JP6941455B2 - Curable composition - Google Patents

Description

The present invention relates to a curable composition that provides good mechanical properties.

A curable material using a material design technique based on silicone modification is known. For example, Patent Document 1 provides a well-balanced and sufficient level of hardness, gas barrier property, heat-resistant yellowing, light resistance, cold-heat impact resistance, and adhesion to a substrate, particularly required for optical semiconductor applications. In order to provide an organopolysiloxane capable of forming a cured product, which is satisfied with the above, one molecule contains one or more unsaturated bond-containing groups, and cyclic organopolysiloxane is used as an essential constituent unit. Organopolysiloxanes are disclosed.

Further, Patent Document 2 is a compound having a polycyclic hydrocarbon skeleton, for the purpose of providing a curable composition capable of providing a cured product having excellent light transmittance particularly in a short wavelength region. A curable composition containing a reaction product using vinyl norbornene as a raw material is disclosed.

WO2012 / 133432 Japanese Patent Application Laid-Open No. 2005-133073

However, since silicone resins generally have soft and brittle properties, it is difficult to improve mechanical properties such as tensile elastic modulus, tensile elongation, and breaking energy.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a curable composition capable of giving a cured product having excellent tensile elastic modulus, tensile elongation, and breaking energy.

As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by using a predetermined silicone resin, and have completed the present invention.

（式（１）中、Ｒ¹は、各々独立して、非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は、非置換若しくは置換の炭素原子数１〜６アルコキシ基であり、Ａは、各々独立して、下記一般式（２）で表される基、又は、フェニレン基であり、Ｂ¹は、各々独立して、付加反応性炭素−炭素二重結合を１つ以上有する、非置換若しくは置換の１価の多環式炭化水素基であり、Ｂ²は、各々独立して、非置換若しくは置換の２価の多環式炭化水素基であり、ｐは０以上の整数である。

（式中、Ｒ²は、各々独立して、非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は、非置換若しくは置換の炭素原子数１〜６のアルコキシ基であり、ｎは０〜１００の整数である。））
ケイ素原子に結合した水素原子を１分子中に３個以上有する化合物（Ｂ）と、を含み、
前記化合物（Ｂ）が、環状シロキサン；環状シロキサンのケイ素原子に結合する１以上の水素原子に代えてノルボルネン骨格又はノルボルナン骨格を有する多環式炭化水素基を有する化合物；及び、環状シロキサンのケイ素原子に結合する１以上の水素原子に代えて下記一般式（５）で表される置換基を有する化合物からなる群より選ばれる少なくとも１つを含み、

（式（１）中、Ｒ ¹ は、各々独立して、非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は、非置換若しくは置換の炭素原子数１〜６アルコキシ基であり、Ａは、各々独立して、下記一般式（２）で表される基、又は、フェニレン基であり、Ｂ ¹ は、各々独立して、付加反応性炭素−炭素二重結合を１つ以上有する、非置換若しくは置換の１価の多環式炭化水素基であり、Ｂ ² は、各々独立して、非置換若しくは置換の２価の多環式炭化水素基であり、ｐは０以上の整数である。

（式中、Ｒ ² は、各々独立して、非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は、非置換若しくは置換の炭素原子数１〜６のアルコキシ基であり、ｎは０〜１００の整数である。））
化合物（Ｂ）中のケイ素原子に結合した水素原子の量は、化合物（Ａ）中の付加反応性炭素−炭素二重結合１ｍｏｌに対して、１．０〜１．５ｍｏｌであり、
上記一般式（１）中、ｐ＝０で表される化合物を化合物（Ａ１）とし、ｐ≧１で表される化合物を化合物（Ａ２）としたとき、
前記化合物（Ａ２）の含有量が、下記条件によるゲルパーミエーションクロマトグラフィーで得られる前記化合物（Ａ１）及び前記化合物（Ａ２）の総面積に対して、５面積％以上２０面積％以下である、
硬化性組成物。
条件：
前記化合物（Ａ）０．１ｇに対して、２ｍｌの割合でクロロホルム溶媒に溶解した溶液を測定試料とする。この測定試料を用いて、東ソー社製ＬＣ−８０２０で測定する。カラムは東ソー社製のＴＳＫガードカラムＨＨＲ−Ｈ、ＴＳＫｇｅｌ Ｇ５０００ＨＨＲ、ＴＳＫｇｅｌ Ｇ３０００ＨＨＲ、ＴＳＫｇｅｌ Ｇ１０００ＨＨＲを直列に連結して使用し、クロロホルムを移動相として１ｍｌ／分の速度で分析する。検出器はＲＩディテクターを使用し、Ｐｏｌｙｍｅｒ Ｌａｂｏｒａｔｏｒｉｅｓ製Ｅａｓｙ Ｃａｌ ＰＳ−２（分子量：３７７４００、９６０００、１９７２０、４４９０、１１８０、１８８７００、４６５００、９９２０、２３６０、５８０）のポリスチレン、及びスチレンモノマー（分子量１０４）を標準物質として数平均分子量及び重量平均分子量を求め、ｐ＝０及び、ｐ≧１のピークを特定し、それぞれのピークの面積比を算出する。
〔２〕
前記化合物（Ａ）が、上記一般式（１）中の下記一般式（３）で表される構成単位として、下記一般式（４）で表される構成単位を有する、〔１〕に記載の硬化性組成物。

〔３〕
前記化合物（Ａ）が、上記一般式（１）中のＢ¹で表される構成単位として、ノルボルネン骨格又はノルボルナン骨格を有する多環式炭化水素基、及び／又は、上記一般式（１）中のＢ²で表される構成単位として、ノルボルナン骨格を有する多環式炭化水素基を有する、〔１〕又は〔２〕に記載の硬化性組成物。
〔４〕
ヒドロシリル化反応触媒（Ｃ）をさらに含む、〔１〕〜〔３〕のいずれか１項に記載の
硬化性組成物。
〔５〕
密着性改良剤（Ｄ）をさらに含む、〔１〕〜〔４〕のいずれか１項に記載の硬化性組成物。
〔６〕
〔１〕〜〔５〕のいずれか1項に記載の硬化性組成物の硬化物。 That is, the present invention is as follows.
[1]
Compound (A) represented by the following general formula (1) and

(In the formula (1), R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms. Yes, A is an independent group represented by the following general formula (2) or a phenylene group, and B ¹ is an independent addition-reactive carbon-carbon double bond. The above-mentioned unsubstituted or substituted monovalent polycyclic hydrocarbon group, B ² is independently unsubstituted or substituted divalent polycyclic hydrocarbon group, and p is 0 or more. Is an integer of.

(In the formula, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms. n is an integer from 0 to 100.)))
Include hydrogen atoms bonded to silicon atoms organic compound 3 or more in one molecule (B), and a,
The compound (B) is a cyclic siloxane; a compound having a polycyclic hydrocarbon group having a norbornene skeleton or a norbornan skeleton instead of one or more hydrogen atoms bonded to a silicon atom of the cyclic siloxane; and a silicon atom of the cyclic siloxane. It contains at least one selected from the group consisting of compounds having a substituent represented by the following general formula (5) in place of one or more hydrogen atoms bonded to.

(In the formula (1), R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms. Yes, A is an independent group represented by the following general formula (2) or a phenylene group, and B ¹ is an independent addition-reactive carbon-carbon double bond. The above-mentioned unsubstituted or substituted monovalent polycyclic hydrocarbon group, B ² is independently unsubstituted or substituted divalent polycyclic hydrocarbon group, and p is 0 or more. Is an integer of.

(In the formula, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms. n is an integer from 0 to 100.)))
The amount of the hydrogen atom bonded to the silicon atom in the compound (B) is 1.0 to 1.5 mol with respect to 1 mol of the addition-reactive carbon-carbon double bond in the compound (A).
In the above general formula (1), when the compound represented by p = 0 is defined as the compound (A1) and the compound represented by p ≧ 1 is designated as the compound (A2).
The content of the compound (A2) is 5 area% or more and 20 area% or less with respect to the total area of the compound (A1) and the compound (A2) obtained by gel permeation chromatography under the following conditions.
Curable composition.
conditions:
A solution prepared by dissolving 0.1 g of the compound (A) in a chloroform solvent at a ratio of 2 ml is used as a measurement sample. Using this measurement sample, measurement is performed with LC-8020 manufactured by Tosoh Corporation. As the column, TSK guard columns HHR-H, TSKgel G5000HHR, TSKgel G3000HHR, and TSKgel G1000HHR manufactured by Tosoh Corporation are used in series, and chloroform is used as a mobile phase for analysis at a rate of 1 ml / min. The detector uses an RI detector, and polystyrene and styrene monomer (molecular weight 104) of Polymer Laboratories Easi Cal PS-2 (molecular weight: 377400, 96000, 19720, 4490, 1180, 188700, 46500, 9920, 2360, 580). The number average molecular weight and the weight average molecular weight are obtained, the peaks of p = 0 and p ≧ 1 are specified, and the area ratio of each peak is calculated.
[2]
The compound (A) according to [1], wherein the compound (A) has a structural unit represented by the following general formula (4) as a structural unit represented by the following general formula (3) in the general formula (1). Curable composition.

[3]
The compound (A) is a ^{polycyclic hydrocarbon group having a norbornene skeleton or a norbornane skeleton as a structural unit represented by B 1} in the general formula (1), and / or in the general formula (1). The curable composition according to [1] or [2], which has a polycyclic hydrocarbon group having a norbornene skeleton as a structural unit represented by ^{B 2.}
[4]
The curable composition according to any one of [1] to [3], further comprising a hydrosilylation reaction catalyst (C).
[5]
The curable composition according to any one of [1] to [4], further comprising an adhesion improver (D).
[6]
The cured product of the curable composition according to any one of [1] to [5].

According to the present invention, it is possible to provide a curable composition capable of giving a cured product having excellent tensile elastic modulus, tensile elongation, and breaking energy.

Hereinafter, embodiments of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from the gist thereof. Is.

（式（１）中、Ｒ¹は、各々独立して、非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は、非置換若しくは置換の炭素原子数１〜６アルコキシ基であり、Ａは、各々独立して、下記一般式（２）で表される基、又は、フェニレン基であり、Ｂ¹は、各々独立して、付加反応性炭素−炭素二重結合を１つ以上有する、非置換若しくは置換の１価の多環式炭化水素基であり、Ｂ²は、各々独立して、非置換若しくは置換の２価の多環式炭化水素基であり、ｐは０以上の整数である。

（式中、Ｒ²は、各々独立して、非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は、非置換若しくは置換の炭素原子数１〜６のアルコキシ基であり、ｎは０〜１００の整数である。））
上記一般式（１）中、ｐ＝０で表される化合物を化合物（Ａ１）とし、ｐ≧１で表される化合物を化合物（Ａ２）としたとき、
前記化合物（Ａ２）の含有量が、ゲルパーミエーションクロマトグラフィーで得られる前記化合物（Ａ１）及び前記化合物（Ａ２）の総面積に対して、０面積％以上５０面積％未満である。 [Curable composition]
The curable composition of the present embodiment contains the compound (A) represented by the following general formula (1).

(In the formula (1), R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms. Yes, A is an independent group represented by the following general formula (2) or a phenylene group, and B ¹ is an independent addition-reactive carbon-carbon double bond. The above-mentioned unsubstituted or substituted monovalent polycyclic hydrocarbon group, B ² is independently unsubstituted or substituted divalent polycyclic hydrocarbon group, and p is 0 or more. Is an integer of.

(In the formula, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms. n is an integer from 0 to 100.)))
In the above general formula (1), when the compound represented by p = 0 is defined as the compound (A1) and the compound represented by p ≧ 1 is designated as the compound (A2).
The content of the compound (A2) is 0 area% or more and less than 50 area% with respect to the total area of the compound (A1) and the compound (A2) obtained by gel permeation chromatography.

[Compound (A)]
The compound (A) is a compound represented by the above general formula (1), and has a linear structure having a structural unit represented by the following ^{general formula (3) and a structural unit represented by B 2.} However, both ends thereof are sealed with ^{B 1} , which is a monovalent polycyclic hydrocarbon group having one or more addition-reactive carbon-carbon double bonds.

(Constituent unit represented by the general formula (3))
The number of carbon atoms of the monovalent hydrocarbon group in the structural unit represented by the general formula (3) is 1 to 12, preferably 1 to 6. Such a monovalent hydrocarbon group is not particularly limited, but for example, a methyl group, an ethyl, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, a sec-hexyl group. Alkyl group such as: cyclopentyl group, cycloalkyl group such as cyclohexyl group; aryl group such as phenyl group, o-, m-, p-tolyl; aralkyl group such as benzyl group, 2-phenylethyl group; vinyl group, allyl Examples include an alkenyl group such as a group, a 1-butenyl group and a 1-hexenyl group; and an alkenylaryl group such as a p-vinylphenyl group.

The substituent of the monovalent hydrocarbon group is not particularly limited, and examples thereof include a halogen atom, a cyano group, and an epoxy ring-containing group. The monovalent hydrocarbon group in which one or more hydrogen atoms bonded to a carbon atom are substituted with such a substituent is not particularly limited, and is, for example, a chloromethyl group, a 3-chloropropyl group, 3,3. Alkyl halide groups such as 3-trifluoropropyl group; 2-cyanoethyl group; 3-glycidoxypropyl group and the like can be mentioned.

The number of carbon atoms of the alkoxy group in the structural unit represented by the general formula (3) is 1 to 6, preferably 1 to 4. Examples of such an alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group and the like. The substituent of the alkoxy group is not particularly limited, and examples thereof include a halogen atom, a cyano group, and an epoxy ring-containing group.

Among the above, the R ¹ is preferably one other than an alkenyl group and an alkenylaryl group, and in particular, ^one in which all of R 1 is a methyl group is easy to industrially produce and easily available. Therefore, it is preferable.

Each of A is independently a group represented by the above general formula (2) or a phenylene group. ^{R 2} in the general formula (2) is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms. Yes, as a specific example thereof, the same as the above-mentioned R ¹ can be mentioned. R ² may be a group similar to or different from ^{R 1.}

In the general formula (2), n is an integer of 0 to 100, preferably an integer of 0 to 50, more preferably an integer of 0 to 10, and even more preferably an integer of 0 to 5. When A is a phenylene group, the hydrogen to be substituted may be in the ortho-position, the meta-position, or the para-position.

Among the above, the structural unit represented by the general formula (3) is not particularly limited, but for example, the structural unit represented by the following general formula (4) is preferable. By having such a structural element, the tensile elastic modulus, tensile elongation, and breaking energy of the obtained cured product tend to be further improved.

(Constituent unit represented by ^{B 1)}
B ¹ is not particularly limited as long as it is an unsubstituted or substituted monovalent polycyclic hydrocarbon group having one or more addition-reactive carbon-carbon double bonds, and for example, the following formula (NB11) to A polycyclic hydrocarbon group having a norbornene skeleton or a norbornane skeleton represented by (NB16) and a polycyclic hydrocarbon group having a dicyclopentadiene-derived skeleton represented by the following formulas (DCP11) to (DCP17) Can be mentioned. Among these, a polycyclic hydrocarbon group having a norbornene skeleton or a norbornane skeleton is preferable. By having such a structural element, the tensile elastic modulus, tensile elongation, and breaking energy of the obtained cured product tend to be further improved. The following polycyclic hydrocarbon groups having a norbornene skeleton or norbornane skeleton are collectively abbreviated as "NB1 group", and the polycyclic hydrocarbon groups having a dicyclopentadiene-derived skeleton are collectively referred to as "DCP1 group". May be abbreviated as.

(Constituent unit represented by ^{B 2)}
The ^{structural unit represented by B 2} is not particularly limited as long as it is an unsubstituted or substituted divalent polycyclic hydrocarbon group, and for example, a norbornane skeleton represented by the following formulas (NB21) to (NB24). Examples thereof include a polycyclic hydrocarbon group having the above, and a polycyclic hydrocarbon group having a dicyclopentadiene-derived skeleton represented by the following formulas (DCP21) to (DCP26). Among these, a polycyclic hydrocarbon group having a norbornane skeleton is preferable. By having such a structural element, the tensile elastic modulus, tensile elongation, and breaking energy of the obtained cured product tend to be further improved. The following polycyclic hydrocarbon groups having a norbornene skeleton or norbornane skeleton are collectively abbreviated as "NB2 groups", and the polycyclic hydrocarbon groups having a dicyclopentadiene-derived skeleton are collectively referred to as "DCP2 groups". May be abbreviated as. B ² may have an addition-reactive carbon-carbon double bond.

The asymmetrical divalent residues represented by the above formula are not limited in the left-right direction as described above, and the above structural formula is substantially 180 for each of the above structures on paper. It may have a structure rotated by a degree.

[Number of addition-reactive carbon-carbon double bonds]
The number of addition-reactive carbon-carbon double bonds contained in one molecule of compound (A) is 2 or more, preferably 2 to 6, and more preferably 2. When the number of addition-reactive carbon-carbon double bonds is two or more, the tensile elastic modulus, tensile elongation, and breaking energy of the obtained cured product are further improved. Further, when the number of addition-reactive carbon-carbon double bonds is 6 or less, the obtained cured product tends to be more suppressed from being easily cracked. The addition-reactive carbon-carbon double bond of compound (A) is ^{derived from B 1} , and may have an addition-reactive carbon-carbon double bond in the side chain.

In the present embodiment, in the above general formula (1), the compound represented by p = 0 is designated as compound (A1), and the compound represented by p ≧ 1 is designated as compound (A2). At this time, the content of the compound (A2) is 0 area% or more and less than 50 area%, preferably 0, with respect to the total area of the compound (A1) and the compound (A2) obtained by gel permeation chromatography. Area% or more and 40 area% or less, more preferably 0 area% or more and 35 area% or less, and further preferably 1 area% or more and 35 area% or less. When the content of the compound (A2) is less than 50 area%, the tensile elastic modulus, tensile elongation, and breaking energy of the obtained cured product are further improved. Further, when the content of the compound (A2) is 1 area% or more, the reflow resistance is further improved, and when the content of the compound (A2) is 25 area% or less, the gas barrier property is further improved. There is a tendency. Further, when the content of the compound (A2) is 5 area% or more and 20 area% or less, the breaking energy tends to be further improved.

The content (area ratio) of the compound (A2) with respect to the total area of the compound (A1) and the compound (A2) obtained by gel permeation chromatography can be measured by the method described in Examples.

Further, p of compound (A2) is 1 or more, preferably 1 to 100, and more preferably an integer of 1 to 10. When the p of the compound (A2) is within the above range, the reflow resistance, the gas barrier property, and the breaking energy tend to be further improved.

The value of p in the general formula (1) is an addition that reacts with 1 mol of the compound (a) having two hydrogen atoms bonded to silicon atoms in one molecule in the method for producing the compound (A) described later. It can be reduced by increasing the amount of the polycyclic hydrocarbon compound (b) having two reactive carbon-carbon double bonds in one molecule. That is, by increasing the amount of the compound (b), the content of the compound (A1) tends to be further increased, and the content of the compound (A2) tends to be further decreased.

The above-mentioned compound (A1) is not particularly limited, and examples thereof include those described below. The meanings of "NB" and "DCP" are as described above. Compound (A1) can be used alone or in combination of two or more.
NB-Me ₂ SiOSiMe _2-NB
NB-Me ₂ SiO (Me ₂ SiO) SiMe _2-NB
NB-Me ₂ SiO (Me ₂ SiO) ₄ SiMe _2-NB
NB-Me ₂ SiO (Me ₂ SiO) ₈ SiMe _2-NB
NB-Me ₂ SiO (Me ₂ SiO) ₁₂ SiMe _2-NB
NB-Me ₂ Si-p-C ₆ H _4- SiMe _2-NB
NB-Me ₂ Si-m-C ₆ H _4- SiMe _2-NB
DCP-Me ₂ SiOSiMe _2-DCP
DCP-Me ₂ SiO (Me ₂ SiO) SiMe _2- DCP
DCP-Me ₂ SiO (Me ₂ SiO) ₄ SiMe _2- DCP
DCP-Me ₂ SiO (Me ₂ SiO) ₈ SiMe _2- DCP
DCP-Me ₂ SiO (Me ₂ SiO) ₁₂ SiMe _2- DCP
DCP-Me ₂ Si-p-C ₆ H _4- SiMe _2- DCP
DCP-Me ₂ Si-m-C ₆ H _4- SiMe _2- DCP

The above-mentioned compound (A2) is not particularly limited, and examples thereof include those described below. The meanings of "NB" and "DCP" are as described above. Further, in the following formula, p is an integer of 1 or more. The compound (A2) can be used alone or in combination of two or more.

[Method for producing compound (A)]
The compound (A) is a compound (a) having two hydrogen atoms bonded to a silicon atom in one molecule and a polycyclic hydrocarbon compound having two addition-reactive carbon-carbon double bonds in one molecule. It can be obtained by subjecting (b) and to an addition reaction.

（式中、Ｒ¹は、各々独立して、非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は、非置換若しくは置換の炭素原子数１〜６アルコキシ基であり、Ａは、下記一般式（２）で表される基、又は、フェニレン基である。

（式中、Ｒ²は、各々独立して、非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は、非置換若しくは置換の炭素原子数１〜６のアルコキシ基であり、ｎは０〜１００の整数である。）） (Compound (a))
The compound (a) is not particularly limited, and examples thereof include a compound represented by the following general formula (6).

(In the formula, R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted carbon atom number 1 to 6 alkoxy group, respectively, and A. Is a group represented by the following general formula (2) or a phenylene group.

(In the formula, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms. n is an integer from 0 to 100.)))

（式中、Ｒ¹及びＲ²は、各々独立して、非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は、非置換若しくは置換の炭素原子数１〜６アルコキシ基であり、ｎは０〜１００の整数である。） (Compound (a) in which A is a group represented by the above general formula (2))
The compound (a) in which A is a group represented by the general formula (2) is not particularly limited, and examples thereof include a compound represented by the following general formula (7).

(In the formula, R ¹ and R ² are independently substituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, or unsubstituted or substituted alkoxy groups having 1 to 6 carbon atoms. Yes, n is an integer from 0 to 100.)

In the general formulas (6), (2), and (7) representing the compound (a), the number of carbon atoms of the monovalent hydrocarbon group is 1 to 12, preferably 1 to 6. Such a monovalent hydrocarbon group is not particularly limited, but for example, a methyl group, an ethyl, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, a sec-hexyl group. Alkyl group such as: cyclopentyl group, cycloalkyl group such as cyclohexyl group; aryl group such as phenyl group, o-, m-, p-tolyl; aralkyl group such as benzyl group, 2-phenylethyl group; vinyl group, allyl Examples include an alkenyl group such as a group, a 1-butenyl group and a 1-hexenyl group; and an alkenylaryl group such as a p-vinylphenyl group.

In the general formulas (6), (2), and (7) representing the compound (a), the substituent of the monovalent hydrocarbon group is not particularly limited, but is, for example, a halogen atom, a cyano group, or an epoxy ring-containing group. And so on. The monovalent hydrocarbon group in which one or more hydrogen atoms bonded to a carbon atom are substituted with such a substituent is not particularly limited, and is, for example, a chloromethyl group, a 3-chloropropyl group, 3,3. Alkyl halide groups such as 3-trifluoropropyl group; 2-cyanoethyl group; 3-glycidoxypropyl group and the like can be mentioned.

Further, in the general formulas (6), (2), and (7) representing the compound (a), the number of carbon atoms of the alkoxy group is 1 to 6, preferably 1 to 4. Examples of such an alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group and the like. The substituent of the alkoxy group is not particularly limited, and examples thereof include a halogen atom, a cyano group, and an epoxy ring-containing group.

^{Among the above, as the above R 1} and R ^{2 in the} general formulas (6), (2) and (7) representing the compound (a), those other than the alkenyl group and the alkenylaryl group are preferable, and in particular, R ¹ And R ² in which all of them are methyl groups are preferable because they are easy to industrially produce and easily available.

Further, in the general formulas (2) and (7) representing the compound (a), n is an integer of 0 to 100, preferably an integer of 0 to 50, and more preferably an integer of 0 to 10. More preferably, it is an integer of 0 to 5.

The compound represented by the general formula (7) is not particularly limited, and examples thereof include compounds represented by the following general formula. Hereinafter, "Me" means a methyl group. The compound (a) represented by the general formula (7) can be used alone or in combination of two or more.
HMe ₂ SiOSiMe ₂ H
HMe ₂ SiO (Me ₂ SiO) SiMe ₂ H
HMe ₂ SiO (Me ₂ SiO) ₄ SiMe ₂ H
HMe ₂ SiO (Me ₂ SiO) ₈ SiMe ₂ H
HMe ₂ SiO (Me ₂ SiO) ₁₂ SiMe ₂ H

（式中、Ｒ¹は、各々独立して、非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は、非置換若しくは置換の炭素原子数１〜６アルコキシ基である。） (Compound (a) in which A is represented by a phenylene group)
The compound (a) in which A is represented by a phenylene group is not particularly limited, and examples thereof include a compound represented by the following general formula (8). The two −SiR ¹ ₂ H groups may be in the ortho-position, meta-position, or para-position.

(In the formula, R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted carbon atom number 1 to 6 alkoxy group.)

^{Examples of R 1} in the general formula (8) include the same groups as those in the general formulas (6), (2), and (7). Among these, those other than the alkenyl group and the alkenylaryl group are preferable, and those in which all of them are methyl groups are particularly preferable.

The compound represented by the general formula (8) is not particularly limited, and examples thereof include a silphenylene compound represented by the following general formula. The compound (a) represented by the general formula (8) can be used alone or in combination of two or more.
HMe ₂ Si-p-C ₆ H _4- SiMe ₂ H: 1,4-bis (dimethylsilyl) benzene HMe ₂ Si-m-C ₆ H _4- SiMe ₂ H: 1,3-bis (dimethylsilyl) benzene

Compound (a) can be used alone or in combination of two or more. As the compound (a), 1,1,3,3,-tetramethyldisiloxane is preferable from the viewpoint of photoyellowing resistance of the cured product of the curable composition of the present embodiment.

(Compound (b))
Compound (b) is a polycyclic hydrocarbon compound having two addition-reactive carbon-carbon double bonds in one molecule. In the present embodiment, the "addition reactivity" means a property capable of receiving the addition of a hydrogen atom bonded to a silicon atom (known as a hydrosilylation reaction).

The compound (b) is not particularly limited, but for example, (i) an addition-reactive carbon-carbon between two adjacent carbon atoms among the carbon atoms forming the polycyclic skeleton of a polycyclic hydrocarbon. Double bonds are formed; (ii) Hydrogen atoms bonded to carbon atoms forming the polycyclic skeleton of polycyclic hydrocarbons are replaced by addition-reactive carbon-carbon double bond-containing groups. Or, of the carbon atoms forming the polycyclic skeleton of (iii) polycyclic hydrocarbons, an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms. In addition, the hydrogen atom bonded to the carbon atom forming the polycyclic skeleton of the polycyclic hydrocarbon is substituted with an addition-reactive carbon-carbon double bond-containing group.

Examples of compound (b) include 5-vinylbicyclo [2.2.1] hept-2-ene represented by the following general formula (x); 6-vinylbicyclo represented by the following general formula (y). [2.2.1] Hept-2-ene, a combination of both (hereinafter, when it is not necessary to distinguish between these three, they may be collectively referred to as "vinyl norbornene"); the following general formula (z). Examples thereof include dicyclopentadiene represented by. The vinyl group substitution position of vinyl norbornene may be either a cis configuration (exo type) or a trans configuration (end type), and currently industrially available vinyl norbornene is a mixture of isomers of both configurations. Therefore, these amounts may be a combination of isomers.

(Addition reaction conditions)
The conditions for the addition reaction between the compound (a) and the compound (b) are not particularly limited as long as the SiH group and the addition-reactive carbon-carbon double bond undergo a hydrosilylation reaction. Hereinafter, suitable reaction conditions in this embodiment will be described, but the reaction conditions in this embodiment are not limited to the following.

The amount of the compound (b) used is preferably more than 10 mol and 30 mol or less, and more preferably 15 mol or more and 25 mol or less with respect to 1 mol of the compound (a). By making the amount of compound (b) used in excess of the amount of compound (a) used, it has two addition-reactive carbon-carbon double bonds derived from the structure of the component (b) in one molecule. Compound (A) can be obtained. The obtained compound (A) has a residue derived from the above component (a), and the residue is derived from the structure of the above component (b) but does not have an addition-reactive carbon-carbon double bond. It may contain a structure linked by a divalent residue of a polycyclic hydrocarbon.

In the addition reaction of compound (a) and compound (b), a hydrosilylation reaction catalyst may be used if necessary. As the hydrosilylation reaction catalyst, all conventionally known catalysts can be used. For example, carbon powder carrying platinum metal, platinum black, second platinum chloride, platinum chloride acid, reaction product of platinum chloride acid and monovalent alcohol, complex of platinum chloride acid and olefins, platinum bisacetoacetate, etc. Platinum-based catalysts; examples thereof include platinum-based metal-based catalysts such as palladium-based catalysts and rhodium-based catalysts. Further, other addition reaction conditions, use of a solvent, etc. are not particularly limited and may be as usual.

[Compound (B)]
The curable composition of the present embodiment may further contain compound (B) having three or more hydrogen atoms bonded to silicon atoms in one molecule. The compound (B) can be added to the compound (A) by the hydrosilylation reaction between the SiH contained in the compound (B) and the addition-reactive carbon-carbon double bond contained in the compound (A). .. At this time, the compound (B) having three or more SiH functions as a cross-linking point having three or more branches. Thereby, a cured product having a three-dimensional network structure can be provided.

（式中、Ｒ１は独立に水素原子又はアルケニル基以外の非置換若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、ｑは３〜１０、好ましくは３〜８の整数、ｒは０〜７、好ましくは０〜２の整数であり、かつｑ＋ｒの和は３〜１０、好ましくは３〜６の整数である） The compound (B) is not particularly limited, and examples thereof include cyclic siloxane compounds represented by the following general formula (9).

(In the formula, R1 is independently an unsubstituted or substituted monovalent hydrocarbon group other than a hydrogen atom or an alkenyl group, preferably 1 to 6 monovalent hydrocarbon groups, and q is 3 to 10, preferably 3. An integer of ~ 8, r is an integer of 0-7, preferably an integer of 0-2, and the sum of q + r is an integer of 3-10, preferably an integer of 3-6).

When R1 in the above general formula (7) is an unsubstituted or substituted monovalent hydrocarbon group other than an alkenyl group, for example, a methyl group, an ethyl, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, etc. Alkyl groups such as pentyl group, isopentyl group, hexyl group, sec-hexyl group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; aryl group such as phenyl group, o-, m-, p-tolyl; benzyl group, 2 -Aralkyl groups such as phenylethyl group; -alkenylaryl groups such as vinylphenyl group; and one or more hydrogen atoms bonded to carbon atoms in these groups are halogen atoms, cyano groups, epoxy ring-containing groups, etc. Substituted alkyl groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group; 2-cyanoethyl group; 3-glycidoxypropyl group and the like can be mentioned.
Among the above, as the R1, those in which all of them are methyl groups are particularly preferable because they are easily industrially produced and easily available.

（式中、ｓは１〜１００、好ましくは１〜１０の整数である） Further, as the compound (B), from the viewpoint of suppressing volatilization of 1,3,5,7-tetramethylcyclotetrasiloxane at the time of curing, for example, one or two of the above vinyl norbornene and 1,3,5,7 Examples of the addition reaction product having three or more SiHs in one molecule obtained by hydrosilylation reaction with tetramethylcyclotetrasiloxane, for example, a compound represented by the following general formula (10) can be mentioned.

(In the formula, s is an integer of 1 to 100, preferably 1 to 10)

（式中、ｔは１〜１００、好ましくは１〜１０の整数である） Further, as the compound (B), for example, from the viewpoint of suppressing volatilization of 1,3,5,7-tetramethylcyclotetrasiloxane during curing, for example, the compound (A) and 1,3,5,7-tetra Examples thereof include addition reaction products having three or more SiHs in one molecule obtained by hydrosilylation reaction with methylcyclotetrasiloxane, for example, a compound represented by the following general formula (11).

(In the formula, t is an integer of 1 to 100, preferably 1 to 10)

Examples of the other compound (B) include Tetrakisdimethylsiloxysilane from Gelest, HMS-013, HMS-031, HMS-064, HMS-071, HMS-082, HMS-151, HMS-301, HMS-H271, HMS. Hydrosiloxanes such as −991, HMS-993, HES-992, HDP-111, HMP-502, HAM-302, HAM-3012, HQM-105, and HQM-107 may be used.

From the viewpoint of reflow resistance and gas barrier property, suitable specific examples of the above compound (B) are shown below, but the present invention is not limited thereto.
(HMeSiO) ₃
(HMeSiO) _{4
(HMeSiO) 3 (Me 2 SiO} )
_{(HMeSiO) 4 (Me 2 SiO} )

（式（１）中、Ｒ¹は、各々独立して、非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は、非置換若しくは置換の炭素原子数１〜６アルコキシ基であり、Ａは、各々独立して、下記一般式（２）で表される基、又は、フェニレン基であり、Ｂ¹は、各々独立して、付加反応性炭素−炭素二重結合を１つ以上有する、非置換若しくは置換の１価の多環式炭化水素基であり、Ｂ²は、各々独立して、非置換若しくは置換の２価の多環式炭化水素基であり、ｐは０以上の整数である。

（式中、Ｒ²は、各々独立して、非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は、非置換若しくは置換の炭素原子数１〜６のアルコキシ基であり、ｎは０〜１００の整数である。）） Compound (B) is a cyclic siloxane; a compound having a polycyclic hydrocarbon group having a norbornene skeleton or a norbornan skeleton instead of one hydrogen atom bonded to the silicon atom of the cyclic siloxane; and a compound bonded to the silicon atom of the cyclic siloxane. It is preferable that at least one selected from the group consisting of compounds having a substituent represented by the following general formula (6) is contained in place of one hydrogen atom. By using such a compound (B), the tensile elastic modulus, tensile elongation, and breaking energy of the obtained cured product tend to be further improved. The cyclic siloxane is not particularly limited, and examples thereof include 1,3,5,7-tetramethylcyclotetrasiloxane.

(In the formula (1), R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms. Yes, A is an independent group represented by the following general formula (2) or a phenylene group, and B ¹ is an independent addition-reactive carbon-carbon double bond. The above-mentioned unsubstituted or substituted monovalent polycyclic hydrocarbon group, B ² is independently unsubstituted or substituted divalent polycyclic hydrocarbon group, and p is 0 or more. Is an integer of.

(In the formula, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms. n is an integer from 0 to 100.)))

Compound (B) can be used alone or in combination of two or more.

The amount of the hydrogen atom bonded to the silicon atom in the compound (B) is preferably 0.1 to 2.0 mol with respect to 1 mol of the addition-reactive carbon-carbon double bond in the compound (A), and more. It is preferably 0.5 to 2.0 mol, and more preferably 0.8 to 1.5 mol. When the amount of hydrogen atoms bonded to the silicon atoms in the compound (B) is within the above range, the hardness of the obtained cured product is further improved, and it tends to be more preferably used for applications such as coating materials. ..

When the curable composition of the present embodiment contains a compound (B') having one or two hydrogen atoms bonded to a silicon atom in one molecule, the silicon in the compound (B) and the compound (B'). The total amount of hydrogen atoms bonded to the atom is preferably 0.5 to 2.0 mol, more preferably 0.8 to 1 with respect to 1 mol of the addition-reactive carbon-carbon double bond in the compound (A). It is 5.5 mol. When the amount of hydrogen atoms bonded to the silicon atoms in the compound (B) and the compound (B') is within the above range, the hardness of the obtained cured product is further improved, and it is more preferably used for applications such as coating materials. Tend to be able to.

When the curable composition of the present embodiment contains a compound (B') having one or two hydrogen atoms bonded to a silicon atom in one molecule, the hydrogen atom bonded to the silicon atom in the compound (B) is contained. The amount of the above is preferably 20 to 100 mol%, more preferably 40 to 100 mol%, based on 100 mol% of the amount of hydrogen atoms bonded to the silicon atom in the compound (B) and the compound (B').

Further, the curable composition of the present embodiment contains a compound (A') having an addition-reactive carbon-carbon double bond other than the compound (A) and a hydrogen atom bonded to a silicon atom in one molecule. When the compound (B') having the individual is contained, the total amount of hydrogen atoms bonded to the silicon atom in the compound (B) and the compound (B') is the addition reactive carbon in the compound (A) and the compound (A'). -With respect to 1 mol of the carbon double bond, it is preferably 0.5 to 2.0 mol, and more preferably 0.8 to 1.5 mol. When the amount of hydrogen atoms bonded to the silicon atoms in the compound (B) and the compound (B') is within the above range, the hardness of the obtained cured product is further improved, and it is more preferably used for applications such as coating materials. Tend to be able to.

When the curable composition of the present embodiment contains a compound (A') having an addition-reactive carbon-carbon double bond other than the compound (A), the addition-reactive carbon-carbon dicarbonate in the compound (A) is contained. The amount of the double bond is preferably 20 to 100 mol%, more preferably 40 to 100 mol, with respect to 100 mol% of the amount of the addition-reactive carbon-carbon double bond in the compound (A) and the compound (A'). %.

[Hydrosilylation reaction catalyst (C)]
The curable composition of the present embodiment may further contain a hydrosilylation reaction catalyst (C). The hydrosilylation reaction catalyst (C) is not particularly limited, and examples thereof include those similar to those described in "Preparation of compound (A)" above.

The content of the hydrosilylation reaction catalyst (C) may be an effective amount as a catalyst and is not particularly limited, but is based on the platinum group metal atom with respect to the total mass of the compound (A) and the compound (B). It is preferably 0.1 to 500 ppm, more preferably 1 to 100 ppm. When the content of the hydrosilylation reaction catalyst (C) is within the above range, the time required for the curing reaction becomes appropriate, and the coloring of the cured product tends to be further suppressed.

[Adhesion improver (D)]
The curable composition of the present embodiment may further contain an adhesion improver (D). By further containing the adhesion improving agent (D), the adhesion to the substrate tends to be further improved.

The adhesion improving agent (D) is not particularly limited, but for example, an acrylic silane coupling agent (for example, methacrylopropyltrimethoxysilane, methacrylopropyldimethoxysilane, methacrylopropyltriethoxysilane, methacrylopropyldi). Ethoxysilane, acrylopropyltrimethoxysilane, acrylopropyldimethoxysilane, acrylopropyltriethoxysilane, acrylopropyldiethoxysilane, etc.); epoxy-based silane coupling agent (glycidylpropyltrimethoxysilane, glycidylpropyltriethoxysilane, etc.) Etc.); A silane coupling agent having a norbornyl group (norbornylethyltrimethoxysilane, norbornylethyldimethoxysilane, norbornylethyltriethoxysilane, norbornylethyldiethoxysilane, etc.) can be used. .. Of these, glycidylpropyltrimethoxysilane is preferable from the viewpoint of improving adhesion strength.

The content of the adhesion improver (D) is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the compound (A) and the compound (B). It is 1 to 5% by mass. When the content of the adhesion improving agent (D) is within the above range, the adhesion of the obtained cured product to the substrate tends to be further improved.

[Other ingredients]
In addition to the above components, other components can be added to the curable composition of the present embodiment, if necessary.

(Antioxidant)
When the cured product of the curable composition of the present embodiment is oxidized by oxygen in the atmosphere, it causes the cured product to be colored. Therefore, coloring can be prevented in advance by adding an antioxidant to the curable composition of the present embodiment, if necessary.

As the antioxidant, all conventionally known ones can be used, for example, 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'- Examples thereof include methylenebis (4-ethyl-6-t-butylphenol), Irganox1010, Irganox1035, Irganox3114 and the like. These can be used alone or in combination of two or more.

The content of the antioxidant may be an effective amount as the antioxidant and is not particularly limited, but is preferably 10 to 10,000 ppm with respect to the total mass of the compound (A) and the compound (B). It is more preferably 100 to 5,000 ppm. When the content is within the above range, the antioxidant ability is sufficiently exhibited, and a cured product having excellent optical characteristics can be obtained without the occurrence of coloring, cloudiness, oxidative deterioration and the like.

[Viscosity adjuster / hardness adjuster]
A linear diorganopoly having an alkenyl group or SiH bonded to a silicon atom in order to adjust the viscosity of the curable composition of the present embodiment or the hardness of the cured product obtained from the curable composition of the present embodiment. Siloxane or reticulated organopolysiloxane; non-reactive (that is, having no alkenyl group bonded to a silicon atom and SiH) linear or cyclic diorganopolysiloxane, silphenylene-based compounds and the like may be blended.

When the curable composition of the present embodiment is blended with organopolysiloxane having various structures having an alkenyl group bonded to a silicon atom, the content thereof is the addition reactivity of the alkenyl group and the compound (A). The amount of SiH in the compound (B) is usually 0.5 to 2.0 mol, preferably 0.8 to 1.5 mol, based on the total amount of 1 mol of the carbon-carbon double bond. .. When organopolysiloxanes having various structures having SiH are blended, the total amount of the SiH and the SiH contained in the compound (B) is the addition reactive carbon contained in the component (a). The amount is usually 0.5 to 2.0 mol, preferably 0.8 to 1.5 mol, based on 1 mol of the carbon-carbon double bond.

<Others>
Further, in order to secure the pot life, an addition reaction control agent such as 1-ethynylcyclohexanol and 3,5-dimethyl-1-hexyne-3-ol can be blended. Further, an inorganic filler such as fumed silica may be blended in order to improve the strength as long as the transparency is not affected, and if necessary, a dye, a pigment, a flame retardant or the like may be blended. May be good.

Further, it is also possible to use a light stabilizer in order to impart resistance to photodegradation due to light energy of sunlight, fluorescent lamps and the like. As this light stabilizer, a hindered amine-based stabilizer that captures radicals generated by photooxidation deterioration is suitable, and when used in combination with an antioxidant, the antioxidant effect is further improved. Specific examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyl-2,2,6,6-tetramethylpiperidine and the like. Further, a plasticizer may be added to prevent cracks. The curing conditions of the curable composition of the present embodiment vary depending on the amount thereof and are not particularly limited, but are usually preferably 60 to 180 ° C. and 5 to 600 minutes.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

で表されるビニル基
及び
下記構造式：

で表される内部２重結合のモル比を算出する事が出来る。
内部２重結合２Ｈ＝ａ−ｂ／２
ビニル基２Ｈ＝ｂ
内部２重結合割合（％）＝（内部２重結合２Ｈ／（内部２重結合２Ｈ＋ビニル基２Ｈ））×１００
ビニル割合（％）＝（ビニル基２Ｈ／（内部ビニル２Ｈ＋ビニル基２Ｈ））×１００ [Calculation of vinyl group ratio and internal double bond ratio of compound (A)]
When vinyl norbornene is used for (b) of compound (A),
A deuterated chloroform solution containing 1 wt% of compound (A) was prepared, and ¹ H-NMR measurement was carried out using a nuclear magnetic resonance apparatus ECZ-400S manufactured by JEOL Ltd. In the obtained NMR chart, the peak of chloroform is set to 7.24 ppm, Si-CH _{3 of} -0.25 to 0.25 ppm is set to 12H, and the integrated value is derived from the double bond of 5.3 to 6.4 ppm. Was a, and the integral value derived from the double bond of 4.75 to 5.3 ppm was b. case,
The following structural formula:

Vinyl group represented by and the following structural formula:

It is possible to calculate the molar ratio of the internal double bond represented by.
Internal double bond 2H = ab / 2
Vinyl group 2H = b
Internal double bond ratio (%) = (internal double bond 2H / (internal double bond 2H + vinyl group 2H)) × 100
Vinyl ratio (%) = (vinyl group 2H / (internal vinyl 2H + vinyl group 2H)) x 100

[Calculation of average molecular weight of compound (A)]
For example, the average molecular weight of compound (A) of Synthesis Example 1-5 was determined by the following formula.
A deuterated chloroform solution containing 1 wt% of compound (A) was prepared, and ¹ H-NMR measurement was carried out using a nuclear magnetic resonance apparatus ECZ-400S manufactured by JEOL Ltd. In the obtained NMR chart, the peak of chloroform is set to 7.24 ppm, Si-CH _{3 of} -0.25 to 0.25 ppm is set to 12H, and the integrated value is derived from the double bond of 5.3 to 6.4 ppm. Was a, and the integral value derived from the double bond of 4.75-5.3 ppm was b.

Double bond 4H = ((ab / 2) /2-b / 2)) × 2
n = (4/2 double bond 4H) -1
Average molecular weight of compound (A) = 374.7 + 254.4 × n

In the above formula, "374.7" is the molecular weight of the structure in which vinyl norbornene is added to both ends of 1,3,5,7-tetramethylcyclotetrasiloxane, and "254.4" is 1,3. , 5,7-Tetramethylcyclotetrasiloxane is the molecular weight of the structure in which vinyl norbornene is added to one end.

[Calculation of compounding ratio of compound (B)]
Based on the average molecular weight determined for the compound (A), it is added according to the total SiH in the predetermined compound (B) / the total carbon-carbon double bond (molar ratio) in the compound (A). The compounding ratio of the compound (B) to be used was calculated.

[Measurement of area% of compound (A1) and compound (A2) by GPC]
A solution prepared by dissolving 0.1 g of compound (A) in a chloroform solvent at a ratio of 2 ml was used as a measurement sample. Using this measurement sample, measurement was performed with LC-8020 manufactured by Tosoh Corporation. As a column, TSK guard columns HHR-H, TSKgel G5000HHR, TSKgel G3000HHR, and TSKgel G1000HHR manufactured by Tosoh Corporation were used in series, and chloroform was used as a mobile phase for analysis at a rate of 1 ml / min. The detector uses an RI detector, and polystyrene and styrene monomer (molecular weight 104) of Polymer Laboratories Easi Cal PS-2 (molecular weight: 377400, 96000, 19720, 4490, 1180, 188700, 46500, 9920, 2360, 580). The number average molecular weight and the weight average molecular weight were determined, and the peaks of p = 0 and p ≧ 1 were specified, and the area ratio of each peak was calculated.
Molecular Weight Details: 377400, 96000, 19720, 4490, 1180, 188700, 46500, 9920, 2360, 580

[Making a hardened plate]
A curable composition obtained by mixing a predetermined amount of the compound (A), the compound (B), and the hydrosilylation reaction catalyst (C), or the components (A), (B), (C), and (D) is stirred and defoamed. After that, a 2 mm thick U-shaped silicone packing was sandwiched between two mirror-finished SUS plates, the composition was injected between the two SUS plates, degassed under reduced pressure to defoam, and then 100 ° C. 1h150 ° C. By curing for 5 hours, a cured plate having a thickness of 2 mm was obtained.

[Tensile test of hardened plate]
A tensile test was performed at 25 ° C. using a Shimadzu AG-5000D hardened plate with a length of 40 mm, a width of 10 mm, and a thickness of 2 mm at a tensile speed of 5 mm per minute using a chuck-to-chuck distance of 20 mm and a 500 kgf load cell. Tensile elongation and breaking energy were determined. The breaking energy was the energy up to the breaking point.

[LED sealing]
B4545ECI1 (LED) manufactured by Generites was die-bonded to 505010-8R (2L) (package) manufactured by Giant Trade Precision Industry Co., Ltd. using KER-3000-M2 (die bond material) manufactured by Shin-Etsu Chemical. After wire bonding with Tanaka Kikinzoku Gold SR-30 (gold wire), the LED frame was cut into 16 small pieces of 4 x 4 LEDs.
A composition obtained by mixing a predetermined amount of the components of compound (A), compound (B), hydrosilylation reaction catalyst (C), and (D) is stirred and defoamed, and then transferred to a syringe whose needle tip is closed with a silicone stopper and degassed under reduced pressure. After that, the silicone stopper was removed, injected into the package, and sealed.

[Reflow test]
After reflowing the sealed LED package at 260 ° C. for 30 seconds, the presence or absence of cracks and peeling was observed with an optical microscope, and a red ink test was performed to observe the presence or absence of cracks and peeling.
◯: No crack and / or peeling Δ: Small crack and / or peeling occurred ×: Large crack and / or peeling occurred

[Evaluation of gas barrier property by sulfur heating]
Put a small amount of sulfur powder in a round airtight bottle, place small pieces of 4 x 4 LED frames that have undergone a reflow test so that they are about 10 mm from the bottom of the bottle, and put them in a constant temperature bath set at 100 ° C. After allowing it to stand for 1 hour, it was taken out, and after returning to room temperature, the frame was taken out, and the degree of corrosion of silver at the bottom was observed with an optical microscope.
◯: Silver corroded to black ×: Silver corroded to black.

[Synthesis Example 1] Preparation of Compound (A) Vinyl norbornene (trade name: V0062, manufactured by Tokyo Kasei Co., Ltd .; 5-vinylbicyclo [2] was placed in a four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer. .2.1] A mixture of approximately equimolar amounts of isomers of hept-2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene; hereinafter also referred to as "VNB") 1981 g (16). .5 mol) was added and heated to 90 ° C. using an oil bath. To this, 22 g of a calstead-catalyzed xylene solution equivalent to 3% platinum atom diluted with toluene so as to be equivalent to 30 ppm platinum atom was added, and 1,1,3,3-tetramethyldisiloxane (hereinafter, "TMDS") was added with stirring. Also referred to as) 73.87 g (0.55 mol) was added dropwise over 60 minutes. After completion of the dropping, the mixture was further heated and stirred at 98 ° C. for 60 hours, and after confirming the disappearance of the peak derived from the SiH group by NMR, the mixture was cooled to room temperature. Then, the excess VNB was distilled off under reduced pressure to obtain a colorless and transparent oily reaction product.

The reaction products were analyzed by NMR and GPC. As a result, it was found that the obtained reaction product contained only the following compound (I) and did not contain the following compound (II). Detailed results are shown in Table 1.
(I) NB-Me ₂ SiOSiMe _2-NB
(II) NB-Me ₂ SiOSiMe _2- (NB-Me ₂ SiOSiMe ₂ ) _p-NB
(P ≧ 1)

[Synthesis Example 2] Preparation of Compound (A) Colorless and transparent by the same operation as in Synthesis Example 1 except that the amount of VNB used was 1656 g (13.55 mol) and the heating and stirring time at 98 ° C. was 48 hours. An oily reaction product was obtained. The reaction products were analyzed by NMR and GPC. As a result, it was found that the obtained reaction product was a mixture containing the compounds (I) and (II). Detailed results are shown in Table 1.

[Synthesis Example 3] Preparation of Compound (A) A colorless and transparent oil was operated in the same manner as in Synthesis Example 1 except that the amount of VNB used was 1321 g (11 mol) and the heating and stirring time at 98 ° C. was 200 hours. The reaction product in the form was obtained. The reaction products were analyzed by NMR and GPC. As a result, it was found that the obtained reaction product was a mixture containing the compounds (I) and (II). Detailed results are shown in Table 1.

[Synthesis Example 4] Preparation of Compound (A) A colorless and transparent oily reaction product was obtained by the same operation as in Synthesis Example 3 except that the heating and stirring time at 98 ° C. was set to 100 hours. The reaction products were analyzed by NMR and GPC. As a result, it was found that the obtained reaction product was a mixture containing the compounds (I) and (II). Detailed results are shown in Table 1.

[Synthesis Example 5] Preparation of Compound (A) 193 g of a colorless and transparent oily reaction product was obtained by the same operation as in Synthesis Example 3 except that the heating and stirring time at 98 ° C. was set to 24 hours. The reaction products were analyzed by NMR and GPC. As a result, it was found that the obtained reaction product was a mixture containing the compounds (I) and (II). Detailed results are shown in Table 1.

[Synthesis Example 6] Preparation of Compound (A) A colorless and transparent oily reaction product was obtained by the same operation as in Synthesis Example 3 except that the mixture was heated and stirred at 98 ° C. for a heating stirring time. The reaction products were analyzed by NMR and GPC. As a result, it was found that the obtained reaction product was a mixture containing the compounds (I) and (II). Detailed results are shown in Table 1.

[Synthesis Example 7] Preparation of Compound (A) Colorless and transparent by the same operation as in Synthesis Example 1 except that the amount of VNB used was 881 g (8.25 mol) and the heating and stirring time at 98 ° C. was 24 hours. An oily reaction product was obtained. The reaction products were analyzed by NMR and GPC. As a result, it was found that the obtained reaction product was a mixture containing the compounds (I) and (II). Detailed results are shown in Table 1.

[Synthesis Example 8] Preparation of Compound (A) Colorless and transparent by the same operation as in Synthesis Example 1 except that the amount of VNB used was 661 g (5.5 mol) and the heating and stirring time at 98 ° C. was 24 hours. An oily reaction product was obtained. The reaction products were analyzed by NMR and GPC. As a result, it was found that the obtained reaction product was a mixture containing the compounds (I) and (II). Detailed results are shown in Table 1.

[Synthesis Example 9-1] Preparation of compound (A) Add 156 g (1.3 mol) of VNB to a four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer, and bring the temperature to 85 ° C. using an oil bath. Heated. To this, 0.05 g of carbon powder carrying 5% by mass of platinum metal was added, and 67 g (0.5 mol) of TMDS was added dropwise over 60 minutes with stirring. After completion of the dropping, the mixture was further heated and stirred at 90 ° C. for 24 hours, and after confirming the disappearance of the peak derived from the SiH group by NMR, the mixture was cooled to room temperature. Then, the platinum metal-supported carbon was filtered off, and excess vinyl norbornene was distilled off under reduced pressure to obtain 170 g of a colorless and transparent oily reaction product.

As a result of analyzing the reaction product by NMR, GPC, and IR, this compound has one (1) -Si-O-Si- bond: NBMe ₂ SiOSiMe ₂ NB 70 mol%, (2) -Si-O. A compound having two or more −Si− bonds: a mixture of 30 mol% was found. In addition, this compound has one (1) -Si-O-Si- bond in terms of GPC area ratio: NBMe ₂ SiOSiMe ₂ NB 50%, and (2) two or more -Si-O-Si- bonds. Compound with: Found to be a mixture of 50%.

[Synthesis Example 9-2] Preparation of Compound (A) Instead of carbon powder carrying 5% by mass of platinum metal, a calstead-catalyzed xylene solution equivalent to 3% platinum atom diluted with toluene so as to be equivalent to 30 ppm platinum atom was used. 170 g of a colorless and transparent oily reaction product was obtained by the same operation as in Synthesis Example 9-1 except that 22 g was used. The obtained reaction product was analyzed by NMR and GPC. As a result, it was found that the obtained reaction product was a mixture containing the compounds (I) and (II). Detailed results are shown in Table 1.

[Synthesis Example 10] Preparation of Compound (A) 39 g (0.33 mol) of VNB and 35 g (0.26 mol) of TMDS were added to a four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer, and the mixture was stirred. However, it was heated to 40 ° C. using an oil bath. To this, 0.5 g of a calstead-catalyzed xylene solution equivalent to 3% platinum atom diluted with toluene so as to be equivalent to 30 ppm platinum atom was added, and the temperature of the oil bath was raised to 80 ° C. over 235 minutes. After further reacting at 80 ° C. for 24 hours, the mixture was cooled to room temperature. Then, excess vinyl norbornene was distilled off under reduced pressure to obtain 70 g of a colorless and transparent oily reaction product. When this reaction product was analyzed by NMR, the SiH group remained, so 9.4 g of vinyl norbornene was further added, and the platinum atom equivalent to 3% was diluted with toluene so as to be equivalent to platinum atom 30 ppm. 1.5 g of the catalytic xylene solution was added, and after 3 hours at 75 ° C., the disappearance of the peak derived from the SiH group was confirmed by NMR. Then, excess vinyl norbornene was distilled off under reduced pressure to obtain 69 g of a colorless and transparent oily reaction product.

The reaction products were analyzed by NMR and GPC. As a result, it was found that the obtained reaction product was a mixture containing the compounds (I) and (II). Detailed results are shown in Table 1.

[Synthesis Example 11] Preparation of Compound (B) In a four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer, 1,3,5,7-tetramethylcyclotetrasiloxane (hereinafter, “D4H”” Also referred to as) 1152 g (4.8 mol) was added and heated to 117 ° C. using an oil bath. To this, 0.5 g of a calcium atom-equivalent calstead-catalyzed xylene solution diluted with toluene was added, and 48 g (0.4 mol) of VNB was added dropwise over 16 minutes with stirring. After completion of the dropping, the mixture was further heated and stirred at 125 ° C. for 16 hours, and then cooled to room temperature. Then, unreacted D4H was distilled off under reduced pressure to obtain a colorless and transparent oily reaction product.

[Synthesis Example 12-1] Preparation of compound (B) 1152 g (4.8 mol) of D4H was added to a 2000 mL four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer, and 117 using an oil bath. Heated to ° C. To this, 0.5 g of a calcium atom-equivalent calstead-catalyzed xylene solution diluted with toluene was added, and the components (A) (0.4 mol) synthesized in Synthesis Example 5 were added dropwise over 16 minutes with stirring. After completion of the dropping, the mixture was further heated and stirred at 125 ° C. for 16 hours, and then cooled to room temperature. Then, unreacted 1,3,5,7-tetramethylcyclotetrasiloxane was distilled off under reduced pressure to obtain a colorless and transparent oily reaction product.

[Synthesis Example 12-2] Preparation of Compound (B) Except that the component (A) (0.4 mol) synthesized in Synthesis Example 9-2 was used instead of the component (A) used in Synthesis Example 12-1. The same experiment as in Synthesis Example 12-1 was carried out to obtain a colorless and transparent oily reaction product.

[Synthesis Example 13] Preparation of Compound (A) Colorless by the same operation as in Synthesis Example 5 except that 1454 g (11 mol) of dicyclopentadiene (hereinafter, also referred to as “DCPD”) was used instead of VNB. A clear oily reaction product was obtained. The reaction products were analyzed by NMR and GPC. As a result, it was found that the obtained reaction product was a mixture containing the following compounds (III) and (IV). Detailed results are shown in Table 1.
(III) DCP-Me ₂ SiOSiMe _2-DCP
(IV) DCP-Me ₂ SiOSiMe _2- (DCP-Me ₂ SiOSiMe ₂ ) _p- DCP (p ≧ 1)

[Synthesis Example 14] Preparation of Compound (A) The amount of DCPD used was 171.86 g (1.3 mol), the heating temperature of the oil bath was 85 ° C, and the amount of TMDS used was 67.16 g (0.5 mol). 170 g of a colorless and transparent oily reaction product was obtained by the same operation as in Synthesis Example 13 except that the heating and stirring temperature was set to 90 ° C. The obtained reaction product was analyzed by NMR and GPC. As a result, it was found that the obtained reaction product was a mixture containing compounds (III) and (IV). Detailed results are shown in Table 1.

[Synthesis Example 15] Preparation of compound (A) 106.931 g (hereinafter, also referred to as "1,4-DMSB") 106.931 g (hereinafter, also referred to as "1,4-DMSB") instead of 93.87 g (0.55 mol) of TMDS. A colorless and transparent oily reaction product was obtained by the same operation as in Synthesis Example 5 except that 0.55 mol) was used. The reaction products were analyzed by NMR and GPC. As a result, it was found that the obtained reaction product was a mixture containing the following compounds (V) and (VI). Detailed results are shown in Table 1.
(V) NB-Me ₂ SiPhSiMe2-NB
(VI) NB-Me ₂ SiPhSiMe _2- (NB-Me ₂ SiPhSiMe ₂ ) _p-NB
(P ≧ 1)

[Synthesis Example 16] Preparation of Compound (A) The amount of VNB used was 156 g (1.3 mol), the heating temperature of the oil bath was 85 ° C, and the amount of 1,4-DMSB used was 97.21 g (0.5 mol). ), And a colorless and transparent oily reaction product was obtained by the same operation as in Synthesis Example 15 except that the heating and stirring temperature was set to 90 ° C. The obtained reaction product was analyzed by NMR and GPC. As a result, it was found that the obtained reaction product was a mixture containing the compounds (V) and (VI). Detailed results are shown in Table 1.

ＴＭＤＳ ：１，１，３，３−テトラメチルジシロキサン
ＶＮＢ ：ビニルノルボルネン
ＤＣＰＤ ：ジシクロペンタジエン
１，４−ＤＭＳＢ：１，４−ビス−ジメチルシリルベンゼン
Ｄ４Ｈ ：１，３，５，７−テトラメチルシクロテトラシロキサン

TMDS: 1,1,3,3-tetramethyldisiloxane VNB: Vinyl Norbornene DCPD: Dicyclopentadiene 1,4-DMSB: 1,4-bis-dimethylsilylbenzene D4H: 1,3,5,7-Tetramethyl Cyclotetrasiloxane

[Example 1]
100 parts by mass of the compound (A) obtained in Synthesis Example 1, 32 parts by mass of D4H as the compound (B), and a calcated catalyst as the hydrosilylation reaction catalyst (C) based on the platinum metal atom. A curable composition was obtained by uniformly mixing 2 ppm with respect to the total mass of D4H and 1 part by mass of glycidylpropyltrimethoxysilane as an adhesion improver (D). The amount of hydrogen atoms bonded to the silicon atom in the compound (B) was 1.0 mol with respect to 1 mol of the addition-reactive carbon-carbon double bond in the compound (A). Using the obtained curable composition, a cured plate was prepared and an LED was sealed. A tensile test was performed on the hardened plate to determine the tensile elastic modulus, tensile elongation, and breaking energy. For LEDs, the gas barrier property was evaluated by sulfur heating after the reflow test and the reflow test. The results are shown in Table 2.

[Examples 2 to 17, Comparative Examples 1 to 12]
The curable composition was prepared by the same operation as in Example 1 except that the composition of the compound (A), the compound (B), the hydrosilylation reaction catalyst (C), and the adhesion improver (D) were set in Table 1. Obtained and evaluated. The results are shown in Tables 2 and 3.

ＳｉＨ／Ｃ＝Ｃ：化合物（Ａ）中の付加反応性炭素−炭素二重結合１ｍｏｌに対する、化合物（Ｂ）中のケイ素原子に結合した水素原子の量
ＨＭＳ−３０１：（Ｇｅｌｅｓｔ製）
ＨＭＳ−９９１：（Ｇｅｌｅｓｔ製）
ＨＱＭ−１０５：（Ｇｅｌｅｓｔ製）
ＱＭ４Ｈ ：テトラキスジメチルシロキシシラン
ＴＭＮＤＳ ：１，１，３，３−Ｔｅｔｒａｍｅｔｈｙｌ−１，３−ｂｉｓ［２−（５−ｎｏｒｂｏｒｎｅｎ−２−ｙｌ）ｅｔｈｙｌ］ｄｉｓｉｌｏｘａｎｅ， ｍｉｘｔｕｒｅ ｏｆ ｅｎｄｏ ａｎｄ ｅｘｏ （アルドリッチ製、内部２重結合割合（％）：ビニル基割合（％）＝９７：３）（このＴＭＮＤＳは、前記一般式（１）中、ｐ＝０で表される化合物を化合物（Ａ１）とし、ｐ≧１で表される化合物を化合物（Ａ２）としたとき、前記化合物（Ａ２）の含有量が、ゲルパーミエーションクロマトグラフィーで得られる前記化合物（Ａ１）及び前記化合物（Ａ２）の総面積に対して、０面積％である）
ＫＣ ：カルステッド触媒
ＬＳ２９４０ ：グリシジルプロピルトリメトキシシラン

SiH / C = C: Amount of hydrogen atom bonded to silicon atom in compound (B) with respect to 1 mol of addition-reactive carbon-carbon double bond in compound (A) HMS-301: (manufactured by Gelest)
HMS-991: (manufactured by Gelest)
HQM-105: (manufactured by Gelest)
QM4H: Tetrax dimethylsiloxysilane TMNDS: 1,1,3,3-Tetramethyl-1,3-bis [2- (5-norbornene-2-yl) ethyl] disiloxane, mixture of endo and exo (manufactured by Aldrich, internal 2) Heavy bond ratio (%): Vinyl group ratio (%) = 97: 3) (In this TMNDS, the compound represented by p = 0 in the general formula (1) is defined as compound (A1), and p ≧ 1. When the represented compound is compound (A2), the content of the compound (A2) is 0 with respect to the total area of the compound (A1) and the compound (A2) obtained by gel permeation chromatography. Area%)
KC: Karstead catalyst LS2940: Glycidylpropyltrimethoxysilane

ＳｉＨ／Ｃ＝Ｃ：化合物（Ａ）中の付加反応性炭素−炭素二重結合１ｍｏｌに対する、化合物（Ｂ）中のケイ素原子に結合した水素原子の量
ＨＭＳ−３０１：（Ｇｅｌｅｓｔ製）
ＨＭＳ−９９１：（Ｇｅｌｅｓｔ製）
ＨＱＭ−１０５：（Ｇｅｌｅｓｔ製）
ＱＭ４Ｈ ：テトラキスジメチルシロキシシラン
ＴＭＮＤＳ ：１，１，３，３−Ｔｅｔｒａｍｅｔｈｙｌ−１，３−ｂｉｓ［２−（５−ｎｏｒｂｏｒｎｅｎ−２−ｙｌ）ｅｔｈｙｌ］ｄｉｓｉｌｏｘａｎｅ， ｍｉｘｔｕｒｅ ｏｆ ｅｎｄｏ ａｎｄ ｅｘｏ （アルドリッチ製、内部２重結合割合（％）：ビニル基割合（％）＝９７：３）（このＴＭＮＤＳは、前記一般式（１）中、ｐ＝０で表される化合物を化合物（Ａ１）とし、ｐ≧１で表される化合物を化合物（Ａ２）としたとき、前記化合物（Ａ２）の含有量が、ゲルパーミエーションクロマトグラフィーで得られる前記化合物（Ａ１）及び前記化合物（Ａ２）の総面積に対して、０面積％である）
ＫＣ ：カルステッド触媒
ＬＳ２９４０ ：グリシジルプロピルトリメトキシシラン

SiH / C = C: Amount of hydrogen atom bonded to silicon atom in compound (B) with respect to 1 mol of addition-reactive carbon-carbon double bond in compound (A) HMS-301: (manufactured by Gelest)
HMS-991: (manufactured by Gelest)
HQM-105: (manufactured by Gelest)
QM4H: Tetrax dimethylsiloxysilane TMNDS: 1,1,3,3-Tetramethyl-1,3-bis [2- (5-norbornene-2-yl) ethyl] disiloxane, mixture of endo and exo (manufactured by Aldrich, internal 2) Heavy bond ratio (%): Vinyl group ratio (%) = 97: 3) (In this TMNDS, the compound represented by p = 0 in the general formula (1) is defined as compound (A1), and p ≧ 1. When the represented compound is compound (A2), the content of the compound (A2) is 0 with respect to the total area of the compound (A1) and the compound (A2) obtained by gel permeation chromatography. Area%)
KC: Karstead catalyst LS2940: Glycidylpropyltrimethoxysilane

The curable composition of the present invention is suitably used for protection, sealing, and adhesion of semiconductor elements such as light emitting diode elements, change or adjustment of wavelength of light emitted from light emitting diode elements, and applications such as lenses. be able to. Further, the curable composition of the present invention is also suitable for various optical materials such as lens materials, optical devices / optical component materials, display materials, insulating materials for electronic devices / electronic components, coating materials, and the like. Can be used.

Claims (6)

Compound (A) represented by the following general formula (1) and

(In the formula (1), R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms. Yes, A is an independent group represented by the following general formula (2) or a phenylene group, and B ¹ is an independent addition-reactive carbon-carbon double bond. The above-mentioned unsubstituted or substituted monovalent polycyclic hydrocarbon group, B ² is independently unsubstituted or substituted divalent polycyclic hydrocarbon group, and p is 0 or more. Is an integer of.

(In the formula, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms. n is an integer from 0 to 100.)))
Contains compound (B) having three or more hydrogen atoms bonded to silicon atoms in one molecule.
The compound (B) is a cyclic siloxane; a compound having a polycyclic hydrocarbon group having a norbornene skeleton or a norbornan skeleton instead of one or more hydrogen atoms bonded to a silicon atom of the cyclic siloxane; and a silicon atom of the cyclic siloxane. It contains at least one selected from the group consisting of compounds having a substituent represented by the following general formula (5) in place of one or more hydrogen atoms bonded to.

(In the formula (1), R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms. Yes, A is an independent group represented by the following general formula (2) or a phenylene group, and B ¹ is an independent addition-reactive carbon-carbon double bond. The above-mentioned unsubstituted or substituted monovalent polycyclic hydrocarbon group, B ² is independently unsubstituted or substituted divalent polycyclic hydrocarbon group, and p is 0 or more. Is an integer of.

(In the formula, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms. n is an integer from 0 to 100.)))
The amount of the hydrogen atom bonded to the silicon atom in the compound (B) is 1.0 to 1.5 mol with respect to 1 mol of the addition-reactive carbon-carbon double bond in the compound (A).
In the above general formula (1), when the compound represented by p = 0 is defined as the compound (A1) and the compound represented by p ≧ 1 is designated as the compound (A2).
The content of the compound (A2) is 5 area% or more and 20 area% or less with respect to the total area of the compound (A1) and the compound (A2) obtained by gel permeation chromatography under the following conditions.
Curable composition.
conditions:
A solution prepared by dissolving 0.1 g of the compound (A) in a chloroform solvent at a ratio of 2 ml is used as a measurement sample. Using this measurement sample, measurement is performed with LC-8020 manufactured by Tosoh Corporation. As the column, TSK guard columns HHR-H, TSKgel G5000HHR, TSKgel G3000HHR, and TSKgel G1000HHR manufactured by Tosoh Corporation are used in series, and chloroform is used as a mobile phase for analysis at a rate of 1 ml / min. The detector uses an RI detector, and polystyrene and styrene monomer (molecular weight 104) of Polymer Laboratories Easi Cal PS-2 (molecular weight: 377400, 96000, 19720, 4490, 1180, 188700, 46500, 9920, 2360, 580). The number average molecular weight and the weight average molecular weight are obtained, the peaks of p = 0 and p ≧ 1 are specified, and the area ratio of each peak is calculated. The first aspect of the present invention, wherein the compound (A) has a structural unit represented by the following general formula (4) as a structural unit represented by the following general formula (3) in the general formula (1). Curable composition.

The compound (A) is a ^{polycyclic hydrocarbon group having a norbornene skeleton or a norbornane skeleton as a structural unit represented by B 1} in the general formula (1), and / or in the general formula (1). The curable composition according to claim 1 or 2, which has a polycyclic hydrocarbon group having a norbornene skeleton as a structural unit represented by ^{B 2.} The curable composition according to any one of claims 1 to 3, further comprising a hydrosilylation reaction catalyst (C). The curable composition according to any one of claims 1 to 4, further comprising an adhesion improver (D). A cured product of the curable composition according to any one of claims 1 to 5.