JP2007224095A - Curing agent, curable composition and cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new curing agent having a polar group and low viscosity, and to provide a curable composition that can give a cured product having optical transparency, crack resistance, and adhesion. <P>SOLUTION: The curing agent comprises at least one sulfonyl group and at least two SiH groups in one molecule and the viscosity at 23°C is less than 1,000 Pa s. The curable composition comprises the above curing agent; an organic compound having in one molecule at least two carbon-carbon double bonds having reactivity with SiH group; and a hydrosilylating catalyst as essential components. The cured products thereof are also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a curing agent, a curable composition using the same, and a cured product thereof, and more particularly to a curable composition having optical transparency, crack resistance, and adhesiveness. .

Many curable compositions using a hydrosilylation reaction and comprising a compound containing a carbon-carbon double bond, a compound containing an SiH group, and a hydrosilylation catalyst have been proposed. For example, Patent Document 1 mentions a curable composition having optical transparency, heat resistance, and light resistance. However, there is a problem that the obtained cured product has insufficient crack resistance and adhesion to the base material during a cold test.
Generally, as a technique for improving the crack resistance and adhesion of a cured product, a method of introducing a polar group into the cured product can be mentioned. However, since a compound having a polar group generally has a high viscosity or a solid, there is a problem that handleability and workability are poor.
For example, as a curable composition using a carbon-carbon double bond-containing compound having a polar group, a curable composition of bisallylnadiimide and a SiH group-containing siloxane (see, for example, Patent Document 2), 3, Examples thereof include a curable composition of 3′-diallyl-4,4′-dihydroxydiphenylsulfone and a SiH group-containing siloxane (see, for example, Patent Document 3). These bisallyl nadiimides and 3,3′-diallyl-4,4′-dihydroxydiphenyl sulfone also have a problem that they are very high in viscosity or solid and are not sufficient in terms of handleability and workability.
JP 2002-317048 A JP-A-7-62103 JP 2003-073548 A

The first object of the present invention is to provide a novel curing agent having a polar group and low viscosity. The second object of the present invention is to provide a curable composition capable of giving a cured product having optical transparency, crack resistance and adhesion.

As described above, a carbon-carbon double bond-containing compound having a polar group (hereinafter referred to as “polar group-containing unsaturated compound”) is highly viscous or solid, and therefore has a curability comprising a polar group-containing unsaturated compound as a component. The reality is that the composition cannot be prepared as intended. As a result of intensive studies in view of such a situation, the present inventors succeeded in reducing the viscosity by modifying a polar group-containing unsaturated compound with a SiH-containing compound. It has been found that the use of this novel compound can easily solve the above-mentioned problems and can overcome the above-mentioned situation, and the present invention has been completed.

That is, the present invention
Regarding a curing agent (claim 1) having at least one sulfonyl group and at least two SiH groups in one molecule and having a viscosity at 23 ° C. of 1000 Pa · s or less,
In one molecule, at least two SiH groups and the following general formula (I)

（式中、Ｒ¹は水素原子、炭素数１〜２０の炭化水素基、水酸基、ハロゲン基、ビニル基、アリル基を表し、Ｒ¹はそれぞれ同一でも異なっていてもよい。）
からなる部分構造を有し、かつ、２３℃における粘度が１０００Ｐａ・ｓ以下である硬化剤（請求項２）に関し、
上記一般式（Ｉ）が、下記一般式（ＩＩ）：

(In the formula, R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a halogen group, a vinyl group, or an allyl group, and R ¹ may be the same or different.)
A curing agent (part 2) having a partial structure consisting of and having a viscosity at 23 ° C. of 1000 Pa · s or less,
The general formula (I) is represented by the following general formula (II):

（式中、Ｒ¹は水素原子、炭素数１〜２０の炭化水素基、水酸基、ハロゲン基、ビニル基、アリル基を表し、Ｒ¹はそれぞれ同一でも異なっていてもよい。）
である、請求項２に記載の硬化剤（請求項３）に関し、
１分子中に、ＳｉＨ基を少なくとも２個および下記一般式（ＩＩＩ）

(In the formula, R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a halogen group, a vinyl group, or an allyl group, and R ¹ may be the same or different.)
The curing agent according to claim 2 (claim 3),
In one molecule, at least two SiH groups and the following general formula (III)

（式中、Ｒ²は水素原子、炭素数１〜２０の炭化水素基、水酸基、ハロゲン基、ビニル基、アリル基を表し、Ｒ²はそれぞれ同一でも異なっていてもよい。）
からなる部分構造を有し、かつ、２３℃における粘度が１０００Ｐａ・ｓ以下である硬化剤（請求項４）に関し、
上記一般式（ＩＩＩ）が、下記一般式（ＩＶ）：

(Wherein R ² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a halogen group, a vinyl group or an allyl group, and R ² may be the same or different.)
And a curing agent (claim 4) having a partial structure consisting of and having a viscosity at 23 ° C. of 1000 Pa · s or less,
The general formula (III) is represented by the following general formula (IV):

（式中、Ｒ²は水素原子、炭素数１〜２０の炭化水素基、水酸基、ハロゲン基、ビニル基、アリル基を表し、Ｒ²はそれぞれ同一でも異なっていてもよい。）
である、請求項４に記載の硬化剤（請求項５）に関し、
上記一般式（ＩＶ）中のＲ²が全て水素原子である、請求項５に記載の硬化剤（請求項６）に関し、
（Ａ）ＳｉＨ基と反応性を有する炭素−炭素二重結合を１分子中に少なくとも２個含有する有機化合物、（Ｂ）ＳｉＨ基を含有する硬化剤、および、（Ｃ）ヒドロシリル化触媒、を必須成分として含有する硬化性組成物であって、上記（Ｂ）成分が請求項１〜６のいずれか一項に記載の硬化剤である硬化性組成物（請求項７）に関し、
請求項７に記載の硬化性組成物を硬化させてなる硬化物に関する。

(Wherein R ² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a halogen group, a vinyl group or an allyl group, and R ² may be the same or different.)
The curing agent according to claim 4 (claim 5),
Regarding the curing agent (claim 6) according to claim 5, wherein all R ² in the general formula (IV) are hydrogen atoms,
(A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, (B) a curing agent containing SiH groups, and (C) a hydrosilylation catalyst. It is a curable composition contained as an essential component, and the component (B) is a curable composition according to any one of claims 1 to 6 (claim 7),
The present invention relates to a cured product obtained by curing the curable composition according to claim 7.

Since the curing agent of the present invention is low in viscosity and liquid, it is excellent in handleability and processability and can be used as a suitable component of a hydrosilylation curing system. The curable composition using the curing agent of the present invention is excellent in handleability and processability, and can give a cured product having optical transparency, crack resistance and adhesion.

The curable composition of the present invention comprises (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, (B) a curing agent containing SiH groups, C) a hydrosilylation catalyst as an essential component, wherein (B) component has at least one sulfonyl group and at least two SiH groups in one molecule, and 23 ° C. A curing agent containing a SiH group having a viscosity of 1000 Pa · s or less is used. By using the novel curing agent of the present invention, a cured product having optical transparency, crack resistance and adhesiveness can be obtained without impairing the handling and workability of the curable composition.
Below, each component used for the curable composition of this invention is demonstrated.

<(A) component>
The component (A) of the present invention will be described.

  The component (A) is not particularly limited as long as it is an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule. Organic compounds do not contain siloxane units (Si-O-Si) such as polysiloxane-organic block copolymers and polysiloxane-organic graft copolymers, but only C, H, N, O, S, and halogen as constituent elements It is preferable that it contains. Those containing siloxane units have gas permeability and repelling problems.

  The bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and may be present anywhere in the molecule.

  The organic compound (A) can be classified into an organic polymer compound and an organic monomer compound.

  Examples of organic polymer compounds include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, phenol-formaldehyde (phenolic resin) ), Polyimide compounds can be used.

  Examples of organic monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene and naphthalene: aliphatic hydrocarbons such as linear and alicyclic: heterocyclic compounds and their A mixture etc. are mentioned.

  (A) Although it does not specifically limit as a carbon-carbon double bond reactive with the SiH group of a component, The following general formula (V)

（式中Ｒ³は水素原子あるいはメチル基を表す。）で示される基が反応性の点から好適である。また、原料の入手の容易さからは、

A group represented by the formula (wherein R ³ represents a hydrogen atom or a methyl group) is preferred from the viewpoint of reactivity. In addition, from the availability of raw materials,

示される基が特に好ましい。

The groups shown are particularly preferred.

  As the carbon-carbon double bond having reactivity with the SiH group of the component (A), an alicyclic group having a partial structure represented by the following general formula (VI) in the ring is the heat resistance of the cured product. Is preferable from the viewpoint of high.

（式中Ｒ⁴は水素原子あるいはメチル基を表す。）また、原料の入手の容易さからは、下記式で表される部分構造を環内に有する脂環式の基が好適である。

(In the formula, R ⁴ represents a hydrogen atom or a methyl group.) From the viewpoint of availability of raw materials, an alicyclic group having a partial structure represented by the following formula in the ring is preferred.

ＳｉＨ基と反応性を有する炭素−炭素二重結合は（Ａ）成分の骨格部分に直接結合していてもよく、２価以上の置換基を介して共有結合していても良い。２価以上の置換基としては炭素数０〜１０の置換基であれば特に限定されないが、構成元素としてＣ、Ｈ、Ｎ、Ｏ、Ｓ、およびハロゲンのみを含むものが好ましい。これらの置換基の例としては、

The carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton portion of the component (A) or may be covalently bonded via a divalent or higher valent substituent. The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms, but preferably includes only C, H, N, O, S, and halogen as constituent elements. Examples of these substituents include

が挙げられる。また、これらの２価以上の置換基の２つ以上が共有結合によりつながって１つの２価以上の置換基を構成していてもよい。

Is mentioned. Moreover, two or more of these divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.

  Examples of the group covalently bonded to the skeleton as described above include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3 -Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyl) Oxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group,

が挙げられる。

Is mentioned.

  Specific examples of the component (A) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetraallyloxyethane. Diarylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (having a purity of 50 to 100%, preferably having a purity of 80 to 100%) , Divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio) 50-100%), Novo Allyl ether of click phenol, allylated polyphenylene oxide,

の他、従来公知のエポキシ樹脂のグルシジル基の一部あるいは全部をアリル基に置き換えたもの等が挙げられる。

In addition, there may be mentioned those in which part or all of the glycidyl group of a conventionally known epoxy resin is replaced with an allyl group.

  As the component (A), low molecular weight compounds that are difficult to express separately as described above for the skeleton portion and the alkenyl group can also be used. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, fats such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. Examples thereof include aromatic cyclic polyene compound systems and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

  The component (A) preferably contains 0.001 mol or more of a carbon-carbon double bond having reactivity with the SiH group per 1 g of the component (A) from the viewpoint of further improving the heat resistance. What contains 0.005 mol or more per is more preferable, and what contains 0.008 mol or more is still more preferable.

  The number of carbon-carbon double bonds having reactivity with the SiH group of component (A) should be on average at least two per molecule, but may exceed 2 if it is desired to further improve the mechanical strength. Preferably, it is 3 or more. When the number of carbon-carbon double bonds having reactivity with the SiH group of component (A) is 1 or less per molecule, only a graft structure is formed even if it reacts with component (B). Don't be.

  From the viewpoint of good reactivity as the component (A), it is preferable that one or more vinyl groups are contained in one molecule, and two or more vinyl groups are contained in one molecule. Is more preferable. Further, from the viewpoint that the storage stability tends to be good, it is preferable that 6 or less vinyl groups are contained in one molecule, and it is more preferable that 4 or less vinyl groups are contained in one molecule.

  As the component (A), those having a molecular weight of less than 900 are preferable from the viewpoint of high mechanical heat resistance and from the viewpoint that the raw material liquid has low stringiness and good moldability, handleability, and coatability. Those less than 700 are more preferred, and those less than 500 are more preferred.

  As the component (A), in order to obtain uniform mixing with other components and good workability, the viscosity is preferably less than 100 Pa · s at 23 ° C., more preferably less than 30 Pa · s. Those less than 3 Pa · s are more preferred. The viscosity can be measured with an E-type viscometer.

  As the component (A), those having a low content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group are preferable from the viewpoint of suppression of coloring, particularly yellowing. What does not contain the compound which has a derivative is preferable. In the present invention, the phenolic hydroxyl group means a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, naphthalene ring, anthracene ring, etc., and a phenolic hydroxyl group derivative means a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted by an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, an acyl group such as an acetoxy group, or the like.

  From the viewpoint that the obtained cured product is less colored and has high light resistance, the component (A) is vinylcyclohexene, dicyclopentadiene, triallyl isocyanurate, diallyl of 2,2-bis (4-hydroxycyclohexyl) propane. Ether and 1,2,4-trivinylcyclohexane are preferable, and triallyl isocyanurate, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, and 1,2,4-trivinylcyclohexane are particularly preferable.

  (A) As a component, you may have another reactive group. Examples of the reactive group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When it has these functional groups, the adhesiveness of the resulting curable composition tends to be high, and the strength of the resulting cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the obtained cured product tends to be high.

  In particular, as the component (A), triallyl isocyanurate, diallyl monoglycidyl isocyanurate and derivatives thereof represented by the following general formula (VII) are particularly preferable from the viewpoint of high heat resistance and light resistance.

（式中Ｒ⁵は炭素数１〜５０の一価の有機基を表し、それぞれのＲ⁵は異なっていても同一であってもよい。）で表される化合物が好ましい。

(Wherein R ⁵ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ⁵ may be different or the same).

R ^{5 in the} general formula (VII) is preferably a monovalent organic group having 1 to 20 carbon atoms from the viewpoint that the heat resistance of the obtained cured product can be further increased. 10 monovalent organic groups are more preferable, and monovalent organic groups having 1 to 4 carbon atoms are more preferable. Examples of these preferable R ⁴ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

等が挙げられる。

Etc.

R ^{5 in the} general formula (VII) is a carbon in which at least one of the three R ^{5 s} contains one or more epoxy groups from the viewpoint that the adhesion of the obtained cured product to various materials can be improved. A monovalent organic group of 1 to 50 is preferable,

で表されるエポキシ基を１個以上含む炭素数１〜５０の一価の有機基であることがより好ましい。これらの好ましいＲ⁵の例としては、グリシジル基、

It is more preferable that it is a C1-C50 monovalent organic group containing 1 or more of epoxy groups represented by these. Examples of these preferable R ⁵ include a glycidyl group,

等が挙げられる。

Etc.

As R ^{5 in the} general formula (VII), from the viewpoint that the chemical thermal stability of the resulting cured product can be improved, it contains 2 or less oxygen atoms, and C, H, O as constituent elements It is preferably a monovalent organic group having 1 to 50 carbon atoms, and more preferably a monovalent hydrocarbon group having 1 to 50 carbon atoms. Examples of these preferable R ⁵ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

等が挙げられる。

Etc.

As R ^{5 in the} general formula (VII), at least one of the three R ⁵ is at least one from the viewpoint of good reactivity.

で表される基を１個以上含む炭素数１〜５０の一価の有機基であることが好ましく、下記一般式（ＶＩＩＩ）

It is preferable that it is a C1-C50 monovalent organic group containing 1 or more groups represented by general formula (VIII) below.

（式中Ｒ⁶は水素原子あるいはメチル基を表す。）で表される基を１個以上含む炭素数１〜５０の一価の有機基であることがより好ましく、
３つのＲ⁵のうち少なくとも２つが下記一般式（ＩＸ）

(Wherein R ⁶ represents a hydrogen atom or a methyl group) and is more preferably a monovalent organic group having 1 to 50 carbon atoms and containing at least one group represented by:
At least two of the three R ⁵ are represented by the following general formula (IX)

（式中Ｒ⁷は直接結合あるいは炭素数１〜４８の二価の有機基を表し、Ｒ⁸は水素原子あるいはメチル基を表す。）で表される有機化合物（複数のＲ⁷およびＲ⁸はそれぞれ異なっていても同一であってもよい。）であることがさらに好ましい。

(Wherein R ⁷ represents a direct bond or a divalent organic group having 1 to 48 carbon atoms, and R ⁸ represents a hydrogen atom or a methyl group) (a plurality of R ⁷ and R ⁸ are More preferably, they may be the same or different.

R ^{7 in the} general formula (IX) is a direct bond or a divalent organic group having 1 to 48 carbon atoms. From the viewpoint that the heat resistance of the resulting cured product can be further increased, the direct bond or carbon It is preferably a divalent organic group having 1 to 20 carbon atoms, more preferably a direct bond or a divalent organic group having 1 to 10 carbon atoms, and a direct bond or a divalent organic group having 1 to 4 carbon atoms. More preferably, it is a group. Examples of these preferred R ⁷ include

等が挙げられる。

Etc.

As R ^{7 in the} above general formula (IX), from the viewpoint that the chemical thermal stability of the resulting cured product can be improved, a direct bond or two or less oxygen atoms and C as a constituent element, It is preferably a C1-C48 divalent organic group containing only H and O, more preferably a direct bond or a C1-C48 divalent hydrocarbon group. Examples of these preferred R ⁷ include

が挙げられる。

Is mentioned.

R ^{8 in the} general formula (IX) is a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of good reactivity.

  However, in the preferred examples of the organic compound represented by the general formula (IX) as described above, it is necessary to contain at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule. is there. From the viewpoint that heat resistance can be further improved, an organic compound containing three or more carbon-carbon double bonds having reactivity with SiH groups in one molecule is more preferable.

  Preferred specific examples of the organic compound represented by the above general formula (IX) include triallyl isocyanurate,

等が挙げられる。

Etc.

  In order to improve the adhesiveness of the cured product, diallyl monoglycidyl isocyanurate is preferred as the component (A).

A mixture of triallyl isocyanurate and diallyl monoglycidyl isocyanurate is preferred in order to achieve both improved adhesion and light resistance of the cured product. Since the mixture has an isocyanuric ring skeleton, it is also effective from the viewpoint of heat resistance. The mixing ratio can be arbitrarily set, but in order to achieve the above object, triallyl isocyanurate / allyl monoglycidyl isocyanurate (molar ratio) = 9/1 to 1/9 is preferable, and 8/2 to 2/8 is more preferable. Preferably, 7/3 to 3/7 is particularly preferable.
(A) A component can be used individually or in mixture of 2 or more types.
<(B) component>
Next, the component (B) will be described.

The component (B) is not particularly limited as long as it is a curing agent having at least one sulfonyl group and at least two SiH groups in one molecule and having a viscosity at 23 ° C. of 1000 Pa · s or less. can do. The sulfonyl group can improve the strength of the cured product and / or the adhesion to the substrate by hydrogen bonding with a group capable of hydrogen bonding in the cured product and / or the surface of the substrate.

  The component (B) is not particularly limited as long as it contains a sulfonyl group, but the following general formula (I):

（式中、Ｒ¹は水素原子、炭素数１〜２０の炭化水素基、水酸基、ハロゲン基、ビニル基、アリル基を表し、Ｒ¹はそれぞれ同一でも異なっていてもよい。）で表される構造として含有されるものが挙げられ、下記一般式（ＩＩ）：

(Wherein R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a halogen group, a vinyl group, or an allyl group, and R ¹ may be the same or different). Examples of the structure include those represented by the following general formula (II):

（式中、Ｒ¹は水素原子、炭素数１〜２０の炭化水素基、水酸基、ハロゲン基、ビニル基、アリル基を表し、Ｒ¹はそれぞれ同一でも異なっていてもよい。）で表される構造が好ましい。
また、下記一般式（ＩＩＩ）

(Wherein R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a halogen group, a vinyl group, or an allyl group, and R ¹ may be the same or different). A structure is preferred.
In addition, the following general formula (III)

（式中、Ｒ²は水素原子、炭素数１〜２０の炭化水素基、水酸基、ハロゲン基、ビニル基、アリル基を表し、Ｒ¹はそれぞれ同一でも異なっていてもよい。）で表される構造として含有されるものも挙げられ、下記一般式（ＩＶ）：

(Wherein R ² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a halogen group, a vinyl group, or an allyl group, and R ¹ may be the same or different). What is contained as a structure is also mentioned, and the following general formula (IV):

（式中、Ｒ²は水素原子、炭素数１〜２０の炭化水素基、水酸基、ハロゲン基、ビニル基、アリル基を表し、Ｒ¹はそれぞれ同一でも異なっていてもよい。）で表される構造が好ましく、より具体的には、一般式（ＩＶ）のＲ²が水素原子であるものが好ましい。

(Wherein R ² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a halogen group, a vinyl group, or an allyl group, and R ¹ may be the same or different). A structure is preferable, and more specifically, a compound in which R ^{2 in} formula (IV) is a hydrogen atom is preferable.

一般的に、（Ａ）成分としてスルホニル基を有する化合物を用いた場合、難溶性固体またはハンドリング困難な粘度となる傾向がある。ところが、スルホニル基を有する化合物を合成により（Ｂ）成分にすることによって、（Ａ）成分との相溶性及び／又はハンドリング性が良好となる上、（Ｂ）成分の揮発性が低くなり得られる組成物からのアウトガスの問題が生じ難いという効果を奏する。そのため、（Ｂ）成分は、ＳｉＨ基と反応性を有する炭素−炭素二重結合を１分子中に１個含有する有機化合物（α２）及び／又はＳｉＨ基と反応性を有する炭素−炭素二重結合を１分子中に少なくとも２個含有する有機化合物（α１）と、１分子中に少なくとも３個のＳｉＨ基を有する環状ポリオルガノシロキサン（β１）を、ヒドロシリル化反応して得ることができる化合物であることが好ましい。スルホニル基は（α２）、（α１）のいずれか一方あるいは両方に含まれておれば良く、耐クラック性の付与という点からは、スルホニル基が（α１）に含まれていることが好ましい。

In general, when a compound having a sulfonyl group is used as the component (A), the viscosity tends to be a hardly soluble solid or difficult to handle. However, by synthesizing a compound having a sulfonyl group into the component (B), compatibility with the component (A) and / or handling properties can be improved, and the volatility of the component (B) can be reduced. There is an effect that the problem of outgas from the composition hardly occurs. Therefore, the component (B) is composed of an organic compound (α2) containing one carbon-carbon double bond reactive with SiH group in one molecule and / or a carbon-carbon double reactive with SiH group. A compound obtained by hydrosilylation reaction of an organic compound (α1) containing at least two bonds in one molecule and a cyclic polyorganosiloxane (β1) having at least three SiH groups in one molecule. Preferably there is. The sulfonyl group may be contained in one or both of (α2) and (α1), and from the viewpoint of imparting crack resistance, the sulfonyl group is preferably contained in (α1).

  Although there are various methods for synthesizing the component (B), one molecule of a cyclic polyorganosiloxane (β1) having at least three SiH groups in one molecule and a carbon-carbon double bond having reactivity with SiH groups. A method obtained by removing an unreacted (β1) after reacting an organic compound (α1) containing at least two in the presence of a hydrosilylation catalyst, and containing at least 3 SiH groups in one molecule In the presence of a hydrosilylation catalyst, a linear and / or cyclic polyorganosiloxane (β1) having an organic compound (α2) containing one carbon-carbon double bond reactive with a SiH group in one molecule is contained. After the reaction in step (b), an organic compound (α1) containing at least two carbon-carbon double bonds having reactivity with SiH groups is reacted in the presence of a hydrosilylation catalyst. A method of obtaining by.

((Β1) component)
The (β1) component of the present invention is a linear and / or cyclic polyorganosiloxane compound having at least 3 SiH groups in one molecule.
The (β1) component is not particularly limited as long as it is a compound containing at least 3 SiH groups in one molecule. For example, it is a compound described in International Publication WO96 / 15194, and at least 3 SiH in one molecule. Those having a group can be used.

  Specifically, for example

が挙げられる。

Is mentioned.

  Among these, from the viewpoint of availability, a linear and / or cyclic organopolysiloxane having at least 3 SiH groups in one molecule is preferable, and the carbon-carbon of the (α1) component and / or the (α2) component. From the viewpoint of good hydrosilylation reactivity with a double bond and good storage stability of the reaction product, the following general formula (X)

（式中、Ｒ⁹は炭素数１〜６の有機基を表し、ｎは３〜１０の数を表す。）で表される、１分子中に少なくとも３個のＳｉＨ基を有する環状オルガノポリシロキサンが好ましい。
一般式（Ｘ）で表される化合物中の置換基Ｒ⁹は、Ｃ、Ｈ、Ｏから構成されるものであることが好ましく、炭化水素基であることがより好ましく、メチル基であることがさらに好ましい。それぞれの置換基Ｒ⁹は異なっていても良く、同一であっても良い。
一般式（Ｘ）で表される化合物としては、入手容易性の観点からは、１，３，５，７−テトラメチルシクロテトラシロキサンであることが好ましい。
（β１）成分は単独又は２種以上のものを混合して用いることが可能である。

(Wherein R ⁹ represents an organic group having 1 to 6 carbon atoms and n represents a number of 3 to 10), and the cyclic organopolysiloxane having at least three SiH groups in one molecule. Is preferred.
The substituent R ⁹ in the compound represented by the general formula (X) is preferably composed of C, H, and O, more preferably a hydrocarbon group, and a methyl group. Further preferred. Each substituent R ⁹ may be different or the same.
From the viewpoint of availability, the compound represented by the general formula (X) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane.
The (β1) component can be used alone or in combination of two or more.

((Α1) component)
The component (α1) can be used without particular limitation as long as it is an organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule. As such an organic compound, the same compounds as those mentioned above for the component (A) can be used.

  As described above, the component (α1) preferably has at least one sulfonyl group in one molecule. Such (α1) component preferably has a structure represented by the following formulas (XI to XIV),

（式中、Ｒ¹⁰は水素原子、炭素数１〜２０の炭化水素基、芳香環、水酸基、ハロゲン基、ビニル基、アリル基を表し、Ｒ¹⁰はそれぞれ同一でも異なっていてもよい。）
（α１）成分としては、ビス〔４−（２−アリルオキシ）フェニル〕スルホンであることが特に好ましい。

(In the formula, R ¹⁰ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aromatic ring, a hydroxyl group, a halogen group, a vinyl group, or an allyl group, and R ¹⁰ may be the same or different.)
The (α1) component is particularly preferably bis [4- (2-allyloxy) phenyl] sulfone.

  In addition, as the (α1) component, an organic compound having at least one sulfonyl group in one molecule and at least two carbon-carbon double bonds reactive with SiH group in one molecule is A part of the compounds listed as component A) can be used.

((Α2) component)
The component (α2) is not particularly limited as long as it is an organic compound containing one carbon-carbon double bond having reactivity with the SiH group in one molecule, but the component (B) is in phase with the component (A). In terms of improved solubility, the compound does not contain a siloxane unit (Si—O—Si) such as a polysiloxane-organic block copolymer or polysiloxane-organic graft copolymer, and C, H, N as constituent elements. , O, S, and halogen are preferred.
The bonding position of the carbon-carbon double bond having reactivity with the SiH group of the (α2) component is not particularly limited and may be present anywhere in the molecule.

The (α2) component compound can be classified into a polymer compound and a monomer compound.
Examples of the polymer compound include polysiloxane, polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, phenol-formaldehyde ( Phenol resin type) and polyimide type compounds can be used.
Examples of monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as straight-chain and alicyclics: heterocyclic compounds, and silicon-based compounds. Examples thereof include compounds and mixtures thereof.

  Although it does not specifically limit as a carbon-carbon double bond reactive with SiH group of ((alpha) 2) component, The following general formula (V)

（式中Ｒ³は水素原子あるいはメチル基を表す。）で示される基が反応性の点から好適である。また、原料の入手の容易さからは、

A group represented by the formula (wherein R ³ represents a hydrogen atom or a methyl group) is preferred from the viewpoint of reactivity. In addition, from the availability of raw materials,

示される基が特に好ましい。

The groups shown are particularly preferred.

  As the carbon-carbon double bond having reactivity with the SiH group of the (α2) component, an alicyclic group having a partial structure represented by the following general formula (VI) in the ring is the heat resistance of the cured product. Is preferable from the viewpoint of high.

（式中Ｒ⁴は水素原子あるいはメチル基を表す。）また、原料の入手の容易さからは、下記式で表される部分構造を環内に有する脂環式の基が好適である。

(In the formula, R ⁴ represents a hydrogen atom or a methyl group.) From the viewpoint of availability of raw materials, an alicyclic group having a partial structure represented by the following formula in the ring is preferred.

ＳｉＨ基と反応性を有する炭素−炭素二重結合は（α２）成分の骨格部分に直接結合していてもよく、２価以上の置換基を介して共有結合していても良い。２価以上の置換基としては炭素数０〜１０の置換基であれば特に限定されないが、（Ｂ）成分が（Ａ）成分と相溶性がよくなりやすいという点においては、構成元素としてＣ、Ｈ、Ｎ、Ｏ、Ｓ、およびハロゲンのみを含むものが好ましい。これらの置換基の例としては、

The carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton portion of the (α2) component, or may be covalently bonded via a divalent or higher substituent. The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms. However, in terms that the component (B) is easily compatible with the component (A), C, Those containing only H, N, O, S and halogen are preferred. Examples of these substituents include

が挙げられる。また、これらの２価以上の置換基の２つ以上が共有結合によりつながって１つの２価以上の置換基を構成していてもよい。

Is mentioned. Moreover, two or more of these divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.

  Examples of the group covalently bonded to the skeleton as described above include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3 -Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyl) Oxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group,

が挙げられる。

Is mentioned.

  Specific examples of the component (α2) include propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-undecene, Idemitsu Petrochemical's linearene, 4,4-dimethyl-1-pentene, 2-methyl-1-hexene, 2,3,3-trimethyl-1-butene, 2,4,4-trimethyl-1-pentene, etc. Chain aliphatic hydrocarbon compounds such as cyclohexene, methylcyclohexene, methylenecyclohexane, norbornylene, ethylidenecyclohexane, vinylcyclohexane, camphene, carene, α-pinene, β-pinene and the like, Styrene, α-methylstyrene, indene, phenylacetylene, 4-ethynyltoluene, allylbenzene, 4- Aromatic hydrocarbon compounds such as phenyl-1-butene, allyl ethers such as alkyl allyl ether and allyl phenyl ether, glycerin monoallyl ether, ethylene glycol monoallyl ether, 4-vinyl-1,3-dioxolane- Substitution of aliphatic compounds such as 2-one, aromatic compounds such as 1,2-dimethoxy-4-allylbenzene, o-allylphenol, monoallyl dibenzyl isocyanurate, monoallyl diglycidyl isocyanurate, etc. Examples include isocyanurates, silicon compounds such as vinyltrimethylsilane, vinyltrimethoxysilane, and vinyltriphenylsilane, and allylphenylsulfone. Further, polyethers such as one-end allylated polyethylene oxide and one-end allylated polypropylene oxide Polymers or oligomers having a vinyl group at one end, such as a resin, a hydrocarbon resin such as one end allylated polyisobutylene, an acrylic resin such as one end allylated polybutyl acrylate, one end allylated polymethyl methacrylate, etc. And the like.

  The structure may be linear or branched, and the molecular weight is not particularly limited, and various types can be used. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, and more preferably 1.5 or less in that the viscosity of the mixture is low and the moldability is likely to be good. More preferably it is.

  When the glass transition temperature of the component (α2) is present, there is no particular limitation on this, and various materials are used, but the glass point transfer temperature is 100 ° C. or less in that the obtained cured product tends to be tough. It is preferably 50 ° C. or lower, more preferably 0 ° C. or lower. Examples of preferred resins include polybutyl acrylate resins. Conversely, the glass transition temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, in that the heat resistance of the cured product obtained is increased. Most preferably, it is 170 ° C. or higher. The glass transition temperature can be determined as a temperature at which tan δ exhibits a maximum in the dynamic viscoelasticity measurement.

  The (α2) component is preferably an aliphatic hydrocarbon compound in that the light resistance of the resulting cured product is increased. In this case, the preferable lower limit of the carbon number is 2, and the preferable upper limit of the carbon number is 10.

  The (α2) component is preferably an aromatic hydrocarbon compound in that the heat resistance of the resulting cured product is increased. In this case, the preferable lower limit of the carbon number is 7, and the preferable upper limit of the carbon number is 10.

  The component (α2) may have other reactive groups. Examples of the reactive group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When it has these functional groups, the adhesiveness of the resulting curable composition tends to be high, and the strength of the resulting cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the obtained cured product tends to be high. Specific examples include monoallyl diglycidyl isocyanurate, allyl glycidyl ether, allyloxyethyl methacrylate, allyloxyethyl acrylate, vinyltrimethoxysilane, and the like.

  Further, from the viewpoint of good handleability, the molecular weight of the component (α2) is preferably 500 or less, and more preferably 300 or less.

  As the above (α2) component, a single component may be used, or a plurality of components may be used in combination.

(Synthesis of component (B))
There are various methods for synthesizing the component (B). As an example, the component (B) is reactive with a cyclic polyorganosiloxane (β1) having at least three SiH groups in one molecule and a SiH group. When using a method obtained by removing an unreacted (β1) after reacting an organic compound (α1) containing at least two carbon-carbon double bonds in one molecule in the presence of a hydrosilylation catalyst In the hydrosilylation reaction of the (α1) component and the (β1) component, the mixing ratio of the (α1) component and the (β1) component is not particularly limited, but the resulting compound has a low viscosity and is easy to handle. From the point, the ratio of the total number (X) of carbon-carbon double bonds having reactivity with SiH groups in the (α1) component and the total number (Y) of SiH groups in the (β1) component to be mixed is Y / X ≧ 6 Preferably, more preferably Y / X ≧ 8. More preferably, Y / X ≧ 10.

  Further, the component (B) contains one cyclic polyorganosiloxane (β1) having at least three SiH groups in one molecule and one carbon-carbon double bond reactive with SiH groups in one molecule. After reacting the organic compound (α2) in the presence of a hydrosilylation catalyst, the organic compound (α1) further containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule In the method obtained by reacting in the presence of the catalyst, the mixing ratio of the (α1) component, the (α2) component, and the (β1) component is not particularly limited, but the average of SiH groups in one molecule of the (β1) component Number (X ′), average number of molecules (Y ′) of component (α2) that undergoes hydrosilylation reaction with (β1) component, and average number of allyl groups of component (α1) that undergoes hydrosilylation reaction with (β1) component If one, this The relationship between (X ′) and (Y ′) is preferably (X′−Y ′) ≦ 3.5 from the viewpoint that the reaction product can be obtained with low viscosity without gelation. It is more preferable that “−Y ′) ≦ 3.0, and it is most preferable that (X′−Y ′) ≦ 2.5. (X ′) and (Y ′) can be determined from the weighed values when each component is charged.

As a catalyst for the hydrosilylation reaction between the (β1) component, the (α1) component and / or the (α2) component, for example, the following can be used. Platinum simple substance, alumina, silica, carbon black or the like supported on solid platinum, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone or the like, platinum-olefin complex (for example, Pt (CH ₂ = CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ ), platinum-vinylsiloxane complex (for example, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ]) _m), a platinum - phosphine complex _{(e.g., Pt (PPh 3) 4,} Pt (PBu 3) 4), platinum - phosphite complex _{(e.g., Pt [P (OPh) 3} ] 4, Pt [P (OBu) 3 ] ₄₎ (in the formula, Me represents a methyl group, Bu a butyl group, Vi is vinyl group, Ph represents a phenyl group, n, m is an integer.), dicarbonyl dichloroplatinum, Karushuteto Karstedt catalyst, and platinum-hydrocarbon complexes described in Ashby US Pat. Nos. 3,159,601 and 3,159,622, and Lamoreaux US Pat. No. 3,220,972. And platinum alcoholate catalysts. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. , Etc.

  Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.

The addition amount of the catalyst is not particularly limited, but the lower limit of the preferred addition amount is sufficient with respect to 1 mol of SiH groups of the (β1) component in order to have sufficient curability and keep the cost of the curable composition relatively low. 10 ^-8 mol, more preferably 10 ^-6 mole, preferable amount of the upper limit (.beta.1) 10 ^-1 moles per mole of the SiH group in component, more preferably 10 ^-2 moles.

In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl-1 Examples include acetylene alcohol compounds such as butyne and 1-ethynyl-1-cyclohexanol, and sulfur compounds such as simple sulfur. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount with respect to 1 mol of the hydrosilylation catalyst is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.

  Various methods can be used for mixing the (α1) component, the (α2) component, the (β1) component, and the catalyst in the reaction, but the catalyst is mixed with the (α1) component and / or the (α2) component. A method of mixing the product with the component (β1) is preferable. It is difficult to control the reaction when the catalyst is mixed with the (α1) component and / or the mixture of the (α2) component and the (β1) component. When the method of mixing the (α1) component and / or the (α2) component with the mixture of the (β1) component and the catalyst, it has reactivity with the water in which the (β1) component is mixed in the presence of the catalyst. Therefore, it may be altered.

  The reaction temperature can be variously set. In this case, the lower limit of the preferable temperature range is 30 ° C., more preferably 50 ° C., and the upper limit of the preferable temperature range is 200 ° C., more preferably 150 ° C. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.

Various reaction times and pressures during the reaction can be set as required.

A solvent may be used during the hydrosilylation reaction. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specifically, hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The solvent can also be used as a mixed solvent of two or more types. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.
In addition, various additives may be used for the purpose of controlling reactivity.

  After reacting the (α1) component and / or the (α2) component and the (β1) component, the solvent or / and the unreacted (β1) component or / and (α1) component or / and (α2) component are removed. You can also. By removing these volatile components, the component (B) obtained does not have volatile components, so that the problem of voids and cracks due to volatilization of the volatile components hardly occurs in the case of curing with the component (A). Examples of the removal method include treatment with activated carbon, aluminum silicate, silica gel and the like in addition to vacuum devolatilization. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. The upper limit of the preferable temperature in this case is 100 ° C, more preferably 80 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

  Examples of the component (B) that is a reaction product of the component (α1) and / or the component (α2) and the component (β1) as described above include bis [4- (2-allyloxy) phenyl] sulfone and 1, Reaction product of 3,5,7-tetramethylcyclotetrasiloxane, reaction product of 3,3-diallyl-4,4′-dihydroxydiphenylsulfone and 1,3,5,7-tetramethylcyclotetrasiloxane, bis (4 -Vinylphenyl) sulfone and 1,3,5,7-tetramethylcyclotetrasiloxane reaction product, 1-hexene and bis [4- (2-allyloxy) phenyl] sulfone and 1,3,5,7-tetramethyl Reaction products of cyclotetrasiloxane, allyl glycidyl ether and bis [4- (2-allyloxy) phenyl] sulfone and 1,3,5,7-tetramethylcyclotetra Reaction product of siloxane, reaction product of 1-hexene and 3,3-diallyl-4,4'-dihydroxydiphenylsulfone and 1,3,5,7-tetramethylcyclotetrasiloxane, allyl glycidyl ether and 3,3-diallyl Reaction product of -4,4'-dihydroxydiphenylsulfone and 1,3,5,7-tetramethylcyclotetrasiloxane, 1-hexene and bis (4-vinylphenyl) sulfone and 1,3,5,7-tetramethyl Examples include a reaction product of cyclotetrasiloxane, a reaction product of allyl glycidyl ether and bis (4-vinylphenyl) sulfone and 1,3,5,7-tetramethylcyclotetrasiloxane.

  From the viewpoint of heat resistance, light resistance and adhesiveness of the cured product, a reaction product of bis [4- (2-allyloxy) phenyl] sulfone and 1,3,5,7-tetramethylcyclotetrasiloxane, allyl glycidyl ether and bis A reaction product of [4- (2-allyloxy) phenyl] sulfone and 1,3,5,7-tetramethylcyclotetrasiloxane is preferred.

(B) From the viewpoint of good handleability and workability of the component, the viscosity at 23 ° C. is 1000 Pa · s or less, preferably 100 Pa · s or less, and more preferably 10 Pa · s or less. . In addition, when using the above reactant as the component (B), the viscosity of the reaction product from which volatile components such as unreacted components have been removed may be 1000 Pa · s or less, preferably 100 Pa · s or less, more preferably 10 Pa · s or less.
Component (B) can be used alone or in combination of two or more.

(Mixing ratio of component (A) and component (B))
The mixing ratio of the component (A) and the component (B) is not particularly limited as long as the strength required for the cured product is not lost, but the number of SiH groups in the component (B) (Y ′) in the component (A) In the ratio (Y ′ / X ′) to the number of carbon-carbon double bonds (X ′), the lower limit of the preferable range is 0.3, more preferably 0.5, still more preferably 0.7, and the preferable range. The upper limit of is 3, more preferably 2, and even more preferably 1.5. When it deviates from the preferred range, sufficient strength may not be obtained or thermal deterioration may easily occur.

<(C) component>
Next, the hydrosilylation catalyst as component (C) will be described.
The hydrosilylation catalyst is not particularly limited as long as it has a catalytic activity for the hydrosilylation reaction. For example, a platinum simple substance, a support made of alumina, silica, carbon black or the like on which solid platinum is supported, chloroplatinic acid, platinum chloride Complexes of acids with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (eg Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ), platinum-vinyl Siloxane complexes (eg, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ), platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phos Fight complexes _{(e.g., Pt [P (OPh) 3} ] 4, Pt [P (OBu) 3] 4) ( in the formula, Me represents a methyl group, Bu a butyl group, Vi represents a vinyl group Ph represents a phenyl group, and n and m represent integers.), Dicarbonyldichloroplatinum, Karstedt catalyst, and also described in Ashby US Pat. Nos. 3,159,601 and 3,159,662. Platinum-hydrocarbon complexes, as well as platinum alcoholate catalysts described in Lamoreaux US Pat. No. 3,220,972. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. , Etc.
Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.

Although the addition amount of the catalyst is not particularly limited, the lower limit of the preferable addition amount is sufficient with respect to 1 mol of SiH groups of the component (B) in order to have sufficient curability and keep the cost of the curable composition relatively low. 10 ^-8 mol, more preferably 10 ^-6 mole, preferable amount of the upper limit (B) 10 ^-1 moles per mole of the SiH group in component, more preferably 10 ^-2 moles.

In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl maleate, 2-hydroxy-2-methyl-1 -Acetylene alcohol compounds, such as butyne, sulfur compounds, such as single-piece | unit sulfur, etc. are mentioned. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount with respect to 1 mol of the hydrosilylation catalyst is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.

  In addition, when using a hydrosilylation catalyst at the time of manufacture of (B) component, and using this hydrosilylation catalyst without removing, the hydrosilylation catalyst which remains in (B) component is also contained in (C) component of this invention. .

<Method for adjusting curable composition and curing method>
The preparation method of this curable composition is not specifically limited, It can prepare by various methods. Various components may be mixed and prepared immediately before curing, or a one-component state in which all components are mixed and prepared in advance may be stored at a low temperature. Alternatively, some components may be mixed and stored in advance so that there are 2 to 3 types, and the respective predetermined amounts may be mixed and prepared immediately before curing. A method of separately storing the component (A) and the component (B) is preferable because there is little deterioration in quality during storage.

  The order of mixing the various components is not particularly limited, but the liquid mixture of the component (A) (C) and the component (B) are stored separately, and the liquid mixture of the component (A) (C) and ( A method of stirring and mixing the component B) is preferred. In the method of mixing the component (C) with the liquid mixture of the component (A) and the component (B), it is not easy to control the reaction. In the method of mixing the component (A) with the mixed solution of the component (B) and the component (C), the component (B) has reactivity with moisture in the environment, and thus may be altered during storage.

  In addition, a method is adopted in which only a part of the functional group in the composition is reacted (B-stage) by controlling reaction conditions and using the difference in the reactivity of the substituents, and then subjected to processing such as molding and further curing. You can also. According to these methods, viscosity adjustment at the time of molding becomes easy.

  As a curing method, the reaction can be performed by simply mixing, or the reaction can be performed by heating. A method of heating and reacting is preferable from the viewpoint that the reaction is fast and generally a material having high heat resistance is easily obtained.

  The curing temperature can be variously set, but the lower limit of the preferable temperature is 30 ° C, more preferably 100 ° C. The upper limit of preferable temperature is 300 degreeC, More preferably, it is 200 degreeC. If the reaction temperature is low, the reaction time for sufficient reaction will be long, and if the reaction temperature is high, molding will tend to be difficult.

  Curing may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. It is preferable to carry out the reaction at a constant temperature while raising the temperature in a multistage or continuous manner in that a cured product with less distortion is easily obtained.

(Additive)
(Curing retarder)
For the purpose of improving the storage stability of the composition of the present invention or adjusting the reactivity of the hydrosilylation reaction during the curing process, a curing retarder can be used. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide, and these may be used in combination.

  Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols such as 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne and 1-ethynyl-1-cyclohexanol. And maleate esters such as ene-yne compounds and dimethyl malate. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

  Among these curing retarders, from the viewpoint of good retarding activity and good raw material availability, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1- Cyclohexanol is preferred.

Although the addition amount of the curing retarder can be variously set, the lower limit of the preferable addition amount relative to 1 mol of the hydrosilylation catalyst to be used is 10 ⁻¹ mol, more preferably 1 mol, and the upper limit of the preferable addition amount is 10 ³ mol, more preferably Is 50 moles.
Moreover, these hardening retarders may be used independently and may be used together 2 or more types.

(Adhesion improver)
An adhesion improver can also be added to the composition of the present invention. In addition to commonly used adhesives as adhesion improvers, for example, various coupling agents, epoxy compounds, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methylstyrene-vinyltoluene A copolymer, polyethylmethylstyrene, aromatic polyisocyanate, etc. can be mentioned.

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

  Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes which can be exemplified.

  The addition amount of the silane coupling agent can be variously set, but the lower limit of the preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] is 0.1 parts by weight, more preferably 0.5 parts. The upper limit of the preferred addition amount is 50 parts by weight, more preferably 25 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  Examples of the epoxy compound include novolak phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and 2,2′-bis (4-glycidyloxycyclohexyl). Propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinyl cyclohexylene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl iso Cyanurate, mention may be made of diallyl monoglycidyl isocyanurate and the like.

  Although the addition amount of the epoxy compound can be variously set, the lower limit of the preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] is preferably 1 part by weight, more preferably 3 parts by weight. The upper limit of the addition amount is 50 parts by weight, more preferably 25 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  These coupling agents, silane coupling agents, epoxy compounds, etc. may be used alone or in combination of two or more.

  In the present invention, a silanol condensation catalyst can be further used to enhance the effect of the coupling agent or the epoxy compound, and the adhesion can be improved and / or stabilized.

Such a silanol condensation catalyst is not particularly limited, but is preferably a boron compound or / and an aluminum compound or / and a titanium compound.
Examples of the boron compound used in the present invention include tri-2-ethylhexyl borate, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, trinormal butyl borate, triborate triborate. Examples thereof include borate esters such as -sec-butyl, tri-tert-butyl borate, triisopropyl borate, trinormal propyl borate, triallyl borate, triethyl borate, trimethyl borate, and boron methoxyethoxide.
These boric acid esters may be used alone or in combination of two or more. Mixing may be performed in advance or may be performed at the time of producing a cured product.
Of these boric acid esters, trimethyl borate, triethyl borate, and trinormal butyl borate are preferable, and trimethyl borate is more preferable among them because it is easily available and has high industrial utility.

From the point of being able to suppress the volatility at the time of curing, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, trinormal butyl borate, tri-sec-butyl borate, boric acid Tri-tert-butyl, triisopropyl borate, tripropylpropyl borate, triallyl borate, and boron methoxyethoxide are preferred. Among these, normal trioctadecyl borate, tri-tert-butyl borate, triphenyl borate, and tributyl normal borate are more preferable. preferable.
From the viewpoint of suppression of volatility and good workability, trinormal butyl borate, triisopropyl borate and trinormal propyl borate are preferable, and trinormal butyl borate is more preferable.
From the viewpoint of low colorability at high temperatures, trimethyl borate and triethyl borate are preferred, and trimethyl borate is more preferred.

  Examples of the aluminum compound used in the present invention include aluminum alkoxides such as aluminum triisopropoxide, sec-butoxyaluminum diisoflopoxide, aluminum trisec-butoxide: ethyl acetoacetate aluminum diisopropoxide, aluminum tris ( Ethyl acetoacetate), aluminum chelate M (manufactured by Kawaken Fine Chemicals, alkyl acetoacetate aluminum diisopropoxide), aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate), etc. Aluminum chelates are more preferable from the viewpoint of handleability.

  Titanium compounds used in the present invention include tetraalkoxy titaniums such as tetraisopropoxy titanium and tetrabutoxy titanium: titanium chelates such as titanium tetraacetylacetonate: general residues having residues such as oxyacetic acid and ethylene glycol And titanate coupling agents.

The amount used in the case of using a silanol condensation catalyst can be variously set, but the lower limit of the preferable addition amount with respect to 100 parts by weight of the coupling agent or the epoxy compound is 0.1 part by weight, more preferably 1 part by weight, which is preferable The upper limit of the addition amount is 50 parts by weight, more preferably 30 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.
These silanol condensation catalysts may be used alone or in combination of two or more.

  In the present invention, a silanol source compound can be further used in order to further enhance the effect of improving adhesiveness, and the adhesiveness can be improved and / or stabilized. Examples of such silanol sources include silanol compounds such as triphenylsilanol and diphenyldihydroxysilane, and alkoxysilanes such as diphenyldimethoxysilane, tetramethoxysilane, and methyltrimethoxysilane.

The amount used in the case of using a silanol source compound can be variously set, but the lower limit of the preferred addition amount with respect to 100 parts by weight of the coupling agent or the epoxy compound is 0.1 parts by weight, more preferably 1 part by weight, The upper limit of the preferable addition amount is 50 parts by weight, more preferably 30 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.
Moreover, these silanol source compounds may be used independently and may be used together 2 or more types.

  In the present invention, carboxylic acids and / or acid anhydrides can be used to enhance the effect of the coupling agent or epoxy compound, and adhesion can be improved and / or stabilized. Such carboxylic acids and acid anhydrides are not particularly limited,

２−エチルヘキサン酸、シクロヘキサンカルボン酸、シクロヘキサンジカルボン酸、メチルシクロヘキサンジカルボン酸、テトラヒドロフタル酸、メチルテトラヒドロフタル酸、メチルハイミック酸、ノルボルネンジカルボン酸、水素化メチルナジック酸、マレイン酸、アセチレンジカルボン酸、乳酸、リンゴ酸、クエン酸、酒石酸、安息香酸、ヒドロキシ安息香酸、桂皮酸、フタル酸、トリメリット酸、ピロメリット酸、ナフタレンカルボン酸、ナフタレンジカルボン酸、およびそれらの単独あるいは複合酸無水物が挙げられる。

2-ethylhexanoic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylheimic acid, norbornene dicarboxylic acid, hydrogenated methylnadic acid, maleic acid, acetylenedicarboxylic acid, Examples include lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, hydroxybenzoic acid, cinnamic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalene carboxylic acid, naphthalene dicarboxylic acid, and single or complex acid anhydrides thereof It is done.

  Of these carboxylic acids and / or acid anhydrides, they react with SiH groups in that they have hydrosilylation reactivity and are unlikely to impair the physical properties of the resulting cured product with little possibility of seepage from the cured product. What contains the carbon-carbon double bond which has property is preferable. Preferred carboxylic acids and / or acid anhydrides include, for example,

テトラヒドロフタル酸、メチルテトラヒドロフタル酸およびそれらの単独あるいは複合酸無水物等が挙げられる。

Examples thereof include tetrahydrophthalic acid, methyltetrahydrophthalic acid, and single or complex acid anhydrides thereof.

The amount used in the case of using carboxylic acids or / and acid anhydrides can be variously set, but the lower limit of the preferred amount of addition relative to 100 parts by weight of the coupling agent or / and epoxy compound is 0.1 parts by weight, more preferably Is 1 part by weight, and the upper limit of the preferable addition amount is 50 parts by weight, more preferably 10 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.
Moreover, these carboxylic acids or / and acid anhydrides may be used alone or in combination of two or more.

(Thermosetting resin)
Various thermosetting resins can be added to the composition of the present invention for the purpose of modifying the properties. Examples of the thermosetting resin include, but are not limited to, epoxy resins, cyanate ester resins, phenol resins, polyimide resins, urethane resins, bismaleimide resins, and the like. Among these, an epoxy resin is preferable from the viewpoint of excellent practical properties such as adhesiveness.

  Examples of the epoxy resin include novolak phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and 2,2′-bis (4-glycidyloxycyclohexyl). Propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinyl cyclohexylene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanate Curing epoxy resins such as nurate and diallyl monoglycidyl isocyanurate with aliphatic acid anhydrides such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, and hydrogenated methyl nadic anhydride Is mentioned. These epoxy resins or curing agents may be used alone or in combination.

The addition amount of the thermosetting resin is not particularly limited, but the lower limit of the preferable use amount is 5% by weight of the entire curable composition, more preferably 10% by weight, and the upper limit of the preferable use amount is the curable composition. The content is 50% by weight, more preferably 30% by weight. If the addition amount is small, it is difficult to obtain the intended effects such as adhesiveness, and if the addition amount is large, the addition tends to be brittle.
These thermosetting resins may be used alone or in combination.

  The thermosetting resin may be a resin raw material or / and a cured product dissolved in the component (A) or / and the component (B) and mixed in a uniform state, or pulverized and mixed in a particle state. Alternatively, it may be dispersed by dissolving in a solvent and mixing. In the point that the obtained hardened | cured material tends to become more transparent, it is preferable to melt | dissolve in (A) component or / and (B) component, and to mix as a uniform state. Also in this case, the thermosetting resin may be directly dissolved in the component (A) or / and the component (B), or may be uniformly mixed using a solvent or the like. It may be in a dispersed state or / and mixed state.

  When the thermosetting resin is used in a dispersed state, the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. There may be a distribution of the particle system, which may be monodispersed or have a plurality of peak particle diameters, but from the viewpoint that the viscosity of the curable composition is low and the moldability tends to be good. The coefficient of variation is preferably 10% or less.

(Thermoplastic resin)
Various thermoplastic resins can be added to the curable composition of the present invention for the purpose of modifying the properties. Various thermoplastic resins can be used. For example, a homopolymer of methyl methacrylate or a polymethyl methacrylate resin such as a random, block or graft polymer of methyl methacrylate and other monomers (for example, Hitachi Chemical) Optretz, etc.), acrylic resins represented by polybutyl acrylate resins such as butyl acrylate homopolymers or random, block or graft polymers of butyl acrylate and other monomers, bisphenol A, 3, A polycarbonate resin such as a polycarbonate resin containing 3,5-trimethylcyclohexylidenebisphenol or the like as a monomer structure (for example, APEC manufactured by Teijin Limited), a norbornene derivative, a vinyl monomer, or the like is copolymerized alone or copolymerized. Cycloolefin resins such as fat, norbornene derivative ring-opening metathesis polymer, or hydrogenated products thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon, ARTON manufactured by JSR, etc.), ethylene and Olefin-maleimide resins such as maleimide copolymers (eg, TI-PAS manufactured by Tosoh Corporation), bisphenols such as bisphenol A and bis (4- (2-hydroxyethoxy) phenyl) fluorene, and diols such as diethylene glycol Polyester resins such as polyester obtained by polycondensation of phthalic acids and aliphatic dicarboxylic acids such as terephthalic acid and isophthalic acid (eg O-PET manufactured by Kanebo Co., Ltd.), polyethersulfone resins, polyarylate resins, polyvinyl acetal resins, Polyethylene resin Polypropylene resins, polystyrene resins, polyamide resins, silicone resins, other like fluorine resin, not natural rubber, but the rubber-like resin is exemplified such EPDM is not limited thereto.

  As a thermoplastic resin, you may have the carbon-carbon double bond or / and SiH group which have a reactivity with SiH group in a molecule | numerator. In the point that the obtained cured product tends to be tougher, the molecule has one or more carbon-carbon double bonds or / and SiH groups having reactivity with SiH groups in the molecule on average. It is preferable.

  The thermoplastic resin may have other crosslinkable groups. Examples of the crosslinkable group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. From the viewpoint that the heat resistance of the obtained cured product tends to be high, it is preferable to have one or more crosslinkable groups in one molecule on average.

  The molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight is preferably 10,000 or less, in terms of easy compatibility with the component (A) or the component (B), and is preferably 5000 or less. It is more preferable that On the contrary, the number average molecular weight is preferably 10,000 or more, and more preferably 100,000 or more in that the obtained cured product tends to be tough. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, in that the viscosity of the mixture tends to be low and the moldability tends to be good. More preferably, it is as follows.

The blending amount of the thermoplastic resin is not particularly limited, but a preferable lower limit of the amount used is 5% by weight of the entire curable composition, more preferably 10% by weight, and a preferable upper limit of the amount used is in the curable composition. Is 50% by weight, more preferably 30% by weight. When the addition amount is small, the obtained cured product tends to be brittle, and when it is large, the heat resistance (elastic modulus at high temperature) tends to be low.
A single thermoplastic resin may be used, or a plurality of thermoplastic resins may be used in combination.

  The thermoplastic resin may be dissolved in the component (A) or / and the component (B) and mixed in a uniform state, pulverized and mixed in a particle state, or dissolved in a solvent and mixed. It may be in a dispersed state. In the point that the obtained hardened | cured material tends to become more transparent, it is preferable to melt | dissolve in (A) component or / and (B) component, and to mix as a uniform state. Also in this case, the thermoplastic resin may be directly dissolved in the component (A) or / and the component (B), or may be mixed uniformly using a solvent or the like, and then the solvent is removed and uniform dispersion is performed. It is good also as a state or / and a mixed state.

  When the thermoplastic resin is dispersed and used, the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. There may be a distribution of the particle system, which may be monodispersed or have a plurality of peak particle diameters, but from the viewpoint that the viscosity of the curable composition is low and the moldability tends to be good. The coefficient of variation is preferably 10% or less.

(Filler)
You may add a filler to the curable composition of this invention as needed.
Various fillers are used. For example, silica-based fillers such as quartz, fume silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, silicon nitride, silver powder, etc. Inorganic fillers such as alumina, aluminum hydroxide, titanium oxide, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate, inorganic balloon As a filler for a conventional sealing material such as an epoxy-based filler, generally used and / or proposed fillers can be mentioned.

(Anti-aging agent)
You may add antioxidant to the curable composition obtained by this invention. Examples of the anti-aging agent include citric acid, phosphoric acid, sulfur-based anti-aging agent and the like in addition to the anti-aging agents generally used such as hindered phenol type.
As the hindered phenol-based anti-aging agent, various types such as Irganox 1010 available from Ciba Specialty Chemicals are used.
Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylates, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.
Moreover, these anti-aging agents may be used independently and may be used together 2 or more types.

(Radical inhibitor)
You may add a radical inhibitor to the curable composition obtained by this invention. Examples of the radical inhibitor include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-t-butylphenol), tetrakis (methylene- Phenol radical inhibitors such as 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondary butyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine, and the like.
Moreover, these radical inhibitors may be used alone or in combination of two or more.

(UV absorber)
You may add a ultraviolet absorber to the curable composition obtained by this invention. Examples of the ultraviolet absorber include 2 (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like. Can be mentioned.
Moreover, these ultraviolet absorbers may be used independently and may be used together 2 or more types.

(Other additives)
The curable composition of the present invention includes other ions such as a colorant, a release agent, a flame retardant, a flame retardant aid, a surfactant, an antifoaming agent, an emulsifier, a leveling agent, an anti-fogging agent, and antimony-bismuth. Trapping agent, thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity The purpose and effect of the present invention include an imparting agent, an antistatic agent, a radiation shielding agent, a nucleating agent, a phosphorus peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a thermal conductivity imparting agent, and a physical property modifier. It can add in the range which does not impair.

(solvent)
The curable composition obtained in the present invention can be used by dissolving in a solvent. Solvents that can be used are not particularly limited. Specific examples include hydrocarbon solvents such as benzene, toluene, hexane, and heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, and the like. An ether solvent, a ketone solvent such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and a halogen solvent such as chloroform, methylene chloride, and 1,2-dichloroethane can be preferably used.
As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane, and chloroform are preferable.

Although the amount of solvent to be used can be set as appropriate, the lower limit of the preferable amount used for 1 g of the curable composition to be used is 0.1 mL, and the upper limit of the preferable amount to be used is 10 mL. If the amount used is small, it is difficult to obtain the effect of using a solvent such as a low viscosity, and if the amount used is large, the solvent tends to remain in the material, causing problems such as thermal cracks, and also from a cost standpoint. It is disadvantageous and the industrial utility value decreases.
These solvents may be used alone or as a mixed solvent of two or more.

  By using the curable composition of the present invention, not only the compatibility and castability are improved, but also the non-colorability of the cured product can be improved.

The curable composition or cured product of the present invention can be used for various applications.
For example, in addition to optical materials and electronic materials, general uses in which thermosetting resins such as epoxy resins are used can be mentioned. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.) In addition to insulating materials (including printed circuit boards and wire coatings), sealants, additives to other resins, and the like.

Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.

The reaction rate, viscosity, functional group value, etc. of the allyl groups of the reaction products obtained in the synthesis examples and comparative synthesis examples were measured as follows.
(NMR)
A 300 MHz NMR apparatus manufactured by Varian Technologies Japan Limited was used. (B) The reaction rate of the allyl group in the component synthesis was measured by adding the reaction solution diluted to about 1% with deuterated chloroform to the NMR tube, the peak of the methylene group derived from the unreacted allyl group, and the reaction. It calculated | required from the peak of the methylene group derived from an allyl group. As the functional group value of the SiH group-containing compound as the reaction product, the SiH group value (mmol / g) and the remaining allyl group value (mmol / g) in terms of dibromoethane were determined.
(GC)
SHIMADZU GAS CHROMATOGRAPH GC-14B / C-R5A manufactured by Shimadzu Corporation was used. As the column, SHIMADZU CBP1-M25-025 was used.
(GPC)
An approximately 1 wt% toluene solution was prepared and measured with an RI detector using LC MODULE 1 manufactured by WATERS, using a toluene solvent at a flow rate of 1 ml / min, a column temperature of 40 ° C., and four columns.
(viscosity)
An E-type viscometer manufactured by Tokyo Keiki Co., Ltd. was used. Measurement was performed at a measurement temperature of 23 ° C. using an EHD type 48φ cone.

The glass transition temperature, the bending test, the tensile test during heating, the die shear adhesion test, the crack resistance test, and the like of the curable compositions and cured products prepared in Examples and Comparative Examples were performed as follows.
(Appearance of cured product)
The prepared test piece having a thickness of 3 mm was placed on a white paper and visually evaluated.
(Glass-transition temperature)
A test piece of 3 mm × 5 mm × 30 mm was cut out from the produced cured product, and using a DVA-200 manufactured by IT Measurement Control Co., Ltd., a tensile mode, a measurement frequency of 10 Hz, a strain of 0.1%, a static / power ratio of 1.5, Dynamic viscoelasticity measurement was performed at a temperature rising rate of 5 ° C./min. The peak temperature of tan δ was taken as the glass transition temperature of the cured product.
(Bending test)
A test piece of 3 mm × 5 mm × 50 mm was cut out from the produced cured product, and the test was performed at 23 ° C. and a test speed of 1.5 mm / min using an autograph 10TB manufactured by Shimadzu Corporation. About other than this, it measured by the method according to JISK6911.
(Tensile test during heating)
On a polyimide film, placing a silicone sheet frame having a thickness of 1mm as a spacer, a curable composition was added to this in the frame, press pressure 33 kg / cm ² by placing the polyimide film thereon, a heating temperature 100 ° C., 10 minutes The semi-cured state was obtained. A dumbbell-shaped No. 6 was cut out from this semi-cured sheet and further cured after 180 ° C. for 30 minutes to prepare a test piece. Using an autograph 10TB manufactured by Shimadzu Corporation, the test piece holding part was performed at a test speed of 1.0 mm / min using a heating and heat retention device capable of holding air at a constant temperature using air as a heat medium. It measured by the method according to JISK6911.
(Die shear adhesion test)
A test piece was prepared using a 2 × 2 mm glass plate as a die on a predetermined substrate. It was cured by heating at 60 ° C. for 6 hours, 70 ° C. for 1 hour, 80 ° C. for 1 hour, 120 ° C. for 1 hour, 150 ° C. for 1 hour, and 180 ° C. for 30 minutes. The adhesive strength was measured with a series 4000 bond tester, DS100KG load cell, manufactured by Daisy. Five samples were measured, and the average of three points excluding the highest value and the lowest value was taken as the adhesive strength.
(Crack resistance test)
Aluminum foil of 13 × 60 × 0.1 mm was adhered to a glass epoxy plate of 100 × 100 × 0.3 mm at intervals of 10 mm (adhered at 120 ° C. for 1 hour using the curable composition of Example 2 as an adhesive). A silicone sheet frame having a thickness of 1 mm and a width of 10 mm is placed on the plate as a spacer, a curable composition is added to the frame, and an aluminum foil with a release agent is placed thereon, and a pressing pressure of 33 kg / cm is applied. ^{2. A} semi-cured state was achieved at a heating temperature of 110 ° C. for 10 minutes. The spacer and the like were removed, the glass epoxy plate was fixed to a glass plate with a clip, and post-cured for 30 minutes at 180 ° C. After a predetermined time, it was immediately placed at room temperature and observed for cracks. The number of generated cracks was 3 or less as small cracks, 4 to 6 as medium cracks, and 7 or more as large cracks.

Example 1
A 500 ml four-necked flask was charged with 218 g of toluene and 109 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was replaced with nitrogen, and then heated and stirred at an oil bath temperature of 90 ° C. 10 g of white powdery bis [4- (2-allyloxy) phenyl] sulfone (BPS-DAE manufactured by Nikka Chemical Co., Ltd.) was added with 3 g of toluene, followed by a xylene solution of a platinum vinylsiloxane complex (3 wt% as platinum). Content) was diluted 1000 times with toluene (hereinafter referred to as “catalyst diluted solution”) 3.93 g was added dropwise with a syringe. Bis [4- (2-allyloxy) phenyl] sulfone dissolved in a few minutes. After 60 minutes, 10 g of bis [4- (2-allyloxy) phenyl] sulfone was added with 3 g of toluene, and 2.62 g of the diluted catalyst solution was added dropwise with a syringe. After another 60 minutes, 10 g of bis [4- (2-allyloxy) phenyl] sulfone was added with 3 g of toluene, and then 1.31 g of the catalyst diluted solution was added dropwise with a syringe. The reaction rate of the allyl group was confirmed to be 95% or more by ¹ H-NMR from the dropping ends after 3 hours. As a gelation inhibitor, 1.58 g of a solution obtained by diluting triphenylphosphine with toluene 100 times was added to the reaction solution. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a concentrate which was a slightly yellow transparent liquid.
The viscosity of the obtained concentrate was 11.3 Pa · s. From the GPC measurement of the concentrate, a multimodal chromatogram was obtained, suggesting a mixture. From the ¹ H-NMR measurement of the concentrate, a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane reacted with the allyl group of bis [4- (2-allyloxy) phenyl] sulfone. Yes, it was found to contain 6.87 mmol / g SiH group and 0.07 mmol / g allyl group.

（比較例１）
２Ｌオートクレーブにトルエン３６２ｇ、１，３，５，７−テトラメチルシクロテトラシロキサン３６２ｇを入れ、気相部を窒素で置換した後、ジャケット温１０５℃で加熱、攪拌した。ジアリルモノグリシジルイソシアヌレート１００ｇ、トルエン１００ｇ及び白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０.０４９ｇの混合液を９０分かけて滴下した。滴下終了から２時間後に¹Ｈ−ＮＭＲでアリル基の反応率が９５％以上であることを確認した。未反応の１，３，５，７−テトラメチルシクロテトラシロキサンとトルエンを減圧留去し、無色透明の液体である濃縮物を得た。
得られた濃縮物の粘度は８.１Ｐａ・ｓであった。濃縮物のＧＰＣ測定より、多峰性のクロマトグラムが得られ、混合物であることが示唆された。濃縮物の¹Ｈ−ＮＭＲ測定より、１，３，５，７−テトラメチルシクロテトラシロキサンのＳｉＨ基の一部がジアリルモノグリシジルイソシアヌレートのアリル基と反応したものであり、７.７４ｍｍｏｌ／ｇのＳｉＨ基と０.１０ｍｍｏｌ／ｇのアリル基を含有していることがわかった。

(Comparative Example 1)
After putting 362 g of toluene and 362 g of 1,3,5,7-tetramethylcyclotetrasiloxane in a 2 L autoclave and replacing the gas phase with nitrogen, the mixture was heated and stirred at a jacket temperature of 105 ° C. A mixed solution of 100 g of diallyl monoglycidyl isocyanurate, 100 g of toluene and 0.049 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 90 minutes. Two hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the allyl group reaction rate was 95% or more. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a concentrate which was a colorless and transparent liquid.
The viscosity of the obtained concentrate was 8.1 Pa · s. From the GPC measurement of the concentrate, a multimodal chromatogram was obtained, suggesting a mixture. From the ¹ H-NMR measurement of the concentrate, a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane was reacted with the allyl group of diallylmonoglycidyl isocyanurate, and was 7.74 mmol / g. It was found to contain SiH groups and 0.10 mmol / g allyl group.

（比較例２）
５Ｌセパラブルフラスコにトルエン６００ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）１２４.８μｌを入れて混合した後、１，３，５，７−テトラメチルシクロテトラシロキサン２０００ｇを入れ、気相部を窒素で置換した後、オイルバス温７０℃で加熱、攪拌した。ビスフェノールＡのジアリルエーテル５１３ｇ、トルエン２８０ｇの混合液を３分割２０分間で滴下した。約７℃の内温上昇が見られた。約３０分間で内温がもとの温度に戻ったところで次滴下した。滴下終了から３０分後に¹Ｈ−ＮＭＲでアリル基の反応率が９５％以上であることを確認した。反応液にゲル化抑制剤として、ベンゾチアゾ−ル０.０３８ｇをトルエン１.０ｇに希釈して添加した。未反応の１，３，５，７−テトラメチルシクロテトラシロキサンとトルエンを減圧留去し、淡黄色透明の液体である濃縮物を得た。
得られた濃縮物のＧＰＣ測定より、多峰性のクロマトグラムが得られ、混合物であることが示唆された。濃縮物の¹Ｈ−ＮＭＲ測定より、１，３，５，７−テトラメチルシクロテトラシロキサンのＳｉＨ基の一部がビスフェノールＡのジアリルエーテルのアリル基と反応したものであり、７.４８ｍｍｏｌ／ｇのＳｉＨ基と０.１４ｍｍｏｌ／ｇのアリル基を含有していることがわかった。

(Comparative Example 2)
In a 5 L separable flask, 600 g of toluene and 124.8 μl of a platinum vinylsiloxane complex xylene solution (containing 3 wt% as platinum) were mixed, and then mixed with 2000 g of 1,3,5,7-tetramethylcyclotetrasiloxane. The phase part was replaced with nitrogen, and then heated and stirred at an oil bath temperature of 70 ° C. A mixed solution of 513 g of diallyl ether of bisphenol A and 280 g of toluene was added dropwise in 3 portions and 20 minutes. An internal temperature increase of about 7 ° C. was observed. When the internal temperature returned to the original temperature in about 30 minutes, it was then added dropwise. 30 minutes after the completion of dropping, ¹ H-NMR confirmed that the allyl group reaction rate was 95% or more. As a gelation inhibitor, 0.038 g of benzothiazol was diluted with 1.0 g of toluene and added to the reaction solution. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a concentrate which was a pale yellow transparent liquid.
From the GPC measurement of the obtained concentrate, a multimodal chromatogram was obtained, suggesting that it was a mixture. From the ¹ H-NMR measurement of the concentrate, a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane was reacted with the allyl group of diallyl ether of bisphenol A, and was 7.48 mmol / g. Of SiH group and 0.14 mmol / g allyl group.

（実施例２）
１Ｌの四つ口フラスコにトルエン３６５ｇ、１，３，５，７−テトラメチルシクロテトラシロキサン１４６ｇを入れ、気相部を窒素で置換した後、ジャケット温５５℃で加熱、攪拌した。アリルグリシジルエーテル１０４ｇ、トルエン１０４ｇ及び白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０.０３０ｇの混合液を１２０分かけて滴下した。６０分後、¹Ｈ−ＮＭＲでアリル基の反応率が９５％以上であることを確認した。ビス〔４−（２−アリルオキシ）フェニル〕スルホン２０ｇをトルエン２０ｇで添加し、ガラス壁についたビス〔４−（２−アリルオキシ）フェニル〕スルホンをトルエン４ｇで流し入れた。ジャケット温９５℃に変更した。内温９５℃に安定したところで、ビス〔４−（２−アリルオキシ）フェニル〕スルホン２０ｇとトルエン２０ｇと白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）をトルエンで１００倍に薄めた溶液０.４９３ｇを添加し、ガラス壁についたビス〔４−（２−アリルオキシ）フェニル〕スルホンをトルエン４ｇで流し入れた。この操作を２０分毎に４回実施した（使用したビス〔４−（２−アリルオキシ）フェニル〕スルホンは１００ｇ）。滴下終了から２時間後に¹Ｈ−ＮＭＲでアリル基の反応率が９５％以上であることを確認した。反応液にゲル化抑制剤として、トリフェニルホスフィンをトルエンで１００倍に希釈した溶液０.１９９ｇを添加した。未反応の１，３，５，７−テトラメチルシクロテトラシロキサンとトルエンを減圧留去し、微黄色透明の液体である濃縮物を得た。
得られた濃縮物の粘度は５.８Ｐａ・ｓであった。濃縮物の¹Ｈ−ＮＭＲ測定より、１，３，５，７−テトラメチルシクロテトラシロキサンのＳｉＨ基の一部がアリルグリシジルエーテル及びビス〔４−（２−アリルオキシ）フェニル〕スルホンのアリル基と反応したものであり、３.１１ｍｍｏｌ／ｇのＳｉＨ基と０.０４ｍｍｏｌ／ｇのアリル基を含有していることがわかった。濃縮物のＧＰＣ測定より、多峰性のクロマトグラムが得られ、１，３，５，７−テトラメチルシクロテトラシロキサンとアリルグリシジルエーテルのみの反応物群と、１，３，５，７−テトラメチルシクロテトラシロキサンとアリルグリシジルエーテルとビス〔４−（２−アリルオキシ）フェニル〕スルホンが反応した化合物群の混合物であることが示唆された。

(Example 2)
Into a 1 L four-necked flask, 365 g of toluene and 146 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and the gas phase portion was replaced with nitrogen, followed by heating and stirring at a jacket temperature of 55 ° C. A mixed solution of 104 g of allyl glycidyl ether, 104 g of toluene and 0.030 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 120 minutes. After 60 minutes, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more. 20 g of bis [4- (2-allyloxy) phenyl] sulfone was added with 20 g of toluene, and bis [4- (2-allyloxy) phenyl] sulfone attached to the glass wall was poured with 4 g of toluene. The jacket temperature was changed to 95 ° C. When the internal temperature was stabilized at 95 ° C., a solution in which 20 g of bis [4- (2-allyloxy) phenyl] sulfone, 20 g of toluene and a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was diluted 100 times with toluene 0 .493 g was added, and bis [4- (2-allyloxy) phenyl] sulfone attached to the glass wall was poured into 4 g of toluene. This operation was performed 4 times every 20 minutes (100 g of bis [4- (2-allyloxy) phenyl] sulfone used). Two hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the allyl group reaction rate was 95% or more. As a gelation inhibitor, 0.199 g of a solution obtained by diluting triphenylphosphine 100 times with toluene was added to the reaction solution. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a concentrate which was a slightly yellow transparent liquid.
The viscosity of the obtained concentrate was 5.8 Pa · s. From the ¹ H-NMR measurement of the concentrate, some of the SiH groups of 1,3,5,7-tetramethylcyclotetrasiloxane are allyl glycidyl ether and allyl groups of bis [4- (2-allyloxy) phenyl] sulfone. It was reacted and found to contain 3.11 mmol / g SiH group and 0.04 mmol / g allyl group. From the GPC measurement of the concentrate, a multimodal chromatogram was obtained. A reaction group consisting of 1,3,5,7-tetramethylcyclotetrasiloxane and allyl glycidyl ether alone, and 1,3,5,7-tetra It was suggested that this was a mixture of compound groups in which methylcyclotetrasiloxane, allyl glycidyl ether, and bis [4- (2-allyloxy) phenyl] sulfone reacted.

（比較例３）
２Ｌオートクレーブにトルエン６００ｇ、１，３，５，７−テトラメチルシクロテトラシロキサン２００ｇを入れ、気相部を窒素で置換した後、ジャケット温５０℃で加熱、攪拌した。アリルグリシジルエーテル１４２ｇ、トルエン１４２ｇ及び白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０.０４１ｇの混合液を９０分かけて滴下した。滴下終了後にジャケット温を６０℃に上げて６０分反応、¹Ｈ−ＮＭＲでアリル基の反応率が９５％以上であることを確認した。ジアリルモノグリシジルイソシアヌレート１１０ｇ、トルエン１１０ｇ及び白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０.２３０ｇの混合液の５分の１量を滴下した後、ジャケット温を１０５℃に上げて、残りの５分の４量を３０分かけて滴下した。滴下終了から２時間後に¹Ｈ−ＮＭＲでアリル基の反応率が９５％以上であることを確認し、冷却により反応を終了した。１，３，５，７−テトラメチルシクロテトラシロキサンの未反応率は１.０％だった。未反応の１，３，５，７−テトラメチルシクロテトラシロキサンとトルエンを減圧留去し、無色透明の液体である生成物を得た。

(Comparative Example 3)
A 2 L autoclave was charged with 600 g of toluene and 200 g of 1,3,5,7-tetramethylcyclotetrasiloxane, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at a jacket temperature of 50 ° C. A mixed solution of 142 g of allyl glycidyl ether, 142 g of toluene and 0.041 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 90 minutes. After completion of the dropwise addition the jacket temperature 60 minutes reaction was raised to 60 ° C., the reaction rate of the allyl group was confirmed to be 95% or more by ¹ H-NMR. After dropwise addition of one-fifth of a mixture of 110 g of diallyl monoglycidyl isocyanurate, 110 g of toluene and 0.230 g of xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), the jacket temperature was raised to 105 ° C., The remaining 4/5 amount was added dropwise over 30 minutes. Two hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling. The unreacted rate of 1,3,5,7-tetramethylcyclotetrasiloxane was 1.0%. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a product which was a colorless and transparent liquid.

The viscosity of the obtained product was 2.0 Pa · s. This product is a product in which a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane has reacted with the allyl group of allyl glycidyl ether and diallyl monoglycidyl isocyanurate, as determined by ¹ H-NMR. It was found to contain 3.29 mmol / g SiH groups. The peak of unreacted allyl group could not be seen. From the GPC measurement of this product, a multimodal chromatogram was obtained. A reaction group consisting of 1,3,5,7-tetramethylcyclotetrasiloxane and allyl glycidyl ether alone, and 1,3,5,7- It was suggested that this was a mixture of compounds in which tetramethylcyclotetrasiloxane, allyl glycidyl ether and diallyl monoglycidyl isocyanurate reacted.

（実施例３〜４および比較例４〜７）
（Ａ）成分としてジアリルモノグリシジルイソシアヌレート、ビス〔４−（２−アリルオキシ）フェニル〕スルホンを用い、（Ｂ）成分として実施例１〜２、比較例１〜３の合成物を用い、（Ｃ）成分として白金−ジビニルテトラメチルジシロキサン錯体のキシレン溶液（白金３重量％含有）を用いて、表１に示した配合で硬化性組成物を作製した。配合方法は、（Ａ）成分と（Ｃ）成分とホウ酸トリメチルと老化防止剤（ＩＲＧＡＮＯＸ１０１０：ペンタエリスリチルテトラキス（３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート）、ＩＲＧＡＦＯＳ１６８：トリス（２,４−ジ−t−ブチルフェニル）ホスファイト、ＤＬ−ＴＤＰ：チオジプロピオン酸ジラウリル）を混合し、攪拌、脱泡したものをＡ液とし、（Ｂ）成分と１−エチニルシクロヘキサノールとγ―グリシドキシプロピルトリメトキシシランを混合し、攪拌、脱泡したものをＢ液とした。これらＡ液とＢ液を混合し、攪拌、脱泡することにより硬化性組成物を作成した。この硬化性組成物を、２枚のガラス板に３ｍｍ厚みのシリコーンゴムシートをスペーサーとして挟み込んで作製したセルに流し込み、６０℃６時間、７０℃１時間、８０℃１時間、１２０℃１時間、１５０℃１時間、１８０℃３０分間加熱し硬化物を得た。
硬化物の評価結果を表１に示す。

(Examples 3-4 and Comparative Examples 4-7)
As the component (A), diallyl monoglycidyl isocyanurate and bis [4- (2-allyloxy) phenyl] sulfone are used, and as the component (B), the composites of Examples 1-2 and Comparative Examples 1-3 are used. ) Using the xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) as a component, a curable composition was prepared with the formulation shown in Table 1. The blending method is (A) component, (C) component, trimethyl borate and anti-aging agent (IRGANOX 1010: pentaerythrityl tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), IRGAFOS 168: tris (2,4-di-t-butylphenyl) phosphite, DL-TDP: dilauryl thiodipropionate) was mixed and stirred and degassed as liquid A. Liquid B was prepared by mixing ethynylcyclohexanol and γ-glycidoxypropyltrimethoxysilane, stirring and degassing. These A liquid and B liquid were mixed, and it stirred and defoamed and created the curable composition. This curable composition was poured into a cell prepared by sandwiching a 3 mm thick silicone rubber sheet as a spacer between two glass plates, 60 ° C. for 6 hours, 70 ° C. for 1 hour, 80 ° C. for 1 hour, 120 ° C. for 1 hour, Heated at 150 ° C. for 1 hour and 180 ° C. for 30 minutes to obtain a cured product.
Table 1 shows the evaluation results of the cured product.

比較例４で使用されたビス〔４−（２−アリルオキシ）フェニル〕スルホンは難溶性固体であり、ビス〔４−（２−アリルオキシ）フェニル〕スルホンが他の成分に溶解しにくく、硬化性組成物を作製するにあたって取扱い性、加工性がよくなかった。一方、実施例３および４で使用されたビス〔４−（２−アリルオキシ）フェニル〕スルホン由来の構造を有する硬化剤は低粘度であり、硬化性組成物を容易に作製でき、取扱い性、加工性が良かった。該硬化剤を用いた硬化物は、光学的透明性、曲げ試験および加熱時引張り試験より伸び性能、耐クラック性試験より耐クラック性能、接着性試験より接着性能を有することが示された。

The bis [4- (2-allyloxy) phenyl] sulfone used in Comparative Example 4 is a hardly soluble solid, and bis [4- (2-allyloxy) phenyl] sulfone is difficult to dissolve in other components and has a curable composition. Handling property and workability were not good in manufacturing the product. On the other hand, the curing agent having a structure derived from bis [4- (2-allyloxy) phenyl] sulfone used in Examples 3 and 4 has a low viscosity and can easily produce a curable composition. Sex was good. The cured product using the curing agent was shown to have an optical transparency, an elongation performance from a bending test and a tensile test during heating, a crack resistance performance from a crack resistance test, and an adhesion performance from an adhesion test.

Claims (8)

A curing agent having at least one sulfonyl group and at least two SiH groups in one molecule and having a viscosity at 23 ° C. of 1000 Pa · s or less. In one molecule, at least two SiH groups and the following general formula (I)

(In the formula, R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a halogen group, a vinyl group, or an allyl group, and R ¹ may be the same or different.)
And a viscosity at 23 ° C. of 1000 Pa · s or less. The general formula (I) is represented by the following general formula (II):

(In the formula, R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a halogen group, a vinyl group, or an allyl group, and R ¹ may be the same or different.)
The curing agent according to claim 2, wherein In one molecule, at least two SiH groups and the following general formula (III)

(Wherein R ² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a halogen group, a vinyl group or an allyl group, and R ² may be the same or different.)
And a viscosity at 23 ° C. of 1000 Pa · s or less. The general formula (III) is represented by the following general formula (IV):

(Wherein R ² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a halogen group, a vinyl group or an allyl group, and R ² may be the same or different.)
The curing agent according to claim 4, wherein A R ² are all hydrogen atoms in the formula (IV), the curing agent according to claim 5. (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, (B) a curing agent containing SiH groups, and (C) a hydrosilylation catalyst. It is a curable composition contained as an essential component, Comprising: The said (B) component is a curable composition which is a hardening | curing agent as described in any one of Claims 1-6.   A cured product obtained by curing the curable composition according to claim 7.