JP2015010131A - Curable resin composition and cured product obtained by curing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition high in heat resistance and lightfastness and excellent in thixotropy and handling ability.SOLUTION: Since a polysiloxane composition consisting of a polysiloxane based compound, an inorganic filler, a polyfunctional acrylate and/or a polyfunctional methacrylate, and a hydrosilylation catalyst can control viscosity and thixotropy, handling ability when sealing an optical semiconductor element is excellent and a molding high in heat resistance, lightfastness and transparency is obtained after curing.

Description

  The present invention relates to a curable resin composition having high heat resistance and light resistance, excellent thixotropy, and good handling properties.

  Polysiloxane composition is excellent in heat resistance, cold resistance, weather resistance, light resistance, chemical stability, electrical properties, flame resistance, water resistance, transparency, colorability, non-adhesiveness, non-corrosion It is used in various industries. For example, in optical semiconductor element sealant applications, many attempts have been made to use polysiloxane compositions in place of conventional materials having oxetanyl groups and epoxy groups as the output of the elements increases. When using a polysiloxane compound in an optical semiconductor element sealant application, it is necessary to control the viscosity and thixotropy of the polysiloxane compound in order to obtain good handling properties and molding processability. For example, when an optical semiconductor element on a support substrate is directly molded and cured using a dispenser, there is a problem that a resin flows and a molded / cured product having a desired shape cannot be obtained. Thus, it is known that if an inorganic filler is added to the polysiloxane compound, the viscosity and thixotropy are improved. However, white turbidity occurs, and it takes time to mix a large amount of filler, which is not practical.

In the optical semiconductor element sealant application, in order to obtain white light, a sealant containing a yellow phosphor with respect to a blue light emitting element is used, or in order to further enhance color rendering, A means such as using a sealant containing a green phosphor and a red phosphor for a blue light emitting element is used, but when the sealant has a low viscosity, There was a problem that the phosphors settled and the emission colors varied. For example, Patent Document 1 discloses a composition using a polysiloxane modified body having a polyhedral structure, and this material is excellent in molding processability, transparency, heat resistance / light resistance, and adhesiveness. There was still room for further improvement in the handleability of the composition.
As described above, it has been desired to develop a material having high heat resistance and light resistance and good handling properties when sealing an optical semiconductor element.

WO08 / 010545

  Provided is a curable resin composition having high heat resistance and light resistance, excellent thixotropy, and good handling properties.

As a result of intensive studies to solve the above problems, the present inventors have
1). A curable resin composition comprising (A) a polysiloxane composition, (B) an inorganic filler, (C) a polyfunctional acrylate and / or a polyfunctional methacrylate, and (D) a hydrosilylation catalyst.

  2). The curable resin composition according to 1), wherein the polysiloxane composition (A) is phenyl silicone.

  3). The curable resin composition according to 1), wherein the polysiloxane composition (A) is methyl silicone.

4). The curable resin composition according to 1), wherein the polysiloxane composition (A) is composed of the following (A-1) and (A-2).
(A-1) a modified polyhedral polysiloxane containing an alkenyl group and / or a hydrosilyl group,
(A-2) A curing agent having two or more hydrosilyl groups and / or alkenyl groups capable of hydrosilylation with the component (A-1).

  5). (A-1) a polyhedral polysiloxane compound (a) having an alkenyl group as component (a), a compound (b) having a hydrosilyl group, an organosilicon compound (c) having one alkenyl group in one molecule, and 4) The curable resin composition according to 4), which is an organically modified polyhedral polysiloxane modified product (A-1) ′ obtained by hydrosilylation reaction with a cyclic olefin compound (d). object.

  6). (A) The curable resin composition according to any one of 1) to 5), wherein the component is liquid at a temperature of 20 ° C.

  7). The curable resin composition according to any one of 1) to 6), wherein the inorganic filler (B) is a metal oxide.

  8). The curable resin composition according to any one of 1) to 7), wherein the inorganic filler (B) is silica.

  9). Any one of 1) to 8), wherein the polyfunctional acrylate and / or polyfunctional methacrylate (C) is a polyfunctional octasilsesquioxane containing an acryl group and / or a methacryl group at the terminal. The curable resin composition described in 1.

  10). The curable resin composition according to any one of 1) to 9), which comprises a photo radical initiator and / or a thermal radical initiator.

  11). The curable resin composition according to any one of 1) to 10), further comprising a curing retardant.

  12). The curable resin composition according to any one of 1) to 11), comprising an adhesiveness-imparting agent.

  13). The curable resin composition according to any one of 1) to 12), comprising a phosphor.

  14). A cured product obtained from the curable resin composition according to any one of 1) to 13).

A curable resin composition having high heat resistance and light resistance, excellent thixotropy, and good handling properties can be provided.

Hereinafter, the present invention will be described in detail.

<Polysiloxane composition (A)>
The polysiloxane composition (A) in the present invention is not particularly limited as long as it is a resin that can be cured by a hydrosilylation reaction using a hydrosilylation catalyst described later. Examples of such a polysiloxane composition (A) include a composition containing a compound having an alkenyl group and a compound having a hydrosilyl group, and the structure thereof is linear, branched, cyclic, or three-dimensionally crosslinked. As long as it has a polyhedral structure, any of them may be used.

  Examples of the alkenyl group-containing compound having a linear structure include polydimethylsiloxane blocked with a dimethylvinylsilyl group, polymethylphenylsiloxane blocked with a dimethylvinylsilyl group, and dimethylvinylsilyl group. End-capped polydiphenylsiloxane, copolymer of dimethylsiloxane unit, methylvinylsiloxane unit and terminal trimethylsiloxy unit, copolymer of methylphenylsiloxane unit, methylvinylsiloxane unit and terminal trimethylsiloxy unit, diphenylsiloxane And a copolymer of the unit with a methylvinylsiloxane unit and a terminal trimethylsiloxy unit.

  Examples of the hydrosilyl group-containing compound having a linear structure include, for example, polydimethylsiloxane blocked with a dimethylhydrogensilyl group, polymethylphenylsiloxane blocked with a dimethylhydrogensilyl group, and dimethylhydrogen. Polydiphenylsiloxanes end-capped with silyl groups, copolymers of dimethylsiloxane units with methylhydrogensiloxane units and terminal trimethylsiloxy units, copolymers of methylphenylsiloxane units with methylhydrogensiloxane units and terminal trimethylsiloxy units And a polymer, a copolymer of a diphenylsiloxane unit, a methylhydrogensiloxane unit, and a terminal trimethylsiloxy unit.

  Examples of the alkenyl group-containing compound having a branched structure include, for example, a copolymer of dimethylsiloxane units and methylsiloxane units blocked at the ends with dimethylvinylsilyl groups, and methylphenyl blocked at the ends with dimethylvinylsilyl groups. Copolymers of siloxane units and methylsiloxane units, copolymers of diphenylsiloxane units and methylsiloxane units capped with dimethylvinylsilyl groups, dimethylsiloxane units, methylsiloxane units, methylvinylsiloxane units, and terminal trimethylsiloxy units Copolymer, methylphenylsiloxane unit, methylsiloxane unit, methylvinylsiloxane unit and terminal trimethylsiloxy unit, diphenylsiloxane unit, methylsiloxane unit and methylvinyl And a copolymer of siloxane units and end trimethylsiloxy units and the like.

 Examples of the hydrosilyl group-containing compound having a branched structure include, for example, a copolymer of dimethylsiloxane units and methylsiloxane units blocked at the ends with dimethylhydrogensilyl groups, and ends blocked at the dimethylhydrogensilyl groups. Copolymers of methylphenylsiloxane units and methylsiloxane units, copolymers of diphenylsiloxane units and methylsiloxane units end-capped with dimethylhydrogensilyl groups, dimethylsiloxane units, methylsiloxane units and methylhydrogensiloxane units, and Copolymer of terminal trimethylsiloxy unit, copolymer of methylphenylsiloxane unit, methylsiloxane unit, methylhydrogensiloxane unit and terminal trimethylsiloxy unit, diphenylsiloxy And copolymers of emission units and methylsiloxane units and methylhydrogensiloxane units and terminal trimethylsiloxy units and the like.

  Examples of the alkenyl group-containing compound having a cyclic structure include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetravinyl- 1,3-dimethyl-5,7-diphenylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7 -Dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-phenyl-3,5,7-trivinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3 , 7-diphenyl-1,3,5,7-tetramethylcyclotetrasiloxane, and the like.

  Examples of the hydrosilyl group-containing compound having a cyclic structure include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrahydrogen. -1,3-dimethyl-5,7-diphenylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydro Gen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-phenyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, Examples include 1,5-dihydrogen-3,7-diphenyl-1,3,5,7-tetramethylcyclotetrasiloxane.

An example of the component (A) having a three-dimensional crosslinked structure is 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 ¹ R ² ₂ SiO _1/2 (2)
R ² ₃ SiO _1/2 (3)
(In the formula, R ¹ is an alkenyl group or a hydrogen atom, R ² is a substituted or unsubstituted monovalent hydrocarbon group other than the alkenyl group and the hydrogen atom, and 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 (2) are exemplified.

  Examples of substituted or unsubstituted monovalent hydrocarbon groups other than alkenyl groups and hydrogen atoms include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, phenyl groups, and tolyl groups. An aryl group such as a group, or the same selected from a chloromethyl group, a trifluoropropyl group, a cyanoethyl group, etc. in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group, etc. Alternatively, a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, which is different or unsubstituted, can be exemplified.

  Phenylsilicone has at least one of the above-mentioned linear, branched, cyclic, or three-dimensional cross-linked structures, and the siloxane unit means a polysiloxane compound that always contains a phenylsiloxane unit. For example, methyl Examples thereof include phenylsiloxane and diphenylsiloxane.

  In addition, methylsilicone is a polysiloxane compound having at least one of the above-mentioned linear, branched, cyclic or three-dimensional cross-linked structure, having no phenylsiloxane unit, and having a dimethylsiloxane unit as a main component. means. Specific examples of phenyl silicone include OE-6630 manufactured by Toray Dow Corning, and specific examples of methyl silicone include JCR-6140 manufactured by Toray Dow Corning.

Examples of the component (A) having a polyhedral structure are not particularly limited, but specifically, for example, the following formula [R ⁸ SiO _3/2 ] _x [R ⁹ SiO _3/2 ] _y
(X + y is an integer of 6 to 24; x is an integer of 1 or more, y is 0 or an integer of 1 or more; R ⁸ is an alkenyl group or a hydrosilyl group, or an alkenyl group or a group having hydrosilyl; R ⁹ is any Organic groups or groups linked to other polyhedral skeleton polysiloxanes)
A polyhedral polysiloxane compound containing an alkenyl group composed of a siloxane unit represented by the formula:
Furthermore, the formula
[AR ⁴ ₂ SiO—SiO _3/2 ] _a [R ⁵ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group or hydrosilyl group; R ⁴ is an alkyl group or an aryl group; R ⁵ is a hydrogen atom , Alkyl groups, aryl groups, or groups linked to other polyhedral skeleton polysiloxanes)
A polyhedral polysiloxane compound composed of a siloxane unit represented by

  Such a polysiloxane composition (A) includes, from the viewpoint of handleability, a modified polyhedral polysiloxane (A-1) containing the above phenylsilicone, methylsilicone, alkenyl group and / or hydrosilyl group, and a hydrosilyl group. A preferred example is a polysiloxane composition comprising a curing agent (A-2) having two or more alkenyl groups.

  From the viewpoints of heat resistance, light resistance and gas barrier properties, a modified polyhedral polysiloxane (A-1) containing an alkenyl group and / or hydrosilyl group, and a curing agent having two or more hydrosilyl groups / and alkenyl groups (A -2) is a more preferred example.

  Hereinafter, (A-1) and (A-2) will be described in detail.

<Modified polyhedral polysiloxane (A-1) containing alkenyl group and / or hydrosilyl group>
The modified polyhedral polysiloxane (A-1) containing an alkenyl group and / or hydrosilyl group in the present invention is a polyhedral polysiloxane compound containing an alkenyl group and / or a hydrosilyl group in the molecular skeleton. Although not particularly limited, specifically, for example, a polyhedral polysiloxane compound containing an alkenyl group and / or a hydrosilyl group has a hydrosilyl group and / or an alkenyl group that can be hydrosilylated with the polysiloxane compound. It can be obtained by modifying the compound. The modified polyhedral polysiloxane obtained in the present invention is preferably in a liquid state at a temperature of 20 ° C. from the viewpoints of handling properties and moldability.

The preferred polyhedral polysiloxane modified body (A-1) in the present invention will be specifically described. A preferred modified polyhedral polysiloxane in the present invention is characterized in that [XR ³ ₂ SiO—SiO _3/2 ] is an essential unit as a siloxane unit having a functional group capable of reaction, and if necessary, An arbitrary siloxane unit [R ⁴ ₃ SiO—SiO _3/2 ] as a physical property adjusting unit is contained as a structural unit, and the following formula:
[XR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; X is a group represented by the general formula (4) or (5); R ³ is an alkyl group or aryl R ⁴ is an alkyl group, an aryl group, an alkenyl group, a hydrogen atom, or a group connected to another polyhedral polysiloxane), and a modified polyhedral polysiloxane having a siloxane unit represented by: Is exemplified. Here, a is an average of 1 or more, preferably 2 or more, and b is 0 or an integer of 1 or more. a + b is an integer of 6 to 24, preferably an integer of 6 to 12.

(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain Yes, it may be the same or different, provided that at least one of Y or Z is an alkenyl group or a hydrogen atom; R is an alkyl group or an aryl group; 4) or the structure of formula (5) may be different, or the structure of formula (4) or formula (5) may be mixed)
Hereinafter, a siloxane unit having a reactive functional group
[XR ³ ₂ SiO—SiO _3/2 ]
Will be described in detail.

  The siloxane unit having a functional group capable of reacting, for example, causes a crosslinking reaction with a curing agent by a hydrosilylation reaction in the presence of a hydrosilylation catalyst described later, or in the presence of a thermal curing initiator or a photocuring initiator. It is a unit that plays a role of crosslinking and curing.

  The modified polyhedral polysiloxane containing an alkenyl group in (A-1) of the present invention has a structure of formula (4) or formula (5) as the group X having a reactive functional group, and at least Although it will not specifically limit if it is a modified body containing one alkenyl group, it is preferable that m is an integer of 1-7, and it is preferable that n is an integer of 2-4.

Moreover, the polyhedral polysiloxane modified body containing a hydrosilyl group in (A-1) of the present invention has a structure of formula (4) or formula (5) as the group X having a reactive functional group. As long as it is a modified product containing at least one hydrosilyl group, m is preferably an integer of 1 to 7, and n is preferably an integer of 2 to 4.
In addition, the modified polyhedral polysiloxane containing an alkenyl group and a hydrosilyl group in (A-1) of the present invention refers to the structure of formula (4) or formula (5) as the group X having a reactive functional group. There is no particular limitation as long as it is a modified product containing at least one alkenyl group and one hydrosilyl group, m is preferably an integer of 1 to 7, and n is an integer of 2 to 4. Is preferred.

As R ³ in the siloxane unit having a reactive functional group, a substituent having substantially no reactivity, specifically, for example, an alkyl group or an aryl group can be used.

  The siloxane unit having a functional group capable of reacting in the present invention preferably contains, on average, two or more siloxane units constituting the polyhedral skeleton. That is, a in the general formula (4) is preferably 2 or more. When there are few siloxane units containing the reactive functional group to contain, sclerosis | hardenability will become inadequate and there exists a possibility that the intensity | strength of the hardened | cured material obtained may fall.

Then any siloxane unit
[R ⁴ ₃ SiO—SiO _3/2 ]
Will be described.
This siloxane unit is a unit for adjusting the physical properties of the modified polyhedral polysiloxane and the resulting cured product in the present invention. Since the present siloxane unit does not substantially contain a reactive substituent, it is possible to adjust the crosslinking density, improve the film property, leveling property, improve brittleness, and the like.

As R ⁴ in the siloxane unit, an alkyl group, an aryl group, an alkenyl group, a hydrogen atom, or a group connected to another polyhedral polysiloxane can be preferably used. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like. May be replaced. Specific examples of the alkyl group partially substituted with a substituent having substantially no reactivity include, for example, a polysiloxanylalkyl group. Leveling properties and film properties, and a curing agent described later and Compatibility with a curing initiator can be imparted, and the properties of the compound can be made liquid.
The polyhedral polysiloxane modified body (A-1) in the present invention is an organic modified polyhedral polysiloxane modified body (A-1) ′ described later from the viewpoint of heat resistance, light resistance and handling properties. Is preferred.
Moreover, the polysiloxane composition (A) in this invention is added to (A-1) component by adding additives, such as a hardening | curing agent (A-2) component and a hardening retarder, as needed. Can be obtained.

<Organic modified polyhedral polysiloxane modified product (A-1) '>
The modified organic polyhedral polysiloxane (A-1) ′ according to the present invention is composed of a polyhedral polysiloxane compound (a) having an alkenyl group and alkenyl in one molecule in the presence of a hydrosilylation catalyst described later. It can be obtained by subjecting an organosilicon compound (c) having one group and / or a cyclic olefin compound (d) to a hydrosilylation reaction with a compound (b) having a hydrosilyl group.

  The method for obtaining the modified polyhedral polysiloxane (A-1) ′ of the present invention is not particularly limited and can be variously set, but after reacting the component (a) and the component (b) in advance, the component (c) And / or (d) component may be reacted, (c) component and / or (d) component and (b) component may be reacted in advance, and then (a) component may be reacted, The component (a) may be reacted with the component (b) in the presence of the component (c) and / or the component (d). After completion of each reaction, for example, volatile unreacted components may be distilled off under reduced pressure and heating conditions, and used as a target product or an intermediate for the next step. In order to suppress the formation of the compound containing only the component (c) and / or the component (d) and the component (b) but not the component (a), the component (a) and the component (b) are reacted. The method of reacting the component (c) and / or the component (d) after distilling off the unreacted component (b) is preferred.

  In the polyhedral polysiloxane modified product (A-1) ′ thus obtained, a part of the alkenyl group of the component (a) used for the reaction may remain.

Although there is no restriction | limiting in particular as addition amount of the hydrosilylation catalyst used at the time of the synthesis | combination of polyhedral polysiloxane modified body (A-1) ', The alkenyl group of (a) component used for reaction, (c) component, and (d) component It is good to use in the range of 10 ^{< -1} > ^-10 < ^-10 > mol with respect to 1 mol. Preferably it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. When there are many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light with a short wavelength, which may cause coloration or decrease the light resistance of the resulting cured product. There is also a risk of foaming. Moreover, when there are few hydrosilylation catalysts, reaction may not progress and there exists a possibility that a target object may not be obtained.

  As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC, More preferably, it is 45-140 degreeC. If the temperature is too low, the reaction does not proceed sufficiently, and if the temperature is too high, gelation may occur and handling properties may deteriorate.

  The polyhedral polysiloxane modified product (A-1) ′ thus obtained can ensure compatibility with various compounds, particularly siloxane compounds, and has a hydrosilyl group introduced into the molecule. Therefore, it is possible to react with compounds having various alkenyl groups. Specifically, a cured product can be obtained by reacting with a polysiloxane having two or more alkenyl groups in one molecule described later.

In addition, the polyhedral polysiloxane modified body (A-1) ′ in the present invention can be liquefied at a temperature of 20 ° C. The polyhedral polysiloxane-modified product (A-1) ′ is preferably in a liquid form because of excellent handling properties.
The modified polyhedral polysiloxane (A-1) ′ in the present invention has the formula
[XR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
[A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom, an alkyl group, an aryl group Or a group linked to another polyhedral skeleton polysiloxane, X has a structure of the following general formula (6) or general formula (7), and when there are a plurality of X, the general formula (6 ) Or the structure of the general formula (7) may be different, or the structure of the general formula (6) or the general formula (7) may be mixed.

{L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Which may be the same or different. Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain, which may be the same or different. However, at least one of Y or Z is a hydrogen atom, and at least one has a structure of the following formula (8).
^{_{- [CH 2] l -R 5}} (8)
(L is an integer of 0 or more; R ⁵ is a group containing an organosilicon compound and / or a cyclic olefin compound); R is an alkyl group or an aryl group}]
It is a polyhedral polysiloxane compound composed of siloxane units represented by the formula:

The polyhedral polysiloxane modified product (A-1) ′ thus obtained has a polyhedral structure by controlling the addition amount of components (a) to (c), reaction sequence, reaction time, reaction temperature, and the like. It is possible to control the viscosity of the modified polysiloxane (A-1) ′. It is also possible to adjust the viscosity of the polysiloxane composition described later by controlling the viscosity of the modified polyhedral polysiloxane (A). The viscosity of the modified polyhedral polysiloxane (A-1) ′ is not particularly limited, but when the modified polyhedral polysiloxane (A-1) ′ is liquid at a temperature of 20 ° C., the viscosity at 20 ° C. The pressure is preferably 0.01 Pa · s to 300 Pa · s, more preferably 1 Pa · s to 100 Pa · s. If the viscosity of the modified polyhedral polysiloxane (A-1) ′ is too low, the viscosity of the polysiloxane composition described later will be low, and additives such as phosphors may settle without dispersing. If the viscosity is too high, the handling property may be deteriorated.
In addition, the polyhedral polysiloxane modified (A-1) ′ has at least three hydrosilyl groups in the molecule from the viewpoint of the strength and hardness of the obtained cured product, and further, heat resistance and light resistance. It is preferable to have.

<Polyhedral polysiloxane compound (a) having an alkenyl group>
The polyhedral polysiloxane compound (a) having an alkenyl group in the present invention is not particularly limited as long as it is a polysiloxane having an alkenyl group in the molecule and having a polyhedral skeleton. Specifically, for example, the following formula [R ⁶ SiO _3/2 ] _x [R ⁷ SiO _3/2 ] _y
(X + y is an integer of 6 to 24; x is an integer of 1 or more, y is 0 or an integer of 1 or more; R ⁶ is an alkenyl group or a group having an alkenyl group; R ⁷ is any organic group, or Groups linked to other polyhedral skeleton polysiloxanes)
An alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by the formula
[AR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b (9)
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ³ is an alkyl group or an aryl group; R ⁴ is a hydrogen atom or an alkyl group , Aryl groups, or groups linked to other polyhedral skeleton polysiloxanes)
An alkenyl group-containing polyhedral polysiloxane compound composed of siloxane units represented by the formula:

  Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.

R ³ is an alkyl group or an aryl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group. Examples of the aryl group include aryl groups such as a phenyl group and a tolyl group. Is done. R ¹ in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.
R ⁴ is a group connected to a hydrogen atom, an alkyl group, an aryl group, or another polyhedral skeleton polysiloxane. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group. Examples of the aryl group include aryl groups such as a phenyl group and a tolyl group. Is done. R ⁴ in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.

  a is not particularly limited as long as it is an integer of 1 or more, but is preferably 2 or more, and more preferably 3 or more, from the handleability of the compound and the physical properties of the resulting cured product. Further, b is not particularly limited as long as it is 0 or an integer of 1 or more.

  The sum of a and b (= a + b) is an integer from 6 to 24, but from the viewpoint of the stability of the compound and the stability of the resulting cured product, it should be 6 to 12, and more preferably 6 to 10. preferable.

The method for synthesizing the component (a) is not particularly limited, and the component can be synthesized using a known method. As a synthesis method, for example, a silane of R ⁸ SiX ^a ₃ (wherein R ⁸ represents R ⁶ or R ⁷ described above, and X ^a represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). It is obtained by the hydrolysis condensation reaction of the compound. Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by hydrolytic condensation reaction of R ⁸ SiX ^a _3, the ring is closed by reacting the same or different trifunctional silane compounds, and polyhedral Methods for synthesizing structural polysiloxanes are also known.

  In addition, for example, there is a method of hydrolytic condensation of tetraalkoxysilane such as tetraethoxysilane in the presence of a base such as quaternary ammonium hydroxide. In this synthesis method, a silicate having a polyhedral structure is obtained by a hydrolytic condensation reaction of tetraalkoxysilane, and the obtained silicate is further reacted with a silylating agent such as an alkenyl group-containing silyl chloride. It is possible to obtain a polyhedral polysiloxane in which Si atoms and alkenyl groups forming a polyhedral structure are bonded through a siloxane bond. In the present invention, the same polyhedral polysiloxane can be obtained from a substance containing silica such as silica or rice husk instead of tetraalkoxylane.

<Compound (b) having hydrosilyl group>
The compound (b) having a hydrosilyl group used in the present invention is not particularly limited as long as it has one or more hydrosilyl groups in the molecule, but the obtained polyhedral polysiloxane modified product has transparency, heat resistance, From the viewpoint of light resistance, it is preferably a siloxane compound having a hydrosilyl group, and more preferably a cyclic siloxane having a hydrosilyl group or a linear polysiloxane. In particular, from the viewpoint of gas barrier properties, a cyclic siloxane is preferable.

  The linear polysiloxane having a hydrosilyl group includes a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, and a copolymer of a diphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit. Copolymers, copolymers of methylphenylsiloxane units and methylhydrogensiloxane units and terminal trimethylsiloxy units, polydimethylsiloxane blocked at the end with dimethylhydrogensilyl groups, polyblocked at the ends with dimethylhydrogensilyl groups Examples thereof include diphenylsiloxane and polymethylphenylsiloxane blocked at the end with a dimethylhydrogensilyl group.

  In particular, as a linear polysiloxane having a hydrosilyl group, a polysiloxane having a molecular end blocked with a dimethylhydrogensilyl group from the viewpoints of reactivity during modification, heat resistance of the resulting cured product, light resistance, etc. Furthermore, polydimethylsiloxane having a molecular end blocked with a dimethylhydrogensilyl group can be suitably used. Specific examples thereof include tetramethyldisiloxane and hexamethyltrisiloxane.

Examples of the cyclic siloxane having a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1. , 3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen -1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7, Examples include 9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane. Specific examples of the cyclic siloxane in the present invention include, for example, 1,3,5,7-tetrahydro, from the viewpoints of industrial availability and reactivity, or heat resistance, light resistance, strength, and the like of the resulting cured product. Gen-1,3,5,7-tetramethylcyclotetrasiloxane can be preferably used.
These compounds (b), which have a hydrosilyl group, may be used alone or in combination of two or more.

<Organic silicon compound (c) having one alkenyl group in one molecule>
In the present invention, the organosilicon compound (c) having one alkenyl group per molecule reacts with the hydrosilyl group of the compound (b) having a hydrosilyl group. By using the component (c), the elastic modulus of the obtained cured product can be reduced, and the thermal shock resistance can be improved.

  Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.

  The component (c) in the present invention is not particularly limited as long as it is an organosilicon compound having one alkenyl group in one molecule, but it is a gas barrier that at least one aryl group is contained in one molecule. From the viewpoint of heat resistance and refractive index, it is more preferable that the aryl group is directly bonded to the silicon atom from the viewpoint of heat resistance and light resistance.

  The component (c) in the present invention is preferably silane or polysiloxane from the viewpoints of heat resistance and light resistance. When the component (c) is a silane having one alkenyl group in one molecule, specifically, for example, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, triphenylvinylsilane, triethylvinylsilane, diethylphenylvinylsilane And ethyldiphenylvinylsilane, allyltrimethylsilane, allyldimethylphenylsilane, allylmethyldiphenylsilane, allyltriphenylsilane, allyltriethylsilane, allyldiethylphenylsilane, allylethyldiphenylsilane, and the like. Among these, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, and triphenylvinylsilane are preferable examples from the viewpoint of heat resistance and light resistance, and dimethylphenylvinylsilane and methyldiphenylvinylsilane are also preferable from the viewpoint of gas barrier properties and refractive index. Triphenylvinylsilane is a preferred example.

  In addition, when the component (c) is a polysiloxane, examples include a linear polysiloxane having one alkenyl group, a polysiloxane having one alkenyl group at the molecular end, and a cyclic siloxane having one alkenyl group. .

  When the component (c) is a linear polysiloxane having one alkenyl group, specifically, for example, polydimethylsiloxane, dimethylvinyl each having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group. Polymethylphenylsiloxane blocked with a silyl group and a trimethylsilyl group each at one end, polydiphenylsiloxane blocked with a dimethylvinylsilyl group and a trimethylsilyl group respectively, and terminated with a dimethylvinylsilyl group and a trimethylsilyl group A copolymer of a dimethylsiloxane unit and a methylphenylsiloxane unit, each of which is blocked one by one, a dimethylsiloxane unit and a diphenylsiloxane unit each having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group. Copolymers, copolymers of terminal and methylphenylsiloxane units and diphenylsiloxane units are blocked one by one, respectively dimethylvinylsilyl group and trimethylsilyl group and the like.

In the case of a polysiloxane having one alkenyl group at the molecular end, specifically, for example, polysiloxane having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group as exemplified above, SiO ₂ unit, SiO _{3 /} Examples include at least one siloxane unit selected from the group consisting of ₂ units, SiO units, and SiO _1/2 units, and polysiloxane composed of one dimethylvinylsiloxane unit.

When the component (c) is a cyclic siloxane having one alkenyl group, specifically, for example, 1-vinyl-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1-vinyl -3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-vinyl-3,5-diphenyl-1,3,5,7,7-pentamethylcyclotetrasiloxane, 1 -Vinyl-3,5,7-triphenyl-1,3,5,7-tetramethylcyclotetrasiloxane and the like are exemplified.
These (c) component organosilicon compounds having one alkenyl group per molecule may be used alone or in combination of two or more.

<Cyclic olefin compound (d) having one alkenyl group in one molecule>
(D) component in this invention should just be a cyclic olefin compound which has one carbon-carbon double bond in 1 molecule, and this carbon-carbon double bond is any of a vinylene group, a vinylidene group, and an alkenyl group. It may be. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.
In addition, the component (d) in the present invention preferably has an average molecular weight of 1000 or less from the viewpoint of reactivity with the component (b). Examples of such cyclic olefin compounds include aliphatic cyclic olefin compounds and substituted aliphatic cyclic olefin compounds.

  Specific examples of the aliphatic cyclic olefin compound include cyclohexene, cycloheptene, cyclooctene, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, allylcyclohexane, allylcycloheptane, allylcyclooctane, and methylenecyclohexane. It is done.

  Specific examples of the substituted aliphatic cyclic olefin compound include norbornene, 1-methylnorbornene, 2-methylnorbornene, 7-methylnorbornene, 2-vinylnorbornane, 7-vinylnorbornane, 2-allylnorbornane, 7-allylnorbornane, 2-methylene norbornane, 7-methylene norbornane, camphene, vinyl norcamphene, 6-methyl-5-vinyl-bicyclo [2,2,1] -heptane, 3-methyl-2-methylene-bicyclo [2,2,1 ] -Heptane, α-pinene, β-pinene, 6,6-dimethyl-bicyclo [3,1,1] -2-heptaene, 2-vinyladamantane, 2-methyleneadamantane and the like.

Among these, cyclohexene, vinylcyclohexane, norbornene, camphene, and pinene are preferable examples from the viewpoint of availability.
These cyclic olefin compounds (d) having one alkenyl group in one molecule may be used alone or in combination of two or more.
The amount of the cyclic olefin compound (d) having one alkenyl group in one molecule is such that the number of alkenyl groups in the component (d) is 0 per hydrosilyl group of the compound (b) having a hydrosilyl group described later. It is preferable to use so that it may become 0.01-0.5 piece. When the addition amount is small, the thermal shock resistance of the resulting cured product may be lowered, and when the addition amount is large, a curing failure may occur in the resulting cured product.

<Curing agent (A-2)>
Next, the curing agent used in the present invention will be described.

  The curing agent can be properly used depending on the type of main reactive group of the modified polyhedral polysiloxane. When the modified polyhedral polysiloxane has a hydrosilyl group as a main reactive group, a compound having an alkenyl can be used as a curing agent, and when it has an alkenyl group as a main reactive group, a compound having a hydrosilyl group can be used as a curing agent. Details will be described below.

  The curing agent having an alkenyl group is not particularly limited as long as it is a compound having an alkenyl group, but preferably contains at least two alkenyl groups in one molecule, a linear polysiloxane having an alkenyl group, Particularly preferred are siloxane compounds such as polysiloxanes having alkenyl groups at the molecular ends and cyclic siloxanes containing alkenyl groups. These compounds having an alkenyl group may be used alone or in combination of two or more.

  Specific examples of the alkenyl group-containing polysiloxane having a linear structure include copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units. Examples include copolymers, copolymers of methylphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, and polysiloxanes whose ends are blocked with dimethylvinylsilyl groups.

Specific examples of the polysiloxane having an alkenyl group at the molecular end include polysiloxanes whose ends are blocked with the dimethylalkenyl groups exemplified above, dimethylalkenylsiloxane units (H (CH ₃ ) ₂ SiO _1/2 units) and SiO Examples thereof include polysiloxane composed of at least one siloxane unit selected from the group consisting of ₂ units, SiO _3/2 units, and SiO units.

  Examples of the cyclic siloxane compound containing an alkenyl group 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, 1,3,5-trivinyl-trimethylcyclotrisiloxane 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9,11-hexavinyl-1,3,5,7 , 9,11-hexamethylcyclohexasiloxane and the like.

  The curing agent having a hydrosilyl group is not particularly limited as long as it is a compound having a hydrosilyl group, but preferably contains at least two hydrosilyl groups in one molecule, a linear polysiloxane having a hydrosilyl group, Siloxane compounds such as polysiloxane having a hydrosilyl group at the molecular terminal and cyclic siloxane having a hydrosilyl group are particularly preferred. These compounds having a hydrosilyl group may be used alone or in combination of two or more.

  Specific examples of hydrosilyl group-containing polysiloxanes having a linear structure include copolymers of dimethylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units. And a copolymer of a methylphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, a polysiloxane having a terminal blocked with a dimethylhydrogensilyl group, and the like.

Specific examples of the polysiloxane having a hydrosilyl group at the molecular end include polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups exemplified above, dimethylhydrogensiloxane units (H (CH ₃ ) ₂ SiO _1/2 units And a polysiloxane composed of at least one siloxane unit selected from the group consisting of SiO ₂ units, SiO _3/2 units, and SiO units.

  Examples of the cyclic siloxane compound containing a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen. -1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-tri Hydrogen-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9,11- Examples include hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane.

  In the present invention, from the viewpoint of heat resistance and light resistance, the Si atom is preferably composed of a hydrogen atom, a vinyl group and a methyl group.

Although the addition amount of the curing agent can be variously set, it is desirable that the amount of hydrogen atoms directly bonded to Si atoms is 0.3 to 5, preferably 0.5 to 2, per alkenyl group.
If the ratio of the alkenyl group is too small, appearance defects due to foaming and the like are likely to occur, and if too large, the physical properties of the cured product may be adversely affected.

<Inorganic filler (B)>
The inorganic filler in the present invention can be used, for example, for the purpose of adjusting the viscosity and / or thixotropy of the curable resin composition. Furthermore, it improves various physical properties such as strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical characteristics, light reflectance, flame retardancy, fire resistance, and gas barrier properties of the cured product. be able to.

The average particle diameter of the primary particles of the inorganic filler (B) used in the present invention is characterized by 20 nm or less, more preferably 18 nm or less, and 10 nm or less for dispersibility and gas barrier properties. More preferable from the viewpoint. Moreover, the particle size distribution of the inorganic filler (B) is not particularly limited. The BET specific surface area of the primary particles of the inorganic filler (B) is preferably 70 m ² / g or more, more preferably 100 m ² / g or more, and particularly preferably 200 m ² / g or more. It is preferable because the effect of improving the property is large.

  Here, the BET specific surface area is the specific surface area of the particles calculated by the gas adsorption method, and the specific surface area of the particles by the gas adsorption method is calculated using a gas molecule whose adsorption occupation area is known like nitrogen gas. The specific surface area of the particles is calculated from the amount adsorbed on the particles. The BET specific surface area can accurately calculate the amount of gas molecules adsorbed directly on the solid surface (monomolecular layer adsorption amount). The BET specific surface area can be calculated using a mathematical formula called a BET formula shown below.

  As shown in the following formula (1), the BET formula shows the relationship between the adsorption equilibrium pressure P and the adsorption amount V at that pressure when the adsorption equilibrium state is maintained at a constant temperature, and is expressed as follows.

Formula (1): P / V (Po−P) = (1 / VmC) + ((C−1) / VmC) (P / Po)
(Po: saturated vapor pressure, Vm: adsorption amount of monomolecular layer, adsorption amount when gas molecules form a monomolecular layer on a solid surface, C: parameters related to heat of adsorption (> 0))
By calculating the monomolecular adsorption amount Vm from the above equation and multiplying this by the cross-sectional area occupied by one gas molecule, the surface area of the particles can be obtained.

  The inorganic filler is not particularly limited as long as it is an inorganic substance or a compound containing an inorganic substance. Specifically, for example, quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, etc. Silica-based inorganic filler, alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, glass flake, alumina fiber, carbon fiber, mica, graphite, carbon black, Examples thereof include ferrite, graphite, diatomaceous earth, white clay, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloon, and silver powder. Among them, silica or metal oxide is preferable, and fumed silica is a more preferable example because of its high dispersibility in the polysiloxane composition of the present invention. As fumed silica, for example, various grades of Aerosil can be used. These may be used alone or in combination of two or more.

  The inorganic filler may be appropriately subjected to a surface treatment. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a silane coupling agent, and the like, but are not particularly limited.

The addition amount of the inorganic filler is not particularly limited, but is 1 to 1000 parts by weight, more preferably 3 to 500 parts by weight, and further preferably 5 to 300 parts by weight with respect to 100 parts by weight of the polysiloxane composition (A). Part. When the amount of the inorganic filler added is large, the fluidity may be deteriorated, and when the amount of the inorganic filler added is small, desired physical properties may not be obtained.
The order of mixing the inorganic filler is not particularly limited, but from the viewpoint of storage stability, the component having the hydrosilyl group is first mixed with the component having the alkenyl group in the polysiloxane composition (A). The method to do is desirable. In addition, in the polysiloxane composition (A), the component having an alkenyl group and the component having a hydrosilyl group, which are reaction components of the polysiloxane composition (A), are well mixed and a stable molded product is easily obtained. It is preferable to mix the orientation filler with the mixture of the component having an alkenyl group and the component having a hydrosilyl group.

  The means for mixing these inorganic fillers is not particularly limited, but specifically, for example, a stirrer such as a two-roll or three-roll, a planetary stirring deaerator, a homogenizer, a dissolver, a planetary mixer, etc. And melt kneaders such as a plast mill. The mixing of the inorganic filler may be performed at normal temperature, may be performed by heating, may be performed under normal pressure, or may be performed under reduced pressure. If the temperature during mixing is high, the composition may be cured before molding.

<Polyfunctional acrylate and / or polyfunctional methacrylate (C)>
The polyfunctional acrylate and / or polyfunctional methacrylate (C) in the present invention can interact with the above-mentioned inorganic filler (B) and arbitrarily adjust the viscosity and / or thixotropy of the resulting curable resin composition. it can.

  The component (C) in the present invention is a compound having two or more acryl groups and / or methacryl groups in one molecule, and is not particularly limited as long as it is compatible with the matrix polysiloxane compound. From the viewpoint of compatibility, the component (C) is preferably liquid at a temperature of 20 ° C. For example, triethylene diacrylate, triethylene dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate However, it is not limited to these. From the viewpoint of heat resistance, polyfunctional octasilsesquioxane (available from Hybrid Plastics) containing an acrylic group or a methacryl group at the terminal is desirable.

  Although the addition amount of (C) component is not specifically limited, 0.01-100 weight part with respect to 100 weight part of polysiloxane composition (A), More preferably, it is 0.1-50 weight part, More preferably Is 0.1 to 10 parts by weight. When the amount of component (C) added is large, heat resistance may deteriorate, and when the amount of component (C) added is small, desired physical properties may not be obtained.

<Hydrosilylation catalyst (D)>
In curing the polysiloxane compound, a hydrosilylation catalyst can be used. The hydrosilylation catalyst is not particularly limited and any catalyst can be used. Specifically, a platinum-olefin complex, chloroplatinic acid, a simple substance of platinum, a carrier (alumina, silica, carbon black, etc.) supported by solid platinum; a platinum-vinylsiloxane complex {for example, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _n }; platinum-phosphine complex {eg Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ }; platinum-phosphite complex {eg Pt [P (OPh) ₃ ] ₄ , Pt [P (O
Bu) ₃ ] ₄ } (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, n and m represent an integer), Pt (acac) ₂ , and Ashby And platinum platinum hydrocarbon catalysts described in US Pat. Nos. 3,159,601 and 3,159,622, and platinum alcoholate catalysts described in US Pat. No. 3,220,972 to Lamoreaux et al.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable.
As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC.

<Curable resin composition>
The curable resin composition in the present invention can be obtained from the above-described polysiloxane composition (A), inorganic filler (B), polyfunctional acrylate and / or polyfunctional methacrylate (C), and hydrosilylation catalyst (D). . The curable resin composition in the present invention can be handled as a liquid resin composition. By using a liquid resin composition, it is possible to easily obtain a molded body according to the application by injecting or applying to a mold, package, substrate or the like and curing. Moreover, in this invention, the order which mixes the said (A)-(D) component is not specifically limited.

  Various additives such as colorants, reaction control agents, release agents, dispersants for fillers, and the like can be optionally added to the curable resin composition of the present invention as necessary. Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like. In addition, 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 curable resin composition of the present invention, the above-described components are uniformly mixed using a kneader such as a roll, a Banbury mixer, a kneader, or a planetary stirring deaerator, and heat-treated as necessary. Or you may.

  The curable resin composition according to the present invention is excellent in heat resistance, light resistance, gas barrier properties, light extraction efficiency, and has good handling properties, so that it can be used as a sealant for optical materials. 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.

A semiconductor light-emitting device can be produced using the curable resin composition of the present invention as an optical element sealant. Specifically, for example, a curable resin composition can be injected or applied to a package or substrate on which an element is mounted. It is possible to seal the element by curing after injection or application. The curable resin composition of the present invention have good (low) moisture permeability, for example ^50g / m 2 / 24h or less, still more forming a sealant having the following low moisture permeability ^40g / m 2 / 24h Is possible. To have a lower moisture permeability 50g ^/ m 2 ^/ 24h, preferably having a particle size in the polysiloxane composition is added to the following inorganic filler 20 nm, more preferably the particle size is below 18 nm, 10 nm More preferably, it is as follows.

  By sealing using the curable resin composition of this invention, components, such as an element, a reflector, and a lead wire, can be protected from an impact, dust, gas, etc. from the outside, for example. In addition, when an optical element sealant having a high gas barrier property is used, it is possible to prevent blackening of reflectors and lead portions due to sulfides.

  The curable resin composition of the present invention can be used as a molded article. As a molding method, any method such as extrusion molding, compression molding, blow molding, calender molding, vacuum molding, foam molding, injection molding, liquid injection molding, and cast molding can be used.

  Specific uses of the molded product obtained in the present invention include, for example, substrate materials in the field of liquid crystal displays, light guide plates, prism sheets, deflection plates, retardation plates, viewing angle correction films, adhesives, color filters, polarizers. Examples of the peripheral material of the liquid crystal display device such as a protective film and a film for liquid crystal such as a passivation film are exemplified. It is also used in PDP (plasma display) sealants, antireflection films, optical correction films, housing materials, front glass protective films, front glass substitute materials, adhesives, color filters, passivation films, and LED display devices. LED element mold material, front glass protective film, front glass substitute material, adhesive, color filter, passivation film, substrate material for plasma addressed liquid crystal display, light guide plate, prism sheet, deflector plate, retardation plate, field of view Corner correction film, adhesive, color filter, polarizer protective film, passivation film, front glass protective film, front glass substitute material, color filter, adhesive, passivation film, and field emission in organic EL displays Various film substrate in Isupurei (FED), front glass protective films, front glass substitute material, adhesive, a color filter, a passivation film is exemplified.

  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. More specifically, optical pickup members such as next-generation DVDs, such as pickup lenses, collimator lenses, objective lenses, sensor lenses, protective films, element sealants, sensor sealants, gratings, adhesives, prisms And a wave plate, a correction plate, a splitter, a hologram, a mirror, and the like.

  In the field of optical equipment, examples include still camera lens materials, viewfinder prisms, target prisms, viewfinder covers, and light receiving sensor sections. In addition, a photographing lens and a viewfinder of a video camera are exemplified. Moreover, the projection lens of a projection television, a protective film, a sealing agent, an adhesive agent, etc. are illustrated. Examples are materials for lenses of optical sensing devices, sealants, adhesives, and films.

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

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

  Examples of the semiconductor integrated circuit peripheral material include an interlayer insulating film, a passivation film, an LSI, and a resist material for microlithography for an LSI material.

  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 / bundling wireness, fuel hoses, automobile lamps, and glass substitutes. Moreover, the multilayer glass for rail vehicles is illustrated. Further, examples thereof include a toughness imparting agent for aircraft structural materials, engine peripheral members, wireness for protection and binding, and corrosion-resistant coating.

  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.

<Hardened product>
A cured product can be obtained by applying heat and / or light to the curable resin composition of the present invention. The temperature is preferably 30 to 400 ° C, more preferably 50 to 250 ° C. If the curing temperature is too high, the resulting cured product tends to have poor appearance, and if it is too low, curing is insufficient. Moreover, you may make it harden | cure combining the temperature conditions of two or more steps. Specifically, for example, by raising the curing temperature stepwise such as 70 ° C., 120 ° C., and 150 ° C., a preferable cured product can be obtained, which is preferable.

  The curing time can be appropriately selected depending on the curing temperature, the amount of the hydrosilylation catalyst to be used and the amount of the reactive group, and other combinations of the composition of the present application. Preferably, a cured product can be obtained by performing the treatment for 10 minutes to 8 hours.

In the case of curing by adding light, the light source may be a light source that emits light having an absorption wavelength of the photoacid generator or sensitizer used, and usually includes a light source having a wavelength in the range of 200 to 450 nm, for example, high pressure. Mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, high power metal halide lamps, xenon lamps, carbon arc lamps, light emitting diodes, and the like can be used. The exposure amount is not particularly limited, but a preferable exposure amount range is 1 to 5000 mJ / cm ² , more preferably 1 to 1000 mJ / cm ² .

<Photoradical generator and / or thermal radical initiator>
In addition, a photo radical generator and / or a thermal radical initiator can be optionally added to the curable resin composition of the present invention as necessary.

  As photo radical generators, acetophenone compounds, benzophenone compounds, acylphosphine oxide compounds, oxime ester compounds, benzoin compounds, biimidazole compounds, α-diketone compounds, titanocene compounds, polynuclear quinone compounds , Xanthone compounds, thioxanthone compounds, triazine compounds, ketal compounds, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoroamine compounds, etc. Can do.

Specific examples of the thermal radical generator include diacyl peroxides such as acetyl peroxide and benzoyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, hydrogen peroxide, tert-butyl hydroperoxide, cumene Hydroperoxides such as hydroperoxides, dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxypivalate, etc. Peroxyesters, azo compounds such as azobisisobutyronitrile, azobisisovaleronitrile, persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate It can be salts and the like are listed.
These radical initiators may be used alone or in combination of two or more.

<Curing retarder>
The curing retarder is a component for improving the storage stability of the curable resin composition of the present invention or adjusting the reactivity of the hydrosilylation reaction during the curing process. In the present invention, as the retarder, known compounds used in addition-type curable resin compositions based on hydrosilylation catalysts can be used. Specifically, compounds containing aliphatic unsaturated bonds, organic phosphorus Examples thereof include compounds, organic sulfur compounds, nitrogen-containing compounds, tin-based compounds, and organic peroxides. These may be used alone or in combination of two or more.

  Specific examples of the compound containing an aliphatic unsaturated bond include 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, and 3,5-dimethyl-1- Examples thereof include propargyl alcohols such as hexyn-3-ol and 1-ethynyl-1-cyclohexanol, ene-yne compounds, maleic acid esters such as maleic anhydride and dimethyl maleate, and the like.

  Specific examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite.

  Specific examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide, and the like.

  Specific examples of nitrogen-containing compounds include N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, and 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 Examples include '-bipyridine.

  Specific examples of tin compounds include stannous halide dihydrate, stannous carboxylate, and the like.

  Specific examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate. Of these, dimethyl maleate, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol can be exemplified as particularly preferred curing retarders.

The addition amount of the curing retarder is not particularly limited, but is preferably used in the range of 10 ⁻¹ to 10 ³ mol, more preferably in the range of 1 to 100 mol, per 1 mol of the hydrosilylation catalyst. preferable. Moreover, these hardening retarders may be used independently and may be used in combination of 2 or more types.

<Adhesive agent>
The adhesion-imparting agent is used for the purpose of improving the adhesion between the curable resin composition and the substrate in the present invention, and is not particularly limited as long as it has such an effect, but the silane coupling agent Can be illustrated as a preferred example.

  The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably 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 from the viewpoint of handling. From the viewpoints of adhesion and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

Specific preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldisilane. Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- Alkoxysilanes having an epoxy functional group such as (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysila Alkoxysilanes having a methacrylic group or an acrylic group such as 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Is mentioned. These may be used alone or in combination of two or more.
As addition amount of a silane coupling agent, it is preferable that it is 0.05-30 weight part with respect to 100 weight part of mixture of (A) component and (B) component, More preferably, it is 0.1-10. Parts by weight. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the cured product may be adversely affected.

  In the present invention, a known adhesion promoter can be used to enhance the effect of the adhesion promoter. Adhesion promoters include, but are not limited to, epoxy-containing compounds, epoxy resins, boronic ester compounds, organoaluminum compounds, and organotitanium compounds.

<Phosphor>
The curable resin composition in the present invention may have a phosphor. The phosphor absorbs light emitted from the light emitting element and generates light of different wavelengths, and the phosphor used in the curable resin composition of the present invention is not particularly limited, and is generally known inorganic A phosphor or an organic phosphor can be used, and any one can be selected in order to obtain a luminescent color required by the semiconductor light emitting device using the curable resin composition of the present invention. Specifically, for example, YAG phosphors, TAG phosphors, orthosilicate alkaline earth phosphors, α-sialon phosphors, β-sialon phosphors, cousin phosphors, nitrides and oxynitride phosphors However, it is not limited to these. These phosphors can be used alone or in combination of two or more in any ratio and combination.

  The particle size of the phosphor used in the present invention is not particularly limited, but the median particle size (D50) is preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 1 μm or more, preferably Is 100 μm or less, more preferably 50 μm or less, and even more preferably 25 μm or less. If the median particle size (D50) is small, the phosphor may aggregate in the curable resin composition, and if the median particle size (D50) is large, the phosphor is unevenly coated or the dispenser is blocked. There is a case. In addition, the particle size distribution (QD) of the phosphor is preferably small in order to align the dispersion state of the particles in the sealant, but in order to reduce the particle size, the classification yield is lowered and the cost is increased. It is 0.03 or more, more preferably 0.05 or more, further preferably 0.07 or more, preferably 0.4 or less, more preferably 0.3 or less, and further preferably 0.2 or less. Further, the shape of the phosphor is not particularly limited, and an arbitrary shape can be used.

  The amount of the phosphor used in the present invention is not particularly limited, and any amount can be used to obtain the light emission color required by the semiconductor light emitting device. Preferably it is 0.1% by weight or more, more preferably 1% by weight or more, further preferably 2% by weight or more, preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 35% by weight or less. is there. If the amount of phosphor used is small, wavelength conversion by the phosphor may be insufficient, and the target emission color may not be obtained. If the amount of phosphor used is large, the handling properties of the sealant will be reduced. Or the use efficiency of the phosphor may be lowered due to optical interference.

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

(viscosity)
An E-type viscometer manufactured by Tokyo Keiki was used. Measurement was performed at a measurement temperature of 23.0 ° C. and an EHD type 48φ 1-fold cone. The thixotropy is calculated by the following formula (1)
Thixotropic = [viscosity at 0.5 rpm (Pa · s) / 5 viscosity at 5 rpm (Pa · s)] (1)
Calculated using

(SiH value)
400 MHz NMR manufactured by Varian Technologies Japan Limited was used. The SiH value of the modified polyhedral polysiloxane is calculated by the following formula (2) by making a mixture of the modified polyhedral polysiloxane and dibromoethane and performing NMR measurement thereof.
SiH value (mol / kg) = [integral value of peak attributed to SiH group of polyhedral polysiloxane modified product] / [integral value of peak attributed to methyl group of dibromoethane] × 4 × [in the mixture Dibromoethane weight] / [Molecular weight of dibromoethane] / [Polyhedral polysiloxane modified weight in mixture] (2)
Calculated using

(Weight average molecular weight)
The weight average molecular weight of the synthesized silicone was HLC-8220GPC (column: TSKgel SuperHZM-N (4) + HZ1000 (1), inner diameter: 4.6 mm × 15 cm, solvent: toluene, flow rate: 0.35 ml / min, manufactured by Tosoh Corporation. ). In addition, the catalog value was referred about the weight average molecular weight of commercially available silicone.

(Production Example 1)
To 1803 g of a 48% choline aqueous solution (trimethyl-2-hydroxyethylammonium hydroxide aqueous solution), 1459 g of tetraethoxysilane was added and stirred vigorously at room temperature for 2 hours. When the reaction system generated heat and became a homogeneous solution, the stirring was loosened and the reaction was further continued for 12 hours. Next, 1400 mL of methanol was added to the solid produced in the reaction system to obtain a uniform solution.

  While vigorously stirring a solution of 1149 g of dimethylvinylchlorosilane, 830 g of trimethylsilyl chloride and 1400 mL of hexane, the methanol solution was slowly added dropwise. After completion of the dropwise addition, the mixture was reacted for 1 hour, and then the organic layer was extracted and concentrated to obtain a solid. Next, the resulting solid is washed by vigorously stirring in methanol and filtered to obtain a polyhedral polysiloxane compound containing 16 Si atoms and an alkenyl group having 4 vinyl groups. 760 g of tetrakis (vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane (Fw = 1178.2) was obtained as a white solid.

(Production Example 2)
10.0 g of tetrakis (vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane, which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1, is dissolved in 20.0 g of toluene, and vinyldiphenylmethylsilane is dissolved. 6.67 g of a xylene solution of platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) 0.50 μL was added. The solution thus obtained was slowly added dropwise to a solution of 8.17 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 8.17 g of toluene. , And reacted at 105 ° C. for 2 hours. After completion of the reaction, 2.8 μl of ethynylcyclohexanol and 0.65 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain 24.2 g of a modified polyhedral polysiloxane having a phenyl group (weight average). Molecular weight: 3200) was obtained.

Example 1
In a 100 ml plastic cup, 1.0 g of A agent and 4.0 g of B agent of phenyl silicone OE6630 (A / B = 1/4 (wt / wt)) manufactured by Dow Silicone Co., Ltd. were added in order, and mixed there. 5 parts (0.25 g) of fumed silica AEROSIL R972 added to the resin, kneaded twice with a ceramic roll, and a polyfunctional octasil containing a methacryl group at the terminal made by Hybrid Plastics as a polyfunctional acrylate Add 1 part (0.053 g) of sesquioxane AcryloPOSS Cage Mixture to the mixture of silicone and filler, mix, and continue stirring and defoaming for 10 minutes using ARKY-310 Awatori Nerita made by Thinky. Thus, the polysiloxane composition of the present invention was obtained. The viscosity and thixotropy of the obtained polysiloxane composition were measured using an E-type viscometer manufactured by Tokyo Keiki, and the results are shown in Table 1.

(Example 2)
The same operation and evaluation as in Example 1 were performed except that methylsilicone JCR6140 manufactured by Dow Silicone Co. was used as the polysiloxane compound constituting the polysiloxane composition, and the viscosity and thixotropy of the composition are shown in Table 1. .

Example 3
In a 100 ml plastic cup, 5.0 g of the modified polyhedral polysiloxane obtained in Production Example 2, 1.59 g of 1,1,5,5-tetramethyl-3,3-diphenyl-1,5-divinyltrisiloxane, A retarder and a hydrosilylation catalyst are sequentially added and mixed, and 5 parts (0.28 g) of fumed silica AEROSIL R972 manufactured by Nippon Aerosil Co., Ltd. is added to the resin and kneaded twice with a ceramic roll. As a functional acrylate, 1 part (0.059 g) of polyfunctional octasilsesquioxane AcrylPOSS Cage Mixture containing a methacryl group at the terminal made by Hybrid Plastics is added to the mixture of silicone and filler, and mixed as it is. Awatori Netaro ARV-310 The polysiloxane composition of the present invention was obtained by performing foaming for 10 minutes. The viscosity and thixotropy of the obtained polysiloxane composition were measured using an E-type viscometer manufactured by Tokyo Keiki, and the results are shown in Table 1.

Example 4
The same operation and evaluation as in Example 3 were performed except that trimethylolpropane triacrylate light acrylate TMP-A manufactured by Kyoeisha Chemical Co. was used as the polyfunctional acrylate, and the viscosity and thixotropy of the composition are shown in Table 1.

(Comparative Example 1)
In a 100 ml plastic cup, 1.0 g of A agent and 4.0 g of B agent of phenyl silicone OE6630 (A / B = 1/4 (wt / wt)) manufactured by Dow Silicone Co., Ltd. were added in order, and mixed there. Add 5 parts (0.25 g) of fumed silica AEROSIL R972 to the resin, knead twice with a ceramic roll, and continue stirring and defoaming for 10 minutes using THINKY's Awatori Nertaro ARV-310. Thus, the polysiloxane composition of the present invention was obtained. The viscosity and thixotropy of the obtained polysiloxane composition were measured using an E-type viscometer manufactured by Tokyo Keiki, and the results are shown in Table 1.

(Comparative Example 2)
The same operation and evaluation as in Comparative Example 1 were performed except that methylsilicone JCR6140 manufactured by Dow Silicone Co. was used as the polysiloxane compound constituting the polysiloxane composition, and the viscosity and thixotropy of the composition are shown in Table 1. .

(Comparative Example 3)
The same operation and evaluation as in Comparative Example 1 were carried out except that the polyhedral polysiloxane modified product obtained in Production Example 2 was used as the polysiloxane compound constituting the polysiloxane composition, and the viscosity and thixotropy of the composition were determined. Are listed in Table 1.

(Comparative Example 4)
In a 100 ml plastic cup, 5.0 g of the modified polyhedral polysiloxane obtained in Production Example 2, 1.59 g of 1,1,5,5-tetramethyl-3,3-diphenyl-1,5-divinyltrisiloxane, A retarder and a hydrosilylation catalyst were sequentially added and mixed, and there was mixed polyfunctional octasilsesquioxane AcrylPOSS Cage Mixture containing a methacryl group at the terminal made by Hybrid Plastics as a polyfunctional acrylate with respect to silicone. (0.056 g) was added and mixed, and the polysiloxane composition of the present invention was obtained by stirring and defoaming for 10 minutes using Awatori Nertaro ARV-310 manufactured by Thinky. The viscosity and thixotropy of the obtained polysiloxane composition were measured using an E-type viscometer manufactured by Tokyo Keiki, and the results are shown in Table 1.

(Comparative Example 5)
In a 100 ml plastic cup, 5.0 g of the modified polyhedral polysiloxane obtained in Production Example 2, 1.59 g of 1,1,5,5-tetramethyl-3,3-diphenyl-1,5-divinyltrisiloxane, A retarder and a hydrosilylation catalyst were added in order and mixed, and the mixture was stirred and defoamed for 10 minutes using Awatori Netaro ARV-310 manufactured by Thinky, thereby obtaining the polysiloxane composition of the present invention. The viscosity and thixotropy of the obtained polysiloxane composition were measured using an E-type viscometer manufactured by Tokyo Keiki, and the results are shown in Table 1.

As shown in Table 1, the viscosity and thixotropy can be improved by using the polysiloxane composition of the present invention. Viscosity and thixotropy are improved even when multiple types of polysiloxane compounds are used as the silicone component (Examples 1 to 3) and when multiple types of polyfunctional acrylates are used (Examples 3 and 4). Obviously it can be.
In addition, the polyhedral polysiloxane modified product obtained in Production Example 2 as the silicone component, Aerosil R972 as the inorganic filler, and AcryloPOSS Cage Module as the polyfunctional acrylate are particularly effective (Example 3). I understand.

Claims (14)

A curable resin composition comprising (A) a polysiloxane composition, (B) an inorganic filler, (C) a polyfunctional acrylate and / or a polyfunctional methacrylate, and (D) a hydrosilylation catalyst. The curable resin composition according to claim 1, wherein the polysiloxane composition (A) is phenyl silicone. 2. The curable resin composition according to claim 1, wherein the polysiloxane composition (A) is methyl silicone. The curable resin composition according to claim 1, wherein the polysiloxane composition (A) comprises the following (A-1) and (A-2).
(A-1) a modified polyhedral polysiloxane containing an alkenyl group and / or a hydrosilyl group,
(A-2) A curing agent having two or more hydrosilyl groups and / or alkenyl groups capable of hydrosilylation with the component (A-1). (A-1) a polyhedral polysiloxane compound (a) having an alkenyl group as component (a), a compound (b) having a hydrosilyl group, an organosilicon compound (c) having one alkenyl group in one molecule, and 5. The curable resin according to claim 4, which is an organically modified polyhedral polysiloxane modified product (A-1) ′ obtained by hydrosilylation reaction with a cyclic olefin compound (d). Composition. The curable resin composition according to any one of claims 1 to 5, wherein the component (A) is liquid at a temperature of 20 ° C. The curable resin composition according to any one of claims 1 to 6, wherein the inorganic filler (B) is a metal oxide. The curable resin composition according to any one of claims 1 to 7, wherein the inorganic filler (B) is silica. The polyfunctional acrylate and / or polyfunctional methacrylate (C) is a polyfunctional octasilsesquioxane containing an acrylic group and / or a methacrylic group at the terminal. The curable resin composition described in 1. The curable resin composition according to claim 1, comprising a photo radical initiator and / or a thermal radical initiator. The curable resin composition according to any one of claims 1 to 10, further comprising a curing retarder. The curable resin composition according to any one of claims 1 to 11, further comprising an adhesiveness imparting agent. It contains fluorescent substance, The curable resin composition of any one of Claims 1-12 characterized by the above-mentioned. Hardened | cured material obtained from the curable resin composition of any one of Claims 1-13.