 61.23% by weight of the organopolysiloxane-toluene solution (0.017 g) obtained in Synthesis Example 3, hydrosilyl-terminated polyorganosiloxane (0.0004 g), and 0.1% by weight A platinum complex-toluene solution (0.0003 g) was used to prepare a 1% by weight solution 2.

This solution 2 was dropped on the sealing layer of the obtained light-emitting semiconductor device, and a spin coater (MIKASA spin coater 1H-DXII) was used to start spinning at 300 rpm for 15 seconds, and then increased to 1500 rpm and rotated Apply to upper part of surface for 30 seconds. The light-emitting semiconductor device was dried in a programmable oven set at 70 degrees / 20 minutes and 150 degrees / 1 hour. The thickness of only the coating layer using the same amount of solution was measured with a thickness gauge (F20 thin film analyzer manufactured by FILMETRICS), and the result was 113 nm. In addition, the total thickness of the layer including the coating layer and the cured layer obtained by curing the phosphor sheet is approximately 400 µm. (Comparative Example 3)

Aerosil (200S, 0.107 g) and methyl isobutyl ketone (1.00 g) were added to a 66.73% by weight organopolysiloxane-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 1 (0.05 g) was diluted with methyl isobutyl ketone (2.56 g) to prepare a 1% by weight solution 3.

This solution 1 was dropped on the sealing layer of the obtained light-emitting semiconductor device, and a spin coater (MIKASA spin coater 1H-DXII) was used to start spinning at 300 rpm for 15 seconds, and then the speed was increased to 1500 rpm and rotated. Apply to upper part of surface for 30 seconds. The light-emitting semiconductor device was dried in a programmable oven set at 70 degrees / 20 minutes and 150 degrees / 1 hour. The thickness of only the coating layer using the same amount of solution was measured with a thickness gauge (F20 thin film analyzer manufactured by FILMETRICS), and the result was 110 nm. In addition, the total thickness of the layer including the coating layer and the cured layer obtained by curing the phosphor sheet is approximately 400 µm. [Evaluation method] Measurement of total radiation beam

For the light-emitting semiconductor device obtained by the above process, the total radiation beam (mW) before and after application of the adjustment solution was measured using a total beam measuring device (manufactured by Otsuka Electronics Co., Ltd.). [Table 2]

In the embodiment of the present invention, the change rate of the total radiation beam of the light-emitting semiconductor device before and after coating is increased, and the light extraction efficiency of the LED wafer is improved. In particular, in Example 2, where the thickness of the solid organic silicon material of the present invention was designed to be approximately twice the average particle diameter (60 nm) of the hollow silica particles, that is, about 113 nm, the light extraction efficiency was greatly improved. .

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Claims (17)

A solid organic silicon material containing: (A) hollow or porous inorganic fine particles having a number average particle diameter of 1 to 100 nm; and (B) having R ^A SiO _{3/2 in the} molecule (where R ^A is carbon An arylsiloxane unit represented by an aryl group having 6 to 14 atoms) and (R ₂ SiO _2/2 ) n (wherein R is an alkyl group or carbon group having 1 to 20 carbon atoms which may be substituted by a halogen atom) An aryl group having 6 to 14 atoms, n is a number in the range of 3 to 1000), and a polydiorganosiloxane structured polyorganosiloxane, and the content of the component (A) is in the range of 10 to 95% by mass . The solid organosilicon material as described in item 1 of the scope of the patent application, wherein the component (A) is an inorganic fine particle containing hollow silica particles having a number average particle diameter of 40 to 70 nm as a main component, and the content of the component (A) The range is 40 to 95% by mass. The solid organosilicon material described in item 1 of the scope of the patent application, wherein the component (B) contains 20 to 80% by mass of R ^A SiO _3/2 (where R ^A is the same group as above) Represents an organopolysiloxane of an arylsiloxane unit. The solid organic silicon material according to item 1 or 3 of the scope of the patent application, wherein the component (B) is composed of {(R ₂ SiO _2/2 )} _a {R ^A SiO _3/2 } _1-a (where R, R ^A are the same groups as described above, and a is a number within the range of 0.8 to 0.2). The solid silicone material according to item 1, 3, or 4 of the scope of the patent application, wherein component (B) is a hot-melt organopolysiloxane. The solid silicone material according to any one of claims 1 to 5 of the patent application scope, which is in the form of a sheet or a film. The solid silicone material according to item 6 of the scope of application for a patent, wherein the film thickness is in a range of 50 to 300 nm. The solid silicone material according to item 6 or 7 of the scope of application for a patent, characterized in that, with respect to the average particle diameter L (nm) of the component (A), the film thickness is in a range of L to 4L (nm). An optical member is composed of the solid organic silicon material described in any one of claims 1 to 8 of the scope of patent application. A laminated body comprising a solid layer composed of the solid silicone material described in any one of claims 1 to 8 of the scope of patent application. The laminated body described in item 9 of the scope of patent application has a structure in which a solid layer composed of the solid silicone material described in any one of the scope of claims 1 to 8 is disposed on the release layer. The laminated body according to item 10 of the scope of patent application, which has a solid layer composed of the solid organosilicon material described in any one of claims 1 to 8, and a layer including at least one phosphor. The laminated body according to item 10 or 12 of the scope of patent application, which has a solid layer composed of the solid silicone material described in any one of claims 1 to 8 of the scope of patent application, and a solid layer including at least one phosphor. Layer, and has a structure in which the solid layer composed of the solid organic silicon material described above is disposed on an interface with air. A light-emitting element comprising at least one light source, a layer containing at least one phosphor formed thereon, and a solid organic material according to any one of claims 1 to 8 of the patent application scope arranged on the interface with the air A solid layer made of silicon material. A laminated body manufacturing method, which is the laminated body manufacturing method described in any one of the items 10 to 13 of the scope of application for a patent, and has any one of the following processes (ⅰ) to (ⅲ): (ⅰ) in other The process of forming the solid organic silicon material described in any one of claims 1 to 5 on the structure into a sheet or film shape; (ⅱ) using any of the claims 1 to 5 The process of dispersing the solid organosilicon material in an organic solvent and coating it on other structures as a flake or film, and then removing the organic solvent; and (ii) any of the items 1 to 5 of the scope of the patent application A process for laminating other structures on a sheet-like or film-like member made of a solid organic silicon material as described in one item. A method for manufacturing a laminated body, which is the method for manufacturing a laminated body described in item 10, 12, or 13 of the scope of patent application, which has the following processes: (a): on the release layer, the scope of the patent application is 1 to 5 The process of dispersing the solid organosilicon material in any one of the organic solvents and coating it on other structures as a sheet or film, and then removing the organic solvent; (b): In the process (a) A process for laminating the same or different organic silicon layers on the obtained flaky or thin-film solid silicone material; (c): laminating the flaky or thin-film solid silicone material obtained in the process (b) A process in which the organic silicon layer is set as a whole and separated from the peeling layer; and (d): a process of laminating the laminated body obtained in the process (c) on other structures. The method for manufacturing a laminated body according to item 15 or 16 of the scope of application for a patent, wherein the laminated body is a light-emitting element, and a sheet-like or film-like member made of a solid organic silicon material is arranged on an interface with air.