JP2009275140A - Silicone polymer particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce a silicone composition that enhances thermal shock resistance while maintaining high transparency and high hardness possessed by the composition. <P>SOLUTION: Silicone polymer particles (A) include a structure in which (A-1) a silicone particle core is coated with (A-2) an alkoxysilane condensate shell having an alkenyl group. The silicone composition comprises the silicone polymer particle, (B) an organohydrogenpolysiloxane having at least two hydrosilyl groups in the molecule, (C) an organopolysiloxane having at least two alkenyl groups in the molecule and (D) a hydrosilylation catalyst. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a silicone composition that can improve thermal shock resistance while maintaining high transparency and hardness.

  In recent years, development of white LEDs has progressed, and an increase in the amount of heat generated due to higher brightness and a shorter wavelength of light emitted from the light emitting element have progressed. For this reason, a silicone compound having excellent heat resistance and UV resistance as well as excellent transparency has been used as an LED sealing resin. Recently, from the viewpoint of protecting a bonding wire connecting an LED semiconductor element and an electrode, a silicone resin having high hardness has been used as a sealing resin.

Such a high-hardness silicone resin does not have sufficient thermal shock resistance and has problems such as generation of cracks, warpage, and peeling, and it is known that silicone polymer particles are blended in order to improve this problem. (For example, Patent Document 1)
However, since these silicone polymer particles have highly active silanol groups on the particle surface, if used as they are, they may inhibit the curing of the silicone resin. It was necessary to carry out complicated operations such as reducing the amount of slag.

In response to the above problems, it has been desired to obtain a silicone resin material excellent in balance between high hardness and thermal shock resistance by a simpler method.
JP 2007-131758 A

  This invention is made | formed in view of the said situation, and it aims at providing the silicone type composition excellent in the balance of high hardness and thermal shock resistance by a simpler method.

  As a result of intensive studies in order to solve the above problems, the present inventors have found that a silicone composition in which specific silicone polymer particles are blended with organopolysiloxane as a matrix resin has a high hardness and thermal shock resistance. The present invention has been completed by finding that it can be obtained by a simpler method than the conventional method, which is excellent in balance of properties and the like.

That is, the present invention relates to the following 1) to 6).
1) (A-1) Silicone polymer particles having a structure in which (A-1) a silicone particle core is covered with an (A-2) alkoxysilane condensate shell having an alkenyl group.
2) The alkoxysilane condensate shell having an alkenyl group as the component (A-2) is obtained by condensing an alkoxysilane containing the following component (a) and / or component (b): The (A) silicone polymer particles as described in 1).
(A) Component: General formula (1)

(Wherein R ²² and R ²³ represent the same or different monovalent alkyl groups, R ²⁴ represents an alkenyl group, and R ²⁵ represents an alkenyl group or a monovalent organic group other than an alkenyl group). , A bifunctional alkoxysilane compound having an alkenyl group and / or a partial condensate thereof.
(B) Component: General formula (2)

(Wherein R ³² , R ³³ and R ³⁴ represent the same or different monovalent alkyl groups and R ³⁵ represents an alkenyl group), and a trifunctional alkoxysilane compound having an alkenyl group and / Or a partial condensate thereof.
3) The alkoxysilane condensate shell having an alkenyl group, which is the component (A-2), is obtained by condensing the alkoxysilane containing the component (a) and the component (c) described below. (A) Silicone polymer particles according to 1) or 2).
(C) Component: General formula (3)

(Wherein R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ represent the same or different monovalent alkyl groups) and / or a partial condensate thereof.
4) The (A) silicone polymer particle according to any one of 1) to 3),
(B) an organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule;
(C) an organopolysiloxane having at least two alkenyl groups in one molecule;
(D) a hydrosilylation catalyst,
A silicone-based composition comprising:
5) The silicone composition according to 4), which contains (E) an adhesion-imparting agent.
6) The silicone composition according to 4) or 5), wherein the silicone polymer particles as component (A) are uniformly dispersed in the composition by a masterbatch method.

  According to the present invention, a silicone composition with improved thermal shock resistance can be obtained by a simpler method while maintaining high hardness and heat / light resistance of the composition.

  The present invention is described in detail below.

<(A) Silicone polymer particles having a structure in which an alkoxysilane condensate shell having an alkenyl group is coated on a silicone particle core>
The component (A) in the present invention can be used, for example, by blending with a matrix resin composed of the component (B), the component (C) and the component (D). In that case, it is possible to obtain a silicone composition which is excellent in balance such as high hardness, elastic modulus and thermal shock resistance and has high transparency.

  By optimizing the composition ratio of the alkoxysilane condensate shell having an alkenyl group as the component (A-2) to the silicone particle core as the component (A-1) in the component (A), for example, (A ) By combining the refractive index of the component and the refractive index of the matrix resin, the transparency of the entire silicone composition can be maintained, and the compatibility between the component (A-2) and the matrix is improved. It is advantageous for improving the strength of objects.

  The component (A) is not particularly limited in composition and the like, but may be any component as long as the component (A-1) is coated with the component (A-2). A polymer obtained by condensation reaction of 3 to 92% by weight of the component (A-2) below is preferred (however, the combined amount of the component (A-1) and the component (A-2) is 100% by weight). Furthermore, it is preferable to carry out a condensation reaction of 5 to 90% by weight of component (A-2) in the presence of 10 to 95% by weight of component (A-1). When the component (A-1) is 8% by weight or less, the refractive index of the component (A) may be greatly different from the refractive index of the matrix, and the transparency of the composition may be impaired, and the component (A-2) However, if it is 3% by weight or less, the compatibility with the matrix may be insufficient.

  The method for producing the component (A-1) used in the present invention is not particularly limited, but it can be obtained by ordinary emulsion polymerization, dispersion polymerization, solution polymerization, etc., and the particle size can be controlled. In view of the convenience of operation and the like, it is preferable to obtain by emulsion polymerization.

  The component (A-1) used in the present invention can also be obtained by ordinary emulsion polymerization. However, seed polymerization is also possible because of the advantage that particles having a smaller particle size can be obtained and the particle size distribution in the latex state can be narrowed. Can be used. 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 (A-1) has the general formula (4)
R ^a _m SiO _{(4-m) / 2} (4)
(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 that it is organosiloxane which has this.

  In the component (A-1), the structural unit of m = 2 in the general formula (4) preferably accounts for 70 mol% or more of the component (A-1), more preferably 80 mol% or more. Preferably. If it is 70 mol% or less, the thermal shock resistance of the silicone composition may be lowered because the flexibility of the component (A-1) is impaired.

  Although the component (A-1) can be obtained by polymerization of organosiloxane, 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 (A-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 (A-2), so that the silicone polymer particles having a stable core-shell structure are formed. Obtainable.

  The component (A-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 preferable than the reaction under alkaline conditions. This is advantageous because the polymerization proceeds rapidly. For example, various raw materials containing the above organosiloxane are made into an emulsion using a homomixer, a colloid mill, a homogenizer and the like 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. The pH at the time of polymerization is not particularly limited, but it is preferably adjusted to pH = 5 or less, particularly pH = 4 or less because the polymerization proceeds sufficiently. 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. Although there is no restriction | limiting in particular in reaction temperature and time, 0-100 degreeC is preferable and 50-95 degreeC is more preferable from the ease of 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 (A-1) is usually in an equilibrium state between cleavage and bond formation. This equilibrium changes depending on the temperature, and the higher the temperature, the easier it is to produce the high molecular weight component (A-1). Therefore, in order to obtain a high molecular weight component (A-1), it is preferable to perform aging by polymerization after heating and then cooling to a polymerization temperature or lower. Specifically, the polymerization is carried out at 50 ° C. or higher, and when the polymerization conversion rate reaches 75 to 90%, more preferably 82 to 89%, the heating is stopped and the temperature is cooled to 10 to 50 ° C., preferably 20 to 45 ° C. Then, aging can be performed for about 5 to 100 hours. In addition, the polymerization conversion rate said here means the conversion rate to the (A-1) component of the organosiloxane of the low volatile content in a raw material.

  There is no restriction | limiting in particular about the quantity of the water used for emulsion polymerization, What is necessary is just a quantity required in order to carry out emulsification dispersion | distribution of various raw materials, and what is necessary is just to use a 1-20 times weight with respect to the total amount of a raw material normally.

  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 (A-1) component. Sufficient emulsifying ability is obtained, and the component (A-1) obtained and the silicone polymer particles as the component (A) obtained therefrom are not adversely affected. It is preferable to use 0.005 to 20% by weight, and it is particularly preferable to use 0.05 to 15% by weight.

  The particle diameter of the component (A-1) can be controlled using a normal emulsion polymerization technique such as increase or decrease in the amount of emulsifier used. For example, by carrying out emulsion polymerization using an alkylbenzene sulfonic acid at an appropriate concentration, silicone particles having a relatively small particle size can be stably obtained. The volume average particle diameter of the latex silicone particles may be in the range of 0.005 μm to 3.0 μm, preferably 0.01 μm to 2.0 μm, and more preferably 0.050 μm to 0.095 μm. It is difficult to stably obtain a volume average particle size of less than 0.005 μm, and if it exceeds 3.0 μm, the transparency of the cured composition 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.

  In the synthesis of the component (A-1) used in the present invention, 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 (A-1) of the present invention include three functional groups that can participate in a condensation reaction such as methyltrimethoxysilane, 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 more than 10 parts by weight, the flexibility of the component (A-1) is impaired, so that the thermal shock resistance at low temperature of the silicone composition may be lowered. Moreover, the elasticity of (A-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.

  The alkoxysilane condensate shell having an alkenyl group that is the component (A-2) used in the present invention covers the surface of the component (A-1), and the component (A) and the component (B) described later The component (A) is a component used to uniformly disperse the component in the silicone composition or to improve the strength of the silicone composition.

The alkoxysilane condensate used in the present invention includes the following (a) component, (b) component, (c) component, alkoxysilane represented by component (d) and (e) component, and partial condensates thereof (alkoxy) A partial condensate obtained by condensing a part of the group) or the like. These can be used alone or in combination of two or more.
(A) Component: General formula (1)

(Wherein R ²² and R ²³ represent the same or different monovalent alkyl groups, R ²⁴ represents an alkenyl group, and R ²⁵ represents an alkenyl group or a monovalent organic group other than an alkenyl group). , A bifunctional alkoxysilane compound having an alkenyl group and / or a partial condensate thereof.
(B) Component: General formula (2)

(Wherein R ³² , R ³³ and R ³⁴ represent the same or different monovalent alkyl groups and R ³⁵ represents an alkenyl group), and a trifunctional alkoxysilane compound having an alkenyl group and / Or a partial condensate thereof.
(C) Component: General formula (3)

(Wherein R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ represent the same or different monovalent alkyl groups) and / or a partial condensate thereof.
(D) Component: General formula (5)

(Wherein R ²⁶ and R ²⁷ represent the same or different monovalent alkyl group, and R ²⁸ and R ²⁹ represent a monovalent organic group other than the same or different alkenyl group). Alkoxysilane compounds and / or partial condensates thereof.
(E) Component: General formula (6)

(Wherein R ³⁶ , R ³⁷ and R ³⁸ represent the same or different monovalent alkyl group, and R ³⁹ represents a monovalent organic group other than an alkenyl group). Compound and / or partial condensate thereof.

  The alkoxysilane condensate which is the component (A-2) in the present invention is a mixture of the above component (a), component (b), component (c), component (d) and component (e), and partial condensate thereof. A shell obtained by hydrolysis / condensation using the above product is preferred.

  The alkoxysilane condensate which is the component (A-2) in the present invention preferably contains the component (a) and / or the component (b). Thereby, an alkenyl group can be introduced into the component (A) by a simple operation. Since the alkenyl group and the organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule as the component (B) are subjected to a hydrosilylation reaction, a bond can be formed between the particle and the matrix. It is preferable because the strength of the entire composition can be improved by improving the interfacial adhesion between the matrix and the matrix. From the viewpoint that the interfacial adhesive force between the particles and the matrix can be improved to improve the strength of the entire composition, the amount of the component (a) and / or the component (b) in 100 mol% of the component (A-2) is The total of the components (a) and (b) is preferably 3 mol% or more, more preferably 5 mol% or more, and particularly preferably 8 mol% or more.

  The alkoxysilane condensate which is the component (A-2) in the present invention preferably contains the component (a) and the component (c). The surface of the component (A-2) thus obtained is preferable because there are few remaining silanol groups derived from alkoxy groups. From the viewpoint that the silanol group derived from the alkoxy group remaining on the surface of the component (A-2) can be reduced, the amount of the component (a) used is preferably 3 mol% or more, and more preferably 5 mol% or more. It is more preferable that the content is 8 mol% or more.

  When the alkoxysilane is condensed by a normal method, a large number of highly active silanol groups derived from the alkoxy group remain, which causes foaming when blended in the composition and thermally cured, In some cases, the matrix resin may inhibit a crosslinking reaction by a hydrosilylation reaction between the component (B) and the component (C). In order to solve such a problem, conventionally, an operation for converting a silanol group into a functional group having a low activity using a surface treatment agent such as a silylating agent has been required. It is simple and preferable.

  In addition, monofunctional alkoxysilane compounds represented by the general formula (7) and partial condensates thereof (partial condensates obtained by condensing alkoxy groups) can be used as long as the effects of the present invention are not hindered. These can be used alone or in combination of two or more.

In General Formula (7), R ¹² represents an alkyl group, and R ¹³ , R ¹⁴ , and R ¹⁵ represent the same or different monovalent organic groups.

  Examples of the alkoxy group mentioned in the general formulas (1) to (3) and (5) to (7) include methoxy, ethoxy, normal propoxy, isopropoxy, normal butoxy, isobutoxy, secondary butoxy, and tertiary. An alkoxy group having 1 to 6 carbon atoms such as butoxy, pentyloxy, hexyloxy and the like. 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.

  Specific examples of the alkoxysilane compound used in the present invention include the same compounds as the above-mentioned crosslinking agent and graft crossing agent, or partial condensates obtained by condensing alkoxy groups thereof.

  As a polymerization method for obtaining the component (A-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 (A-2) can be produced by a conventional emulsion polymerization method carried out under acidic or basic conditions, but the reaction under acidic conditions is more effective than the reaction under alkaline conditions. This is advantageous because it is easy to suppress gelation during the condensation reaction of silane.

  The method for separating the particles from the silicone polymer particle latex (A) 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.

  Furthermore, in the present invention, it is preferable to use the masterbatch method because the component (A) can be uniformly dispersed in the matrix resin and a transparent composition can be obtained.

  Here, the masterbatch method is an organic solvent 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.), etc. Is added to release the emulsified state of the particles in the latex, and the particles are slowly agglomerated, and then the loose agglomerates are collected by a method such as centrifugal sedimentation or filtration, and the particles are re-dispersed in a solvent that can disperse them. In this method, the dispersion is mixed with a matrix resin and the solvent is distilled off.

  You may surface-treat (A) component in the range which does not prevent the effect of this invention. By performing the surface treatment, the affinity between the component (A) and the components (B) and (C) 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, hexamethyldisiloxane, hexamethyl (di) silazane, trimethylmethoxysilane, and trimethylethoxysilane. These silylating agents may be used alone or in combination of two or more.

  Further, a functional group capable of binding to the component (B), such as an alkenyl group or an alkynyl group, may be introduced to the surface of the component (A) as long as the effect of the present invention is not hindered. By doing so, a bond is formed between the component (A) and the matrix, and the strength of the entire silicone composition can be improved.

  As a silylating agent for introducing a functional group having a binding ability with the component (B) onto the polymer surface, generally an alkenyl silane such as chlorodimethylvinylsilane, dichloromethylvinylsilane, dichlorodivinylsilane, trichlorovinylsilane, Tetramethyldivinyldisiloxane is mentioned. These silylating agents may be used alone or in combination of two or more.

  The addition amount of the silylating agent is preferably 2 to 1000 parts by weight and more preferably 10 to 400 parts by weight with respect to 100 parts by weight of component (A). When the addition amount of the silylating agent is less than 2 parts by weight, the silanol groups on the surface of the component (A) cannot be sufficiently reduced, and the affinity between the component (A) and the matrix cannot be sufficiently secured. There is. Moreover, when there are more addition amounts of a silylating agent than 1000 weight part, there exists a possibility that the silylating agent which was not able to react with the silanol group of (A) component surface may mix in in a composition as an impurity.

  In the present invention, silicone polymer particles having a structure in which an alkoxysilane condensate shell having an alkenyl group is coated on the silicone particle core as component (A), and at least 2 hydrosilyl groups in one molecule as component (B) Alternatively, a modified particle-organopolysiloxane obtained by hydrosilylation reaction may be synthesized. The purpose of synthesizing the particle-organopolysiloxane modified material is a means for uniformly dispersing the particles as component (A) in a matrix composed of component (B) and component (C). Thermal shock resistance can be improved while maintaining high transparency and hardness.

  The particle-organopolysiloxane modified method is prepared by dissolving the components (A) and (B) in a solvent in which both components are soluble, It is obtained by reacting a part of the hydrosilyl group of the component in the presence of a hydrosilylation catalyst which is the later-described component (D) and distilling off the solvent. Specific examples of the solvent in which both components are soluble include toluene, hexane, xylene and the like.

  The amount of component (A) and component (B) used for the synthesis of the modified particle-organopolysiloxane is preferably 10 parts by weight: 90 parts by weight to 90 parts by weight: 10 parts by weight, and 20 parts by weight: 80 parts by weight. Parts to 80 parts by weight: 20 parts by weight is more preferable. The amount of the component (D) used for the synthesis of the modified particle-organopolysiloxane is preferably in the range of 0.01 to 1000 ppm as a platinum atom with respect to the component (A).

  The temperature at which a part of the alkenyl group of component (A) and a part of the hydrosilyl group of component (B) are reacted is a temperature of 10 to 180 ° C., more preferably 20 to 150 ° C. in the presence of component (D). It is preferable to set it as ° C. If the temperature is too low, the reaction does not proceed, and if the temperature is too high, the reaction proceeds more than necessary, and the resulting modified particle-organopolysiloxane gels and a liquid is obtained at room temperature. It becomes difficult to handle.

  Further, since the modified particle-organopolysiloxane is easy to handle, it is preferably liquid at room temperature after distilling off the solvent after the hydrosilylation reaction, and the viscosity at room temperature is 1,000 Pa · s or less. It is preferable that it is 100 Pa · s or less.

  A curing retarder can be used for the purpose of improving the storage stability of the modified particle-organopolysiloxane of the present invention or adjusting the reactivity of the hydrosilylation reaction in the course of the reaction. 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 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, 3,5-dimethyl-1-hexyne-3- Examples thereof include propargyl alcohols such as all, 1-ethynyl-1-cyclohexanol, ene-yne compounds, maleic acid esters such as maleic anhydride and dimethyl maleate, and the like. 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. Specific examples of 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. are 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.

  Among these curing retarders, benzothiazole, thiazole, dimethyl maleate, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-from the viewpoint of good retarding activity and good raw material availability More preferred are 1-butyn-3-ol, 1-ethynyl-1-cyclohexanol, N, N, N ′, N′-tetramethylethylenediamine.

Although the addition amount of a curing retarder is not particularly limited, 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.

<(B) Organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule>
(B) component in this invention hardens | cures with the below-mentioned (C) component by hydrosilylation reaction, and forms a silicone resin matrix. For this reason, there is no particular limitation 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.

Examples of the component (B) having a three-dimensional crosslinked structure are not particularly limited,
SiO _4/2 (8)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formula (9).
R ^b ₃ SiO _1/2 (9)
(In the formula, R ^b is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
A polymer having a structure blocked with a monofunctional structural unit represented by the formula (II) and having at least two hydrosilyl groups is preferable because a cured product having high hardness can be obtained.

    Examples of the substituted or unsubstituted monovalent hydrocarbon group other than the alkenyl group of the general formula (9) 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, and a phenyl group. A group, an aryl group such as a tolyl group, or a chloromethyl group, a trifluoropropyl group, a cyanoethyl group, etc. 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 The same or different, preferably an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. Among these, a methyl group is 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 50 to 500 mol%, preferably 100 to 300 mol% with respect to the alkenyl group of the component (C) described later. Is desirable.

  Furthermore, the component (B) is preferably liquid at room temperature because it is easy to handle, and its viscosity at room temperature is preferably 1,000 Pa · s or less, and preferably 100 Pa · s or less. More preferred. When such a component (B) is used, it is easy to handle, and the modified particle-organopolysiloxane obtained by hydrosilylation reaction with the component (A) can be made liquid. preferable.

<(C) Organopolysiloxane having at least two alkenyl groups in one molecule>
(C) component in this invention hardens | cures by the hydrosilylation reaction with the above-mentioned (B) component, and forms a silicone resin matrix. For this reason, there is no particular limitation as long as it is an organohydrogenpolysiloxane containing two or more alkenyl 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 (C) component include a copolymer of dimethylsiloxane units and methylvinylsiloxane units, a copolymer of dimethylsiloxane units and terminal dimethylvinylsiloxy units, and the like.

  Examples of the cyclic (C) component may include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane.

Examples of the component (C) having a three-dimensional crosslinked structure are not particularly limited,
SiO _4/2 (8)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formula (10).
R ^c ₃ SiO _1/2 (10)
(Wherein R ^c is an alkenyl group or a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, and may be the same or different.)
A polymer having a structure blocked with a monofunctional structural unit represented by the formula (1) and having at least two alkenyl groups in one molecule is preferable. When a tetrafunctional structural unit represented by the general formula (8) is used for the main structure, a main skeleton having a high crosslinking density can be obtained, so that the strength and hardness of the composition after thermosetting can be increased. It is advantageous. When the terminal of the main structure is blocked with a monofunctional structural unit represented by the general formula (10), an alkenyl group that becomes a crosslinking point of the composition by hydrosilylation reaction can be introduced by a simple method. It is. In addition, the amount of the alkenyl group in the component (C) can be adjusted by adjusting the ratio of the alkenyl group of R ^{c to} the substituted or unsubstituted monovalent hydrocarbon group other than the alkenyl group. The crosslinking density is excellent because it can be obtained by a simple method.

  The alkenyl group in the general formula (10) is a vinyl group, an allyl group, a butenyl group, a hexenyl group or the like, and a vinyl group is preferable from the viewpoint of availability.

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

  The component (C) may have at least two alkenyl groups in one molecule, but the content of the alkenyl group in the component (C) is 0.1 to 10 mol / kg, particularly 0.5. It is preferably ˜9 mol / kg. If the amount is 0.1 mol / kg or less, the cured composition cannot have sufficient hardness, and if it is 10 mol / kg or more, the crosslinking density is too high and the thermal shock resistance is lowered.

  Furthermore, the component (C) is preferably liquid at room temperature because it is easy to handle, and its viscosity at room temperature is preferably 1,000 Pa · s or less, and preferably 100 Pa · s or less. More preferred.

<(D) Hydrosilylation catalyst>
As the hydrosilylation catalyst as component (D) in the present invention, for example, a platinum-based catalyst, a palladium-based catalyst, and a rhodium-based catalyst can be added. As the platinum-based catalyst, known ones can be used, specifically, platinum element alone, platinum compound, platinum complex, chloroplatinic acid, alcohol compound of chloroplatinic acid, aldehyde compound, ether compound, various olefins. Examples include complexes. The addition amount of the platinum-based catalyst is desirably in the range of 0.01 to 1000 ppm as platinum atoms with respect to the component (C).

<(E) Adhesiveness imparting agent>
The adhesiveness imparting agent as the component (E) in the present invention is a component that imparts adhesiveness to the cured product obtained from the polysiloxane composition.

  As the component (E) in the present invention, a silane coupling agent, a boron coupling agent, a titanium coupling agent, an aluminum coupling agent, or the like can be suitably 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, and 3-acrylonitrile. Examples include, but are not limited to, loxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

  Examples of the boron-based coupling agent include trimethyl borate, triethyl borate, tri-2-ethylhexyl borate, normal trioctadecyl borate, tri-normal 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.

  In the present invention, the (E) adhesion-imparting agent 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 (B) and the component (C). In addition, depending on the type or addition amount of the adhesion-imparting agent, there are those that inhibit the hydrosilylation reaction, so the influence on the hydrosilylation reaction must be considered.

<Composition>
About the compounding quantity of (A) component, it is preferable that (A) component is a ratio of 100 to 1 weight% in a silicone type composition, and it is more preferable that it is a ratio of 90 to 5 weight%. When the proportion of the component (A) is greater than 100% by weight, the viscosity may increase during blending, or the transparency of the composition may decrease. If it is less than 1% by weight, the thermal shock resistance may be insufficient.

  A curing retarder can be used for the purpose of improving the storage stability of the silicone-based composition of the present invention 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 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, 3,5-dimethyl-1-hexyne-3- Examples thereof include propargyl alcohols such as all, 1-ethynyl-1-cyclohexanol, ene-yne compounds, maleic acid esters such as maleic anhydride and dimethyl maleate, and the like. 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. Specific examples of 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. are 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.

  Among these curing retarders, benzothiazole, thiazole, dimethyl maleate, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-from the viewpoint of good retarding activity and good raw material availability More preferred are 1-butyn-3-ol, 1-ethynyl-1-cyclohexanol, N, N, N ′, N′-tetramethylethylenediamine.

Although the addition amount of a curing retarder is not particularly limited, 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 silicone composition used 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.

  In addition, the silicone composition of the present invention is used for various additives such as a colorant and a heat resistance improver, a reaction control agent, a mold release agent, or a filler as long as the effects of the present invention are not hindered. A dispersant or the like can be optionally 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 order to make the silicone composition 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, and glass flake are added. May be. 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 silicone composition used in the present invention, the above components are uniformly mixed using a kneader such as a two-roll, Banbury mixer, kneader, or a planetary stirring deaerator, and heat-treated as necessary. It can be obtained by applying.

  The silicone composition of the present invention can be used as a molded article. Examples of molding include arbitrary molding methods such as extrusion molding, compression molding, blow molding, calendar molding, vacuum molding, foam molding, injection molding, and cast molding.

  The silicone composition of the present invention preferably has a light transmittance at a wavelength of 450 nm at room temperature of 50% or more (2 mm thickness). If the light transmittance is 50% or more, light can be efficiently extracted, and therefore, it can be suitably used in applications such as LED encapsulants that require high transparency.

  The silicone composition referred to in the present invention means a silicone composition having physical properties suitable for use as an optical material. The optical material mentioned here refers to general materials used for the purpose of allowing light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material.

  The silicone composition of 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, examples include still camera lens materials, viewfinder prisms, target prisms, viewfinder covers, and light receiving sensor sections. In addition, a photographing lens and a viewfinder of a video camera 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, automobile protection Examples include rusted steel plates, interior panels, interior materials, protective and binding 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.

  Next, although the composition of this invention is demonstrated in detail based on an Example, this invention is not limited only to these Examples.

<Test method>
(Curing property)
The properties of a 2 mm thick test piece were visually evaluated.
(Type D durometer hardness)
In accordance with the method described in JIS K7215, measurement was performed using a durometer HD-1120 manufactured by Ueshima Seisakusho. The average value of the measurement values of five measurements was adopted. The test piece used was conditioned at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 5% for 24 hours or more before the test.

(Cooling test)
Enomoto Co., Ltd. LED package (product name: TOP LED 1-IN-1), 0.4mm x 0.4mm x 0.2mm single crystal silicon chip, Henkel Japan Co., Ltd. epoxy adhesive (product name) : LOCTITE 348), and fixed in an oven at 150 ° C. for 30 minutes. A composition was injected into the LED package and thermally cured for a predetermined time to prepare a sample. The sample was immersed in a 260 ° C. solder bath (product name: SOLDERING BATH HP-410, manufactured by Ishizaki Electric Co., Ltd.) for 10 seconds, and immediately immersed in cooling water at 20 ° C. for 10 seconds. This operation was repeated 5 times, and the sample was observed. When there was no change, it was evaluated as “◯”, and when cracks occurred or peeling occurred between the packages, it was evaluated as “X”.

Example 1
400 parts by weight of pure water and 12 parts by weight (solid content) of 10% by weight aqueous sodium dodecylbenzenesulfonate were mixed in a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer. Thereafter, 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 0.008 μm).

  Next, in a five-necked flask equipped with a stirrer, a reflux condenser, a nitrogen blowing port, a monomer addition port, and a thermometer, 2.0 parts by weight (solid content) of the above seed polymer, 10 wt% dodecylbenzenesulfone. After charging 1.5 parts by weight of 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 15 minutes and then the system was heated to 80 ° C. under a nitrogen atmosphere. The temperature was raised. Separately, a mixture of 150 parts by weight of pure water, 0.5 part by weight of 5% by weight sodium dodecylbenzenesulfonate aqueous solution (solid content), and 100 parts by weight of octamethylcyclotetrasiloxane was homomixed at 7000 rpm for 5 minutes. After forced emulsification, this mixed solution was continuously added over 5 hours. Further, post-polymerization was performed for 2 hours, and the polymerization was terminated by cooling to 25 ° C. and leaving it for 20 hours to obtain a latex containing silicone core particles (volume average particle size 0.090 μm).

In a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port and thermometer, 90 parts by weight (solid content) of the above-mentioned silicone core particles were charged, and the temperature was raised to 40 ° C. in a nitrogen atmosphere. It was. Separately, 50 parts by weight of pure water and 0.6 part by weight (solid content) of 5% by weight aqueous solution of sodium dodecylbenzenesulfonate, ethyl silicate condensate (trade name: ethyl silicate 40, SiO, manufactured by Tama Chemical Industry Co., Ltd.) ₂ content: 39.0 to 42.0% by weight) 12.4 parts by weight (corresponding to 5.0 parts by weight in terms of a complete condensate of the structural unit represented by SiO ₂ ), dimethoxymethylvinylsilane After forcibly emulsifying a mixture consisting of 7 parts by weight (corresponding to 5.0 parts by weight in terms of a complete condensate of the structural unit represented by CH ₃ ViSiO _2/2 ) at 7000 rpm for 5 minutes with a homomixer, Added dropwise over a period of minutes. This solution was stirred for 24 hours while being kept at 40 ° C. to obtain a latex containing silicone polymer particles having a vinyl group (volume average particle size 0.097 μm).

  Particles obtained by adding 175 parts by weight of methyl ethyl ketone to 25 parts by weight of the resin solid content of the latex (resin solid content concentration 22% by weight) containing the silicone polymer particles having a vinyl group as the component (A). After agglomeration, the mixture was centrifuged at 6000 rpm for 10 minutes using a centrifuge. The obtained precipitate was dispersed and washed in a mixed solvent of methyl ethyl ketone / methanol = 1/1 (vol / vol), and then centrifuged with a centrifuge at 6000 rpm for 10 minutes. After this washing was performed three times in total, 375 parts by weight of toluene was added to 25 parts by weight of the resulting precipitate to obtain a toluene solution of silicone polymer particles having a vinyl group.

(Comparative Example 1)
Instead of 7.7 parts by weight of dimethoxymethylvinylsilane used in Example 1, 10.1 parts by weight of trimethoxymethylsilane (converted to a complete condensate of structural units represented by CH ₃ SiO _3/2 is 5. A latex containing silicone polymer particles (volume average particle size of 0.095 μm) was obtained in the same manner except that (corresponding to 0 part by weight) was used.

  After adding 175 parts by weight of methyl ethyl ketone to 25 parts by weight of the resin solid content of the latex (resin solid content concentration: 22% by weight) containing the silicone polymer particles, the particles are aggregated, and then 6000 rpm in a centrifuge. Centrifuged for 10 minutes. The obtained precipitate was dispersed and washed in a mixed solvent of methyl ethyl ketone / methanol = 1/1 (vol / vol), and then centrifuged with a centrifuge at 6000 rpm for 10 minutes. After this washing was performed three times in total, 375 parts by weight of toluene was added to 25 parts by weight of the resulting precipitate to obtain a toluene solution of silicone polymer particles.

(Example 2)
The hydrosilyl group having the three-dimensional structure as the component (B) with respect to 25 parts by weight of the resin solid content of the toluene solution of the silicone polymer particles containing the vinyl group as the component (A) obtained in Example 1 64.8 parts by weight of a polysiloxane containing a polysiloxane (manufactured by Clariant, trade name MQH-5, hydrosilyl group content 2.3 mol / kg), and a hydrosilyl group-containing polysiloxane having the same three-dimensional structure as component (B) ( 6.5 parts by weight of Clariant, trade name MQH-8, hydrosilyl group content 7.5 mol / kg) was added and dissolved, and 1% xylene solution of 1-ethynyl-1-cyclohexanol was added to 0%. 0083 parts by weight, 0.0075 parts by weight of 1% xylene solution of N, N, N ′, N′-tetraethylethylenediamine, and xylene solution of platinum vinylsiloxane complex (0.03 wt% content of platinum) was added 0.0014 part by weight.

  About the reaction solution obtained in this way, toluene was distilled off with a rotary evaporator. Then, a liquid composition was obtained at room temperature.

  With respect to 96.3 parts by weight of the liquid composition thus obtained, a vinyl group-containing polysiloxane having a three-dimensional structure as component (C) (manufactured by Clariant, trade name MQV-7, vinyl group content 3 0.5 mol / kg), 28.4 parts by weight, 5 parts by weight of SH6040 manufactured by Toray Dow Corning, which is 3-glycidoxypropyltrimethoxysilane, which is component (E), and further, component (E) After adding 1 part by weight of trimethyl borate, stirring and defoaming were performed with a planetary stirring deaerator to obtain a liquid mixture.

  The liquid mixture is poured into a mold and cured by heating at 60 ° C. for 3 hours, 80 ° C. for 1 hour, 100 ° C. for 1 hour, 120 ° C. for 1 hour, and 150 ° C. for 1 hour. Got. Various evaluation results are shown in Table 1.

(Comparative Example 2)
Except that the toluene solution of the silicone polymer particles obtained in Comparative Example 1 was used in place of the toluene solution of the silicone polymer particles having a vinyl group as the component (A) obtained in Example 1. A cured product for evaluation was obtained in the same manner as in Example 2. Various evaluation results are shown in Table 1.

  As shown in Table 1, the cured product of Example 2 was confirmed to have high hardness and excellent transparent thermal shock resistance without causing curing failure such as foaming when compared with the cured product of Comparative Example 2. The effectiveness of the component (A) was confirmed.

Claims (6)

(A-1) Silicone polymer particles having a structure in which (A-2) an alkoxysilane condensate shell having an alkenyl group is coated on a silicone particle core. The alkoxysilane condensate shell having an alkenyl group as the component (A-2) is obtained by condensing an alkoxysilane containing the following component (a) and / or component (b): The (A) silicone polymer particle according to claim 1.
(A) Component: General formula (1)
(Wherein R ²² and R ²³ represent the same or different monovalent alkyl groups, R ²⁴ represents an alkenyl group, and R ²⁵ represents an alkenyl group or a monovalent organic group other than an alkenyl group). , A bifunctional alkoxysilane compound having an alkenyl group and / or a partial condensate thereof.
(B) Component: General formula (2)
(Wherein R ³² , R ³³ and R ³⁴ represent the same or different monovalent alkyl groups and R ³⁵ represents an alkenyl group), and a trifunctional alkoxysilane compound having an alkenyl group and / Or a partial condensate thereof. The alkoxysilane condensate shell having an alkenyl group as the component (A-2) is obtained by condensing an alkoxysilane containing the component (a) and the following component (c), The (A) silicone polymer particle according to claim 1 or 2.
(C) Component: General formula (3)
(Wherein R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ represent the same or different monovalent alkyl groups) and / or a partial condensate thereof. (A) silicone-based polymer particles according to any one of claims 1 to 3,
(B) an organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule;
(C) an organopolysiloxane having at least two alkenyl groups in one molecule;
(D) a hydrosilylation catalyst,
A silicone-based composition comprising: (E) Adhesiveness imparting agent is contained, The silicone type composition of Claim 4 characterized by the above-mentioned. 6. The silicone composition according to claim 4 or 5, wherein the silicone polymer particles (A) are uniformly dispersed in the composition by a masterbatch method.