JP4520251B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition containing a polycyclic hydrocarbon skeleton-containing component useful as an optical device or optical component material, an electronic device or electronic component insulating material, or a coating material.

  Conventionally, an epoxy resin is generally used as a sealing material for an optical device or an optical component material, particularly a light emitting diode (LED) element. In addition, regarding silicone resin, attempts have been made to use it as a mold member for LED elements (see Patent Document 1 and Patent Document 2) and as a color filter material (see Patent Document 3). There are few examples of use.

  In recent years, while white LEDs have been attracting attention, problems such as yellowing due to ultraviolet rays etc. of epoxy sealing materials, which has not been a problem so far, and cracks due to an increase in the amount of heat generated due to miniaturization have occurred and can be handled It is an urgent need. As a countermeasure for these, the use of a cured silicone resin having a large amount of phenyl groups in the molecule has been studied. However, as light sources for future LEDs, those that generate light with shorter wavelengths tend to be used, and epoxy encapsulants and phenyl group-containing silicone resin encapsulants are light transmissive in the short wavelength region. Due to the poor nature, there has been a problem in application to LEDs that generate light in the short wavelength region.

  An optical material composition comprising, as essential components, an organic compound having at least two carbon-carbon double bonds in one molecule and a silicon compound having at least two hydrogen atoms bonded to a silicon atom in one molecule. Have also been proposed (see Patent Documents 4 to 8). However, when these compositions are heat-cured to obtain a cured product, there are problems such as foaming or curing shrinkage, and coloring of the cured product.

Japanese Patent Laid-Open No. 10-228249 Japanese Patent Laid-Open No. 10-242513 JP 2000-123981 A JP 2002-324920 A JP 2002-327114 A JP 2002-327126 A JP 2002-338833 A JP 2002-341101 A

  In view of the above-described problems of the prior art, the present invention is useful as an optical device or optical component material, an electronic device or electronic component insulating material or a coating material, has high hardness and strength, and further transmits light in a short wavelength region. It aims at providing the curable composition which gives the hardened | cured material excellent in 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) The following general formula (1):

［式中、Ａは、下記一般式(2)：

[Wherein A represents the following general formula (2):

（式中、Ｒ'は独立に非置換もしくは置換の炭素原子数１〜12の１価炭化水素基または炭素原子数１〜６のアルコキシ基であり、ｎは０〜100の整数である）
で表される基、および下記構造式(3)：

(In the formula, R ′ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n is an integer of 0 to 100)
And the following structural formula (3):

で表される基から成る群から選ばれる２価の基であり、
Ｒは独立に非置換もしくは置換の炭素原子数１〜12の１価炭化水素基または炭素原子数１〜６アルコキシ基である］
で表されるケイ素原子に結合した水素原子を１分子中に２個有する化合物と、
(b)付加反応性炭素−炭素二重結合を１分子中に２個有する多環式炭化水素との付加反応生成物であって、かつ、付加反応性炭素−炭素二重結合を１分子中に少なくとも２個有する付加反応生成物、
(Ｂ)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、および
(Ｃ)ヒドロシリル化反応触媒
を含む硬化性組成物を提供するものである。

A divalent group selected from the group consisting of groups represented by:
R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
A compound having two hydrogen atoms bonded to a silicon atom represented by
(b) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and the addition-reactive carbon-carbon double bond in one molecule An addition reaction product having at least two
(B) a compound having three or more hydrogen atoms bonded to a silicon atom in one molecule, and
(C) A curable composition containing a hydrosilylation reaction catalyst is provided.

  The curable composition of the present invention has high hardness and strength, no curing shrinkage, high light transmittance even for light in the short wavelength region, and can provide a cured product having excellent transparency. Therefore, it can be suitably used for applications such as protection, sealing or adhesion, wavelength change or adjustment of light emitting diode elements, or lenses. Further, it is also useful as a lens material, various optical materials such as an optical device or an optical component sealing material, a display material, an electronic device or an insulating material for an electronic component, and a coating material.

The present invention will be described in detail below.
[Component (A)]
The component (A) of the composition of the present invention is
(a) The following general formula (1):

［式中、Ａは、下記一般式(2)：

[Wherein A represents the following general formula (2):

（式中、Ｒ'は独立に非置換もしくは置換の炭素原子数１〜12の１価炭化水素基または炭素原子数１〜６のアルコキシ基であり、ｎは０〜100の整数である）
で表される基、および下記構造式(3)：

(In the formula, R ′ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n is an integer of 0 to 100)
And the following structural formula (3):

で表される基から成る群から選ばれる２価の基であり、
Ｒは独立に非置換もしくは置換の炭素原子数１〜12の１価炭化水素基または炭素原子数１〜６アルコキシ基である］
で表されるケイ素原子に結合した水素原子を１分子中に２個有する化合物と、
(b)付加反応性炭素−炭素二重結合を１分子中に２個有する多環式炭化水素との付加反応生成物であって、かつ、付加反応性炭素−炭素二重結合を１分子中に少なくとも２個有する付加反応生成物である。

A divalent group selected from the group consisting of groups represented by:
R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
A compound having two hydrogen atoms bonded to a silicon atom represented by
(b) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and the addition-reactive carbon-carbon double bond in one molecule Is an addition reaction product having at least two.

<(A) component>
This reaction raw material of component (A) has (a) two hydrogen atoms bonded to the silicon atom represented by the general formula (1) (hereinafter sometimes referred to as “SiH”) in one molecule. In the compound, when A in the general formula (1) is a divalent group represented by the general formula (2), the compound includes the following general formula (4):

（式中、ＲおよびＲ'はそれぞれ独立に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１価炭化水素基または炭素原子数１〜６、好ましくは１〜４のアルコキシ基であり、ｎは０〜100、好ましくは０〜10の整数である）
で表される化合物が挙げられる。

Wherein R and R ′ are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12, preferably 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. And n is an integer of 0 to 100, preferably 0 to 10)
The compound represented by these is mentioned.

  In the above formula, when R and R ′ are the above monovalent hydrocarbon group, 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, or a 1-hexenyl group; an alkenyl aryl group such as a p-vinylphenyl group; and one or more hydrogen atoms bonded to carbon atoms in these groups; Substituted with a halogen atom, a cyano group, an epoxy ring-containing group, etc., for example, a halogenated amine such as a chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc. Kill group; 2-cyanoethyl group; such as 3-glycidoxypropyl group.

  Examples of the case where R and R ′ are the above alkoxy groups include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group.

  Among the above, as R and R ′, those other than alkenyl and alkenylaryl groups are preferable, and those in which all of them are methyl groups are easy to produce industrially and easily available. This is preferable.

  Structural formulas of preferred specific examples of the compound represented by the above general formula (4) are shown below, but the compounds are not limited to those of the following structural formula. Hereinafter, “Me” means a methyl group.

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
In addition, the compound represented by the general formula (4) can be used alone or in combination of two or more.

  In the compound having (a) two SiHs represented by the above general formula (1) in one molecule, which is a reaction raw material of the component (A), A in the general formula (1) is the structural formula ( In the case of the divalent group represented by 3), the compound includes the following general formula (5):

（式中、Ｒは上記一般式(4)に関して定義のとおりである）
で表される化合物が挙げられる。

(Wherein R is as defined above for general formula (4))
The compound represented by these is mentioned.

  Examples of R in the general formula (5) include the same groups as those described for R in the general formula (4), and those other than alkenyl groups and alkenyl aryl groups are preferable. Those in which all are methyl groups are preferred.

As the compound represented by the general formula (5), for example,
Structural _{formula: HMe 2 Si-p-C} 6 H 4 -SiMe 2 H
1,4-bis (dimethylsilyl) benzene represented by
Structural _{formula: HMe 2 Si-m-C} 6 H 4 -SiMe 2 H
And a silphenylene compound such as 1,3-bis (dimethylsilyl) benzene.
The compound represented by the general formula (5) can be used alone or in combination of two or more.
Furthermore, the component (a), which is a reaction raw material for the component (A), can be used alone or in combination of two or more.

<(B) component>
In (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, which is a reaction raw material of component (A), the “addition reactivity” is bonded to a silicon atom. Means the property of being able to undergo the addition of hydrogen atoms (known as hydrosilylation reactions).

In addition, the component (b) includes (i) an addition reactive carbon-carbon double bond formed between two adjacent carbon atoms among the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon. (Ii) a hydrogen atom bonded to a carbon atom forming the polycyclic skeleton of a polycyclic hydrocarbon is replaced by an addition-reactive carbon-carbon double bond-containing group, or (Iii) an addition reactive carbon-carbon double bond is formed between two adjacent carbon atoms among the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon, and the polycyclic The hydrogen atom bonded to the carbon atom forming the polycyclic skeleton of the formula hydrocarbon may be any substituted with an addition-reactive carbon-carbon double bond-containing group.
Examples of the component (b) include 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、
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、これら両者の組み合わせ（以下、これら３者を区別する必要がない場合は、「ビニルノルボルネン」と総称することがある）；下記構造式(z)：

(y)
6-vinylbicyclo [2.2.1] hept-2-ene, a combination of the two (hereinafter, when there is no need to distinguish these three, they may be collectively referred to as “vinyl norbornene”); The following structural formula (z):

(z)
で表されるジシクロペンタジエン等が挙げられる。

(z)
The dicyclopentadiene etc. which are represented by these are mentioned.

  Incidentally, the substitution position of the vinyl group of the vinyl norbornene may be either a cis configuration (exo type) or a trans configuration (end type). Since there is no difference in the above, it is possible to use a combination of both isomers.

<Preparation of component (A)>
The component (A) of the composition of the present invention has two addition-reactive carbon-carbon double bonds in one molecule per mole of the component (a) having two SiH in one molecule. (b) An addition reaction product having no SiH is obtained by subjecting an excess of more than 1 mole to 10 moles or less, preferably more than 1 mole to 5 moles or less in the presence of a hydrosilylation reaction catalyst. Obtainable.
The component (A) thus obtained is derived from the component (a) in addition to the addition-reactive carbon-carbon double bond derived from the component (b) (specifically, R in the general formula (1) and And / or an addition-reactive carbon-carbon double bond (derived from R ′ in the general formula (2)), so that at least two addition-reactive carbon-carbon double bonds are contained in one molecule. The number is preferably 2 to 6, more preferably 2. When there are too many this addition reactive carbon-carbon double bonds, it will become easy to produce a crack in the hardened | cured material obtained by hardening the composition of this invention.

  Any conventionally known hydrosilylation reaction catalyst can be used. For example, carbon powder carrying platinum metal, platinum black, secondary platinum chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, complex of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. Platinum group catalysts such as platinum group catalysts such as palladium catalysts and rhodium catalysts. Moreover, about addition reaction conditions, use of a solvent, etc., it may just be as usual without being specifically limited.

  As mentioned above, when preparing the component (A), the component (b) is used in an excess molar amount with respect to the component (a). Therefore, the component (A) is derived from the structure of the component (b). It has two addition-reactive carbon-carbon double bonds in one molecule. Furthermore, the component (A) has a residue derived from the component (a), and the residue is derived from the structure of the 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.

That is, as the component (A), for example, the following general formula (6):
Y-X- (Y'-X) p-Y (6)
Wherein X is a divalent residue of the compound of the component (a), Y is a monovalent residue of the polycyclic hydrocarbon of the component (b), and Y ′ is the above (b ) Component divalent residue, p is an integer of 0 to 10, preferably 0 to 5)
The compound represented by these is mentioned.

In addition, about the value of p which is the number of repeating units represented by said (Y'-X), adjusting the excess molar amount of said (b) component made to react with respect to 1 mol of said (a) component. It is possible to set by.
As Y in the general formula (6), specifically, for example, the following structural formula:

で表される一価の残基（以下、これら６者を区別する必要がない場合は、これらを「ＮＢ基」と総称し、また、前記６者の構造を区別せずに「ＮＢ」と略記することがある。）；

(Hereinafter, when it is not necessary to distinguish these six members, they are collectively referred to as “NB group”, and “NB” without distinguishing the structure of the six members) May be abbreviated.);

で表される一価の残基（以下、これら７者を区別する必要がない場合は、これらの構造を「ＤＣＰ」と略記することがある。）が挙げられる。
上記一般式(6)中のＹ'としては、具体的には、例えば、下記構造式：

(Hereinafter, these structures may be abbreviated as “DCP” when it is not necessary to distinguish these seven members.)
As Y ′ in the general formula (6), specifically, for example, the following structural formula:

で表される二価の残基が挙げられる。

The bivalent residue represented by these is mentioned.

  However, the asymmetrical divalent residue represented by the above structural formula is not limited in the left-right direction as described above. It also shows the structure rotated 180 degrees.

Preferred specific examples of the component (A) represented by the general formula (6) are shown below, but are not limited thereto. (The meanings of “NB” and “DCP” are as described above.)
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

（式中、ｐは１〜10の整数である。）

(In the formula, p is an integer of 1 to 10.)

（式中、ｐは１〜10の整数である。）

(In the formula, p is an integer of 1 to 10.)

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

（式中、ｐは１〜10の整数である。）

(In the formula, p is an integer of 1 to 10.)

（式中、ｐは１〜10の整数である。）
更に、本発明の(Ａ)成分は、１種単独でも２種以上を組み合わせても使用することができる。

(In the formula, p is an integer of 1 to 10.)
Furthermore, the component (A) of the present invention can be used singly or in combination of two or more.

[Component (B)]
The component (B) of the present invention is a compound having 3 or more SiH molecules in one molecule. SiH in the component (B) is added by an addition reactive carbon-carbon double bond and at least two of the component (A) in one molecule and a hydrosilylation reaction to form a cured product having a three-dimensional network structure. give.
Examples of the component (B) include the following general formula (7):

（式中、Ｒ¹は独立に水素原子またはアルケニル基以外の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、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）
で表される環状シロキサン系化合物が挙げられる。

(In the formula, R ¹ is independently a monovalent hydrocarbon group having 1 to 12, preferably 1 to 6 carbon atoms that are unsubstituted or substituted other than a hydrogen atom or an alkenyl group, and q is 3 to 10, preferably An integer of 3-8, r is an integer of 0-7, preferably 0-2, and the sum of q + r is an integer of 3-10, preferably 3-6)
The cyclic siloxane type compound represented by these is mentioned.

Examples of the case where R ¹ in the general formula (7) is an unsubstituted or substituted monovalent hydrocarbon group other than an alkenyl group include, for example, methyl group, ethyl, propyl group, isopropyl group, butyl group, tert-butyl Group, alkyl group such as pentyl group, isopentyl group, hexyl group, sec-hexyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group; aryl group such as phenyl group, o-, m-, p-tolyl; benzyl group An aralkyl group such as 2-phenylethyl group; an alkenylaryl group such as p-vinylphenyl group; and one or more hydrogen atoms bonded to carbon atoms in these groups contain a halogen atom, a cyano group or an epoxy ring Substituted with, for example, a halogenated alkyl group such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group; 2-cyanoethyl group; Sid hydroxypropyl group and the like.

Among these, as R ¹ , those in which all of them are methyl groups are particularly preferable because they are easy to produce industrially and are easily available.

  In addition, as the component (B), for example, SiH obtained by hydrosilylation reaction of one or two kinds of vinyl norbornene and 1,3,5,7-tetramethylcyclotetrasiloxane may be added in 3 molecules in one molecule. Addition reaction product having at least one, for example, the following general formula (8):

（式中、ｓは１〜100、好ましくは１〜10の整数である）
で表される化合物が挙げられる。

(Wherein s is an integer of 1 to 100, preferably 1 to 10)
The compound represented by these is mentioned.

Although the preferable example of the said (B) component is shown below, it is not limited to this.
(HMeSiO) ₃
(HMeSiO) ₄
(HMeSiO) ₃ (Me ₂ SiO)
(HMeSiO) ₄ (Me ₂ SiO)

本発明の(Ｂ)成分は、１種単独でも２種以上を組み合わせても使用することができる。

The component (B) of the present invention can be used singly or in combination of two or more.

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 (B) and / or an addition-reactive carbon-carbon bond bonded to a silicon atom other than the component (A). 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 0.5 to 2.0 mol, preferably 0.8 to 1.5 moles. And the ratio of the hydrogen atom couple | bonded with the silicon atom in the said (B) 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 addition-reactive carbon-carbon double bond in the component (A) in the addition-reactive carbon-carbon double bond bonded to the silicon atom in the composition is usually 20 to 100 mol%. , 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.
When the above-mentioned optional components are not included, the blending amount of the component (B) in the composition of the present invention is the amount of the addition reactive carbon-carbon double bond in 1 mol of the component (A). The amount of SiH in the component (B) is usually 0.5 to 2.0 mol, preferably 0.8 to 1.5 mol.

[Component (C)]
The hydrosilylation reaction catalyst which is the component (C) of the present invention is the same as that described in the above “Preparation of the component (A)”.
The compounding amount of the component (C) in the composition of the present invention is not particularly limited as long as it is an effective amount as a catalyst, but the platinum group is based on the total mass of the component (A) and the component (B). As a metal atom, it is preferable to mix | blend normally the quantity used as 1-500 ppm, especially about 2-100 ppm. By setting the blending amount within the above range, the time required for the curing reaction becomes appropriate, and problems such as coloring of the cured product do not occur.

[Other ingredients]
In addition to the above components (A) to (C), it is optional to add other components to the composition of the present invention within a range that does not impair the objects and effects of the present invention.

<Antioxidant>
In the cured product of the curable resin composition of the present invention, the addition-reactive carbon-carbon double bond in the component (A) may remain unreacted, or
The following structural formula (i):

2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl group and / or the following structural formula (ii):

(ii)
で表される 2-(ビシクロ[2.2.1]ヘプト-2-エン-6-イル)エチル基の開環メタセシス反応により生じる炭素−炭素二重結合が含まれている場合がある。そして、前記炭素−炭素二重結合が含まれていると、大気中の酸素により酸化され前記硬化物が着色する原因となる。
そこで、本発明組成物に、必要に応じ、酸化防止剤を配合することにより前記着色を未然に防止することができる。

(ii)
It may contain a carbon-carbon double bond generated by a ring-opening metathesis reaction of 2- (bicyclo [2.2.1] hept-2-en-6-yl) ethyl group represented by And when the said carbon-carbon double bond is contained, it will be oxidized by oxygen in air | atmosphere and will cause the said hardened | cured material to color.
Then, the said coloring can be prevented beforehand by mix | blending antioxidant with this invention composition as needed.

  As the antioxidant, all conventionally known antioxidants 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'- And methylenebis (4-ethyl-6-t-butylphenol). These can be used singly or in combination of two or more.

  In addition, when using this antioxidant, the blending amount thereof is not particularly limited as long as it is an effective amount as an antioxidant, but with respect to the total mass of the component (A) and the component (B). Usually, it is preferable to add about 10 to 10,000 ppm, particularly about 100 to 1,000 ppm. By setting the blending amount within the above range, the antioxidant ability is sufficiently exhibited, and a cured product having excellent optical characteristics without coloration, white turbidity, oxidative deterioration and the like is obtained.

<Viscosity / Hardness modifier>
In order to adjust the viscosity of the composition of the present invention or the hardness of the cured product obtained from the composition of the present invention, a linear diorganopolysiloxane or network organopolysiloxane having an alkenyl group or SiH bonded to a silicon atom; A reactive (that is, having no alkenyl group bonded to a silicon atom and SiH), a linear or cyclic diorganopolysiloxane, a silphenylene compound, and the like may be blended.

  When the organopolysiloxane having various structures having an alkenyl group bonded to a silicon atom is blended with the composition of the present invention (D1), the blending amount is the addition reactive carbon of the alkenyl group and the component (A). -It is good to set it as the quantity from which SiH in the said (B) component is 0.5-2.0 mol normally with respect to 1 mol of total amounts with a carbon double bond, Preferably it is 0.8-1.5 mol. In addition, when (D2) SiH-containing organopolysiloxanes with various structures are blended, the blending amount is the total amount of the SiH and the SiH that the (B) component has, and the addition that the (A) component has The amount is usually 0.5 to 2.0 moles, preferably 0.8 to 1.5 moles per mole of reactive carbon-carbon double bond.

<Others>
Moreover, in order to ensure pot life, an addition reaction control agent such as 1-ethynylcyclohexanol and 3,5-dimethyl-1-hexyn-3-ol can be blended. Furthermore, an inorganic filler such as fumed silica may be blended in order to improve the strength within a range that does not affect transparency, and if necessary, a dye, pigment, flame retardant, etc. may be blended. Also good.

Furthermore, it is also possible to use a light stabilizer in order to impart resistance to light degradation caused by light energy such as sunlight and fluorescent lamps. As this light stabilizer, a hindered amine stabilizer that captures radicals generated by photooxidation degradation is suitable, and the antioxidant effect is further improved by using it together with the antioxidant. 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.
Moreover, when using this invention composition as a sealing material, in order to improve adhesiveness with a base material, you may mix | blend a silane coupling agent and may add a plasticizer for crack prevention. Good.
In addition, about the hardening conditions of this invention composition, it changes with the quantity, Although it does not restrict | limit in particular, Usually, it is preferable to set it as 60-180 degreeC and the conditions for 5 to 180 minutes.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Synthesis Example 1] Preparation of Component (A) Into a 500 mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd .; 5-vinylbicyclo) 156 g (1.3 mol) of [2.2.1] hept-2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene in an approximately equimolar amount of an isomer mixture), and using an oil bath. Heated to ° C. To this, 0.05 g of carbon powder supporting 5 mass% platinum metal was added, and 67 g (0.5 mol) of 1,1,3,3-tetramethyldisiloxane was added dropwise over 60 minutes with stirring. After completion of dropping, the mixture was further stirred at 90 ° C. for 24 hours, and then cooled to room temperature. Thereafter, platinum metal-supported carbon was removed by filtration, and excess vinylnorbornene was distilled off under reduced pressure to obtain 170 g of a colorless and transparent oily reaction product (viscosity at 25 ° C .: 110 mm ² / s).

As a result of analyzing the reaction product by FT-IR, NMR, GPC, etc.,
(1) Compound having one -Si-O-Si- bond: NBMe ₂ SiOSiMe ₂ NB about 70 mol%,
(2) Compound having two -Si-O-Si- bonds: about 25 mol% (an example of a typical structural formula is shown below),

および、(3) -Ｓｉ-Ｏ-Ｓｉ-結合を３個有する化合物：約５モル％（下記に代表的な構造式の一例を示す）

And (3) a compound having three -Si-O-Si- bonds: about 5 mol% (an example of a typical structural formula is shown below)

の混合物であることが判明した。また、前記混合物全体としての付加反応性炭素−炭素二重結合の含有割合は、0.46モル/100ｇであった。

It was found to be a mixture of Moreover, the content rate of the addition reactive carbon-carbon double bond as the whole mixture was 0.46 mol / 100 g.

[Synthesis Example 2] Preparation of component (A) Into a 500 mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd .; 5-vinylbicyclo) 60 g (0.5 mol) of [2.2.1] hept-2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene in approximately equimolar amount) Heated to ° C. To this, 0.02 g of carbon powder supporting 5% by mass of platinum metal was added, and 38.8 g (0.2 mol) of 1,4-bis (dimethylsilyl) benzene was added dropwise over 25 minutes while stirring. After completion of dropping, the mixture was further stirred at 90 ° C. for 24 hours, and then cooled to room temperature. Thereafter, platinum metal-supported carbon was removed by filtration, and excess vinylnorbornene was distilled off under reduced pressure to obtain 79 g of a colorless and transparent oily reaction product (viscosity at 25 ° C .: 1220 mm ² / s).

As a result of analyzing the reaction product by FT-IR, NMR, GPC, etc.,
(1) Compound having one p-phenylene group: NBMe ₂ Si—p—C ₆ H ₄ —SiMe ₂ NB about 72 mol%,
(2) Compound having two p-phenylene groups: about 24 mol% (an example of a typical structural formula is shown below),

および、(3) ｐ-フェニレン基を３個有する化合物：約４モル％（下記に代表的な構造式の一例を示す）

And (3) a compound having three p-phenylene groups: about 4 mol% (an example of a typical structural formula is shown below)

の混合物であることが判明した。また、前記混合物全体としての付加反応性炭素−炭素二重結合の含有割合は、0.40モル/100ｇであった。

It was found to be a mixture of Moreover, the content rate of the addition reactive carbon-carbon double bond as the whole mixture was 0.40 mol / 100 g.

Synthesis Example 3 Preparation of Component (B) To a 500 mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, 80 g of toluene and 1,3,5,7-tetramethylcyclotetrasiloxane 115.2 g (0.48 mol) was added and heated to 117 ° C. using an oil bath. To this, 0.05 g of carbon powder supporting 5% by mass of platinum metal was added, and while stirring, 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 approximately equimolar amount of isomer mixture with 6-vinylbicyclo [2.2.1] hept-2-ene was added dropwise over 16 minutes. After completion of dropping, the mixture was further stirred with heating 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 152 g of a colorless and transparent oily reaction product (viscosity at 25 ° C .: 2,500 mm ² / s).

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

(2) テトラメチルシクロテトラシロキサン環を２個有する化合物：約 25モル％（下記に代表的な構造式の一例を示す）、

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

(3) テトラメチルシクロテトラシロキサン環を３個有する化合物：約 16モル％（下記に代表的な構造式の一例を示す）

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

(4) テトラメチルシクロテトラシロキサン環を４個有する：約 11モル％（下記に代表的な構造式の一例を示す）、

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

および、(5) テトラメチルシクロテトラシロキサン環を５〜12個有する化合物：残余（下記に代表的な構造式の一例を示す）

And (5) a compound having 5 to 12 tetramethylcyclotetrasiloxane rings: the remainder (an example of a typical structural formula is shown below)

（式中、ｎは４〜11の整数である。）
の混合物であることが判明した。なお、前記混合物全体としてのＳｉＨの含有割合は、0.63モル/100ｇであった。

(In the formula, n is an integer of 4 to 11.)
It was found to be a mixture of In addition, the content rate of SiH as the said mixture whole was 0.63 mol / 100g.

[Example 1]
(A1) Reaction product obtained in Synthesis Example 1: 5 parts by mass, (A2) Reaction product obtained in Synthesis Example 2: 60 parts by mass,
(B1) (MeHSIO) ₄ : 5 parts by mass, (B2) Reaction product obtained in Synthesis Example 3: 30 parts by mass (Note that the total SiH in the components (B1) and (B2) / (A1 ) And the total carbon-carbon double bond (molar ratio) in the component (A2) = 1.03 Hereinafter, in the same manner as described above, the molar ratio of SiH / carbon-carbon double bond is “SiH / C = C ( Molar ratio) ”.)
(C) platinum-vinylsiloxane complex: an amount of 20 ppm relative to the total mass of (A1), (A2), (B1) and (B2) as a platinum metal atom, and
1-Ethynylcyclohexanol: 0.03 part by mass was uniformly mixed to obtain a composition. This composition was poured into a mold made of glass plates to a thickness of 4 mm and heated at 150 ° C. for 2 hours to obtain a cured product.

[Example 2]
(A2) Reaction product obtained in Synthesis Example 2: 81 parts by mass
(B1) (MeHSIO) ₄ : 19 parts by mass (SiH / C = C (molar ratio) = 0.98)
(C) platinum-vinylsiloxane complex: an amount of 20 ppm relative to the total mass of (A2) and (B1) as platinum metal atoms, and
1-Ethynylcyclohexanol: 0.03 part by mass was uniformly mixed to obtain a composition. This composition was poured into a mold made of glass plates to a thickness of 4 mm and heated at 150 ° C. for 2 hours to obtain a cured product.

[ Reference Example 1 ]
(A1) Reaction product obtained in Synthesis Example 1: 58 parts by mass
(B2) Reaction product obtained in Synthesis Example 3: 42 parts by mass (SiH / C = C (molar ratio) = 0.99)
(C) platinum-vinylsiloxane complex: an amount of 20 ppm relative to the total mass of (A1) and (B2) as platinum metal atoms, and
1-Ethynylcyclohexanol: 0.03 part by mass was uniformly mixed to obtain a composition. This composition was poured into a mold made of glass plates to a thickness of 4 mm and heated at 150 ° C. for 2 hours to obtain a cured product.

[Example 3 ]
(A2) Reaction product obtained in Synthesis Example 2: 61 parts by mass
(B2) Reaction product obtained in Synthesis Example 3: 39 parts by mass (SiH / C = C (molar ratio) = 1.00)
(C) platinum-vinylsiloxane complex: an amount of 20 ppm relative to the total mass of (A2) and (B2) as platinum metal atoms, and
1-Ethynylcyclohexanol: 0.03 part by mass was uniformly mixed to obtain a composition. This composition was poured into a mold made of glass plates to a thickness of 4 mm and heated at 150 ° C. for 2 hours to obtain a cured product.

[Example 4 ]
(A1) Reaction product obtained in Synthesis Example 1: 10 parts by mass, (A2) Reaction product obtained in Synthesis Example 2: 55 parts by mass,
(B1) (MeHSIO) ₄ : 5 parts by mass, (B2) Reaction product obtained in Synthesis Example 3: 30 parts by mass (SiH / C = C (molar ratio) = 1.02)
(C) platinum-vinylsiloxane complex: an amount of 20 ppm relative to the total mass of (A1), (A2), (B1) and (B2) as a platinum metal atom, and
1-Ethynylcyclohexanol: 0.03 part by mass was uniformly mixed to obtain a composition. This composition was poured into a mold made of glass plates to a thickness of 4 mm and heated at 150 ° C. for 2 hours to obtain a cured product.

[Comparative Example 1]
In place of the components (A1) and (A2) described in Example 1, 59 parts by mass of (A ′) (ViMeSiO) ₄ (wherein Vi is a vinyl group), and component (B1) The same amount as in Example 1 except that 5 parts by mass of (MeHSIO) ₄ is changed to 41 parts by mass and the component (B2) is not used (SiH / Vi (molar ratio) = 1.0). Thus, a composition and a cured product were obtained.

[Comparative Example 2]
In a mold in which a phenyl silicone resin curable composition (trade name: X-34-1195, manufactured by Shin-Etsu Chemical Co., Ltd., phenyl group content: about 50 mol%) is assembled with a glass plate in the same manner as in Example 1. The resulting product was poured to a thickness of 4 mm and heated at 150 ° C. for 8 hours to obtain a cured product.

<Performance evaluation method>
(1) The performance of the cured products obtained in the above Examples , Reference Examples and Comparative Examples was evaluated according to the following method.
-Appearance-
The appearance of each cured product was visually observed. The observation results are shown in Table 1.
-Hardness-
The hardness (Shore D) of each cured product was measured according to ASTM D 2240. The measurement results are shown in Table 1.
-Elastic modulus-
A test piece of 10 mm (width) × 100 mm (length) was produced from each cured product of 4 mm thickness, and the elastic modulus (MPa) was measured by a three-point bending test according to JIS K-6911. The measurement results are shown in Table 1.

(2) Measurement of shrinkage rate The resin composition obtained in each of the above Examples , Reference Examples and Comparative Example 1 (for Comparative Example 2, the phenyl silicone resin-based curable composition) was 4 mm × 10 mm × 100 mm. It was poured into a mold and heated at 150 ° C. for 2 hours to be cured. After cooling, the cured product was taken out.
The shrinkage rate upon curing was determined by the following formula. The measurement results are shown in Table 1.
Shrinkage rate (%) = (length of cured product / length of mold part) x 100

(3) Light transmittance The light transmittance of each cured product was measured using a spectrophotometer at four measurement wavelengths: 800, 600, 400 nm, and 300 nm (ultraviolet region). The measurement results are shown in Table 2.

[Evaluation]
In contrast to the comparative example, all of the cured products of the examples are excellent in hardness and elastic modulus and have very small curing shrinkage. It can also be seen that the light transmittance is particularly excellent at a short wavelength of 300 nm (ultraviolet region).

Claims (8)

(A) (a) The following general formula (1):

[In the formula, A is under Symbol structural formula (3):

In a divalent group which Ru represented,
R are independently unsubstituted or halogen atom, a monovalent hydrocarbon group or a C 1 -C 6 alkoxy group which has been C1-12 cyano group or a glycidoxy group]
A compound having two hydrogen atoms bonded to a silicon atom represented by
(b) An addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and the addition-reactive carbon-carbon double bond in one molecule 2 to 6 addition reaction products
(B) a compound having three or more hydrogen atoms bonded to a silicon atom in one molecule, and
(C) A curable composition containing a hydrosilylation reaction catalyst.   The curable composition according to claim 1, wherein the polycyclic hydrocarbon of (b) is 5-vinylbicyclo [2.2.1] hept-2-ene or 6-vinylbicyclo [2.2.1] hept. A curable composition that is 2-ene or a combination of both. A curable group formed composition according to claim 1 or 2, wherein component (B) is 1,3,5,7-tetramethylcyclotetrasiloxane, curable compositions. A curable group formed product according to claim 1 or 2, wherein component (B) is 5-vinylbicyclo [2.2.1] hept-2-ene, 6-vinylbicyclo [2.2.1] hept -2 A curable composition, which is an addition reaction product of -ene or a combination of the two and 1,3,5,7-tetramethylcyclotetrasiloxane. The component (A) undergoes an addition reaction between the (a) and an excess molar amount of the (b) with respect to the (a) in the presence of platinum metal-supported carbon, and then the platinum metal-supported carbon is filtered. The curable composition according to any one of claims 1 to 4, wherein the curable composition is an addition reaction product obtained by a method including removing by a step. It is a curable composition which concerns on any one of Claims 1-5, Comprising: The said curable composition in which the hardened | cured material has high transparency. The curable composition according to claim 6, wherein the light transmittance of the cured product having a thickness of 4 mm is 89% or more at 800, 600 and 400 nm and 60% or more at 300 nm. The curable composition which concerns on any one of Claims 1-7 used as an optical device or a material for optical components.