JP2010248384A - Silicone composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technology capable of keeping high transparency of a cured product obtained by curing a silicone composition without causing whitening, even under high-temperature high-humidity conditions. <P>SOLUTION: The silicone composition comprises (A) an organopolysiloxane having at least two alkenyl groups within a molecule, (B) an organohydrogenpolysiloxane having at least two hydrosilyl groups within a molecule, (C) silicone polymer particles, (D) a hydrosilylating catalyst, (E) a silane coupling agent having two alkoxy groups directly bound to a silicon atom within a molecule, and (F) at least one chosen from a boron coupling agent, a titanium coupling agent, an aluminum coupling agent and a zirconium coupling agent. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a silicone composition that provides a cured product that does not become cloudy even under high temperature and high humidity conditions.

  Silicone-based materials such as silicone rubber, gel, and resin are widely used as sealants for light-emitting diodes (LEDs), optical waveguide materials, and contact protectors for electrical circuits because of their high transparency, heat resistance, and light resistance. It is used.

  It is widely known that a silane coupling agent is blended for the purpose of improving the adhesion of these silicone materials (for example, Patent Document 1), and a silane coupling agent and a boron coupling agent are used in combination. It is also known to further improve the adhesiveness (for example, Patent Document 2).

  However, most of the conventional techniques use a silane coupling agent having three alkoxy groups bonded directly to a silicon atom in one molecule, and such a system includes a boron-based cup. Even if the cured product obtained from the silicone composition combined with the ring agent does not impair the transparency of the cured product under normal use, for example, the transparency of the cured product is further maintained under high temperature and high humidity conditions. It was hoped to do.

JP 2004-292777 A JP 2004-137404 A

  The present invention has been made in view of the above circumstances, and a technology in which a cured product obtained by curing a silicone-based composition can maintain high transparency without being clouded even under high temperature and high humidity conditions. The purpose is to provide.

  As a result of intensive studies to solve the above problems, the present inventors cured a silicone composition containing a silane coupling agent having two alkoxy groups bonded directly to silicon atoms in one molecule. The present cured product was found to be able to maintain high transparency without becoming clouded under high temperature and high humidity conditions, and the present invention was completed. That is, the present invention has the following configuration.

1) (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) silicone polymer particles,
(D) a hydrosilylation catalyst,
(E) Silane coupling agent having two alkoxy groups directly bonded to silicon atoms in one molecule, and (F) Boron-based coupling agent, titanium-based coupling agent, aluminum-based coupling agent, and zirconium-based cup At least one selected from ring agents,
A silicone-based composition comprising:

  2) (C) Silicone polymer particles are added with a first shell component (C-2) obtained by adding and condensing alkoxysilane to silicone particles (C-1), and then an alkoxysilane condensate is added. 1) The silicone composition according to 1), which has a silicone particle core-alkoxysilane condensate shell structure comprising the second shell component (C-3) obtained by condensation.

3) The second shell layer made of the alkoxysilane condensate as the component (C-3) has the following component (a) as an essential component, and includes the following component (b), component (c) and component (d) below. 2. The silicone composition according to 2), which is obtained by condensing at least one selected.
(A) Component: General formula (1)

(Wherein R ¹² represents an alkyl group, and R ¹³ , R ¹⁴ and R ¹⁵ represent the same or different monovalent organic groups) and / or a partial condensation thereof. object.
(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.

4) A first shell layer comprising an alkoxysilane condensate as component (C-2) is obtained by condensing at least one selected from the following components (b), (c) and (d). The silicone composition according to any one of 2) to 3), wherein:
(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.

  5) (C) The 1st shell layer which consists of alkoxysilane condensate which is (C-2) component with respect to 40 to 98 weight% of silicone particles which are (C-1) component is a silicone type polymer particle. 1 to 40% by weight of a polymer coated with 1 to 30% by weight of a second shell layer made of an alkoxysilane condensate as component (C-3) (however, the components (C-1) and (C-2) And the component (C-3) are 100% by weight), and the silicone composition according to any one of 2) to 4).

  6) The component (E) is a silane coupling agent having at least one organic group selected from an epoxy group, a methacryl group, an acrylic group, and a vinyl group, and any one of 1) to 5) The silicone composition according to one item.

  7) The silicone composition according to any one of 1) to 6), wherein the component (F) is a boron coupling agent.

  8) A cured product obtained by curing the silicone composition according to any one of 1) to 7).

  9) The light transmittance at a wavelength of 450 nm of a cured product (1 mm thickness) is T1 (%), and the cured product is cured at 85 ° C. and 85% RH for 3 hours, and the light transmittance at a wavelength of 450 nm is T2 (%). The cured product according to 8), wherein T1-T2 ≦ 5 is satisfied.

  10) LED which used the silicone type composition as described in any one of 1) -9) as a sealing agent.

  11) The method for producing a silicone composition according to any one of 1) to 7), wherein the component (C) is uniformly dispersed in the composition by a master batch method.

  According to the present invention, a silicone composition can be obtained from which a cured product that does not become cloudy even under high temperature and high humidity conditions can be obtained.

  The present invention is described in detail below.

<(A) Organopolysiloxane having at least two alkenyl groups in one molecule>
The component (A) in the present invention forms a silicone matrix by curing with an organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule, which will be described later as the component (B), by a hydrosilylation reaction. is there. Therefore, any organopolysiloxane containing two or more alkenyl groups in one molecule is not particularly limited, 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 (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 (5)
SiO _4/2 (5)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (6) and (7).
R ^a1 R ^a2 ₂ SiO _1/2 (6)
R ^a2 ₃ SiO _1/2 (7)
(Wherein R ^a1 is an alkenyl group, and R ^a2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
And a structure in which at least two ends of the main structure are blocked by the general formula (6) are exemplified. In this case, those having good compatibility with the component (B) and (C) are preferable.

  The alkenyl group is preferably a vinyl group, an allyl group, a butenyl group, or a hexenyl group, and more preferably a vinyl group from the viewpoints of availability, heat resistance, and light resistance.

  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. An unsubstituted or substituted monovalent hydrocarbon group, preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, is preferred. Among these, a methyl group is more preferable from the viewpoint of heat resistance and light resistance.

  When the component (A) represented by the general formula (5), the general formula (6), and the general formula (7) is used, the cured product obtained from this composition has a high crosslink density. Since a hardened | cured material of intensity | strength is obtained, it is preferable.

  Furthermore, the component (A) is preferably liquid at room temperature because of easy handling, and its viscosity at room temperature is preferably 1000 Pa · s or less, more preferably 100 Pa · s or less.

<(B) Organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule>
In the present invention, the component (B) is cured by a hydrosilylation reaction with the component (A) to form a silicone 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.

Further, examples of the component (B) having a three-dimensional crosslinked structure are not particularly limited, but the general formula (5)
SiO _4/2 (5)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (8) and (9).
R ^b1 R ^b2 ₂ SiO _1/2 (8)
R ^b2 ₃ SiO _1/2 (9)
(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.)
And having a structure in which at least two ends of the main structure are blocked by the general formula (8), and the component (A) and A thing with favorable compatibility with (C) is illustrated as a preferable thing.

  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. An unsubstituted or substituted monovalent hydrocarbon group, preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, is preferred. Among these, a methyl group is more preferable from the viewpoint of heat resistance and light resistance.

  When the component (B) represented by the above general formula (5), general formula (8) and general formula (9) is used, the cured product obtained from this composition has a high crosslink density, and thus has high hardness and high hardness. It is preferable because a cured product having a high strength can be obtained.

  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.

  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) Silicone polymer particles>
Component (C) is a silicone-based particle and preferably has a core-shell structure. 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 that of the monomer component forming the core in the presence of the core particle. 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.

  (C-1) Component (C) by having a core-shell structure of silicone particles as component, first shell component as component (C-2), and second shell component as component (C-3) 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 silicone type composition which mix | blended (C) component has low hygroscopicity, for example, and can also improve cold-heat shock resistance.

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

  Furthermore, with respect to the silicone particles 35 to 96% by weight as the component (C-1), the first shell layer made of the alkoxysilane condensate as the component (C-2) is 2 to 37% by weight, (C-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 are few (C-1) components, since the softness | flexibility of particle | grains will be impaired, the thermal shock resistance of the hardened | cured material obtained from the composition which mix | blended (C) component may fall, (C-2) When the amount of the component is small, the component (C) cannot maintain the original particle shape, and the component (C) flows out into the matrix, which may lead to a decrease in physical properties such as decreasing the strength of the blended composition.

  Moreover, when there are few (C-3) components, the silanol group of the (C) 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 silicone composition blended with the component (C) may increase and the thermal shock resistance may decrease.

The component (C-1) may be silicone particles, but the general formula (10)
^{_{R c m SiO (4-m}} ) / 2 (10)
(Wherein R ^c 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 (C-1), the structural unit of m = 2 in the general formula (10) preferably occupies 70 mol% or more of the component (C-1), more preferably 80 mol% or more. Preferably. When the amount of this component is small, the flexibility of the component (C-1) is impaired, so that the thermal shock resistance after curing of the silicone composition obtained by blending the component (C) into the matrix is lowered. There is.

  Although the component (C-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 (C-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 (C-2), and therefore, a silicone polymer particle having a stable core-shell structure is formed. Obtainable.

  The method for producing the component (C-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 (C-1) preferably uses seed polymerization from the viewpoint of obtaining particles having a smaller particle diameter and further reducing the particle diameter in the latex state. 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 (C-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 carried out under acidic conditions, the Si—O—Si bond forming the skeleton of the component (C-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 a high molecular weight (C-1) component. Therefore, in order to obtain a high molecular weight component (C-1), 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 (C-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 (C-1) component.

  The amount of the emulsifier used does not adversely affect the physical properties of the obtained (C-1) component and the silicone polymer particles that are the (C) component obtained from the obtained component (C-1). Therefore, if it dares to illustrate, it is preferable to use 0.005-20 weight% in an emulsion, and it is preferable to use 0.05-15 weight% especially.

  The volume average particle size of the silicone particles in the latex state as the component (C-1) is preferably 0.005 μm to 3.0 μm, more preferably 0.01 μm to 2.0 μm, and particularly 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 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.

  When the component (C-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 (C-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 (C-1) is impaired. Therefore, when the component (C) is blended into the matrix, the thermal shock resistance at low temperatures of the silicone composition is lowered. There is a case. Moreover, the elasticity of (C-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 (C-2) in the present invention, it is possible to maintain the morphology of the component (C) as particles. For example, it can contribute to the improvement of the thermal shock resistance of a cured product obtained from a silicone composition.

The alkoxysilane used for the component (C-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. (C-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 (C-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 (C-2) can be produced by a usual emulsion polymerization method performed under acidic or basic conditions. However, 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.

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

  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 phenomenon can also be solved.

  The component (C-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 (1) 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 (1), R ¹² represents an alkyl group, and R ¹³ , R ¹⁴ , and R ¹⁵ represent the same or different monovalent organic groups.)

  Further, the component (C-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 component (b), component (c) and component (d), component (a) can be efficiently incorporated into component (C). 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 (C). When the alkenyl group is introduced into the component (C), when the component (C) is blended with the matrix component comprising the component (A) and the component (B) that are cured by the hydrosilylation reaction, the component (C) and the component (B) Since a bond is formed between the cured product obtained from the silicone composition of the present invention, the strength of the cured product can be improved.

  As a polymerization method for obtaining the component (C-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 (C-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 effective 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 the particles from the latex of the silicone polymer particles (C) 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 the latex, it is preferable to use a masterbatch method in that the component (C) can be uniformly dispersed in the matrix resin and a transparent cured product can be obtained.

  Master batches are water-soluble or partially soluble organic solvents in aqueous latex solutions, such as alcohols (methanol, ethanol, 2-propanol, etc.), ketones (methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), acetate esters (Ethyl acetate, butyl acetate, methyl acetate) and the like are added to slowly aggregate the particles, and then the loose aggregate is recovered by a method such as centrifugal sedimentation or filtration, and the solvent in which the loose aggregate can be dispersed It can be obtained by a method of re-dispersing in a mixture and mixing with a matrix resin and distilling off the solvent.

  The obtained component (C) can be surface-treated within a range not impairing the characteristics of the present invention. By performing the surface treatment, the affinity between the component (C) 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 (C), so that a bond is formed between the component (C) and the matrix component. As a result, the strength of the entire silicone 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.

<(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. 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.

<(E) Silane coupling agent having two alkoxy groups directly bonded to silicon atoms in one molecule>
The component (E) in the present invention is a component that is used together with the following component (F) and imparts adhesiveness to a cured product obtained from the silicone composition. The (E) component in the present invention is excellent because the cured product does not become cloudy even under high temperature and high humidity conditions when a silicone composition is prepared in combination with the following (F) component. Yes.

  An example of a silane coupling agent having two alkoxy groups directly bonded to a silicon atom in one molecule is a silane coupling agent having two alkoxy groups directly bonded to a silicon atom and an organic group in one molecule. Although there is no particular limitation, a silane coupling agent having 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 as the organic group is preferable. Among the organic groups, an epoxy group, a methacryl group, an acrylic group, and a vinyl group are particularly preferable from the viewpoint of curability and adhesiveness, and an epoxy group is most preferable.

  Specifically, examples of the silane coupling agent having two epoxy groups bonded directly to a silicon atom in one molecule include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldisilane. Examples include ethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane.

  Moreover, as a silane coupling agent having two methacrylic or acrylic groups and two alkoxy groups bonded directly to silicon atoms in one molecule, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane , 3-acryloxypropylmethyldimethoxysilane, and 3-acryloxypropylmethyldiethoxysilane.

  The amount of component (E) added is preferably 0.05 to 30% by weight of the total amount of component (A) and component (B). In addition, depending on the type or amount of component (E), there are those that inhibit the hydrosilylation reaction, so the influence on the hydrosilylation reaction must be considered.

<(F) At least one selected from a boron coupling agent, a titanium coupling agent, an aluminum coupling agent, and a zirconium coupling agent>
The component (F) in the present invention is a component that is used together with the component (E) and imparts adhesiveness to a cured product obtained from the silicone composition.

  As the component (F) in the present invention, a boron-based coupling agent, a titanium-based coupling agent, an aluminum-based coupling agent, or the like can be suitably used. Of these, boron-based coupling agents are preferred from the viewpoints of adhesiveness and storage stability of the blended composition.

  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.

  (F) component in this invention may be used individually by 1 type, and may use 2 or more types together. 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 addition amount of component (F), there are those that inhibit the hydrosilylation reaction, so the influence on the hydrosilylation reaction must be considered.

<Silicone-based composition>
The blending amount of the component (A), the component (B) and the component (C) in the silicone-based composition of the present invention is 100 weights of the total weight of the component (A), the component (B) and the component (C). The following ratios are raised as preferable ranges when the parts are used.

In the silicone-based composition, the component (A) is preferably 98 to 1 part by weight, the component (B) is preferably 98 to 1 part by weight, and the component (C) is preferably 50 to 1 part by weight. More preferably, 3 parts by weight, 94-3 parts by weight of component (B) and 45-3 parts by weight of component (C).
When the proportion of the component (A) is large, a cured product having sufficient hardness may not be obtained or the cured product may be colored. If the amount is too small, a cured product having sufficient hardness may not be obtained.
When the ratio of the component (B) is large, a cured product with sufficient hardness may not be obtained, or foaming may occur during the curing and bubbles may remain in the cured product. If the amount is too small, a cured product having sufficient hardness may not be obtained.
When there are many ratios of (C) component, it may increase the viscosity at the time of a mixing | blending or the transparency of a composition may fall. On the other hand, if it is less, the thermal shock resistance may be insufficient.

  The viscosity of the silicone composition may gradually increase from the viscosity immediately after compounding, but the increase is preferably small from the viewpoint of ease of handling and quality stability. The range of increase in the viscosity is preferably within 20%, more preferably within 10% of the value after standing for 24 hours at 25 ° C. compared to the value immediately after blending.

  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 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 silicone composition used in the present invention, a silane coupling agent having three alkoxy groups directly bonded to a silicon atom in one molecule may be added as necessary, as long as the effects of the present invention are not hindered. Good.

  Specifically, examples of the silane coupling agent having three epoxy groups bonded directly to a silicon atom in one molecule include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxy. Examples thereof include silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

  Further, as a silane coupling agent having three methacrylic groups or acrylic groups and three alkoxy groups bonded directly to silicon atoms in one molecule, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, Examples include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

  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 flakes 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 method for curing the silicone composition of the present invention is not particularly limited, but it can be reacted by simply mixing the components, or can be reacted by heating. From the viewpoint that the reaction is fast and generally a material having high heat resistance is easily obtained, a method of heating and reacting is preferable.

  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 cured product obtained from the silicone composition of the present invention preferably has a light transmittance of a wavelength of 450 nm at room temperature of 85% or more (1 mm thickness). If the light transmittance is 85% or more, light can be extracted efficiently, and therefore, it can be suitably used in applications such as LED encapsulants that require high transparency.

  Examples of the method for measuring the light transmittance of the cured product obtained from the silicone composition of the present invention include a method using an ultraviolet-visible spectrophotometer and an ultraviolet-visible spectrophotometer with an integrating sphere.

  The cured product (1 mm thickness) obtained from the silicone-based composition of the present invention has a light transmittance at a wavelength of 450 nm of T1 (%), and the cured product is cured at 85 ° C. and 85% RH for 3 hours at a wavelength of 450 nm. It is preferable that T1−T2 ≦ 5 when the light transmittance is T2 (%).

  When T1-T2 is larger than 5, when the cured product obtained from the silicone-based composition of the present invention is used as an LED sealant, the luminance and luminous intensity of the LED gradually decrease when the LED is lit for a long time. There is a risk of

  The conditions for exposing the cured product obtained from the silicone-based composition of the present invention to high temperature and high humidity conditions are preferably 85 ° C. and 85% RH. By using this condition, it is possible to efficiently absorb moisture in the cured product in a short time. The curing time is preferably 3 hours. In less than 3 hours, sufficient moisture absorption may not be achieved. In addition, this condition reproduces the condition when the decrease in brightness and luminous intensity becomes a problem when the LED is turned on for a long time when the cured product obtained from the silicone composition of the present invention is used for the LED sealant. It is preferable because it is possible.

  Cured product obtained from silicone-based composition containing silane coupling agent having two alkoxy groups bonded directly to silicon atoms in one molecule, which is a cured product (E) component obtained from silicone-based composition of the present invention Is excellent because white turbidity does not occur even under high temperature and high humidity conditions when the component (F) is used.

  The cured product obtained from the silicone composition of the present invention can be used 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 cured product 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.

(High temperature and high humidity curing conditions)
The cured product for evaluation was cured for 3 hours with a thermo-hygrostat (manufactured by Espec Corp., PR-2KP) set to 85 ° C. and 85% RH.

(Light transmittance measurement)
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 450 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 (C-1) Obtained.

(Synthesis Example 2)
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 silicone particles (C-1) component obtained in Synthesis Example 1; Then, 0.45 part 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. (C-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.

  (C-3) component was formed by stirring this solution for 4.5 hours, keeping at 40 degreeC. This 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 (C) 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 (C) 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 at 2000 rpm for 5 minutes with a centrifuge. 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 resulting precipitate to obtain an ethyl acetate solution of component (C).

  With respect to 30 parts by weight of the resin solid content of the silicone polymer particles as the component (C) thus obtained, a vinyl group-containing polysiloxane having a three-dimensional structure as the component (A) (trade name MQV, manufactured by Clariant). -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-glycidoxypropylmethyldiethoxysilane as component (E), 1.0 part by weight of trimethyl borate as component (F), 1% xylene of 1-ethynyl-1-cyclohexanol 0.0011 part by weight of solution, 0.0010 part by weight of 1% xylene solution of N, N, N ′, N′-tetramethylethylenediamine, 0.0062 part of xylene solution of platinum vinylsiloxane complex (containing 3% by weight as platinum) After adding parts by weight, stirring and defoaming were performed with a planetary stirring and defoaming machine 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-glycidoxypropylmethyldimethoxysilane was used instead of 5.0 parts by weight of 3-glycidoxypropylmethyldiethoxysilane. 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.

(Comparative Example 1)
A method similar to the method described in Example 1, except that 5.0 parts by weight of 3-glycidoxypropyltrimethoxysilane was used instead of 5.0 parts by weight of 3-glycidoxypropylmethyldiethoxysilane. 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 (11)

(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) silicone polymer particles,
(D) a hydrosilylation catalyst,
(E) Silane coupling agent having two alkoxy groups directly bonded to silicon atoms in one molecule, and (F) Boron-based coupling agent, titanium-based coupling agent, aluminum-based coupling agent, and zirconium-based cup At least one selected from ring agents,
A silicone-based composition comprising:   (C) Silicone polymer particles are obtained by adding a first shell component (C-2) obtained by adding and condensing alkoxysilane to silicone particles (C-1), and then adding an alkoxysilane condensate. The silicone composition according to claim 1, which has a silicone particle core-alkoxysilane condensate shell structure comprising a second shell component (C-3) obtained by condensation. The second shell layer made of the alkoxysilane condensate as the component (C-3) has the following component (a) as an essential component, and is selected from the following component (b), the following component (c), and the following component (d). The silicone composition according to claim 2, wherein the silicone composition is obtained by condensing at least one kind.
(A) Component: General formula (1)

(Wherein R ¹² represents an alkyl group, and R ¹³ , R ¹⁴ and R ¹⁵ represent the same or different monovalent organic groups) and / or a partial condensation thereof. object.
(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. The first shell layer comprising the alkoxysilane condensate as component (C-2) is obtained by condensing at least one selected from the following components (b), (c) and (d). The silicone composition according to any one of claims 2 to 3, characterized in that
(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.   (C) The 1st shell layer which consists of the alkoxysilane condensate which is (C-2) component with respect to 40 to 98 weight% of silicone particles which are (C-1) component is 1 to 1 based on silicone polymer particles. 40% by weight of a polymer coated with 1 to 30% by weight of a second shell layer made of an alkoxysilane condensate as component (C-3) (however, (C-1) component and (C-2) component and ( The silicone-based composition according to any one of claims 2 to 4, which is 100% by weight in combination of C-3) components.   The component (E) is a silane coupling agent having at least one organic group selected from an epoxy group, a methacryl group, an acrylic group, and a vinyl group. 2. The silicone-based composition according to 1.   (F) A component is a boron coupling agent, The silicone type composition as described in any one of Claims 1-6 characterized by the above-mentioned.   Hardened | cured material formed by hardening | curing the silicone type composition as described in any one of Claims 1-7.   When the light transmittance at a wavelength of 450 nm of a cured product (thickness 1 mm) is T1 (%), and after curing the cured product at 85 ° C. and 85% RH for 3 hours, the light transmittance at a wavelength of 450 nm is T2 (%). The cured product according to claim 8, wherein T1-T2 ≦ 5 is satisfied.   LED which used the silicone type composition as described in any one of Claims 1-9 as sealing agent.   The method for producing a silicone-based composition according to any one of claims 1 to 7, wherein the component (C) is uniformly dispersed in the composition by a master batch method.