JP2010276855A - Light-diffusing resin and light-emitting device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light-diffusing resin capable of controlling a diffusing effect on light, and to provide a light-emitting device using the resin. <P>SOLUTION: The light-diffusing resin capable of controlling the diffusing effect on light is obtained by using a light-diffusing resin having a specified ratio of transmittance for a straight beam to transmittance for whole rays and containing silicone particles. The light-emitting device uses the resin. The light-diffusing resin contains silicone particles, and in the light-diffusing resin, the ratio (transmittance (%) for the straight beam)/(transmittance (%) for whole rays) of the transmittance for the straight beam to the transmittance for whole rays at a wavelength of 400 nm is controlled. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a light diffusing resin suitably used as a sealant for a light source element such as a light emitting diode, and a light emitting device using the resin.

  Conventionally used light emitting diode (LED) elements generally use a technique of scattering light by dispersing an inorganic light scattering material in a light-transmitting sealing agent such as epoxy resin. ing. Although this technology can diffuse the light of a highly directional LED, the emission wavelength is in the nano order, whereas the particle size of a general light scattering material is in the micron order. When the light hits, there is a problem that light loss occurs, the light extraction efficiency decreases, and the luminance decreases.

  In order to solve the above problem, a method using a light scattering material having a size smaller than the wavelength of light has been proposed (for example, Patent Document 1). Although it is possible to reduce the loss of light by such a method, since the nano-order particles used are inorganic materials and have a high specific gravity, they are uniformly dispersed in the sealant. In addition, the particle size distribution of the nano-order particles used is generally wide, and it is difficult to control the light scattering effect that focuses on light of a specific wavelength.

Japanese Patent Laid-Open No. 2005-332951

  The present invention has been made in view of the above-described situation, and an object thereof is to provide a light diffusing resin capable of controlling the light diffusion effect without lowering the light extraction efficiency and a light emitting device using the resin. .

  As a result of intensive investigations to solve the above problems, the present inventors have developed a light diffusing resin containing silicone-based particles having a specific linear light transmittance and total light transmittance ratio, for example, for LEDs. By using it as a sealant or the like, it has been found that good light extraction efficiency can be obtained and the light diffusion effect can be controlled, and the present invention has been completed. That is, the present invention has the following configuration.

  1) A light diffusing resin comprising silicone-based particles (D) as an essential component, having a total light transmittance of 80% or more at a wavelength of 400 nm, and a linear light transmittance and a total light transmittance at a wavelength of 400 nm. The light diffusion resin characterized in that the ratio (linear light transmittance (%) / total light transmittance (%)) is 0.001 to 0.2.

  2) The light diffusing resin according to 1), wherein the variation coefficient of the particle size distribution of the silicone-based particles (D) is 40% or less.

  3) The light-diffusion resin in any one of 1) or 2) whose particle diameter of silicone type particle | grains (D) is 0.001-5.0 micrometers.

  4) The resin for light diffusion according to any one of 1) to 3), wherein the silicone-based particles (D) have a core-shell structure.

  5) The light diffusing resin according to any one of 1) to 4), wherein the light diffusing resin contains 3 to 50 wt% of silicone-based particles (D).

  6) The light diffusing resin according to any one of 1) to 5), wherein the light diffusing resin is a polysiloxane resin (E) containing the silicone particles (D) as an essential component.

  7) The polysiloxane resin (E) is (A) an organopolysiloxane having at least two alkenyl groups in one molecule, (B) an organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule, (C) The light diffusing resin according to 6) obtained by curing a composition comprising a hydrosilylation catalyst.

  8) A light emitting device obtained using the light diffusing resin according to any one of 1) to 7).

  ADVANTAGE OF THE INVENTION According to this invention, the light-diffusion resin which shows favorable light extraction efficiency and can control the light-diffusion effect, and the light-emitting device using this resin can be provided.

  The light diffusing resin in the present invention contains silicone-based particles (D), and the ratio of linear light transmittance and total light transmittance at a wavelength of 400 nm (linear transmittance (%) / total light transmittance (%). ) Is controlled.

  The total light transmittance of the light diffusing resin in the present invention at a wavelength of 400 nm is preferably 80% or more, and more preferably 85% or more. And the ratio of the linear light transmittance and the total light transmittance at 400 nm (linear transmittance (%) / total light transmittance (%)) is 0.001 to 0.2, and further 0.002 to 0 .15, in particular 0.01 to 0.1. If the total light transmittance at a wavelength of 400 nm is less than 80%, the light extraction efficiency from the light emitting device may be reduced. Moreover, if the ratio of the linear light transmittance and the total light transmittance at a wavelength of 400 nm is larger than 0.2, sufficient light scattering effect cannot be obtained, and if smaller than 0.001, the light emitting device The light extraction efficiency may be reduced.

  The linear light transmittance refers to a light transmittance that does not substantially contain scattered light. In the present invention, the linear light transmittance can be measured using a UV-visible spectrophotometer with a test piece having a thickness of 1 mm. The total light transmittance can be measured by attaching an integrating sphere to an ultraviolet-visible spectrophotometer with a test piece having a thickness of 1 mm.

  Next, details of the silicone-based particles (D) in the present invention will be described.

<(D) Silicone particles>
The silicone-based particle (D) is a component that plays a role in controlling light diffusibility and light extraction efficiency of the light-emitting device in the resin. The silicone particles can be used by being blended with an organopolysiloxane resin.

  (D) As for the particle diameter of the silicone type particle | grains of a component, 0.001 micrometer-5.0 micrometers are preferable, 0.01 micrometer-1.0 micrometer are more preferable, 0.05 micrometer-0.5 micrometer are more preferable. If the particle size is too small, the light diffusibility becomes insufficient, and if the particle size is too large, the light extraction efficiency may be reduced. Further, the coefficient of variation of the particle size distribution of the component (D) is preferably 40% or less, and more preferably 30% or less. Here, the variation coefficient of the particle size distribution is defined as a ratio between the standard deviation of the particle size and the average particle size, and is an index representing the width of the particle size distribution. In addition, the measurement of an average particle diameter can be performed using nano track particle size analyzer UPA150 (made by Nikkiso Co., Ltd.), for example. Here, if the coefficient of variation is large, the light extraction efficiency may decrease, and the light distribution characteristics of the light-emitting device obtained may decrease.

  The blending amount of the component (D) in the present invention is preferably 50 to 3% by weight, more preferably 45 to 5% by weight in the light diffusion resin in the present invention, and 40 to 10% by weight. Is more preferable. When the component (D) is more than 50% by weight, the viscosity may increase during blending, or the transparency of the cured product may decrease. on the other hand. When the component (D) is less than 3% by weight, it may be difficult to obtain a light diffusion effect.

  The silicone-based particles (D) in the present invention preferably have a core-shell structure. When the silicone-based particles (D) have a core-shell structure, specifically, for example, it is possible to improve the strength, cold shock resistance, and the like of the light diffusion resin made of the obtained organopolysiloxane.

  Here, the core-shell structure in the present invention can be obtained, for example, by reacting a monomer component having a composition or component different from the monomer component forming the core in the presence of particles serving as the core. It is possible to form a core-shell structure while absorbing the shell component into the core particle, or to form an inclined structure from the core part to the shell part, etc., but use a shell component that has reactivity with the core particle. Examples of a preferable structure include particles having a structure in which a shell portion is formed outside the core particle.

  By having a core-shell structure of silicone particles as component (D-1), first shell component as component (D-2), and second shell component as component (D-3), component (D) Can reduce silanol groups on the surface. Thereby, for example, the affinity and compatibility with the matrix can be improved, and the viscosity of the blend when blended in the matrix can be prevented from becoming too high. Furthermore, it is possible to prevent the change of the blend over time, particularly the increase in viscosity.

  Moreover, the hardened | cured material obtained from the organopolysiloxane composition which mix | blended (D) component has low hygroscopicity, for example, and it can also improve cold-heat shock resistance.

  The first shell layer made of the alkoxysilane condensate as the component (D-2) is 1 to 40% by weight with respect to 40 to 98% by weight of the silicone particles as the component (D-1), and the component (D-3). A polymer coated with 1 to 30% by weight of a second shell layer made of an alkoxysilane condensate (wherein (D-1), (D-2) and (D-3) are combined to add 100% by weight) %).

  Furthermore, with respect to the silicone particles 35 to 96% by weight as the component (D-1), the first shell layer made of the alkoxysilane condensate as the component (D-2) is 2 to 37% by weight, (D-3 It is more preferable that the second shell layer made of the alkoxysilane condensate as a component is a polymer coated by 2 to 28% by weight.

  When there is little (D-1) component, since the softness | flexibility of particle | grains will be impaired, the thermal shock resistance of the hardened | cured material obtained from the organopolysiloxane composition which mix | blended (D) component may fall, (D -2) When the component is small, the component (D) cannot maintain the original particle shape, and the component (D) flows out into the matrix, reducing the strength of the cured product obtained from the organopolysiloxane composition, etc. The physical properties may be degraded.

  Moreover, when there are few (D-3) components, the silanol group of the (D) component surface cannot fully be reduced, for example, compatibility with a matrix becomes inadequate or the viscosity of a compounding composition becomes high. Or the viscosity of the cured product obtained from the organopolysiloxane composition containing the component (D) may increase and the thermal shock resistance may decrease.

The component (D-1) may be silicone particles, but the general formula (1)
R ^a _m SiO _{(4-m) / 2} (1)
(Wherein, R ^a is a substituted or unsubstituted monovalent hydrocarbon group, which may be the same or different, and m represents an integer of 0 to 3). It is preferable to consist of organosiloxane having

  In the component (D-1), the structural unit of m = 2 in the general formula (1) preferably occupies 70 mol% or more of the component (D-1), more preferably 80 mol% or more. Preferably. When the amount of this component is small, the flexibility of the component (D-1) is impaired, so that the cold-heat shock resistance after curing of the organopolysiloxane composition obtained by blending the component (D) into the matrix may decrease. There is a case.

  The component (D-1) can be obtained by polymerization of organosiloxane, and the organosiloxane may be any of linear, branched and cyclic structures, but from the viewpoint of availability and cost, It is preferable to use an organosiloxane having a cyclic structure.

  Specific examples of the organosiloxane include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and trimethyltriphenylcyclotrisiloxane. In addition to cyclic compounds such as these, linear or branched organosiloxanes can be mentioned. These organosiloxanes can be used alone or in combination of two or more.

  Examples of the substituted or unsubstituted monovalent hydrocarbon group possessed by the organosiloxane include a methyl group, an ethyl group, a propyl group, a phenyl group, and a substituted hydrocarbon group obtained by substituting them with a cyano group. it can.

  Moreover, it is preferable that the terminal of the molecule | numerator of (D-1) component is a silanol group. By having a silanol group at the end of the molecule, a bond is formed by a condensation reaction with the later-described component (D-2). Therefore, silicone polymer particles having a stable core-shell structure are formed. Obtainable.

  The method for producing the component (D-1) is not particularly limited, but it can be obtained by ordinary emulsion polymerization, dispersion polymerization, solution polymerization, and the like. In view of the convenience of the above, it is preferable to obtain by emulsion polymerization.

  The component (D-1) preferably uses seed polymerization in view of the advantage that particles having a smaller particle diameter can be obtained and the particle diameter in the latex state can be narrowed. The seed polymer used for seed polymerization is not particularly limited, but rubber components such as butyl acrylate rubber, butadiene rubber, butadiene-styrene and butadiene-acrylonitrile rubber, butyl acrylate-styrene copolymer, styrene-acrylonitrile copolymer, etc. A polymer can be used.

  The component (D-1) can be produced, for example, by an ordinary emulsion polymerization method performed under acidic or basic conditions, but the reaction under acidic conditions is more than the reaction under basic conditions. This is advantageous because the condensation reaction of alkoxysilane proceeds rapidly. For example, various raw materials containing the above organosiloxane are made into an emulsion using a homomixer, colloid mill, homogenizer, etc. together with an emulsifier and water, and then the pH of the system is adjusted to 5 or less, preferably 4 or less with an acid component, Polymerize by heating. As the acid component used in this case, it is preferable that the emulsion polymerization can proceed stably and also has an emulsifying ability itself, and examples thereof include alkylbenzenesulfonic acid, alkylsulfuric acid, alkylsulfosuccinic acid and the like. .

  After adding all of the raw materials at once, the pH may be adjusted to an arbitrary value after stirring for a certain period of time, or the remaining raw materials in an emulsion in which a part of the raw materials are charged and the pH is adjusted to an arbitrary value May be added sequentially. In the case of sequential addition, it may be added as it is or mixed with water and an emulsifier to form an emulsified liquid, but since the polymerization rate can be increased, a method of adding in an emulsified state is used. It is preferable. The reaction temperature and time are preferably from 0 to 100 ° C, more preferably from 50 to 95 ° C, because of easy reaction control. The reaction time is preferably 1 to 100 hours, more preferably 3 to 50 hours.

  When polymerization is performed under acidic conditions, the Si—O—Si bond forming the skeleton of the component (D-1) is usually in an equilibrium state between cleavage and bond formation. This equilibrium changes depending on the temperature, and the higher the temperature becomes, the easier it is to produce a high molecular weight (D-1) component. Therefore, in order to obtain a high molecular weight (D-1) component, it is preferable to perform aging by polymerizing by heating and then cooling to a polymerization temperature or lower.

  Specifically, the polymerization is carried out at 50 ° C. or higher, and the heating is stopped when the polymerization conversion rate reaches 75 to 90%, more preferably 82 to 89%, and the temperature is lower than the polymerization temperature, for example, 10 to 50 ° C., preferably Can be cooled to 20 to 45 ° C. and aged for about 5 to 100 hours. In addition, the polymerization conversion rate said here means the conversion rate to the (D-1) component of the organosiloxane of the low volatile content in a raw material.

  The amount of water used for the emulsion polymerization is not particularly limited, and may be any amount necessary to emulsify and disperse various raw materials. For example, a weight of 1 to 20 times the total amount of normal raw materials is used. It ’s fine.

  As the emulsifier used for the emulsion polymerization, any known emulsifier can be used without particular limitation as long as it does not lose the emulsifying ability in the pH range where the reaction is carried out. Examples of such emulsifiers include, for example, alkylbenzene sulfonic acid, sodium alkylbenzene sulfonate, sodium alkyl sulfate, sodium alkyl sulfosuccinate, sodium polyoxyethylene nonylphenyl ether sulfonate, and the like. Moreover, there is no limitation in particular in the usage-amount of this emulsifier, What is necessary is just to adjust suitably according to the particle diameter of the target (D-1) component.

  If sufficient emulsification ability is obtained, and it does not adversely affect the physical properties of the obtained (D-1) component and the silicone-based polymer particles which are the (D) component obtained therefrom, it will be exemplified It is preferable to use 0.005 to 20% by weight in the emulsion, and it is particularly preferable to use 0.05 to 15% by weight.

  The volume average particle size of the latex particles of the component (D-1) is preferably 0.001 μm to 5.0 μm, more preferably 0.01 μm to 1.0 μm, and even more preferably 0.05 μm to 0.5 μm. . If the volume average particle size is small, it is difficult to obtain stably, and if it is large, the transparency of the cured product may deteriorate. In addition, the measurement of a volume average particle diameter can be performed using nano track particle size analyzer UPA150 (made by Nikkiso Co., Ltd.), for example.

  When the component (D-1) used in the present invention is synthesized, what is called a crosslinking agent or a graft crossing agent can be added as necessary.

  Examples of the crosslinking agent that can be used for the synthesis of the component (D-1) of the present invention include three functional groups that can participate in a condensation reaction such as trimethoxymethylsilane, phenyltrimethoxysilane, and ethyltriethoxysilane. So-called trifunctional crosslinking agent, tetraethoxysilane, 1,3-bis [2- (dimethoxymethylsilyl) ethyl] benzene, 1,4-bis [2- (dimethoxymethylsilyl) ethyl] benzene, 1,3-bis [ 1- (dimethoxymethylsilyl) ethyl] benzene, 1,4-bis [1- (dimethoxymethylsilyl) ethyl] benzene, 1- [1- (dimethoxymethylsilyl) ethyl] -3- [2- (dimethoxymethylsilyl) ) Ethyl] benzene, 1- [1- (dimethoxymethylsilyl) ethyl] -4- [2-dimethoxymethylsilyl] Le] so-called four-functional crosslinking agent 4 containing a functional group capable of participating in condensation reactions such as benzene, more can be mentioned partial condensate obtained by condensation of alkoxy groups of these crosslinking agents.

  These crosslinking agents can be used alone or in combination of two or more as required. The addition amount of the crosslinking agent is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the organosiloxane. When the addition amount of the crosslinking agent is large, the flexibility of the component (D-1) is impaired. Therefore, when the component (D) is blended with the matrix, the low temperature thermal shock resistance of the organopolysiloxane composition is lowered. There is a case. Moreover, the elasticity of (D-1) component can be arbitrarily adjusted by changing the crosslinking degree by adjusting the addition amount of a crosslinking agent.

  Examples of the grafting agent that can be used in the present invention include p-vinylphenylmethyldimethoxysilane, p-vinylphenylethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, and 3- (p-vinylbenzoate). Iloxy) propylmethyldimethoxysilane, p-vinylphenylmethyldimethoxysilane, vinylmethyldimethoxysilane, tetravinyltetramethylcyclosiloxane, allylmethyldimethoxysilane, mercaptopropylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, etc. It is done.

  By using the first shell component (D-2) in the present invention, it is possible to maintain the morphology of the component (D) as particles. For example, it can contribute to the improvement of the thermal shock resistance of a cured product obtained from the organopolysiloxane composition.

The alkoxysilane used for the component (D-2) of the present invention is a bifunctional alkoxysilane compound (b) represented by the following general formula (2), represented by the general formula (3) (c) ) Component trifunctional alkoxysilane compounds, tetrafunctional alkoxysilane compounds represented by the general formula (4), and partial condensates thereof (partial condensates obtained by condensing alkoxy groups) can be used. (D-2) component is obtained by hydrolyzing and condensing these. These alkoxysilanes can be used alone or in combination of two or more.
(B) Component: General formula (2)

(Wherein R ²² and R ²³ represent the same or different monovalent alkyl groups, and R ²⁴ and R ²⁵ represent the same or different monovalent organic groups) and / Or a partial condensate thereof.
(C) Component: General formula (3)

(Wherein R ³² , R ³³ and R ³⁴ represent the same or different monovalent alkyl groups, and R ³⁵ represents a monovalent organic group) and / or The partial condensate.
(D) Component: General formula (4)

(Wherein R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ represent the same or different monovalent alkyl group) and / or a partial condensate thereof.

  Examples of the alkoxy group mentioned in the general formulas (2) to (4) include methoxy, ethoxy, normal propoxy, isopropoxy, normal butoxy, isobutoxy, secondary butoxy, tertiary butoxy, pentyloxy, hexyloxy and the like. These are alkoxy groups having 1 to 6 carbon atoms. Examples of the monovalent organic group other than the alkoxy group include an alkyl group, an alkenyl group, an allyl group, and an aralkyl group.

  As a polymerization method for obtaining the component (D-2) using an alkoxysilane compound, emulsion polymerization can be used. Although general conditions can be applied for the emulsion polymerization, it is particularly preferable to pay attention to the polymerization temperature. It is preferable to apply 20-85 degreeC as the temperature in superposition | polymerization. Moreover, 1 to 50 hours of polymerization time can be applied.

  The component (D-2) can be produced by a usual emulsion polymerization method carried out under acidic or basic conditions, but the reaction under acidic conditions is more effective than the reaction under basic conditions. This is advantageous for the reason that gelation is easily suppressed during the condensation reaction of alkoxysilane.

  With the alkoxysilane condensate (D-3) used in the present invention, a large number of silanol groups present on the surfaces of the components (D-1) and (D-2) can be reduced. As a result, various problems derived from the silanol groups on the particle surface, such as a problem that the compatibility and affinity between the component (D) and the matrix decrease, and the viscosity of the compound when blended with silicone rubber or silicone resin It is possible to solve the problem of becoming too high and the problem of the viscosity gradually increasing as the composition changes with time.

  In addition, when such particles containing a large number of silanol groups are blended, for example, the cured product may absorb moisture, and cracks may occur during the cold test, but such a problem can be solved.

  The component (D-3) of the present invention uses a condensate of alkoxysilane. As the alkoxysilane, monofunctional alkoxysilane compounds which are the component (a) represented by the following general formula (5) and those compounds It is preferable to use a partial condensate (partial condensate obtained by condensing an alkoxy group) as an essential component. These can be used alone or in combination of two or more.

In the general formula (5), R ¹² represents an alkyl group, and R ¹³ , R ¹⁴ , and R ¹⁵ represent the same or different monovalent organic groups.

  Furthermore, the component (D-3) preferably contains at least one selected from the component (b), the component (c) and the component (d). By combining (a) component with at least one selected from (b) component, (c) component and (d) component, component (a) can be efficiently incorporated into component (D). Become.

  In addition, when a component containing an alkenyl group is used in any of (a) to (d), the alkenyl group can be introduced into the component (D). Introducing an alkenyl group into component (D) forms a bond between component (D) and the matrix component when component (D) is blended with another resin component (matrix component) that is cured by a hydrosilylation reaction. It is preferable because the strength of the cured product obtained from the organopolysiloxane composition of the present invention can be improved.

  As a polymerization method for obtaining the component (D-3) using an alkoxysilane compound, emulsion polymerization can be used. Although general conditions can be applied for the emulsion polymerization, it is particularly preferable to pay attention to the polymerization temperature. It is preferable to apply 20-85 degreeC as the temperature in superposition | polymerization. Moreover, 1 to 50 hours of polymerization time can be applied.

  The component (D-3) can be produced by a usual emulsion polymerization method carried out under acidic or basic conditions, but the reaction under acidic conditions is more preferable than the reaction under basic conditions. This is advantageous for the reason that gelation is easily suppressed during the condensation reaction of alkoxysilane.

  The method for separating particles from the latex of silicone polymer particles (D) obtained by emulsion polymerization is not particularly limited. For example, a metal salt such as calcium chloride, magnesium chloride or magnesium sulfate is added to the latex. Examples of the method include adding the latex to coagulate, separate, wash, dehydrate, and dry the latex. A spray drying method can also be used.

  As a method for separating particles from latex, it is preferable to use a masterbatch method in that component (D) can be uniformly dispersed in a matrix resin and a transparent cured product can be obtained.

  The master batch method is an organic solvent that is soluble or partially soluble in water in an aqueous latex solution, such as alcohols (methanol, ethanol, 2-propanol, etc.), ketones (methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), acetate ester After adding particles (ethyl acetate, butyl acetate, methyl acetate), etc., the particles are slowly aggregated, and then the loose aggregates are recovered by a method such as centrifugal sedimentation or filtration. It can be obtained by redispersing in a solvent, mixing with a matrix resin, and distilling off the solvent.

  The obtained component (D) can be surface-treated within the range not impairing the characteristics of the present invention. By performing the surface treatment, the affinity between the component (D) and the matrix component can be improved.

  As the surface treating agent used at this time, for example, a silylating agent can be used. Examples of the silylating agent used here generally include alkylsilanes such as trimethylchlorosilane, dimethyldichlorosilane, and hexamethyl (di) silazane. These silylating agents can be used alone or in combination of two or more.

  In addition, when the surface treatment is performed, a functional group having binding ability with the matrix component, for example, an alkenyl group, an alkynyl group, or the like is introduced into the surface of the component (D), so that a bond is formed between the component (D) and the matrix component. As a result, the strength of the entire organopolysiloxane composition can be improved.

  As the silylating agent for introducing a functional group having a binding ability with the matrix component to the polymer surface, alkenylsilanes such as chlorodimethylvinylsilane, dichloromethylvinylsilane, dichlorodivinylsilane, and trichlorovinylsilane are generally used. . These silylating agents can be used alone or in combination of two or more.

<Light diffusion resin>
The light diffusing resin in the present invention contains the silicone-based particles (D) and has a ratio of linear light transmittance and total light transmittance at a wavelength of 400 nm (linear light transmittance (%) / total light transmittance ( %)) Is not particularly limited as long as it is within a specific range, but specifically, for example, it is preferable that the silicone-based particles (D) are dispersed in the polysiloxane-based resin (E).

  The aryl group content of the polysiloxane resin (E) is preferably 5 mol% or less, more preferably 1 mol% or less, and particularly preferably 0 mol%. When the content is large, the heat resistance and light resistance are lowered, and coloring or the like may occur.

  Specifically, the polysiloxane resin (E) is, for example, (A) an organopolysiloxane having at least two alkenyl groups in one molecule, and (B) one molecule from the viewpoint of productivity, handling properties, and processability. A suitable example is a polysiloxane obtained by curing a composition comprising an organohydrogenpolysiloxane having at least two hydrosilyl groups therein and (C) a hydrosilylation catalyst.

  Hereinafter, the components (A) to (C) will be described in detail.

<(A) Organopolysiloxane having at least two alkenyl groups in one molecule>
The component (A) in the present invention is cured by hydrosilylation reaction with the organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule, which is the component (B), in the presence of the component (C) described later. A matrix resin is formed. The component (A) in the present invention is not particularly limited as long as it is an organopolysiloxane containing two or more alkenyl groups in one molecule, and widely known ones can be used. Also, the structure may be any of linear, branched, cyclic and three-dimensional crosslinked structures.

  Examples of the linear component (A) include polysiloxanes whose ends are blocked with dimethylvinylsilyl groups, copolymers of dimethylsiloxane units, methylvinylsiloxane units, and terminal trimethylsiloxy units.

  Examples of the cyclic (A) component include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1 3,5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, and the like.

In addition, examples of the component (A) having a three-dimensional crosslinked structure are not particularly limited, but the general formula (6)
SiO _4/2 (6)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (7) and (8).
R ^s1 R ^s2 ₂ SiO _1/2 (7)
R ^s2 ₃ SiO _1/2 (8)
(In the formula, R ^s1 is an alkenyl group, and R ^s2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
An organo, characterized in that it has a structure blocked with a monofunctional structural unit represented by the formula (II) and the terminal of the main structure is blocked with at least two units represented by the formula (7): Polysiloxane is exemplified.

Here, as the alkenyl group (R ^s1 ), a vinyl group, an allyl group, a butenyl group, and a hexenyl group are preferable, and a vinyl group is more preferable from the viewpoint of availability, heat resistance, and light resistance.

Examples of substituted or unsubstituted monovalent hydrocarbon groups (R ^s2 ) other than alkenyl groups include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, phenyl groups, An aryl group such as a tolyl group, or a chloromethyl group, a trifluoropropyl group, a cyanoethyl group, or the like in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group, or the like. An unsubstituted or substituted monovalent hydrocarbon group which is the same or different, preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, can be exemplified. Among these, a methyl group is more preferable from the viewpoint of heat resistance and light resistance.

  The polysiloxane resin (E) in the present invention preferably uses the component (A) represented by the above general formula (6), general formula (7), and general formula (8) from the viewpoints of hardness and strength. .

  The component (A) in the present invention is preferably liquid at room temperature because it is easy to handle, and its viscosity at room temperature is preferably 1000 Pa · s or less, more preferably 100 Pa · s or less. preferable.

<(B) Organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule>
(B) component in this invention hardens | cures by (A) component and hydrosilylation reaction in presence of the below-mentioned (C) component, and forms matrix resin.

  The component (B) in the present invention is not particularly limited as long as it is an organohydrogenpolysiloxane containing two or more hydrosilyl groups in one molecule, and widely known ones can be used. The structure may be any of linear, branched, cyclic and three-dimensional cross-linked structures.

  Examples of the linear component (B) include polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups, and copolymers of dimethylsiloxane units with methylhydrogensiloxane units and terminal trimethylsiloxy units. sell.

  Examples of the cyclic component (B) include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydro Examples include Gen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane.

Further, examples of the component (B) having a three-dimensional crosslinked structure are not particularly limited, but the general formula (6)
SiO _4/2 (6)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (9) and (10).
R ^b1 R ^b2 ₂ SiO _1/2 (9)
R ^b2 ₃ SiO _1/2 (10)
(Wherein R ^b1 is a hydrogen atom, and R ^b2 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
An organo, characterized in that it has a structure blocked with a monofunctional structural unit represented by the formula (II) and the terminal of the main structure is blocked with at least two units represented by the formula (9): Hydrogen polysiloxane is shown as a preferred example.

  The cured product obtained from the organopolysiloxane composition blended with the component (B) represented by the general formula (6), the general formula (9) and the general formula (10) has a high cross-linking density, and thus has high hardness. This is preferable because a high-strength cured product can be obtained.

Examples of the substituted or unsubstituted monovalent hydrocarbon group (R ^b2 ) other than the hydrogen atom or alkenyl group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cycloalkyl group such as a cyclohexyl group, An aryl group such as a phenyl group, a tolyl group, or the like, or a chloromethyl group, a trifluoropropyl group, a cyanoethyl group, etc. in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group, etc. Preferred examples are the same or different selected, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, unsubstituted or substituted monovalent hydrocarbon groups. Among these, a methyl group is more preferable from the viewpoint of heat resistance and light resistance.

  The addition amount of the organohydrogenpolysiloxane is such that the hydrosilyl group of the component (B) is 30 to 500 mol%, preferably 40 to 200 mol% with respect to the alkenyl group of the component (A). Is desirable. When the amount is more than 500 mol%, a cured product having sufficient hardness may not be obtained, or foaming may occur during the curing and bubbles may remain in the cured product. On the other hand, if it is less than 30 mol%, a cured product having sufficient hardness may not be obtained.

  Furthermore, the component (B) is preferably liquid at room temperature because it is easy to handle. The viscosity at room temperature is preferably 1000 Pa · s or less, and more preferably 100 Pa · s or less. .

<(C) Hydrosilylation catalyst>
As the hydrosilylation catalyst that is the component (C) in the present invention, for example, a platinum-based catalyst, a palladium-based catalyst, and a rhodium-based catalyst can be added. Known platinum-based catalysts can be used. Specifically, platinum element alone, platinum compounds, platinum complexes, chloroplatinic acid, chloroplatinic acid alcohol compounds, aldehyde compounds, ether compounds, various olefins and vinyl Examples include complexes with siloxane. The addition amount of the platinum-based catalyst is preferably in the range of 10 ⁻¹ to 10 ⁻¹⁰ mol as a platinum atom with respect to 1 mol of the alkenyl group of the component (A), and in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. More preferably it is used. If the platinum catalyst is too much, light having a short wavelength is absorbed, and thus the light resistance of the obtained cured product may be lowered. If it is too little, the matrix may not be cured.

<Composition>
A curing retarder can be used for the purpose of improving the storage stability of the composition or adjusting the reactivity of the hydrosilylation reaction during the curing process. Known curing retarders can be used, and specific examples include compounds containing aliphatic unsaturated bonds, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds, and organic peroxides. . These may be used alone or in combination of two or more.

  Examples of the compound containing an aliphatic unsaturated bond include 2-phenyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 3 -Methyl-1-hexyn-3-ol, 3-ethyl-1-pentyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, en-in Examples thereof include compounds, maleic esters such as maleic anhydride and dimethyl maleate.

  Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide, and the like.

  Nitrogen-containing compounds include N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, N, N-dibutyl-1,3 -Propanediamine, N, N-dimethyl-1,3-propanediamine, N, N, N ', N'-tetraethylethylenediamine, N, N-dibutyl-1,4-butanediamine, 2,2'-bipyridine, etc. Is mentioned.

  Examples of tin compounds include stannous halide dihydrate, stannous carboxylate, and the like. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

The addition amount of the curing retardant is not particularly limited, but it is preferably used in the range of 10 ⁻¹ to 10 ⁴ mol, preferably in the range of 1 to 10 ³ mol, per 1 mol of the hydrosilylation catalyst. More preferred. Moreover, these hardening retarders may be used independently and may be used in combination of 2 or more types.

  In the present invention, an adhesion-imparting agent can be added in order to ensure adhesion with a substrate or the like.

  As the adhesion-imparting agent in the present invention, a silane coupling agent, a boron-based coupling agent, a titanium-based coupling agent, an aluminum-based coupling agent, or the like can be preferably used.

  Examples of the silane coupling agent include at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group in the molecule, and a silicon atom-bonded alkoxy group. A silane coupling agent having a group is preferred. About the said functional group, an epoxy group, a methacryl group, and an acryl group are especially preferable in a molecule | numerator from the point of sclerosis | hardenability and adhesiveness especially.

  Specifically, as the organosilicon compound having an epoxy functional group and a silicon atom-bonded alkoxy group, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxy) And cyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

  Examples of the organosilicon compound having a methacryl group or an acryl group and a silicon atom-bonded alkoxy group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acrylonitrile. Examples include, but are not limited to, loxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

  Examples of the boron coupling agent include trimethyl borate, triethyl borate, tri-2-ethylhexyl borate, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, Examples include, but are not limited to, tributylbutyl borate, tri-sec-butyl borate, tri-tert-butyl borate, triisopropyl borate, trinormalpropyl borate, triallyl borate, and boron methoxyethoxide.

  Examples of the titanium coupling agent include tetra (n-butoxy) titanium, tetra (i-propoxy) titanium, tetra (stearoxy) titanium, di-i-propoxy-bis (acetylacetonate) titanium, i- Propoxy (2-ethylhexanediolate) titanium, di-i-propoxy-diethylacetoacetate titanium, hydroxy-bis (lactate) titanium, i-propyltriisostearoyl titanate, i-propyl-tris (dioctylpyrophosphate) titanate, Tetra-i-propyl) -bis (dioctyl phosphite) titanate, tetraoctyl-bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) et Renchitaneto, i- propyl trioctanoyl titanate, but i- propyl dimethacrylate -i- stearoyl titanate is exemplified, but not limited thereto.

  Examples of the aluminum coupling agent include, but are not limited to, aluminum butoxide, aluminum isopropoxide, aluminum acetylacetonate, aluminum ethylacetoacetonate, and acetoalkoxyaluminum diisopropylate.

  The adhesiveness imparting agent in the present invention may be used alone or in combination of two or more. The addition amount is preferably 0.05 to 30% by weight of the total amount of the component (A) and the component (B). In addition, depending on the type or amount of the adhesion-imparting agent, there are those that inhibit the hydrosilylation reaction of the matrix resin, so the influence on the hydrosilylation reaction must be considered.

  In the present invention, fillers such as pulverized quartz, calcium carbonate, carbon and the like may be added as a bulking agent as necessary within a range not impeding the effects of the present invention.

  Further, in the present invention, various additives such as a colorant and a heat resistance improver, a reaction control agent, a mold release agent, a dispersant for a filler, etc. are arbitrarily selected as long as the effects of the present invention are not hindered. Can be added.

  Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like.

In addition, in order to make the light diffusion resin of the present invention flame-retardant and fire-resistant, known additives such as titanium dioxide, manganese carbonate, Fe ₂ O ₃ , ferrite, mica, glass fiber, glass flake are added. Also good. In addition, it is preferable to stop these arbitrary components to the minimum addition amount so that the effect of this invention may not be impaired.

  In the present invention, the above components are mixed uniformly using a kneader such as a two-roll, Banbury mixer, kneader, or a planetary stirring and defoaming machine, and subjected to heat treatment as necessary. Obtainable.

  Although various reaction temperatures can be set, a temperature range of 25 ° C to 300 ° C is preferable, 30 ° C to 280 ° C is more preferable, and 35 ° C to 260 ° C is more preferable. When the reaction temperature is lower than 25 ° C, the reaction time for sufficient reaction tends to be long, and when the reaction temperature is higher than 300 ° C, the product tends to be thermally deteriorated.

  The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. Rather than carrying out the reaction at a constant temperature, the reaction is preferably carried out while raising the temperature in a multistage manner or continuously in that a uniform cured product without distortion can be easily obtained.

  The pressure during the reaction can be variously set as required, and the reaction can be carried out at normal pressure, high pressure or reduced pressure.

  The light diffusing resin containing the silicone-based particles (D) of the present invention is useful as, for example, a sealing agent for LED elements and has excellent heat resistance and light resistance, so that the light emitting elements are blue LED elements and ultraviolet LEDs. It is also useful as a sealant for LED elements that are elements.

  The light diffusing resin obtained from the present invention can be used for various applications. As specific examples of applications, in the field of liquid crystal displays, liquid crystal display devices such as substrate materials, light guide plates, prism sheets, deflection plates, retardation plates, viewing angle correction films, adhesives, polarizer protective films, and other liquid crystal films Peripheral materials are illustrated.

  In addition, color PDP (plasma display) sealants, antireflection films, optical correction films, housing materials, front glass protective films, front glass substitutes, adhesives, and plasma addresses, which are expected as next-generation flat panel displays Substrate materials in liquid crystal (PALC) displays, light guide plates, prism sheets, deflector plates, retardation plates, viewing angle correction films, adhesives, polarizer protective films, and front glass protective films in organic EL (electroluminescence) displays, Examples include a front glass substitute material, an adhesive, and various film substrates, a front glass protective film, a front glass substitute material, and an adhesive in a field emission display (FED).

  In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Examples include pickup lenses, protective films, sealants, and adhesives.

  In the field of optical equipment, a camera taking lens, a lens material, a finder, a finder prism, a target prism, a finder cover, and a light receiving sensor unit are exemplified. Moreover, the projection lens of a projection television, a protective film, a sealing agent, an adhesive agent, etc. are illustrated. Examples are materials for lenses of optical sensing devices, sealants, adhesives, and films.

  In the field of optical components, fiber materials, lenses, waveguides, element sealants, adhesives and the like around optical switches in optical communication systems are exemplified. Examples include optical fiber materials, ferrules, sealants, adhesives and the like around the optical connector. Examples of optical passive components and optical circuit components include lenses, waveguides, LED element sealants, adhesives, and the like. Examples include substrate materials, fiber materials, element sealants, adhesives, and the like around an optoelectronic integrated circuit (OEIC).

  In the field of optical fibers, examples include sensors for industrial use such as lighting and light guides for decorative displays, displays and signs, and optical fibers for communication infrastructure and for connecting digital devices in the home.

  Examples of the semiconductor integrated circuit peripheral material include resist materials for microlithography for LSI and VLSI materials.

  In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, and automotive defenses Examples include rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, glass substitutes, and automotive window glass interlayers. Moreover, the multilayer glass intermediate film for rail vehicles is illustrated. Further, in aircraft applications, toughness imparting agents for structural materials, engine peripheral members, protective / bundling wireness, corrosion-resistant coatings, and window glass interlayers are exemplified.

  In the construction field, interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials are exemplified. In agriculture, a house covering film is exemplified.

  Next-generation DVDs, organic EL element peripheral materials, organic photorefractive elements, light-amplifying elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, etc. Examples thereof include fiber materials, element sealants, and adhesives.

  The present invention will be described in more detail based on the following examples, but the present invention is not limited only to these examples.

(Create cured product for evaluation)
The resulting liquid mixture is poured into a polytetrafluoroethylene mold and thermally cured in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 5 hours. A cured product for evaluation was prepared.

(Measurement of linear transmittance)
Using a test piece having a thickness of 1 mm, a transmitted light spectrum at a wavelength of 400 nm at 25 ° C. was measured using an ultraviolet-visible spectrophotometer (V-560 manufactured by JASCO Corporation).

(Measurement of total light transmittance)
Using a test piece having a thickness of 1 mm, an integrating sphere (JASCO-made ISV-469) was attached to an ultraviolet-visible spectrophotometer (JASCO-made V-560), and a transmitted light spectrum at a wavelength of 400 nm at 25 ° C. was measured. .

(Synthesis Example 1)
After mixing 400 parts by weight of pure water and 12 parts by weight of sodium dodecylbenzenesulfonate (solid content) in a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer The temperature was raised to 50 ° C. in a nitrogen atmosphere. Thereafter, 10 parts by weight of butyl acrylate (BA), 3 parts by weight of t-dodecyl mercaptan and 0.01 part by weight of paramentane hydroperoxide (solid content) were added.

  After 30 minutes, 0.18 part of sodium formaldehyde sulfoxylate (SFS), 0.019 part by weight of ethylenediaminetetraacetic acid (EDTA) and 0.019 part by weight of ferrous sulfate were added and stirred for 1 hour. A mixed solution of 90 parts by weight of BA, 27 parts by weight of t-dodecyl mercaptan and 0.18 parts by weight of paramentane hydroperoxide (solid content) was continuously added over 3 hours. Further, post-polymerization was performed for 1 hour to obtain a latex containing a seed polymer (volume average particle size 0.020 μm).

  Next, in a five-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port, and a thermometer, 2.0 parts by weight (solid content) of the above seed polymer (10 wt% aqueous solution dodecylbenzene) After charging 1.5 parts by weight of sulfonic acid (solid content) and 300 parts by weight of pure water (including the carry-in from the latex containing the seed polymer), the mixture was stirred for 10 minutes and then the system was heated to 80 ° C. under a nitrogen atmosphere. The temperature was raised to. Separately, a mixture of 150 parts by weight of pure water, 0.5 parts by weight of 5% by weight aqueous sodium dodecylbenzenesulfonate (solid content), 97 parts by weight of octamethylcyclotetrasiloxane, and 3 parts by weight of trimethoxymethylsilane was homogenized. After forcedly emulsifying with a mixer at 8000 rpm for 5 minutes, this mixed solution was continuously added over 3.5 hours. Further, after 2.5 hours of post-polymerization, cooled to 25 ° C. and allowed to stand for 20 hours to complete the polymerization, a latex containing silicone particles (volume average particle size 0.110 μm) as component (D-1) Obtained.

(Synthesis Example 2)
In a five-necked flask equipped with a stirrer, reflux condenser, nitrogen blowing port, monomer addition port, thermometer, 90 parts by weight (solid content) of silicone particles (D-1) component obtained in Synthesis Example 1; In addition, 0.45 parts by weight (solid content) of 10% by weight aqueous solution of dodecylbenzenesulfonic acid was charged, and the temperature was raised to 40 ° C. in a nitrogen atmosphere.

Separately, 40 parts by weight of pure water, 0.1 part by weight (solid content) of 15% by weight aqueous solution of sodium dodecylbenzenesulfonate, 7.30 parts by weight of dimethoxydimethylsilane ((CH ₃ ) ₂ SiO _2/2 Equivalent to 4.5 parts by weight in terms of a complete condensate of the structural unit represented by the following formula: ethyl silicate condensate (manufactured by Tama Chemical Industries, trade name: ethyl silicate 40, SiO ₂ content: 39.0 to 42) 0.0 wt%) 11.16 parts by weight (corresponding to 4.5 parts by weight in terms of the complete condensate of the structural unit represented by SiO ₂ ) was forcibly emulsified with a homomixer at 5000 rpm for 5 minutes. Later, it was added dropwise over 20 minutes. (D-2) component was formed by stirring this solution for 5 hours, keeping at 40 degreeC.

Next, in this solution, 27 parts by weight of pure water and 0.03 part by weight (solid content) of a 15% by weight aqueous solution of sodium dodecylbenzenesulfonate, 1.40 parts by weight of ethoxydimethylvinylsilane (Vi (CH ₃ ) ₂ SiO ₁ Equivalent to 1.0 part by weight in terms of the complete condensate of the structural unit represented by _{/ 2} , and 6.42 parts by weight of the structural unit represented by (CH ₃ ) ₃ SiO _1/2 Equivalent to 5.0 parts by weight in terms of a complete condensate) and 0.81 parts by weight of dimethoxydimethylsilane (in terms of a complete condensate of a structural unit represented by (CH ₃ ) ₂ SiO _2/2 . Equivalent to 5 parts by weight), ethyl silicate condensate (manufactured by Tama Chemical Industry Co., Ltd., trade name: ethyl silicate 40, SiO ₂ content: 39.0 to 42.0% by weight) 1.24 parts by weight (expressed as SiO ₂ 0 in terms of the complete condensate of the structural unit The mixture was forcibly emulsified with a homomixer at 5000 rpm for 5 minutes and added dropwise over 10 minutes.

  (D-3) component was formed by stirring this solution for 4.5 hours, keeping at 40 degreeC. The system was cooled to 25 ° C. and allowed to stand for 20 hours to complete the polymerization, and a latex containing silicone polymer particles (volume average particle size 0.112 μm) as component (D) was obtained.

Example 1
A mixed solvent comprising ethyl acetate / methanol = 6/4 (vol / vol) with respect to 35 parts by weight of the resin solid content of the latex (resin solid content concentration 16% by weight) containing the component (D) obtained in Synthesis Example 2. After adding 200 parts by weight to agglomerate the particles, they were spun down at 2000 rpm for 5 minutes in a centrifuge. The obtained precipitate was dispersed and washed in 200 parts by weight of a mixed solvent of ethyl acetate / methanol = 3/7 (vol / vol), and then centrifuged with a centrifuge at 2000 rpm for 5 minutes. The obtained precipitate was further dispersed and washed in 200 parts by weight of a mixed solvent of ethyl acetate / methanol = 4/6 (vol / vol), and then centrifuged with a centrifuge at 2000 rpm for 5 minutes. After this washing was performed three times in total, 350 parts by weight of ethyl acetate was added to 35 parts by weight of the obtained precipitate to obtain an ethyl acetate solution of component (D).

  The vinyl group-containing polysiloxane having a three-dimensional structure as component (A) (made by Clariant, trade name MQV) with respect to 30 parts by weight of the resin solid content of the silicone polymer particles as component (D) thus obtained. -7, vinyl group content 3.5 mol / kg) 36.2 parts by weight, component (B) hydrosilyl group-containing polysiloxane having a three-dimensional structure (manufactured by Clariant, trade name MQH-5, hydrosilyl group) The content of 2.3 mol / kg) is 57.9 parts by weight, and the hydrosilyl group-containing polysiloxane having the same three-dimensional structure as component (B) (manufactured by Clariant, trade name MQH-8, hydrosilyl group content 7) .5 mol / kg) was blended in an amount of 5.9 parts by weight, and the mixture was concentrated by a rotary evaporator to distill off ethyl acetate.

  Thereafter, 5.0 parts by weight of 3-glycidoxypropyltrimethoxysilane, 1.0 part by weight of trimethyl borate, 0.0011 part by weight of 1% xylene solution of 1-ethynyl-1-cyclohexanol, N, N, N ′ , N'-tetramethylethylenediamine 1% xylene solution 0.0010 parts by weight and platinum vinylsiloxane complex xylene solution (containing 3% by weight platinum) 0.0062 parts by weight, The mixture was stirred and degassed to obtain a liquid mixture.

  The liquid mixture was poured into a mold, heated for a predetermined time and cured to obtain a cured product for evaluation. Various evaluation results are shown in Table 1.

(Example 2)
A method similar to the method described in Example 1, except that 5.0 parts by weight of 3-glycidoxypropylmethyldiethoxysilane was used instead of 5.0 parts by weight of 3-glycidoxypropyltrimethoxysilane. A liquid mixture was obtained.

  The liquid mixture was poured into a mold, heated for a predetermined time and cured to obtain a cured product for evaluation. Various evaluation results are shown in Table 1.

Claims (8)

A light diffusing resin containing silicone-based particles (D) as an essential component, the total light transmittance at a wavelength of 400 nm is 80% or more, and the ratio of the linear light transmittance and the total light transmittance at a wavelength of 400 nm A light diffusing resin having a (linear light transmittance (%) / total light transmittance (%)) of 0.001 to 0.2. The light diffusion resin according to claim 1, wherein the variation coefficient of the particle size distribution of the silicone-based particles (D) is 40% or less. The light diffusion resin according to any one of claims 1 and 2, wherein the particle size of the silicone-based particles (D) is 0.001 to 5.0 µm. The resin for light diffusion according to any one of claims 1 to 3, wherein the silicone-based particles (D) have a core-shell structure. The light diffusing resin according to any one of claims 1 to 4, wherein the light diffusing resin contains 3 to 50 wt% of silicone-based particles (D). The light diffusing resin according to any one of claims 1 to 5, wherein the light diffusing resin is a polysiloxane resin (E) containing silicone particles (D) as an essential component. The polysiloxane resin (E) is (A) an organopolysiloxane having at least two alkenyl groups in one molecule, (B) an organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule, (C The light diffusing resin according to claim 6, which is obtained by curing a composition comprising a hydrosilylation catalyst. The light-emitting device obtained using the light-diffusion resin of any one of Claims 1-7.