JP2011084592A - Curable composition containing rare earth metal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition with the excellent productivity with a quick-curing property, and the excellent heat resistance and transparency. <P>SOLUTION: The curable composition includes (A) an organopolysiloxane containing an alkenyl group, (B) an organohydrogen polysiloxane, (C) a silicone-based polymer particle, (D) a hydrosilylating catalyst, and (E) a rare earth metal. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a curable composition that is fast in curing, excellent in productivity, excellent in heat resistance and transparency.

Light emitting diodes (LEDs) are small and efficiently emit bright colors. Moreover, since it is a semiconductor element, there is no ball breakage. It has excellent drive characteristics and is strong against vibration and repeated ON / OFF lighting. Therefore, it is used as various indicators and various light sources. In general, an LED is bonded to a substrate with a resin paste such as an epoxy compound or a silicone compound. In recent years, with the expansion of the application field of LEDs, there has been a demand for LEDs that are more reliable and can emit light with high brightness over a long period of time. Since an LED capable of emitting light with high luminance generates a large amount of heat, the resin bonding the LED is required to have high heat resistance in addition to adhesiveness. Further, the light passing through the adhesive resin is reflected by a substrate made of a highly reflective material. Therefore, light is partially confined in the vicinity of the LED, and the light density in the vicinity of the LED becomes extremely high. Therefore, the resin bonding the LED is required to have high transparency in addition to adhesiveness and heat resistance. As such a material, for example, an epoxy-silicone resin is known (Patent Document 1). However, since the molding process requires heating at a high temperature for a long time, it is simpler in the manufacturing process of the product. Means are sought.

JP 2007-2233 A

  In view of the above circumstances, an object of the present invention is to provide a curable composition that is rapidly cured and excellent in productivity, and excellent in adhesion to a substrate, heat resistance, and transparency.

  In view of the above circumstances, as a result of intensive studies by the present inventors, it has been found that the above problem can be solved by using a resin composition containing a rare earth metal having the following features, and the present invention has been 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,
A curable composition comprising (D) a hydrosilylation catalyst and (E) a compound containing a rare earth metal.

2) The curable composition according to 1), wherein the component (A) is represented by the following structural formula.
General formula (1)
SiO _4/2 (1)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (2) and (3).
R ^a1 R ^a2 ₂ SiO _1/2 (2)
R ^a2 ₃ SiO _1/2 (3)
(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.)
At least two alkenyl groups in one molecule having a structure blocked with a monofunctional structural unit represented by the formula (II) and having at least two terminals of the main structure blocked with the general formula (2). One organopolysiloxane.

3) The curable composition according to 1) or 2), wherein the component (B) is represented by the following structural formula.
General formula (4)
SiO _4/2 (4)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (5) and (6).
R ^b1 R ^b2 ₂ SiO _1/2 (5)
R ^b2 ₃ SiO _1/2 (6)
(Wherein R ^b1 is a hydrogen atom, and R ^b2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
And having at least 2 hydrosilyl groups in one molecule having a structure blocked with a monofunctional structural unit represented by formula (1) and having at least two terminals of the main structure blocked with the general formula (5) One organohydrogenpolysiloxane.

  4) The curability according to any one of 1) to 3), wherein the component (C) is 1 to 50 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B). Composition.

  5) The component (C) is obtained by adding and condensing an alkoxysilane to the silicone particle (C-1) and then adding and condensing the alkoxysilane. The curable composition according to any one of 1) to 4), which is a silicone polymer particle having a silicone particle core-alkoxysilane condensate shell structure, comprising the second shell component (C-3). object.

6) A first shell layer comprising an alkoxysilane condensate as component (C-2) is obtained by condensing at least one component selected from component (b), component (c) and component (d). 5) The curable composition according to 5).
(B) Component: General formula (7)

(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 (8)

(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 (9)

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

7) The second shell layer comprising the alkoxysilane condensate as component (C-3) has (a) component as an essential component, and at least selected from (b) component, (c) component and (d) component The curable composition according to 5) or 6), which is obtained by condensing one or more kinds of components.
(A) Component: General formula (10)

(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 (7)

(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 (8)

(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 (9)

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

  8) The 1st shell layer which consists of the alkoxysilane condensate which is (C-2) component is 1 to 40 weight% with respect to 40 to 98 weight% of silicone particles which are (C-1) component, (C-3) ) A polymer coated with 1 to 30% by weight of a second shell layer comprising an alkoxysilane condensate as a component (however, the (C-1) component, the (C-2) component, and the (C-3) component are combined) 100% by weight), and the curable composition according to any one of 5) to 7).

  9) The component (E) is selected from oxides and hydroxides of rare earth metal oxides, hydroxides, basic carbonates, and Si-OM (M is a lanthanum rare earth metal) bond. The curable composition according to any one of 1) to 8), which is at least one compound.

  10) A cured product obtained by curing the curable composition according to any one of 1) to 9).

  11) The method for curing a composition according to any one of 1) to 9), wherein the composition is irradiated with radiation.

  The composition containing the rare earth metal of the present invention is easily cured and becomes a cured product excellent in adhesiveness, heat resistance and transparency. In addition, the composition is more easily cured by irradiation with radiation. Therefore, it is useful for bonding various substrates, for example. In addition, since the curing speed is high, for example, effects such as improvement in productivity, energy saving, omission of heat history and the like in the manufacture of products using the composition can be obtained.

The details of the invention will be described.

<(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.

Further, examples of the component (A) having a three-dimensional crosslinked structure are not particularly limited, but the general formula (1)
SiO _4/2 (1)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (2) and (3).
R ^a1 R ^a2 ₂ SiO _1/2 (2)
R ^a2 ₃ SiO _1/2 (3)
(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.)
A polymer having a structure blocked with a monofunctional structural unit represented by the formula (II) and having at least two ends blocked with the general formula (2) is exemplified as a preferred example.
When the tetrafunctional structural unit represented by the general formula (1) is used for the main structure, it is preferable because a main skeleton having a high crosslink density can be obtained, and the strength and hardness of the cured product can be increased.

It has a structure in which the ends of the main structure are blocked with monofunctional structural units represented by the general formulas (2) and (3), and at least two ends of the structure are blocked with the general formula (2) The resulting polymer is advantageous in that an alkenyl group that becomes a crosslinking point of the composition by a hydrosilylation reaction can be introduced by a simple method. Moreover, the amount of the alkenyl group in the component (A) can be adjusted by adjusting the ratio of the alkenyl group of R ^{a1 to} the substituted or unsubstituted monovalent hydrocarbon group other than the alkenyl group of R ^a2. Therefore, any crosslink density is preferable because it can be obtained by a simple method.

  In addition, when the main structure of the component (B) described later is a tetrafunctional structural unit, and the polymer is a polymer in which the end of the main structure is blocked with a monofunctional structural unit, the component (A) and the component (B) It is preferable because a cured product having good compatibility with the components, high transparency, and high hardness can be obtained.

  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. Identical or selected from aryl groups and chloromethyl groups, trifluoropropyl groups, cyanoethyl groups, etc. in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. Non-substituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, which are different from each other can be exemplified. Among these, a methyl group is more preferable from the viewpoint of heat resistance and light resistance.

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

  Furthermore, the component (A) is preferably liquid at room temperature because of easy handling, and the 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.

Moreover, as an example of (B) component which has a three-dimensional crosslinked structure, although it does not specifically limit, General formula (4)
SiO _4/2 (4)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (5) and (6).
R ^b1 R ^b2 ₂ SiO _1/2 (5)
R ^b2 ₃ SiO _1/2 (6)
(Wherein R ^b1 is a hydrogen atom, and R ^b2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
And those having a structure in which at least two terminals of the main structure are blocked by the general formula (5) are exemplified.
When the tetrafunctional structural unit represented by the general formula (4) is used for the main structure, a main skeleton having a high crosslink density can be obtained, so that the strength and hardness of the cured product can be increased.

It has a structure in which the ends of the main structure are blocked with monofunctional structural units represented by the general formulas (5) and (6), and at least two ends of the structure are blocked with the general formula (5) The polymer thus obtained is advantageous in that a hydrogen atom group that becomes a crosslinking point of the composition by the hydrosilylation reaction can be introduced by a simple method. It is also possible to adjust the amount of hydrosilyl group in component (B) by adjusting the ratio of the hydrogen atom group of R ^{b1 to} the substituted or unsubstituted monovalent hydrocarbon group other than the alkenyl group of R ^b2. Therefore, an arbitrary crosslink density is preferable because it can be obtained by a simple method.

  Further, when the main structure of the component (A) is a tetrafunctional structural unit and the end of the main structure is a polymer blocked with a monofunctional structural unit, the component (A) and the component (B) It is preferable because a cured product having good compatibility with the components, high transparency, and high hardness can be obtained.

  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. Identical or selected from aryl groups and chloromethyl groups, trifluoropropyl groups, cyanoethyl groups, etc. in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. Non-substituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, which are different from each other can be exemplified. Among these, a methyl group is more preferable from the viewpoint of heat resistance and light resistance.

  The amount of the organohydrogenpolysiloxane added is 0.3 to 5 mol, preferably 0.4 to 2 mol of the hydrosilyl group of the component (B) with respect to 1 mol of the alkenyl group of the component (A). A ratio is desirable. When the amount of the hydrosilyl group of the component (B) is small, the cured product cannot obtain sufficient hardness, and when the amount of the hydrosilyl group of the component (B) is large, the shrinkage of curing may be increased.

  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>
The component (C) in the present invention can provide improved heat resistance, crack resistance and mechanical stress relaxation ability of the silicone-based cured product while maintaining high hardness and transparency, which are characteristics of the matrix resin. it can.

  About the compounding quantity of (C) component, when the total weight of (A) and (B) component is 100 weight part, it is preferable that (C) component is 50-1 weight part, 45-3 weight part It is more preferable that When there are many (C) components, it may thicken at the time of mixing | blending or transparency of hardened | cured material may fall. Moreover, when there are few (C) components, heat resistance and crack resistance may become inadequate.

  The component (C) in the present invention is not particularly limited as long as it is a silicone polymer particle. In particular, the component (C) comprises a shell obtained by condensing an alkoxysilane condensate with the silicone particle as a core. A silicone polymer particle can be illustrated as a suitable thing.

  The core-shell structure in the present invention can be obtained, for example, by reacting a monomer component having a composition or component different from the monomer component forming the core in the presence of 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.

  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 the component is a polymer coated with 2 to 28% by weight (provided that the component (C-1), the component (C-2), and the component (C- 3) 100% by weight of the ingredients).

  When the component (C-1) is small, the flexibility of the particles is impaired, so the heat resistance and crack resistance of the matrix resin containing the component (C) may be reduced, and the component (C-2) is small. In this case, the component (C) cannot maintain the original particle shape, and the component (C) flows out into the matrix, leading to a decrease in physical properties such as reducing the strength of the matrix resin containing the component (C). is there. Moreover, when there are few (C-3) components, the silanol group of the (C) component surface cannot fully be reduced, for example, compatibility with matrix resin becomes inadequate, or the viscosity of a compounding composition is high. Or may thicken over time.

The component (C-1) may be silicone particles, but the general formula (11)
R ^a _m SiO _{(4-m) / 2} (11)
(Wherein, R ^a is a substituted or unsubstituted monovalent hydrocarbon group, which may be the same or different, and m represents an integer of 0 to 3). It is preferable to consist of organosiloxane having

  In the component (C-1), the structural unit of m = 2 in the general formula (11) preferably accounts for 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 heat resistance and crack resistance after curing of the matrix resin containing the component (C) may be lowered.

  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, 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. 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.

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

  The volume average particle size of the 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. . When the volume average particle size is small, it is difficult to obtain stably, and when the volume average particle size is large, the transparency of the cured product may be deteriorated. 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, so that the heat resistance and crack resistance when the component (C) is blended with the matrix resin may be lowered. 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, vinylmethyldimethoxysilane, tetravinyltetramethylcyclosiloxane, allylmethyldimethoxysilane, mercaptopropylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane and the like.

  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 in heat resistance and crack resistance of a cured product obtained from a matrix resin containing the component (C).

The alkoxysilane used for the component (C-2) of the present invention is a bifunctional alkoxysilane compound (b) represented by the following general formula (7), represented by the general formula (8) (c ) Component trifunctional alkoxysilane compound, general formula (9) (d) component tetrafunctional alkoxysilane compound, and partial condensates thereof (partial condensates obtained by condensing alkoxy groups) Etc. can be used, and the component (C-2) can be obtained by hydrolyzing and condensing them. These alkoxysilanes can be used alone or in combination of two or more.
(B) Component: General formula (7)

(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 (8)

(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 (9)

(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 (7) to (9) 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 include hydrocarbon groups such as 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 silanol groups on the particle surface, such as a problem that the compatibility and affinity between the component (C) and the matrix decrease, and the viscosity of the compound when blended with silicone rubber or silicone resin are reduced. It is possible to solve the problem of becoming too high and the problem of the viscosity gradually increasing as the composition changes with time.

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

  The component (C-3) of the present invention uses a condensate of alkoxysilane, and as the alkoxysilane, monofunctional alkoxysilane compounds which are the component (a) represented by the following general formula (10) 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 (10), 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 formula (10) include methoxy, ethoxy, normal propoxy, isopropoxy, normal butoxy, isobutoxy, secondary butoxy, tertiary butoxy, pentyloxy, hexyloxy and the like. 1 to 6 alkoxy groups.
Examples of the monovalent organic group include hydrocarbon groups such as an alkyl group, an alkenyl group, an allyl group, and an aralkyl group.

  Furthermore, it is preferable that (C-3) component contains at least 1 or more types chosen from said (b) component, said (c) component, and said (d) component. By combining (a) component with at least one or more selected from (b) component, (c) component and (d) component, (a) component can be efficiently incorporated into (C-3) component. It becomes possible.

  Here, if a component containing an alkenyl group is used in at least one of the components (a) to (d), an alkenyl group can be introduced into the component (C). A composition in which the component (C) having an alkenyl group introduced is mixed with a matrix resin that is cured by a hydrosilylation reaction is obtained from the composition because a bond is formed between the component (C) and the matrix resin. Since the intensity | strength of hardened | cured material can be improved, it is preferable.

  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.

  It is preferable to use the masterbatch method because the component (C) obtained in the present invention can be uniformly dispersed in the matrix resin and a transparent cured product can be obtained.

  Masterbatch methods include water-soluble or partially soluble organic solvents such as alcohols (methanol, ethanol, 2-propanol, etc.), ketones (methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), acetic acid. By adding esters (ethyl acetate, butyl acetate, methyl acetate), etc., the particles can be slowly aggregated, and then the aggregate can be recovered by centrifugal sedimentation or filtration. An example is a method of redispersing in a suitable solvent, mixing with a matrix resin, and distilling off the solvent.

<(D) Hydrosilylation catalyst>
There is no restriction | limiting in particular as a hydrosilylation catalyst which is (D) component in this invention, For example, arbitrary things can be used, For example, a platinum-type catalyst, a palladium-type catalyst, and a rhodium-type catalyst can be used. 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) Compound containing rare earth metal>
(E) A component is a component for improving the sclerosis | hardenability of the curable composition of this invention. The component (E) in the present invention includes oxides such as lanthanum, cerium, neodymium, and samarium, hydroxides, basic carbonates, and silicon represented by Si—OM (where M is a lanthanum rare earth metal). Any oxide or hydroxide that has a bond between a metal and a rare earth metal may be used. The rare earth metal compound containing silicon is, for example, a silane represented by the general formula R _d SiX _(4-d) (R is a monovalent hydrocarbon group, X is a hydrolyzable group, d = 0 to 3). Alternatively, it may be obtained by cohydrolyzing the partially hydrolyzed product and the rare earth metal compound.
In the present invention, the amount of component (E) added is 0.01 to 20 parts by weight, preferably 0.1 to 100 parts by weight of component (A), component (B) and component (C). 10 parts by weight. If the amount added is too small, the effect of curing acceleration is insufficient, and if the amount added is too large, the transparency of the cured composition may be impaired.

<Curable composition>
The curable composition containing the rare earth metal of the present invention is easily cured and becomes a cured product excellent in adhesiveness, heat resistance and transparency. In addition, it hardens more easily when irradiated with radiation. Therefore, it is useful for bonding various substrates. In addition, since the curing speed is high, effects such as improvement in productivity, energy saving, and omission of heat history can be obtained. Examples of the radiation source include ultraviolet rays and electron beams. The intensity of radiation and the irradiation time are arbitrarily set according to the application and production process. When curing is insufficient only by irradiation, curing may be further advanced by subsequent annealing. Although it sets arbitrarily as annealing temperature, the temperature range of 25-300 degreeC is preferable, 30-280 degreeC is more preferable, and 35-260 degreeC is further more preferable. When the reaction temperature is lower than 25 ° C., the time required for sufficient curing tends to be long, and when the reaction temperature is higher than 300 ° C., the product tends to be thermally deteriorated. The annealing may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as necessary. The pressure at the time of curing can be variously set according to need, and can be cured at normal pressure, high pressure or reduced pressure.
In the curable composition of the present invention, an adhesion imparting agent can be added in order to improve the adhesion to the substrate.

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

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

  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 trinormal butyl borate, tri-s-butyl borate, tri-t-butyl borate, triisopropyl borate, trinormal propyl borate, triallyl borate, and boron methoxyethoxide.

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

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

  The adhesiveness imparting agent in the present invention may be used alone or in combination of two or more. The addition amount is preferably 0.05 to 30% by weight of the total weight of the component (A), the component (B) and the component (C). In addition, depending on the type or addition amount of the adhesion-imparting agent, there is a risk of inhibiting the curing of the composition, so the influence must be taken into consideration.

  A curing retarder can be used for the purpose of improving the storage stability of the curable composition of the present invention or adjusting 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, relative to 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.
Moreover, you may add fillers, such as a grinding | pulverization quartz, a calcium carbonate, carbon, as an extender as needed in the range which does not prevent the effect of this invention to the curable composition of this invention.

  Further, the curable 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 necessary, as long as the effects of the present invention are not hindered. A dispersant or the like can be optionally added.

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

  The curable 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 curable 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.

  Color PDP (plasma display) sealant, antireflection film, optical correction film, housing material, front glass protective film, front glass substitute material, adhesive, and substrate material for plasma addressed liquid crystal (PALC) display, Light guide plate, prism sheet, deflector plate, retardation plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film for organic EL (electroluminescence) display, front glass substitute material, adhesive, Examples include various film substrates, front glass protective films, front glass substitute materials, and adhesives in field emission displays (FEDs).

  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, 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.

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.

(Heat resistance test)
As a heat resistance test, the obtained cured product was annealed in air at 160 ° C. for 24 hours, and the properties of the cured product were visually observed. The case where there was no change in the properties of the cured product was rated as ◯, and the case where the color changed was marked as x.

(Synthesis Example 1)
After mixing 400 parts by weight of pure water and 12 parts by weight of 10% by weight sodium dodecylbenzenesulfonate aqueous solution (solid content) in a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, additional monomer 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 parts by weight of sodium formaldehyde sulfoxylate (SFS), 0.019 parts by weight of disodium ethylenediaminetetraacetate (EDTA) and 0.019 parts 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 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 10 minutes, and 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), 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; In addition, 0.45 parts by weight (solid content) of 10% by weight aqueous solution of dodecylbenzenesulfonic acid was charged, and the temperature was raised to 40 ° C. in a nitrogen atmosphere.

Separately, 40 parts by weight of pure water, 0.1 part by weight (solid content) of 15% by weight aqueous solution of sodium dodecylbenzenesulfonate, 7.30 parts by weight of dimethoxydimethylsilane ((CH ₃ ) ₂ SiO _2/2 Equivalent to 4.5 parts by weight in terms of a complete condensate of the structural unit represented by the following formula: ethyl silicate condensate (manufactured by Tama Chemical Industries, trade name: ethyl silicate 40, SiO ₂ content: 39.0 to 42) 0.0 wt%) 11.16 parts by weight (corresponding to 4.5 parts by weight in terms of the complete condensate of the structural unit represented by SiO ₂ ) was forcibly emulsified with a homomixer at 5000 rpm for 5 minutes. Later, it was added dropwise over 20 minutes. (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 sodium dodecylbenzenesulfonate in a 15% by weight aqueous solution and 6.42 parts by weight of methoxytrimethylsilane ((CH ₃ ) ₃ SiO _{1 / 2} equivalent to 5.0 parts by weight in terms of the complete condensate of the structural unit represented by ₂ ), 1.40 parts by weight of ethoxydimethylvinylsilane (Vi (CH ₃ ) ₂ SiO _1/2 Equivalent to 1.0 part by weight in terms of a complete condensate), 0.81 part by weight of dimethoxydimethylsilane (corresponding to 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.

(Synthesis Example 3)
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. Washing with a mixed solvent of ethyl acetate / methanol = 4/6 (vol / vol) was further performed twice (total 3 times), and 350 parts by weight of ethyl acetate was added to 35 parts by weight of the obtained precipitate. An ethyl acetate solution of component C) was obtained.

(Synthesis Example 4)
To the ethyl acetate solution of the component (C) obtained in Synthesis Example 3, a vinyl group-containing polysiloxane having a three-dimensional structure as the component (A) (manufactured by Clariant, trade name MQV-7, vinyl group content 3. 36.2 parts by weight of 5 mol / kg), hydrosilyl group-containing polysiloxane having a three-dimensional structure as component (B) (manufactured by Clariant, trade name MQH-5, hydrosilyl group content 2.3 mol / kg) And 57.9 parts by weight of hydrosilyl group-containing polysiloxane having the same three-dimensional structure as component (B) (manufactured by Clariant, trade name MQH-8, hydrosilyl group content of 7.5 mol / kg). 9 parts by weight was dissolved, and the mixture was concentrated with a rotary evaporator to distill off ethyl acetate to obtain a composition comprising the component (A), the component (B) and the component (C).

Example 1
3 parts by weight of cerium oxide (manufactured by Wako Pure Chemical Industries, Ltd.) as component (E) with respect to 100 parts by weight of the composition comprising component (A), component (B) and component (C) obtained in Synthesis Example 4 , 5.0 parts by weight of 3-glycidoxypropyltrimethoxysilane, 1.0 parts by weight of trimethyl borate, 0.0011 parts by weight of 1% xylene solution of 1-ethynyl-1-cyclohexanol, N, N, N ′, After adding 0.0010 parts by weight of a 1% xylene solution of N′-tetramethylethylenediamine and 0.0062 parts by weight of a xylene solution of platinum vinylsiloxane complex (containing 3% by weight of platinum) as component (D) in this order. Then, stirring and defoaming were performed with a planetary stirring deaerator to obtain a liquid composition. The obtained composition was stretched onto a polyimide film with a 150 μm thick applicator, brought into contact with a 2 mm square glass die, and the liquid composition was adhered to one side of the die. Placed on glass epoxy and polyphthalamide flat plates respectively. When this sample was irradiated for 30 seconds by a radiation irradiation apparatus (made by Eye Graphics, irradiation distance 80 mm, using a 3000 W metal halide lamp), it was observed that the die was fixed and the curing proceeded.

  Further, the liquid composition was filled into a mold so as to have a thickness of 1 mm, and irradiated with a radiation irradiation apparatus for 30 seconds. Using the obtained cured product, the above heat resistance test was performed.

(Comparative Example 1)
In the above Examples, a liquid composition was prepared in the same manner without adding the component (E). In the same manner as in the examples, this liquid composition was attached to one side of a glass die and then placed on a glass epoxy plate and a polyphthalamide plate. This sample was irradiated for 30 seconds by a radiation irradiation apparatus, but the die flowed easily.
Further, the liquid composition was filled in a mold so as to have a thickness of 1 mm, and irradiated with a radiation irradiation apparatus for 30 seconds, but a cured product was not obtained.
The test 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,
A curable composition comprising (D) a hydrosilylation catalyst and (E) a compound containing a rare earth metal. (A) A component is represented by the following structural formula, The curable composition of Claim 1 characterized by the above-mentioned.
General formula (1)
SiO _4/2 (1)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (2) and (3).
R ^a1 R ^a2 ₂ SiO _1/2 (2)
R ^a2 ₃ SiO _1/2 (3)
(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.)
At least two alkenyl groups in one molecule having a structure blocked with a monofunctional structural unit represented by the formula (II) and having at least two terminals of the main structure blocked with the general formula (2). One organopolysiloxane. The (B) component is represented by the following structural formula, The curable composition of Claim 1 or 2 characterized by the above-mentioned.
General formula (4)
SiO _4/2 (4)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (5) and (6).
R ^b1 R ^b2 ₂ SiO _1/2 (5)
R ^b2 ₃ SiO _1/2 (6)
(Wherein R ^b1 is a hydrogen atom, and R ^b2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
And having at least 2 hydrosilyl groups in one molecule having a structure blocked with a monofunctional structural unit represented by formula (1) and having at least two terminals of the main structure blocked with the general formula (5) One organohydrogenpolysiloxane. The curability according to any one of claims 1 to 3, wherein the component (C) is 1 to 50 parts by weight with respect to 100 parts by weight of the total of the component (A) and the component (B). Composition. Component (C) is a first shell component (C-2) obtained by adding and condensing alkoxysilane to silicone particles (C-1), and then a second shell obtained by adding and condensing alkoxysilane. It is a silicone type polymer particle which has a silicone particle core-alkoxysilane condensate shell structure which consists of a shell component (C-3), The curable composition as described in any one of Claims 1-4 characterized by the above-mentioned. object. The first shell layer comprising the alkoxysilane condensate as component (C-2) is obtained by condensing at least one component selected from component (b), component (c) and component (d). The curable composition according to claim 5.
(B) Component: General formula (7)

(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 (8)

(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 (9)

(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 second shell layer comprising the alkoxysilane condensate as component (C-3) has component (a) as an essential component, and at least one selected from component (b), component (c) and component (d) The curable composition according to claim 5, which is obtained by condensing the above components.
(A) Component: General formula (10)

(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 (7)

(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 (8)

(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 (9)

(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 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) %)), The curable composition according to any one of claims 5 to 7. (E) The component is at least selected from oxides, hydroxides, rare earth metal oxides, hydroxides, basic carbonates, oxides having Si-OM (M is a lanthanum rare earth metal) bond It is 1 type of compounds, The curable composition as described in any one of Claims 1-8 characterized by the above-mentioned. Hardened | cured material obtained by hardening the curable composition as described in any one of Claims 1-9. The method for curing a composition according to any one of claims 1 to 9, wherein the composition is irradiated with radiation.