JP4578338B2 - Curable composition and cured product thereof - Google Patents

Description

  The present invention relates to a curable composition and a cured product thereof. More specifically, the present invention relates to a curable composition in which the non-coloring property of the cured product is improved and without substantial decrease in curable property, and the cured product.

  A curable composition comprising an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, a compound containing at least two SiH groups in one molecule, and a hydrosilylation catalyst Various products have been proposed (for example, Patent Document 1, Patent Document 2, and Patent Document 3).

  It is well known to add phosphite compounds to curable compositions that cure by hydrosilylation reactions, ensuring working time in the room temperature range due to the features that inhibit hydrosilylation reactions of phosphite compounds. Have been proposed (for example, Patent Document 4, Patent Document 5, and Patent Document 6). However, while the working time in the room temperature region can be secured by the addition of the phosphorous acid-based compound, there is a tendency that the reactivity decreases during the heat curing and the curing time is delayed (decrease in curability).

  As a method for suppressing this decrease in curability, a curable composition comprising a polysiloxane containing a carbon-carbon double bond reactive with SiH groups, a polyhydrogensiloxane containing SiH groups, and a hydrosilylation catalyst is bulky. Techniques for adding a phosphorous acid compound having a high group have been proposed (for example, Patent Document 7, Patent Document 8, and Patent Document 9).

When these curable compositions are used for optical materials, coating materials and the like, the obtained cured product is required to have high light transmittance. However, the curability is composed of an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, a compound containing at least two SiH groups in one molecule, and a hydrosilylation catalyst. Although the detailed cause of the composition is not known, since the cured product immediately after curing may be colored brown, it is important to reduce the coloring property, that is, to improve the non-coloring property of the cured product. It becomes a challenge.
International Publication WO01-81475 Pamphlet Japanese Patent No. 2558224 JP 05-295270 A US Pat. No. 3,188,300 JP-A-56-20051 JP-A-7-238185 JP-A-9-183906 JP-T-2001-508096 JP-T-2001-527111

  Therefore, the present invention provides a curable composition that can give a cured product with improved coloring that occurs when the curable composition is cured, without being accompanied by a substantial decrease in curability under curing conditions. With the goal.

  As a result of intensive studies, the present inventors have found that an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule and a compound containing at least two SiH groups in one molecule When a specific phosphite compound is further added to the curable composition comprising the hydrosilylation catalyst and the hydrosilylation catalyst, surprisingly, a decrease in the curable property under the curing conditions is suppressed, and the curable property is not substantially decreased. The present inventors have found that the coloration of the resulting cured product can be improved and have completed the present invention.

That is, the present invention
Organic compound (A) containing at least two carbon-carbon double bonds reactive with SiH group in one molecule, compound (B) containing at least two SiH groups in one molecule, hydrosilylation catalyst (C) and general formula (VII)

（式中Ｒ⁸は炭素数１〜５の一価有機基である。）で表される亜リン酸系化合物（Ｄ）を必須成分として含有することを特徴とする、硬化性組成物
（請求項１）であり、
（Ｄ）成分がビス［２，４−ビス（１，１−ジメチルエチル）−６−メチルフェニル］エチルエステル亜リン酸である、請求項１に記載の硬化性組成物（請求項２）であり、
（Ａ）成分および／または（Ｂ）成分に下記式

(Wherein R ⁸ is a monovalent organic group having 1 to 5 carbon atoms.) Containing a phosphorous acid compound (D) as an essential component (claim) Item 1)
In the curable composition (Claim 2) according to claim 1, wherein the component (D) is bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid. Yes,
In the component (A) and / or (B), the following formula

で表されるイソシアヌル酸骨格を含有する化合物を含むことを特徴とする、請求項１または２に記載の硬化性組成物（請求項３）であり、
請求項１〜３のいずれか一項に記載の硬化性組成物を硬化させてなる硬化物（請求項４）である。

The curable composition according to claim 1 or 2 (claim 3), comprising a compound containing an isocyanuric acid skeleton represented by:
It is hardened | cured material (Claim 4) formed by hardening | curing the curable composition as described in any one of Claims 1-3.

  If the curable composition of this invention is used, the hardened | cured material with which the non-coloring property was improved will be obtained, without being accompanied by substantial sclerosis | hardenability fall.

  The curable composition according to the present invention comprises an organic compound (A) containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and at least two SiH groups in one molecule. It contains the compound (B) to be contained, the hydrosilylation catalyst (C), and the phosphorous acid compound (D) represented by the general formula (VII) as essential components.

Each component contained in the curable composition according to the present invention will be described below.
((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 SiH group of a component, The following general formula (I)

（式中Ｒ¹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 ¹ 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 (II) in the ring is the heat resistance of the cured product. Is preferable from the viewpoint of high.

（式中Ｒ²は水素原子あるいはメチル基を表す。それぞれのＲ²は異なっていても同一であっても良い。）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 ² represents a hydrogen atom or a methyl group. Each R ² may be different or the same.) From the viewpoint of availability of raw materials, a partial structure represented by the following formula An alicyclic group having 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 those containing only C, H, N, O, S, and halogen as constituent elements are preferable. 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. Two or more of these divalent or higher valent substituents may be connected by a covalent bond to form 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 1000 poise at 23 ° C., more preferably less than 300 poise, More preferred is less than 30 poise.

  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 suppressing 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, in the point that the heat resistance of the obtained hardened | cured material tends to become high, it is preferable to have at least 1 reactive group in 1 molecule on average.

  In particular, the component (A) has the following formula from the viewpoint of high heat resistance and light resistance:

で表されるイソシアヌル環骨格を含有する化合物として一般式（ＩＩＩ）で表されるトリアリルイソシアヌレート及びその誘導体が特に好ましい。

As the compound containing an isocyanuric ring skeleton represented by the formula, triallyl isocyanurate represented by the general formula (III) and derivatives thereof are particularly preferable.

（式中Ｒ³は炭素数１〜５０の一価の有機基を表し、それぞれのＲ³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 ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same).

As R < ³ > of the said general formula (III), it is preferable that it is a C1-C20 monovalent organic group from a viewpoint that the heat resistance of the hardened | cured material obtained can become higher, and C1-C1 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 ³ include 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 ^{3 in the} above general formula (III) is a carbon in which at least one of the three R ^{3 s} contains one or more epoxy groups from the viewpoint that adhesion of the obtained cured product with 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Ｒ³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 preferred R ³ include a glycidyl group,

等が挙げられる。

Etc.

As R ³ of the general formula (III), from the viewpoint that the chemical thermal stability of the obtained 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 ³ include 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 ^{3 in the} general formula (III) is at least one of three R ³ from the viewpoint of improving the 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（ＩＶ）

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

（式中Ｒ⁴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Ｒ³のうち少なくとも２つが下記一般式（Ｖ）

(Wherein R ⁴ 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 ³ are represented by the following general formula (V)

（式中Ｒ⁵は直接結合あるいは炭素数１〜４８の二価の有機基を表し、Ｒ⁶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Ｒ⁵およびＲ⁶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 ⁵ represents a direct bond or a divalent organic group having 1 to 48 carbon atoms, and R ⁶ represents a hydrogen atom or a methyl group) (a plurality of R ⁵ and R ⁶ are More preferably, they may be the same or different.

R ^{5 in the} general formula (V) is a direct bond or a divalent organic group having 1 to 48 carbon atoms. From the viewpoint that the heat resistance of the obtained 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 ⁵ include

等が挙げられる。

Etc.

Examples of the R ⁵ of the general formula (V), the chemical heat from the viewpoint of stability can be a good cured product obtained, C as contain and an element directly coupled or two or less oxygen atoms, 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 ⁵ include

が挙げられる。

Is mentioned.

R ^{6 in the} general formula (V) is a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint of good reactivity.

  However, in the preferred examples of the organic compound represented by the general formula (III) 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.

  Preferable specific examples of the organic compound represented by the general formula (III) as described above 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 set arbitrarily, but when light resistance is more important, triallyl isocyanurate / allyl monoglycidyl isocyanurate (molar ratio) = 99/1 to 51/49 is preferable, and adhesion and toughness are more important. In this case, 1/99 to 50/50 is 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) of the present invention is a compound containing at least two SiH groups in one molecule.

  The component (B) is not particularly limited as long as it is a compound containing at least two SiH groups in one molecule. For example, it is a compound described in International Publication WO96 / 15194, and at least two SiH groups in one molecule. Those having a group can be used.

  Among these, from the viewpoint of availability, a chain and / or cyclic organopolysiloxane having at least two SiH groups in one molecule is preferable, and from the viewpoint of good compatibility with the component (A), Furthermore, the following general formula (VI)

（式中、Ｒ⁷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２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。

(Wherein R ⁷ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10). Cyclic organopolysiloxane having at least two SiH groups in one molecule. Is preferred.

The substituent R ⁷ in the compound represented by the general formula (VI) is preferably composed of C, H and O, more preferably a hydrocarbon group, and a methyl group. Further preferred.

  From the viewpoint of availability, the compound represented by the general formula (VI) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane.

The molecular weight of the component (B) is not particularly limited, and any one can be suitably used. However, from the viewpoint that the fluidity of the curable composition can be more easily controlled, those having a low molecular weight are preferably used. In this case, the lower limit of the preferable molecular weight is 50, and the upper limit of the preferable molecular weight is 100,000, more preferably 10,000, and still more preferably 1,000.
(B) A component can be used individually or in mixture of 2 or more types.

From the viewpoint of having good compatibility with the component (A), and from the viewpoint that the problem of outgas from the composition that can reduce the volatility of the component (B) is less likely to occur, the component (B) is a SiH group. An organic compound (α) containing at least one carbon-carbon double bond having reactivity with one molecule, and a linear and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule (Β) is preferably a compound that can be obtained by a hydrosilylation reaction.
((Α) component)
Here, the component (α) is the component (A) described above, and the same component (α1) as the organic compound containing at least two carbon-carbon double bonds reactive with the SiH group in one molecule is used. Can do. When the component (α1) is used, the resulting cured product has a high crosslink density and tends to be a cured product having high mechanical strength.

  In addition, an organic compound (α2) containing one carbon-carbon double bond having reactivity with the SiH group in one molecule can also be used. When the (α2) component is used, the obtained cured product tends to have low elasticity.

  Further, when the (α1) component and the (α2) component are used in combination, the compatibility with the (A) component can be easily controlled, and a cured product having low elasticity and excellent mechanical strength can be obtained.

  The component (α) has the following formula from the viewpoint of high heat resistance and light resistance:

で表されるイソシアヌル環骨格を含有する化合物を用いることが好ましい。
（（α２）成分）
（α２）成分としては、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るという点においては、化合物としてはポリシロキサン−有機ブロックコポリマーやポリシロキサン−有機グラフトコポリマーのようなシロキサン単位（Ｓｉ−Ｏ−Ｓｉ）を含むものではなく、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であることが好ましい。

It is preferable to use a compound containing an isocyanuric ring skeleton represented by:
((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 which has the reactivity with SiH group of ((alpha) 2) component, The following general formula (I)

（式中Ｒ¹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 ¹ 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 (II) in the ring is the heat resistance of the cured product. Is preferable from the viewpoint of high.

（式中Ｒ²は水素原子あるいはメチル基を表す。それぞれのＲ²は異なっていても同一であっても良い。）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 ² represents a hydrogen atom or a methyl group. Each R ² may be different or the same.) From the viewpoint of availability of raw materials, a partial structure represented by the following formula An alicyclic group having 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. Two or more of these divalent or higher valent substituents may be connected by a covalent bond to form 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. Furthermore, polyether resins such as one-end allylated polyethylene oxide and one-end allylated polypropylene oxide, hydrocarbon resins such as one-end allylated polyisobutylene, one-end allylated polybutyl acrylate, one-end allylated polymethyl methacrylate Examples thereof also include polymers or oligomers having a vinyl group at one end, such as acrylic resins.

  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, in the point that the heat resistance of the obtained hardened | cured material tends to become high, it is preferable to have at least 1 reactive group in 1 molecule on average. Specific examples of such (α2) component 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.
((Β) component)
The component (β) is a linear and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule.

  Specifically, for example

が挙げられる。

Is mentioned.

  Here, from the viewpoint of easy compatibility with the component (α), the following general formula (VI)

（式中、Ｒ⁷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基を有する環状ポリオルガノシロキサンが好ましい。

(Wherein R ⁷ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10). Cyclic polyorganosiloxane having at least 3 SiH groups in one molecule. Is preferred.

The substituent R ⁷ in the compound represented by the general formula (VI) is preferably composed of C, H and O, more preferably a hydrocarbon group, and a methyl group. Further preferred.

  In view of availability, 1,3,5,7-tetramethylcyclotetrasiloxane is preferable.

Various (β) components as described above can be used alone or in admixture of two or more.
(Reaction of (α) component and (β) component)
Next, hydrosilylation of (α) component and (β) component in the case of using a compound obtained by hydrosilylation reaction of (α) component and (β) component as component (B) of the present invention The reaction will be described.

  In addition, when the (α) component and the (β) component are subjected to a hydrosilylation reaction, a mixture of a plurality of compounds containing the (B) component of the present invention may be obtained, but without separating the (B) component therefrom. The curable composition of the present invention can also be produced using the mixture as it is.

  The mixing ratio of the (α) component and the (β) component when the (α) component and the (β) component are subjected to a hydrosilylation reaction is not particularly limited, but the hydrosilylation of the obtained (B) component and (A) component is not limited. When considering the strength of the cured product due to the above, since it is preferable that the component (B) has a large amount of SiH groups, the total number of carbon-carbon double bonds having reactivity with the SiH groups in the component (α) to be mixed ( The ratio of X) to the total number of SiH groups (Y) in the (β) component to be mixed is preferably Y / X ≧ 2, and more preferably Y / X ≧ 3. Moreover, it is preferable that it is 10> = Y / X from the point that compatibility with the (A) component of (B) component becomes easy, and it is more preferable that it is 5> = Y / X.

  When the (α) component and the (β) component are subjected to a hydrosilylation reaction, the proportion of each component is not particularly limited even when the (α1) component and the (α2) component are used in combination as the (α) component. When the molar ratio of the (α2) component and the (β) component contained in the component is (X2) and (Y1), respectively, from the viewpoint of the effect of lowering the elastic modulus and / or glass transition temperature due to the reduction of the crosslinking density (X2 The preferable lower limit of / Y1) is 0.6, more preferably 1.0, and still more preferably 1.4. From the viewpoint of the strength of the cured product, (X2 / Y1) has a preferred upper limit of 2.5, more preferably 2.1, and even more preferably 1.7. The molar ratio of the (α1) component and the (β) component contained in the obtained component (B) is changed to (X1), (Y1), and carbon-carbon dioxygen having reactivity with the SiH group in the component (α1). Assuming that the average number of heavy bonds is (Z1), the range of ((Y1 / X1) / Z1) is preferably 0.7 or more and 1 or less, and more preferably 0. 8 or more and 1 or less, and a more preferable range is 0.9 or more and 1 or less. The upper limit of ((Y1 / X1) / Z1) is preferably 0.8, more preferably 0.7, and still more preferably 0.6 from the viewpoint of good compatibility with the component (A).

When the (α) component and the (β) component are subjected to a hydrosilylation reaction, an appropriate catalyst may be used. As the catalyst, 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 (for example, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ) (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, n and m are integers.), dicarbonyldichloroplatinum, Karstedt catalyst, and Ashby US Pat. No. 3,159,601 and Platinum is described in JP 3159662 specification - hydrocarbon complexes and platinum alcoholate catalysts are exemplified as described in U.S. Pat during Specification No. 3,220,972 of Ramoro (Lamoreaux). 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 mole of SiH group of the (β) 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 is 10 ^-1 moles per mole of the SiH group (beta) 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 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 (α) component, the (β) component, and the catalyst in the reaction. The (α) component mixed with the catalyst is mixed with the (β) component. The method is preferred. If the catalyst is mixed with the mixture of the (α) component and the (β) component, the reaction tends to be difficult to control. When the method of mixing the (β) component with the mixture of the (β) component and the catalyst, the (β) component is reactive in the presence of the catalyst and may be altered due to its reactivity with water. .

  As the method of mixing the (α) component, the (β) component, and the catalyst in the case where the (α1) component and the (α2) component are used in combination as the (α) component, various methods can be taken. When it is desired to obtain the component (B), a method in which the (α2) component mixed with the catalyst is mixed with the (β) component and reacted, and then the (α1) component is added and mixed to react. When it is desired to obtain the component (B) having a greater effect of lowering the elastic modulus and / or glass transition temperature, the (α1) component mixed with the catalyst is mixed with the (β) component and reacted, and then the unreacted ( A method in which the β) component is once removed, followed by addition and mixing of the (α2) component, and a reaction is preferred.

  As a method of mixing the (α) component, the (β) component, and the catalyst when a plurality of (α1) components are used in combination as the (α) component, various methods can be taken, but the (B) component can be more simply used. In the case where it is desired to obtain, a method in which a mixture of a plurality of (α1) components with a catalyst is mixed with the (β) component and reacted. When it is desired to obtain the component (B) from which a cured product having more excellent mechanical properties can be obtained, a mixture of a higher functional (α1) component and a catalyst is mixed with the (β) component and reacted to cause no reaction. The (β) component is removed once, and then the lower-functional (α1) component is added and mixed to react.

  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 lower than 30 ° C, the reaction time for sufficient reaction tends to be long, and if the reaction temperature is higher than 200 ° C, it tends to be impractical. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. Also, the reaction time and the pressure during the reaction can be variously set as required.

  A solvent may be used during the hydrosilylation reaction. The solvent is not particularly limited as long as it does not inhibit the hydrosilylation reaction. Specifically, hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1,3- Ether solvents such as 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 said solvent may be used independently and can also be used as 2 or more types of mixed solvents. 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 (α) component and the (β) component, the solvent or / and the unreacted (α) component or / and the (β) component can be removed. 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 it is processed at a temperature higher than 100 ° C., it tends to be accompanied by alteration such as thickening.

  Among the components (B) that are the reaction products of the components (α) and (β) as described above, the reaction products of the components (α1) and (β) are not particularly limited, but preferred compounds include divinylbenzene and Reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of bisphenol A diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, vinylcyclohexene and 1,3,5,7- Reaction product of tetramethylcyclotetrasiloxane, reaction product of dicyclopentadiene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane , Reaction product of diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane The reaction product of triallyl isocyanurate having an isocyanuric ring skeleton and 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and 1 More preferred is a reaction product of 3,5,7-tetramethylcyclotetrasiloxane. The reaction product of the component (α2) and the component (β) is not particularly limited, but preferred compounds include a reaction product of allyl glycidyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, α-methylstyrene and 1,3. , 5,7-tetramethylcyclotetrasiloxane reaction product, monoallyl diglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane reaction product, etc., good heat and light resistance Therefore, a reaction product of monoallyl diglycidyl isocyanurate having an isocyanuric ring skeleton and 1,3,5,7-tetramethylcyclotetrasiloxane is more preferable.

  Among the components (B) that are the reaction product of the component (α) and the component (β), the reaction product of the components (α1) and the component (β) is not particularly limited, but a preferable compound is at least one ( The α1) component preferably contains either one selected from the group consisting of triallyl isocyanurate having an isocyanuric ring skeleton and diallyl monoglycidyl isocyanurate because of good heat resistance and light resistance, and triallyl isocyanurate and Reaction product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of triallyl isocyanurate and bisphenol A diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, triallyl isocyanate Nurate and vinylcyclohexene and 1,3,5,7-tetra Reactants of tilcyclotetrasiloxane, triallyl isocyanurate and dicyclopentadiene with 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and divinylbenzene and 1,3,5,7 -Reactants of tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and bisphenol A diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and vinylcyclohexene and 1,3 , 5,7-tetramethylcyclotetrasiloxane reactant, diallylmonoglycidyl isocyanurate and dicyclopentadiene and 1,3,5,7-tetramethylcyclotetrasiloxane reactant, triallyl And the like reactants cyanurate and diallyl monoglycidyl isocyanurate-1,3,5,7-tetramethylcyclotetrasiloxane.

  A reaction product of triallyl isocyanurate and diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane can be mentioned as a more preferable one from the viewpoint of heat resistance, light resistance and adhesiveness of the cured product. .

  Among the components (B) that are the reaction product of the components (α) and (β), the reactants of the components (α1), (α2), and (β) are not particularly limited, but preferred compounds include divinyl Reaction product of benzene and 1-hexene with 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of divinylbenzene and α-methylstyrene with 1,3,5,7-tetramethylcyclotetrasiloxane, divinylbenzene and Reaction product of allyl glycidyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of bisphenol A diallyl ether and 1-hexene and 1,3,5,7-tetramethylcyclotetrasiloxane, bisphenol A diallyl Reaction of ether and α-methylstyrene with 1,3,5,7-tetramethylcyclotetrasiloxane Reaction product of bisphenol A diallyl ether and allyl glycidyl ether with 1,3,5,7-tetramethylcyclotetrasiloxane, reaction of vinylcyclohexene and 1-hexene with 1,3,5,7-tetramethylcyclotetrasiloxane A reaction product of vinylcyclohexene and α-methylstyrene with 1,3,5,7-tetramethylcyclotetrasiloxane, a reaction product of vinylcyclohexene and allyl glycidyl ether with 1,3,5,7-tetramethylcyclotetrasiloxane, Reaction product of dicyclopentadiene and 1-hexene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of dicyclopentadiene and α-methylstyrene and 1,3,5,7-tetramethylcyclotetrasiloxane, Dicyclopentadiene and allylgue Reaction product of ricidyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, triallyl isocyanurate and reaction product of 1-hexene and 1,3,5,7-tetramethylcyclotetrasiloxane, triallyl isocyanate Reaction product of nurate and α-methylstyrene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of triallyl isocyanurate and allyl glycidyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl Reaction of monoglycidyl isocyanurate and 1-hexene with 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and α-methylstyrene and 1,3,5,7-tetramethylcyclotetrasiloxane Reactant, diallyl monoglycidyl iso Examples thereof include compounds such as a reaction product of cyanurate and allyl glycidyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane.

  From the viewpoint of heat resistance and light resistance, triallyl isocyanurate and allyl glycidyl ether containing isocyanuric ring skeleton and 1,3,5,7-tetramethylcyclotetrasiloxane reaction product, diallyl monoglycidyl isocyanurate and allyl glycidyl ether And a reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane.

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 ′) (Y ′ / X ′), the lower limit of the preferable range is 0.3, more preferably 0.5, still more preferably 0.7, and the preferable range. Is preferably 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.

  In addition, from the point that the heat resistance and light resistance of the cured product are improved, at least one of the component (A) and the component (B)

で表されるイソシアヌル環骨格を含有する化合物を含むことが好ましい。（Ａ）成分及び（Ｂ）成分中の上記イソシアヌル環骨格を含有する化合物の含有量は３０重量％以上が好ましく、５０重量％以上がより好ましく、７０重量％以上がさらにより好ましい。
（（Ｃ）成分）
次に（Ｃ）成分であるヒドロシリル化触媒について説明する。

It is preferable that the compound containing the isocyanuric ring skeleton represented by these is included. The content of the compound containing the isocyanuric ring skeleton in the component (A) and the component (B) is preferably 30% by weight or more, more preferably 50% by weight or more, and still more preferably 70% by weight or more.
((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 ) (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent integers.), Dicarbonyldichloroplatinum, Kartstedt catalyst, as well as the platinum-hydrocarbon complexes described in Ashby U.S. Pat. Nos. 3,159,601 and 3,159,622, and Lamoreaux, U.S. Pat. No. 3,220,972. Mention may be made of the platinum alcoholate catalysts described. 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 is 10 ^-1 moles per mole of the SiH group (beta) 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. .
((D) component)
Next, the phosphorous acid type compound which is (D) component is demonstrated.

  Component (D) is represented by the general formula (VII)

（式中Ｒ⁸は炭素数１〜５の一価有機基である。）で表される亜リン酸系化合物であり、この（Ｄ）成分の添加により実質的な硬化性低下を伴なうことなく、その硬化物の非着色性が改善できる。

(Wherein R ⁸ is a monovalent organic group having 1 to 5 carbon atoms) and is accompanied by a substantial decrease in curability by the addition of component (D). The non-coloring property of the cured product can be improved.

The component (D) is not particularly limited, but bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester in which R ⁸ is an ethyl group is available from the viewpoint of availability. Phosphoric acid is preferred.

  Although the addition amount of (D) component is not specifically limited, it was used as the number of P atoms (P1) of the phosphite compound contained in the curable composition and the hydrosilylation catalyst contained in the curable composition. The upper limit of the ratio (P1 / M1) of the number of metal atoms (M1) is preferably 5, more preferably 4, and even more preferably 3. When (P1 / M1) exceeds 3, a substantial decrease in curability may occur. The lower limit of (P1 / M1) is preferably 0.2, and more preferably 0.4. When (P1 / M1) is less than 0.2, the non-coloring improvement effect tends to be insufficient.

  In the present invention, “without substantial decrease in curability” is not particularly limited as long as the delay in curing time due to the addition of component (D) is not practically limited, but component (D) is added. The ratio (T1 / T2) of the curing time (T1) at 100 to 130 ° C. of the cured curable composition of the present invention and the curing time (T2) at the same temperature when the component (D) is not added is 1.3 or less. Preferably there is. The curing time can be measured by various methods, but when a drop of the curable composition is dropped on a temperature-controlled hot plate and stirred with a spatula, the time until fluidity is lost is measured. This makes it possible to measure the curing time.

The level of “improvement of non-coloration of the cured product” in the present invention is not particularly limited as long as a practical reduction in coloring is recognized, but as an evaluation method, a comparison of the degree of coloration of the cured product by visual observation is made. The comparison of the light transmittance of the cured product plate, the comparison of the yellowness of the cured product plate, etc. can be exemplified, and the non-coloring improvement effect can be confirmed by these methods.
(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 adhesion and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  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 the total amount of the component (A) and the component (B) is 0.1 part by weight, more preferably 0.8 parts. The upper limit of the preferable 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.

  The addition amount of the epoxy compound can be variously set, but the lower limit of the preferable addition amount with respect to 100 parts by weight of the total amount of the component (A) and the component (B) is 1 part by weight, more preferably 3 parts by weight. The upper limit of the preferable 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 parts 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, naphthalenecarboxylic 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 added 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 preferred 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.
(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 resins obtained by ring-opening metathesis polymerization of fats and norbornene derivatives, 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 (for example, 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 that the compatibility with the component (A) or the component (B) tends to be good. The following is more preferable. 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. A state or / and a mixed state may be used.

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. Although there is no limitation in particular as a compounding quantity of a filler, from a viewpoint of reduction of a linear expansion coefficient, 10 weight part or more is preferable with respect to 100 weight part of total amounts of (A) component and (B) component, 30 weight Part or more is more preferable.

(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.

The blending amount of the anti-aging material is not particularly limited, but from the viewpoint of heat resistance, the preferred lower limit is 0.1 parts by weight, more preferably 1 part per 100 parts by weight of the total amount of the component (A) and the component (B). Parts by weight. A preferred upper limit is 10 parts by weight, more preferably 5 parts by weight.
(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.
The blending amount of the radical inhibitor is not particularly limited, but from the viewpoint of storage stability, the preferred lower limit is 0.1 parts by weight, more preferably 100 parts by weight of the total amount of the components (A) and (B). 1 part by weight. A preferred upper limit is 10 parts by weight, more preferably 5 parts by weight.
(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.
The blending amount of the UV absorber is not particularly limited, but from the viewpoint of light resistance, the preferred lower limit is 0.1 parts by weight, more preferably 100 parts by weight of the total amount of the component (A) and the component (B). 1 part by weight. A preferred upper limit is 10 parts by weight, more preferably 5 parts by weight.
(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, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, 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 preferred amount of use for 1 g of the curable composition to be used is 0.1 mL, and the upper limit of the preferred amount of use 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.

(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 all components may be mixed and prepared in advance and stored at a low temperature. When storing in one liquid state, it is preferable to store at 0 degrees C or less from the point of ensuring storage stability, and -18 degrees C or less is more preferable. 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) Organic compound containing at least two carbon-carbon double bonds reactive with SiH group as component, and at least two SiH groups per molecule as component (B) A method of separately storing the compounds to be used is preferable since there is little deterioration in quality during storage.

  The order of mixing the various components is not particularly limited. However, the mixed solution of the component (C) and the component (B) tends to react with moisture and easily thicken, so that the component (C) is the component (A). It is preferable to store separately from the component (B), for example, by mixing with the component (B). The component (D) may reduce the catalytic activity of the hydrosilylation reaction of the component (C), and the component (B) contains a small amount of the component (C) used in the production of the component (B). May improve the storage stability of the component (B), so the component (D) is stirred and mixed with the component (B) and stored, and the liquid mixture of the component (A) and the component (C) before curing. And a method of stirring and mixing and curing.

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.
(Cured product)
Next, the cured product of the present invention is obtained by curing the curable composition. 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 while raising the temperature in a multistage manner or continuously, as compared with the case where the temperature is constant, in that a cured product with less distortion is easily obtained.
(Use)
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.
(Analysis method)
Analysis in the following synthesis examples and comparative synthesis examples was measured as follows.
(GPC)
An approximately 1% by weight toluene solution was prepared and LC MODULE 1 manufactured by WATERS was used. The flow rate was 1 ml / min with a toluene solvent, the column temperature was 40 ° C., and the connection columns were four columns manufactured by Showa Denko KK (KF806L / KF804L / KF8025 / KF802). ) Using a RI detector.
(viscosity)
The viscosity at 23.0 ° C. was measured using “TV-20 viscometer / corn plate type” manufactured by Toki Sangyo Co., Ltd.
(Evaluation methods)
Evaluation in the following Examples and Comparative Examples was performed by the following method.
(120 ° C curing time)
A drop of the curable composition was dropped on a hot plate controlled at 120 ± 2 ° C., and the curing time was measured by measuring the time until fluidity disappeared when stirring with a spatula was continued.
(Non-colorability of cured product)
Pour into a cell made using two glass plates coated with 100 mm x 100 mm fluorine-based release agent and 3 mm thick silicone rubber, 60 ° C / 6 hours, 70 ° C / 1 hour, 80 ° C / 1 hour 120 ° C./1 hour, 150 ° C./1 hour. The obtained cured product of about 80 mm × 70 mm × 3 mm was allowed to cool to room temperature, carefully taken out from the glass cell, and the cured product was sandwiched between two glass plates and further heated at 180 ° C. for 30 minutes. A 10 mm × 30 mm test piece was cut out from the cured product, and the appearance of the cured product was visually observed to evaluate the coloring state. The evaluation criteria were ◯ for colorless and transparent, Δ for slightly brownish transparency, × for light brownish transparency, and XX for brown transparency.
(Synthesis example)
720 g of toluene and 240 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 2 L autoclave, the gas phase was replaced with nitrogen, and then heated and stirred at a jacket temperature of 50 ° C. A mixed solution of 171 g of allyl glycidyl ether, 171 g of toluene, and 0.039 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 60 minutes. After completion of dropping, the jacket temperature was raised to 60 ° C. for 40 minutes, and ¹ H-NMR confirmed that the reaction rate of allyl group was 95% or more. The jacket temperature was raised to 105 ° C., and a mixed solution of 83 g of triallyl isocyanurate, 83 g of toluene and 0.039 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 60 minutes. 5.5 hours after the completion of dropping, ¹ H-NMR confirmed that the allyl group reaction rate was 95% or more, and the reaction was terminated by cooling. When the reaction solution was measured with a gas chromatograph, 1,3,5,7-tetramethylcyclotetrasiloxane was 99% or more reacted. Toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid. This was designated as “partial reactant B”.

The viscosity of “partial reactant B” is 2.0 Pa · s, and ¹ H-NMR measurement shows that a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane is allyl glycidyl ether and triallyl isocyanate. It reacted with the allyl group of nurate and was found to contain 3.8 mmol / g of SiH group. When the GPC measurement of “partial reactant B” is performed, a multimodal chromatogram is obtained.

を有する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反応物群「部分反応物Ｂ−１」と、下記構造式

1,3,5,7-tetramethylcyclotetrasiloxane and allyl glycidyl ether reactant group “partial reactant B-1” having the following structural formula:

を有する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トリアリルイソシアヌレートが反応した化合物群「部分反応物Ｂ−２」の混合物であることがわかった。尚、本生成物中にはＰｔ金属を５ｐｐｍ含有していた。
（実施例１〜５、比較例１〜９）
表１に示す配合量で（Ａ）成分としてトリアリルイソシアヌレート及びジアリルモノグリシジルイソシアヌレート、（Ｂ）成分として合成例１で製造した１分子中に少なくとも２個のＳｉＨ基を含有する化合物（（Ｃ）成分としてヒドロシリル化触媒をＰｔ金属として５ｐｐｍ含む）、（Ｃ）成分である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）、（Ｄ）成分として亜リン酸系化合物、その他にペンタエリスリトールテトラキス［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］（ＩＲＧＮＯＸ １０１０ チバ・スペシャルティ・ケミカルズ株式会社製）、１−エチニル−１−シクロヘキサノール、ほう酸トリメチル、γ−グリシドキシプロピルトリメトキシシランを攪拌混合し、硬化性組成物を調製した。

It was found to be a mixture of the compound group “partial reactant B-2” obtained by reacting 1,3,5,7-tetramethylcyclotetrasiloxane having allyl, allyl glycidyl ether and triallyl isocyanurate. The product contained 5 ppm of Pt metal.
(Examples 1-5, Comparative Examples 1-9)
Compound (A) containing triallyl isocyanurate and diallyl monoglycidyl isocyanurate as component (A) and compound containing at least two SiH groups in one molecule produced in Synthesis Example 1 as component (B) (( C) Hydrosilylation catalyst as a Pt metal (containing 5 ppm) as component (C), platinum vinylsiloxane complex xylene solution (containing 3 wt% as platinum), (D) component as phosphorous acid compound, and pentane Erythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (IRGNOX 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.), 1-ethynyl-1-cyclohexanol, trimethyl borate, γ- Stir and mix glycidoxypropyltrimethoxysilane A curable composition was prepared.

  Ratio of the number of P atoms (P1) of the phosphite compound contained in the curable composition to the number of metal atoms (M1) used as the hydrosilylation catalyst contained in the curable composition (P1 / M1) ) Was calculated. The 120 degreeC hardening time of this curable composition was measured. The ratio (T1 / T2) of the curing time (T1) at 120 ° C. of the curable composition to which the phosphorous acid compound was added and the curing time (T2) at the same temperature when no phosphorous acid compound was added was shown. . Moreover, the hardened | cured material was produced, the external appearance of the hardened | cured material was observed, and non-coloring property was evaluated. The results are shown in Table 1.

尚、（Ｄ）成分として用いた亜リン酸系化合物は、
Ｐ−１：下記構造式を有するビス［２，４−ビス（１，１−ジメチルエチル）−６−メチルフェニル］エチルエステル亜リン酸、商品名「ＩＲＧＦＯＳ ３８」分子量５１４（チバ・スペシャルティ・ケミカルズ株式会社製）

The phosphorous acid compound used as component (D) is:
P-1: Bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid having the following structural formula, trade name “IRGFOS 38” molecular weight 514 (Ciba Specialty Chemicals) (Made by Co., Ltd.)

Ｐ−２：下記構造式を有する「ＩＲＧＦＯＳ １６８」分子量６４７（チバ・スペシャルティ・ケミカルズ株式会社製）

P-2: “IRGFOS 168” molecular weight 647 having the following structural formula (manufactured by Ciba Specialty Chemicals)

Ｐ−３：下記構造式を有する商品名「ＩＲＧＦＯＳ Ｐ−ＥＰＱ」分子量９９１（チバ・スペシャルティ・ケミカルズ株式会社製）

P-3: Trade name “IRGFOS P-EPQ” molecular weight 991 having the following structural formula (manufactured by Ciba Specialty Chemicals)

Ｐ−４：下記構造式を有する商品名「アデカ スタブ ＨＰ−１０」分子量５８３（旭電化工業株式会社製）

P-4: Trade name “Adeka Stub HP-10” molecular weight 583 having the following structural formula (manufactured by Asahi Denka Kogyo Co., Ltd.)

Ｐ−５：下記構造式を有する商品名「ＩＲＧＦＯＳ １２」分子量１４６３（チバ・スペシャルティ・ケミカルズ株式会社製）

P-5: Trade name “IRGFOS 12” having the following structural formula, molecular weight 1463 (manufactured by Ciba Specialty Chemicals Co., Ltd.)

である。

It is.

  From the results of Table 1 above, when the component (D) of the present invention is used, a curable composition capable of improving the coloring of the cured product without substantial decrease in curable properties is obtained. With other phosphorous acid compounds, it is difficult to maintain both curability and improve coloring of the cured product.

  If the curable composition of this invention is used, the hardened | cured material with which non-coloring property was improved will be obtained, without being accompanied by substantial sclerosis | hardenability fall.

Claims (4)

Organic compound (A) containing at least two carbon-carbon double bonds reactive with SiH group in one molecule, compound (B) containing at least two SiH groups in one molecule, hydrosilylation catalyst (C) and general formula (VII)

(In the formula, R ⁸ is a monovalent organic group having 1 to 5 carbon atoms.) A phosphite compound (D) represented by the following formula is contained as an essential component.   The curable composition according to claim 1, wherein the component (D) is bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid. In the component (A) and / or (B), the following formula

The curable composition of Claim 1 or 2 characterized by including the compound containing the isocyanuric ring skeleton represented by these.   Hardened | cured material formed by hardening | curing the curable composition as described in any one of Claims 1-3.