JP4520248B2 - Curable silicone resin composition - Google Patents

Description

  The present invention relates to a curable silicone resin composition useful for optical devices / materials for optical parts, insulating materials for electronic devices / electronic parts, coating materials, and the like.

  Conventionally, epoxy resin is generally used as a sealing material for optical devices and optical component materials, particularly light emitting diode (LED) elements. However, in recent years, while white LEDs have been attracting attention, yellowing and cracking of epoxy resin-based sealing materials due to heat and ultraviolet rays, which have not been a problem until now, have become a problem, and urgent action is required.

  As countermeasures against these problems, use of a cured silicone resin excellent in heat resistance and light resistance has been studied. For example, it has been proposed to use a silicone resin for a mold member of an LED element (Patent Documents 1 and 2), a color filter material (Patent Document 3), etc., but these general silicone resins are used. In such a case, there is a problem that cracks are generated due to thermal shock or the like.

Japanese Patent Laid-Open No. 10-228249 Japanese Patent Laid-Open No. 10-242513 JP 2000-123981 A

  In view of the above problems, the present invention is a curable silicone resin composition useful for optical devices / materials for optical devices, insulating materials for electronic devices / electronic components, coating materials, and the like, and has heat resistance, light resistance, and resistance. It aims at providing the composition which gives the hardened | cured material excellent in crack property.

As a result of intensive studies to achieve the above object, the present inventors have completed the present invention. That is, the present invention
(A) (a) a siloxane compound having three or more hydrogen atoms bonded to a silicon atom in one molecule, and (b) a polycyclic compound having two addition-reactive carbon-carbon double bonds in one molecule. A siloxane-polycyclic hydrocarbon compound which is an addition reaction product with a hydrocarbon and has two or more hydrogen atoms bonded to a silicon atom in one molecule;
(B) an organic compound having a total of two or more acryloyl groups and / or methacryloyl groups in one molecule;
(C) a hydrosilylation reaction catalyst, and (D) a hindered amine compound,
A curable silicone resin composition containing
I will provide a.

  The curable silicone resin composition of the present invention can provide a cured product excellent in heat resistance, light resistance and crack resistance while maintaining initial characteristics such as appearance, hardness, and light transmittance. . Therefore, it is useful for applications such as protection, sealing, adhesion, wavelength change or adjustment of light emitting diode elements, and lenses. Further, the composition is also useful for various optical materials such as lens materials, optical device / optical component materials, display materials, electronic device / electronic component insulating materials, coating materials, and the like.

The present invention will be described in detail below.
The composition of the present invention contains the following components (A) to (D), and further contains other optional components as necessary. In the present specification, “room temperature” means 25 ° C.

[(A) Siloxane-polycyclic hydrocarbon compound]
The (A) component siloxane-polycyclic hydrocarbon compound has two or more hydrogen atoms bonded to silicon atoms (hereinafter also referred to as “silicon atom-bonded hydrogen atoms”) in one molecule, It is a hydrocarbon compound having a siloxane structure and a polycyclic structure. This siloxane-polycyclic hydrocarbon compound includes (a) a siloxane compound having 3 or more hydrogen atoms bonded to a silicon atom in one molecule, and (b) an addition-reactive carbon-carbon double bond. An addition reaction product with two polycyclic hydrocarbons in the molecule.

  The siloxane-polycyclic hydrocarbon compound of this component preferably has 2 to 100, more preferably 2 to 50, silicon-bonded hydrogen atoms in one molecule. The (a) siloxane compound preferably has 3 to 10 silicon atom-bonded hydrogen atoms in one molecule, and more preferably 3 to 5 silicon atoms.

<(A) component>
Examples of the siloxane compound having three or more hydrogen atoms bonded to a silicon atom (a) as a reaction raw material of the component (A) include, for example, a cyclic siloxane compound represented by the general formula (1) Alternatively, a linear siloxane compound represented by the following general formula (2) is preferable.

（式中、Ｒ¹、Ｒ²およびＲ³は、独立に、水素原子または非置換もしくは置換の炭素原子数１〜12、好ましくは１〜６の一価炭化水素基であり、ｎは３〜10、好ましくは３〜８、ｍは０〜７、好ましくは０〜２、の整数であり、かつｎ＋ｍの和は３〜10、好ましくは３〜６の整数である。）

Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12, preferably 1 to 6 carbon atoms, and n is 3 to 3. 10, preferably 3-8, m is an integer of 0-7, preferably 0-2, and the sum of n + m is an integer of 3-10, preferably 3-6.)

R ¹ ₃ SiO— (HR ¹ SiO) q (R ² R ³ SiO) p-SiR ¹ ₃ (2)
Wherein R ¹ , R ² and R ³ are as defined in the general formula (1), q is 3 to 50, preferably 3 to 30, p is 0 to 47, preferably 0 to 20 And the sum of q + p is an integer of 3 to 50, preferably 3 to 30.)
Examples of the case where R ¹ , R ² and R ³ are monovalent hydrocarbon groups include, for example, methyl group, ethyl, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group Alkyl groups such as sec-hexyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, o-, m-, and p-tolyl; aralkyl groups such as benzyl group and 2-phenylethyl group An alkenyl group such as a vinyl group, an allyl group, a 1-butenyl group, and a 1-hexenyl group; an alkenyl aryl group such as a p-vinyl-phenyl group; and one or more hydrogen atoms of these groups are a halogen atom, a cyano group, Substituted with an epoxy group-containing group, for example, a halogenated alkyl group such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, Anoethyl group, 3-glycidoxypropyl group and the like can be mentioned. Among these, those other than alkenyl groups and alkenylaryl groups are preferable, and those in which all of them are methyl groups are particularly preferable.

Preferred specific examples of the component (a) are shown below, but are not limited thereto.
(HMeSiO) ₃
(HMeSiO) ₄
(HMeSiO) ₃ (Me ₂ SiO)
(HMeSiO) ₄ (Me ₂ SiO)
Me ₃ SiO— (HMeSiO) ₅ (Me ₂ SiO) ₅ —SiMe ₃
Me ₃ SiO— (HMeSiO) ₂₀ (Me ₂ SiO) ₂₀ —SiMe ₃
The component (a) can be used alone or in combination of two or more.

<(B) component>
In addition, (b) polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, which is the other reaction raw material of component (A), “addition reactivity” means silicon It means the property of being able to undergo the addition of a hydrogen atom bonded to an atom (known as a hydrosilylation reaction).
Examples of the polycyclic hydrocarbon of the component (b) include (i) addition reactive carbon between two adjacent carbon atoms among the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon. A carbon double bond is formed, or (ii) a hydrogen atom bonded to a carbon atom forming a polycyclic skeleton of a polycyclic hydrocarbon is added by an addition-reactive carbon-carbon double bond-containing group An substituted reactive carbon-carbon double bond is formed between two adjacent carbon atoms among the carbon atoms forming the polycyclic skeleton of the substituted, (iii) polycyclic hydrocarbon In addition, a hydrogen atom bonded to a carbon atom forming a polycyclic skeleton of a polycyclic hydrocarbon is substituted with an addition-reactive carbon-carbon double bond-containing group.

The siloxane-polycyclic hydrocarbon compound of this component is not particularly limited as long as it satisfies the above requirements, but the following general formula (3):
HX- (YX) _p- Y '(3)
(In the formula, X is a divalent residue of the (a) siloxane compound, Y is a divalent residue of the (b) polycyclic hydrocarbon, and Y ′ is the (b) polyvalent residue. A monovalent residue of a cyclic hydrocarbon, H is a hydrogen atom, and p is an integer of 0 to 1000, preferably 0 to 100).
The following general formula (4):
H-X- (Y-X) _n -H (4)
(Wherein X, Y and H are the same as above, and n is an integer of 1 to 1000, preferably 1 to 100).
Or the following general formula (5):
Y'-X- (YX) _q- Y '(5)
(In the formula, X, Y and Y ′ are the same as described above, and q is an integer of 1 to 1000, preferably 1 to 100.)
The compound represented by these is preferable.

  In the above formulas (3) to (5), as X (that is, the divalent residue of the (a) siloxane compound), for example, the following general formula:

（上記式中、Ｒは、独立に、炭素原子数１〜12、好ましくは１〜６の一価炭化水素基またはアルコキシ基であり、ｍは１以上、好ましくは２以上の整数であり、より好ましくは２である。）
で表される環状または鎖状の二価の基が挙げられる。

(In the above formula, R is independently a monovalent hydrocarbon group or alkoxy group having 1 to 12, preferably 1 to 6 carbon atoms, m is an integer of 1 or more, preferably 2 or more, and Preferably it is 2.)
The cyclic | annular or chain | strand-shaped bivalent group represented by these is mentioned.

  Examples of the monovalent hydrocarbon group represented by R include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group and n-hexyl group; aryl such as phenyl group Groups and the like. Examples of the alkoxy group represented by R include a methoxy group, an ethoxy group, and a propoxy group.

  Examples of X include the following formula:

（式中、「Ｍｅ」はメチル基を表す。以下、同様である。）
で表される環状シロキサン残基、下記式：

(In the formula, “Me” represents a methyl group. The same shall apply hereinafter.)
A cyclic siloxane residue represented by the following formula:

で表される鎖状シロキサン残基等が挙げられる。

The chain siloxane residue represented by these is mentioned.

  Examples of Y (that is, the divalent residue of the polycyclic hydrocarbon of (b) above) include, for example, the following structural formula:

で表される２価の残基等が挙げられる。

The bivalent residue etc. which are represented by these are mentioned.

  In the above formulas (3) to (5), Y ′ (that is, the monovalent residue of the (b) polycyclic hydrocarbon) is, for example, the following structural formula:

で表される２価の残基等が挙げられる。

The bivalent residue etc. which are represented by these are mentioned.

  Preferable specific examples of the siloxane-polycyclic hydrocarbon compound of this component include the following structural formula:

（式中、ｎは前記一般式(4)において定義のとおりである。）
で表されるもの等が挙げられる。この好ましいシロキサン−多環式炭化水素系化合物は、具体的には下記工程により合成することができる。

(In the formula, n is as defined in the general formula (4).)
The thing etc. which are represented by are mentioned. This preferable siloxane-polycyclic hydrocarbon compound can be specifically synthesized by the following steps.

  That is, as the component (a), cyclic 1,3,5,7-tetramethylcyclotetrasiloxane, and as the component (b), the following structural formula (x):

(x)
で表される5-ビニルビシクロ[2.2.1]ヘプト-2-エン、および下記構造式(y)：

(x)
5-vinylbicyclo [2.2.1] hept-2-ene represented by the following structural formula (y):

(y)
で表される6-ビニルビシクロ[2.2.1]ヘプト-2-エンの少なくとも一方（以下、これらを区別せずに「ビニルノルボルネン」という）とを、後述の（ｃ）成分であるヒドロシリル化反応触媒（例えば、白金等）の存在下で付加反応させることによって合成することができる。前記ビニルノルボルネンのビニル基の置換位置は、エンド形であっても、エキソ形であってもよく、また前記両配置の異性体の組み合わせであってもよい。

(y)
And at least one of 6-vinylbicyclo [2.2.1] hept-2-ene represented by the following (hereinafter referred to as “vinyl norbornene” without distinction) and hydrosilylation reaction as component (c) described later It can be synthesized by an addition reaction in the presence of a catalyst (for example, platinum or the like). The substitution position of the vinyl group of the vinyl norbornene may be an endo form or an exo form, or may be a combination of the two isomers.

  In the addition reaction, the amount of component (a) and component (b) used is usually 0.5 to 2 moles, preferably 1 to 1.5 moles per mole of component (b). More preferably, the amount is 1.1 to 1.3 mol.

  The (A) component siloxane-polycyclic hydrocarbon compound may be used alone or in combination of two or more.

[(B) (Meth) acryloyl group-containing organic compound]
The organic compound having two or more acryloyl groups and / or methacryloyl groups in one molecule as the component (B) has a function of adding a component (A) by a hydrosilylation reaction to give a cured product. The acryloyl group and / or methacryloyl group preferably has a total of 2 to 6 and more preferably 2 to 4 in one molecule.

  This component is not particularly limited as long as it satisfies the above requirements. For example, the following general formula (6):

(6)
（式中、Ａは、下記式（a1）：

（a1）
で表される基、または下記式（a2）：

（a2）
で表される基であり、Ｒは水素原子またはメチル基を表す。）
で表される有機化合物等が挙げられる。

(6)
(In the formula, A represents the following formula (a1):

(A1)
Or a group represented by the following formula (a2):

(A2)
R represents a hydrogen atom or a methyl group. )
The organic compound etc. which are represented by these are mentioned.

  Examples of the organic compound of this component include, but are not limited to, the following.

トリシクロデカンジメタノールジアクリレート
（新中村化学製、商品名：ＮＫエステルＡ−ＤＣＰ）

Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-DCP)

トリシクロデカンジメタノールジメタクリレート
（新中村化学製、商品名：ＮＫエステルＤＣＰ）

Tricyclodecane dimethanol dimethacrylate (made by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester DCP)

（日本化薬製、商品名：KAYARAD R-604）

(Nippon Kayaku, product name: KAYARAD R-604)

  The blending amount of component (B) is preferably set as follows. As will be described later, the composition of the present invention comprises a component having a hydrogen atom bonded to a silicon atom other than the component (A) and / or an addition-reactive carbon-carbon bond bonded to a silicon atom other than the component (B). A component having a heavy bond can be contained. Therefore, the amount of hydrogen atoms bonded to silicon atoms in the composition relative to 1 mol of addition-reactive carbon-carbon double bonds bonded to silicon atoms in the composition is usually 0.3 to 3.0 mol, preferably 0.8 to 2.0 mol. And the ratio of the hydrogen atom couple | bonded with the silicon atom in the said (A) component which occupies for the hydrogen atom couple | bonded with the silicon atom in this composition is 20-100 mol% normally, Preferably it is 40-100 mol%. is there. Moreover, the ratio of the alkenyl group which the acryloyl group and methacryloyl group in the said (B) component occupy for the addition reactive carbon-carbon double bond couple | bonded with the silicon atom in this composition is 20-20 mol% normally. , Preferably it is 40-100 mol%. When the blending amount of the component (B) satisfies such conditions, a cured product having sufficient hardness can be obtained when applied to applications such as coating materials.

  (B) The organic compound of a component may be used individually by 1 type, or may use 2 or more types together.

[(C) Hydrosilylation reaction catalyst]
As the hydrosilylation reaction catalyst as the component (C), any conventionally known catalyst can be used. Specific examples include platinum black, platinous chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohol, complexes of chloroplatinic acid and olefins, platinum-based catalysts such as platinum bisacetoacetate, etc. And platinum group metal catalysts such as palladium catalyst and rhodium catalyst.

  (C) The compounding quantity of a component should just be an effective amount as a catalyst, and although it does not restrict | limit, as a platinum group metal atom with respect to the total mass of (A) component and (B) component, 1 It is preferably ~ 500ppm, particularly 2 ~ 100ppm. When the blending amount is 1 to 500 ppm, the time required for the curing reaction becomes appropriate, and problems such as coloring of the cured product do not occur.

  (C) The hydrosilylation reaction catalyst of a component may be used individually by 1 type, or may use 2 or more types together.

[(D) hindered amine compound]
The cured product obtained from the composition of the present invention contains the platinum group metal in the component (C). When the cured product is exposed to light for a long time or placed in a high temperature state, it causes an interaction with a carbon-carbon double bond due to the presence of a platinum group metal, particularly platinum, There arises a problem that coloring and white turbidity are caused, and strength and hardness are lowered due to oxidative deterioration. The hindered amine compound as component (D) has a function of preventing the occurrence of coloring and the like.

  As the hindered amine compound of this component, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: ADK STAB LA77Y, manufactured by Asahi Denka), bis (1-octyloxy-2,2 , 6,6 Tetramethyl-4-piperidyl) sebacate (trade name: TINUVIN123, manufactured by Ciba Specialty Chemicals), 4-benzoyl-2,2,6,6-tetramethylpiperidine, dimethyl succinate / 1- ( 2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (trade name: TINUVIN622LD, manufactured by Ciba Specialty Chemicals), poly [{6- (1,1,3 , 3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2, 6,6-tetramethyl-4-piperidyl) imino}] (trade name: CHIMASSORB 944 LD, CHIMASSORB 944 FD, manufactured by Ciba Specialty Chemicals Etc. The.

  The blending amount of the component (D) is not particularly limited as long as it is an effective amount. It is preferably 1,000 ppm. When the blending amount is in the range of 10 to 20,000 ppm, the resulting cured product has excellent light stability and heat stability, and has excellent optical properties with no occurrence of coloring, white turbidity, oxidation deterioration, etc. You can get things.

  The hindered amine compound (D) may be used alone or in combination of two or more.

[Other optional ingredients]
In addition to the above components (A) to (D), other optional components can be blended in the composition of the present invention as necessary. Examples of the optional component include an antioxidant, an adhesion improver, an addition reaction control agent, an inorganic filler, a dye, a pigment, a flame retardant, and an organopolysiloxane having a silicon atom-bonded hydrogen atom other than the component (A), (B) Organopolysiloxane having an addition-reactive carbon-carbon double bond bonded to a silicon atom other than the component, a combination thereof and the like.

  As the antioxidant, all conventionally known antioxidants can be used. Specific examples thereof include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone, 4,4′-butylidenebis ( 3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), etc. .

  In the case of using an antioxidant, the blending amount thereof is not particularly limited as long as it is an effective amount as an antioxidant, but it is usually based on the total mass of the component (A) and the component (B). 10 to 10,000 ppm, particularly preferably 100 to 1,000 ppm. When the blending amount is 10 to 10,000 ppm, the antioxidant ability is sufficiently exerted, and a cured product having excellent optical characteristics without coloring, white turbidity, oxidation deterioration and the like is obtained.

  The organopolysiloxane having a silicon atom-bonded hydrogen atom other than the component (A) and the organopolysiloxane having an addition reactive carbon-carbon double bond bonded to the silicon atom other than the component (B) are the viscosity and curing of the composition. Linear diorganopolysiloxane or reticulated organopolysiloxane having a silicon atom-bonded alkenyl group or silicon atom-bonded hydrogen atom, which may be blended to adjust the hardness of the product, prevent cracks, etc., Non-reactive linear or cyclic diorganopolysiloxane, silphenylene compound and the like.

  Examples of the adhesion improver include various silane coupling agents having an alkoxysilyl group, 1- (2-trimethoxysilylethyl) -1,3,5,7-tetramethylcyclotetrasiloxane, 1- (2 -Trimethoxysilylethyl) -3- (3-glycidoxypropyl) -1,3,5,7-tetramethylcyclotetrasiloxane, vinyltrimethoxysilane, vinyltriethoxysilane and the like.

  The addition reaction control agent is a component that may be blended to ensure the pot life of the resulting composition, such as 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, etc. Is mentioned.

  An inorganic filler is a component for improving the intensity | strength of the hardened | cured material obtained, Comprising: For example, a fumed silica etc. are mentioned.

  Other optional components may be used alone or in combination of two or more.

[Method of preparing composition / cured product]
The composition of the present invention can be prepared by uniformly stirring the above components (A) to (D) and optionally other optional components. The order of mixing these components is not particularly limited. For example, (A) component and organopolysiloxane having silicon-bonded hydrogen atoms other than (A) component, and (D) component are stirred and mixed uniformly. The first solution, and then the (B) component and the organopolysiloxane having an addition reactive carbon-carbon double bond bonded to a silicon atom other than the (B) component and the (C) component are uniformly stirred and mixed. The second liquid can be prepared by finally stirring and mixing the first liquid and the second liquid uniformly. The cured composition can be obtained by heating and curing the composition. The curing conditions vary depending on the amount of the composition and are not particularly limited. However, it is usually preferable to heat at a temperature of 60 to 180 ° C. for 5 to 180 minutes.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not restrict | limited to the following Example at all.

<Synthesis Example> (Preparation of component (A))
To a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer, add 80 g of toluene and 115.2 g (0.48 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane, and add an oil bath. And heated to 117 ° C. To this, 0.05 g of carbon powder supporting 5% by mass of platinum metal was added and stirred with vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd .; 5-vinylbicyclo [2.2.1] hept-2-ene and 48 g (0.4 mol) of an isomer mixture of approximately equimolar amount with 6-vinylbicyclo [2.2.1] hept-2-ene was added dropwise over 16 minutes. After completion of the dropwise addition, the mixture was further stirred at 125 ° C. for 16 hours and then cooled to room temperature. Thereafter, platinum metal-supported carbon was removed by filtration, and toluene was distilled off under reduced pressure to obtain 150 g of a colorless and transparent oily reaction product (viscosity at 25 ° C .: 2,500 mPa · s).

As a result of analyzing the reaction product by FT-IR, NMR, GPC, etc., the reactive organism was
(1) Compound having one tetramethylcyclotetrasiloxane ring: about 6 mol%
(An example of a typical structural formula is shown below),

(2) Compound having two tetramethylcyclotetrasiloxane rings: about 25 mol%
(An example of a typical structural formula is shown below),

(3) Compound having three tetramethylcyclotetrasiloxane rings: about 16 mol%
(An example of a typical structural formula is shown below)

(4) having four tetramethylcyclotetrasiloxane rings: about 11 mol%
(An example of a typical structural formula is shown below),

And (5) Compound having 5 to 12 cyclotetrasiloxane rings: residue (an example of a typical structural formula is shown below)

（式中、ｎは４〜20の整数である。）
の混合物であることが判明した。また、これらの反応生成物が有するケイ素原子結合水素原子の量は、平均して6.25mmol/gであった。

(In the formula, n is an integer of 4 to 20.)
It was found to be a mixture of The amount of silicon atom-bonded hydrogen atoms contained in these reaction products was 6.25 mmol / g on average.

<Example 1>
In the following examples, optional components of the composition of the present invention are shown as (Other 1) and (Other 2).
(A) Reaction product obtained in synthesis example: 50 parts by mass,
(B) Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical, trade name: NK ester A-DCP): 38 parts by mass,
(Other 1) ViMe ₂ SiO (Me ₂ SiO) ₈ SiMe ₂ Vi (Vi represents a vinyl group): 2 parts by mass ([silicon atom-bonded hydrogen atom in component (A)] / [in component (B) Vinyl group + (other 1) vinyl group in component] (molar ratio) = 1.5)
(C) Platinum-vinylsiloxane complex: As a platinum metal atom, 20 ppm on a mass basis with respect to the total amount of the component (A) and the component (B),
(D) Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (manufactured by Asahi Denka Co., Ltd., trade name: Kastab LA77Y): mass relative to the sum of component (A) and component (B) 500ppm by standard,
(Other 2) 1- (2-Trimethoxysilylethyl) -3- (3-glycidoxypropyl) -1,3,5,7-tetramethylcyclotetrasiloxane: 10 parts by mass, and (Other 3) 1 -Ethynylcyclohexanol: A composition was obtained by uniformly mixing 0.03 parts by mass. This composition was poured into a mold made of glass plates to a thickness of 2 mm and heated at 150 ° C. for 2 hours to obtain a cured product.

<Example 2>
In Example 1, instead of tricyclodecane dimethanol diacrylate as component (B), 38 parts by mass of tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester DCP) was used ([( Except for A) silicon-bonded hydrogen atom in component] / [isopropenyl group in component (B) + vinyl group in component 1) (molar ratio) = 1.6), the same as in Example 1. A composition and a cured product were obtained.

<Example 3>
In Example 1, 38 parts by mass of a diacrylate compound (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD R-604) was used in place of the tricyclodecane dimethanol diacrylate of the component (B) ([(A) component In the same manner as in Example 1, except that the silicon atom-bonded hydrogen atom] / [vinyl group in component (B) + (vinyl group in component 1)] (molar ratio) = 1.5) A cured product was obtained.

<Comparative Example 1>
As the composition, a phenyl silicone resin-based curable composition (trade name: X-34-1195, manufactured by Shin-Etsu Chemical Co., Ltd., phenyl group content: about 50 mol%) was used, and the composition was assembled with a glass plate. Poured into a mold to a thickness of 2 mm and heated at 150 ° C. for 8 hours to obtain a cured product.

<Evaluation method>
About the composition and hardened | cured material which were prepared in the said Example and comparative example, the initial stage performance and durability were evaluated in accordance with the following method. The obtained results are shown in Table 1.
1. Initial performance-(1) Appearance-
The appearance of each cured product was visually observed. A case where the cured product is colorless and transparent is evaluated as “good” as A, and a case where yellowing is observed is evaluated as “bad” as B.
− (2) Hardness−
The hardness (Shore D) of each cured product was measured according to ASTM D2240.
− (3) Light transmittance−
Using a spectrophotometer, the light transmittance (%) of each cured product at a wavelength of 400 nm was measured.

2. Durability-(4) Light resistance test-
Using an eye super UV tester W151 type (trade name, manufactured by Iwasaki Electric Co., Ltd., metal halide lamp type), each cured product was irradiated with ultraviolet rays (irradiation amount: 140 MJ / m ² ), and light transmittance at a wavelength of 400 nm (%) Was measured.
− (5) Heat resistance test−
When each cured product was stored in an environment of 150 ° C. for 500 hours, the light transmittance (%) at a wavelength of 400 nm was measured.
− (6) Crack resistance test−
Each composition was encapsulated in a 0.2 mm square optical semiconductor in a 3 mmφ polyphthalamide LED cup with electrodes and wire-bonded with a gold wire, and then cured. With respect to the obtained LED element, the presence or absence of cracks and the adhesiveness were observed when 50 cycles of -40 ° C. and 100 ° C. were performed. Evaluate as “A” when cracks are not observed and peeling is not recognized, and indicate “A”, and when cracks are observed or peeling is evaluated as “bad” Shown as B.

<Evaluation>
The cured products prepared in Examples 1 to 3 were all excellent in light resistance, heat resistance and crack resistance. On the other hand, the cured product (cured product obtained by curing the conventional resin composition) prepared in Comparative Example 1 that does not satisfy the requirements of the present invention is light resistant, compared with the cured products of Examples 1 to 3 above. The heat resistance and crack resistance were extremely inferior.

Claims (3)

(A) (a) 1,3,5,7-tetramethylcyclotetrasiloxane and (b) 5-vinylbicyclo [2.2.1] hept-2-ene and 6-vinylbicyclo [2.2.1] hept- A siloxane-polycyclic hydrocarbon compound which is an addition reaction product with at least one of 2-enes and has two or more hydrogen atoms bonded to a silicon atom in one molecule;
(B) an organic compound having a total of two or more acryloyl groups and / or methacryloyl groups in one molecule;
(C) a hydrosilylation reaction catalyst, and (D) a hindered amine compound,
A curable silicone resin composition containing   The amount of hydrogen atoms bonded to silicon atoms in the composition is 0.3 to 3.0 moles per mole of addition-reactive carbon-carbon double bonds bonded to silicon atoms in the composition. The proportion of hydrogen atoms bonded to silicon atoms in the component (A) in the hydrogen atoms bonded to silicon atoms is 20 to 100 mol%, and the addition reactive carbon bonded to silicon atoms in the composition is − The composition according to claim 1, wherein the proportion of alkenyl groups of the acryloyl group and methacryloyl group in the component (B) in the carbon double bond is 20 to 100 mol%. The component (B) has the following formula:

(In the formula, A represents the following formula (a1):

(A1)
Or a group represented by the following formula (a2):

(A2)
R represents a hydrogen atom or a methyl group. )
The composition according to claim 1 or 2 , which is an organic compound represented by the formula: