JP4504077B2 - Method for producing curable composition - Google Patents

Description

  The present invention relates to a method for producing a curable composition, and more particularly to a method for producing a curable composition having an appropriate fluidity and good moldability.

Conventionally, a composition having a polysiloxane skeleton is well known as a curable composition utilizing a hydrosilylation reaction as a curing reaction. Recently, in order to expand the technical scope of application, a curing system using an organic compound composed of an organic skeleton instead of polysiloxane as a component containing a carbon-carbon double bond has been proposed. When the organic compound and the low molecular weight compound are used, the viscosity of the curable composition is 1 poise or less, so that the moldability such as press molding and cast molding is not always good. A curable composition in which a part of the reactive carbon-carbon double bond and a part of the SiH group of the component (B) are reacted by a hydrosilylation reaction and the viscosity is in the range of 20-120 poise is the above moldability. It is disclosed that this problem can be solved. Further, it is also disclosed that an inorganic filler is added to the composition as required. However, when the inorganic filler is added, one of the carbon-carbon double bonds having reactivity with the SiH group of the component (A) is disclosed. There is no disclosure regarding a specific embodiment in which a part and a part of the SiH group of the component (B) are subjected to a hydrosilylation reaction.
JP 55-778055 A JP 2003-73552 A

  Accordingly, an object of the present invention is to provide a method for producing a curable composition containing a filler having good moldability and fluidity at a temperature of 150 ° C. or lower.

  In order to solve such a problem, the present inventors have conducted intensive research, and as a result, (A) an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups, (B) 1 A compound containing at least two SiH groups in the molecule, (C) a hydrosilylation catalyst, and (D) an inorganic filler as essential components is prepared, and reacted with SiH groups of component (A) in the mixture The carbon-carbon double bond having the property and the SiH group of (B) are reacted in the range of 10-60% in theory while maintaining the temperature of the mixture not to be higher than the ambient temperature by 10 ° C. or more. As a result, a curable composition having fluidity was obtained even at a temperature of 150 ° C. or lower, and it was found that the above problems could be solved, leading to the present invention.

That is, the present invention
(A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, (B) a compound containing at least two SiH groups in one molecule, (C) A hydrosilylation catalyst, (D) a mixture containing an inorganic filler as an essential component is prepared, a carbon-carbon double bond having reactivity with the SiH group of component (A) in the mixture, and the SiH group of (B) Is obtained by the reaction in the range of 10-60% of the theory while maintaining the temperature of the mixture not to be higher than the ambient temperature by more than 10 ° C, and has a fluidity at a temperature of 150 ° C or less. A method for producing a composition (claim 1),
The inorganic filler as component (D) is titanium oxide and / or silica, and the production method according to claim 2 (claim 2),
The thickness of the mixture is maintained at 3 mm or less when the reactive carbon-carbon double bond having reactivity with the SiH group of component (A) and the SiH group of (B) are reacted. Or it is the manufacturing method of Claim 2 (Claim 3).

  The production method of the present invention can provide a curable composition having appropriate fluidity, that is, moldability and good curability.

Hereinafter, the present invention will be described in detail.
((A) component)
First, the component (A) in 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.
(Skeleton of component (A))
Organic compounds do not contain siloxane units (Si-O-Si), such as polysiloxane-organic block copolymers and polysiloxane-organic graft copolymers, and elements other than C, H, N, O, S and halogen A compound containing no element is more preferable. Those containing siloxane units have gas permeability and repelling problems.

The organic compound (A) can be classified into an organic polymer compound and an organic monomer compound.
(Example when component (A) is a polymer)
As the component (A) of the organic polymer system, for example, polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, unsaturated hydrocarbon-based, polyacrylate ester-based, polyamide-based, phenol-formaldehyde Examples thereof include those having a skeleton of a system (phenolic resin system) or a polyimide system.

  Among these, examples of the polyether polymer include polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and the like. More specific examples:

（式中、Ｒ¹、Ｒ²は構成元素としてＣ、Ｈ、Ｎ、Ｏ、Ｓ、ハロゲン以外の元素を含まない炭素数１〜６の２価の有機基、ｎ、ｍ、ｌは１〜３００の数を表す。）
等が挙げられる。

(In the formula, R ¹ and R ² are C 1 -C 6 divalent organic groups containing no elements other than C, H, N, O, S and halogen as constituent elements, n, m, and l are 1 to 1; Represents a number of 300.)
Etc.

  Examples of other polymers include dibasic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydrophthalic acid, and glycols such as ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, and neopentyl glycol. Polyester polymers obtained by condensation or ring-opening polymerization of lactones, ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene and butadiene, acrylonitrile, styrene Copolymer, polybutadiene, butadiene and styrene, acrylonitrile, etc., polyisoprene, polybutadiene, isoprene or butadiene and acrylonitrile, styrene, etc. Polyolefins obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate, and acrylic acid esters such as ethyl acrylate and butyl acrylate, and acetic acid. Acrylate ester copolymer with vinyl, acrylonitrile, methyl methacrylate, styrene, etc., graft polymer obtained by polymerizing vinyl monomer in the organic polymer, polysulfide polymer, ring-opening polymerization of ε-aminocaprolactam Nylon 6, Nylon 66 by polycondensation of hexamethylenediamine and adipic acid, Nylon 610 by polycondensation of hexamethylenediamine and sebacic acid, Nylon 11 by polycondensation of ε-aminoundecanoic acid, ε-aminolaurolactam Nylon 12 by ring-opening polymerization, a polyamide polymer such as copolymer nylon having two or more components among the above nylons, for example, a polycarbonate polymer produced by polycondensation from bisphenol A and carbonyl chloride, Examples of the diallyl phthalate polymer and the phenol-formaldehyde (phenolic resin) skeleton include novolac type phenolic resin, resol type phenolic resin, ammonia resol type phenolic resin, and benzylic ether type phenolic resin.

  An alkenyl group having a carbon-carbon double bond can be introduced into these polymer skeletons to obtain the component (A).

  In this case, the alkenyl group having a carbon-carbon double bond may be present anywhere in the molecule, but is preferably present in the side chain or the terminal in terms of reactivity.

  Various methods for introducing an alkenyl group into the polymer skeleton can be used. However, the method can be roughly divided into a method for introducing an alkenyl group after polymerization and a method for introducing an alkenyl group during polymerization. Can do.

As a method for introducing an alkenyl group after polymerization, for example, an organic polymer having a functional group such as a hydroxyl group, an alkoxide group, a carboxyl group, or an epoxy group at the terminal, main chain, or side chain is reactive with the functional group. An alkenyl group can be introduced into the terminal, main chain or side chain by reacting an organic compound having both an active group and an alkenyl group. Examples of organic compounds having both an active group and an alkenyl group that are reactive with the functional group include C3-C20 unsaturated compounds such as acrylic acid, methacrylic acid, vinyl acetic acid, acrylic acid chloride, and acrylic acid bromide. fatty acids, acid halides, acid anhydrides or allyl chloroformate _{(CH 2 = CHCH 2 OCOCl)} , allyl bromo formate (CH ₂ = CHCH ₂ OCOBr) unsaturated aliphatic alcohol-substituted carbonic halide C3~C20 such, Allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1 -Hexenyl (chloromethoxy) benzene, Riruokishi (chloromethyl) benzene, allyl isocyanate.

  There is also a method of introducing an alkenyl group using a transesterification method. This method is a method of transesterifying an alcohol residue of an ester portion of a polyester resin or an acrylic resin with an alkenyl group-containing alcohol or an alkenyl group-containing phenol derivative using a transesterification catalyst. The alkenyl group-containing alcohol and alkenyl group-containing phenol derivative used for exchange with an alcohol residue may be any alcohol or phenol derivative having at least one alkenyl group and having at least one hydroxyl group. It is preferable to have it. A catalyst may or may not be used, but a titanium-based catalyst and a tin-based catalyst are preferable.

  Examples of the above compounds are vinyl alcohol, allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, and 7-octene-1. -Ol, 8-nonen-1-ol, 9-decen-1-ol, 2- (allyloxy) ethanol, neopentyl glycol monoallyl ether, glyceryl diallyl ether, trimethylolpropane triallyl ether, trimethylolethane triallyl ether , Pentaerythritol tetraallyl ether, 1,2,6-hexanetriol triallyl ether, sorbitan triallyl ether,

などが挙げあれる。この中でも、入手の容易さから、アリルアルコール、ビニルアルコール、３−ブテン−１−オール、２−（アリルオキシ）エタノール、および

And so on. Among these, allyl alcohol, vinyl alcohol, 3-buten-1-ol, 2- (allyloxy) ethanol, and

が好ましい。

Is preferred.

  Furthermore, the ester residue of the above-mentioned alcohol or phenol derivative such as acetate ester and the ester part of the polyester resin or acrylic resin are transesterified using a transesterification catalyst, and the alcohol residue of the ester part of the produced polyester resin or acrylic resin There is also a method of introducing an alkenyl group by a method of distilling low molecular weight esterified products such as acetates out of the system by vacuum devolatilization or the like.

  Moreover, after polymerizing methyl (meth) acrylate etc. by living polymerization, an alkenyl group can also be introduce | transduced into the terminal by the method of stopping a living terminal with the compound which has an alkenyl group.

  As a method for introducing an alkenyl group during the polymerization, for example, in the case of producing the organic polymer skeleton of the component (A) used in the present invention by radical polymerization, radical reactivity in the molecule of allyl methacrylate, allyl acrylate, etc. By using a vinyl monomer having a low alkenyl group or a radical chain transfer agent having a low alkenyl group such as allyl mercaptan, an alkenyl group can be introduced into the side chain or terminal of the organic polymer skeleton. .

As the component (A), the molecular weight is not particularly limited, but any of 100 to 100,000 can be suitably used, and an alkenyl group-containing organic polymer is particularly preferably 500 to 20,000. When the molecular weight is 500 or less, characteristics due to the use of an organic polymer such as imparting flexibility are hardly exhibited, and when the molecular weight is 100,000 or more, the effect of crosslinking due to the reaction between the alkenyl group and the SiH group is hardly exhibited.
(Example when component (A) is a monomer)
Examples of the organic monomer-based component (A) include, for example, aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as linear and alicyclic: heterocyclic compounds And mixtures thereof.
(Carbon-carbon double bond of component (A))
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.

  (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), the following general formula (II)

（式中Ｒ²は水素原子あるいはメチル基を表す。）で示される脂環式の基が、硬化物の耐熱性が高いという点から好適である。また、原料の入手の容易さからは、

An alicyclic group represented by the formula (wherein R ² represents a hydrogen atom or a methyl group) is preferred from the viewpoint that the heat resistance of the cured product is high. In addition, from the availability of raw materials,

示される脂環式の基が特に好ましい。
（（Ａ）成分の炭素−炭素二重結合と骨格の結合基）
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、およびハロゲン以外の元素を含まないものが好ましい。これらの置換基の例としては、

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

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

Is mentioned. 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。
（（Ａ）成分の具体例）
有機重合体系の（Ａ）成分の具体的な例としては、１，２−ポリブタジエン（１、２比率１０〜１００％のもの、好ましくは１、２比率５０〜１００％のもの）、ノボラックフェノールのアリルエーテル、アリル化ポリフェニレンオキサイド、

Is mentioned.
(Specific examples of component (A))
Specific examples of the component (A) of the organic polymer system include 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio of 50 to 100%), novolak phenol Allyl ether, allylated polyphenylene oxide,

（式中、Ｒ¹はＨまたはＣＨ₃、Ｒ²、Ｒ³は構成元素としてＣ、Ｈ、Ｎ、Ｏ、Ｓ、ハロゲン以外の元素を含まない炭素数１〜６の２価の有機基、Ｘ、Ｙは炭素数０〜１０の２価の置換基、ｎ、ｍ、ｌは１〜３００の数を表す。）

(In the formula, R ¹ is H or CH ₃ , R ² , R ³ is a C 1 -C 6 divalent organic group containing no elements other than C, H, N, O, S and halogen as constituent elements, X and Y are divalent substituents having 0 to 10 carbon atoms, and n, m, and l are numbers 1 to 300.)

（式中、Ｒ¹はＨまたはＣＨ₃、Ｒ⁴、Ｒ⁵は炭素数１〜６の２価の有機基、Ｘ、Ｙは炭素数０〜１０の２価の置換基、ｎ、ｍ、ｌは１〜３００の数を表す。）

(Wherein R ¹ is H or CH ₃ , R ⁴ , R ⁵ is a divalent organic group having 1 to 6 carbon atoms, X and Y are divalent substituents having 0 to 10 carbon atoms, n, m, l represents a number from 1 to 300.)

（式中、Ｒ¹はＨまたはＣＨ₃、Ｒ⁶、Ｒ⁷は炭素数１〜２０の２価の有機基、Ｘ、Ｙは炭素数０〜１０の２価の置換基、ｎ、ｍ、ｌは１〜３００の数を表す。）

(Wherein R ¹ is H or CH ₃ , R ⁶ , R ⁷ is a divalent organic group having 1 to 20 carbon atoms, X and Y are divalent substituents having 0 to 10 carbon atoms, n, m, l represents a number from 1 to 300.)

（式中、Ｒ¹はＨまたはＣＨ₃、Ｒ⁸、Ｒ⁹は炭素数１〜６の２価の有機基、Ｘ、Ｙは炭素数０〜１０の２価の置換基、ｎ、ｍ、ｌは１〜３００の数を表す。）

(Wherein R ¹ is H or CH ₃ , R ⁸ , R ⁹ is a divalent organic group having 1 to 6 carbon atoms, X and Y are divalent substituents having 0 to 10 carbon atoms, n, m, l represents a number from 1 to 300.)

（式中、Ｒ¹はＨまたはＣＨ₃、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²は炭素数１〜６の２価の有機基、Ｘ、Ｙは炭素数０〜１０の２価の置換基、ｎ、ｍ、ｌ、ｐは１〜３００の数を表す。）
等が挙げられる。

Wherein R ¹ is H or CH ₃ , R ¹⁰ , R ¹¹ , R ¹² is a divalent organic group having 1 to 6 carbon atoms, X and Y are divalent substituents having 0 to 10 carbon atoms, n , M, l, and p represent numbers from 1 to 300.)
Etc.

  Specific examples of the organic monomer type (A) component include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2 , -Tetraallyloxyethane, diarylidenepentaerythritol, triallyl cyanurate, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (having a purity of 50 to 100%, preferably a purity of 80 ˜100%), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof,

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.
(Preferred requirements for component (A))
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.

  The component (A) preferably has a molecular weight of less than 900, preferably less than 700, from the viewpoint of high mechanical heat resistance and from the viewpoint of low formability of the raw material liquid and good moldability and handleability. More preferably, those less than 500 are more preferable.

  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. The viscosity can be measured with an E-type viscometer.

  As the component (A), those having a low content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group are preferable from the viewpoint of higher light resistance. A phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group is preferable. What does not contain the compound which has 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.

  Further, from the viewpoint of particularly good light resistance, the weight ratio of the component (A) in the aromatic ring is preferably 50% by weight or less, more preferably 40% by weight or less, and more preferably 30% by weight. The following are more preferable. Most preferred are those that do not contain an aromatic hydrocarbon ring.

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.
(Preferred structure 1 of component (A))
As the component (A), from the viewpoint of particularly high heat resistance and light resistance, the following general formula (III)

（式中Ｒ¹は炭素数１〜５０の一価の有機基を表し、それぞれのＲ¹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 ¹ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same).

As R < ¹ > 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 ¹ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

等が挙げられる。

Etc.

As R ¹ of the general formula (III), from the viewpoint that the adhesiveness of the curable composition obtained in the present invention can be improved, or the mechanical strength of the obtained cured product can be increased, 3 R it is preferred that at least one of the ^one is a monovalent organic group having 1 to 50 carbon atoms containing one or more epoxy groups,

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Ｒ¹の例としては、グリシジル基、

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

等が挙げられる。

Etc.

R ^{1 in the} general formula (III) is a carbon containing two or less oxygen atoms and containing only C, H, and O as constituent elements from the viewpoint that the heat resistance of the resulting cured product can be improved. A monovalent organic group having 1 to 50 carbon atoms is preferable, and a monovalent hydrocarbon group having 1 to 50 carbon atoms is more preferable. Examples of these preferable R ¹ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

等が挙げられる。

Etc.

R ^{1 in the} general formula (III) is at least one of three R ¹ from the viewpoint of good reactivity.

で表される基を１個以上含む炭素数１〜５０の一価の有機基であることが好ましく、下記一般式（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Ｒ²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Ｒ¹のうち少なくとも２つが下記一般式（Ｖ）

(Wherein R ² represents a hydrogen atom or a methyl group) 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 ¹ are represented by the following general formula (V)

（式中Ｒ³は直接結合あるいは炭素数１〜４８の二価の有機基を表し、Ｒ⁴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Ｒ³およびＲ⁴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 ³ represents a direct bond or a divalent organic group having 1 to 48 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group) (a plurality of R ³ and R ⁴ are More preferably, they may be the same or different.

R ^{3 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 resulting package can be further increased, the direct bond or the carbon number It is preferably a divalent organic group having 1 to 20, 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. Examples of these preferred R ³ include

等が挙げられる。

Etc.

As R ^{3 in the} general formula (V), from the viewpoint that the heat resistance of the resulting package can be improved, only C, H, or O is included as a constituent element including a direct bond or two or less oxygen atoms. A divalent organic group having 1 to 48 carbon atoms is preferable, and a direct bond or a divalent hydrocarbon group having 1 to 48 carbon atoms is more preferable. Examples of these preferred R ³ include

が挙げられる。

Is mentioned.

R ^{4 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。
（（Ａ）成分の好ましい構造２）
また、（Ｂ）成分と良好な相溶性を有するという観点、および（Ａ）成分の揮発性が低くなり、本発明で得られる硬化性組成物から発生するアウトガスが低減するため、得られる成形体にボイドなどが生じ難いという観点からは、（Ａ）成分の例として上記したような、ＳｉＨ基と反応性を有する炭素−炭素二重結合を１分子中に少なくとも２個含有する有機化合物から選ばれた１種以上の化合物と、ＳｉＨ基を有する鎖状及び／又は環状オルガノポリシロキサン（β）との反応物も好ましい。
（（β）成分）
（β）成分は、ＳｉＨ基を有する鎖状及び／又は環状のポリオルガノシロキサンである。

Etc.
(Preferred structure 2 of component (A))
Further, from the viewpoint of having good compatibility with the component (B), and because the volatility of the component (A) is reduced and the outgas generated from the curable composition obtained in the present invention is reduced, the resulting molded product is obtained. From the viewpoint that voids and the like are not easily generated, an organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group as described above as an example of the component (A) is selected. A reaction product of the one or more kinds of compounds and a linear and / or cyclic organopolysiloxane (β) having a SiH group is also preferable.
((Β) component)
The (β) component is a linear and / or cyclic polyorganosiloxane having a SiH group.

  Specifically, for example

が挙げられる。

Is mentioned.

  Here, from the viewpoint that compatibility with an organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule is likely to be improved, the following general formula (VI)

（式中、Ｒ¹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 ¹ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10). Cyclic polyorganosiloxane having at least three SiH groups in one molecule. Is preferred.

The substituent R ¹ in the compound represented by the general formula (VI) preferably does not contain a constituent element other than 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 an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH group in one molecule and (β) component)
Next, as component (A) of the present invention, an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule and (β) component are obtained by hydrosilylation reaction. The hydrosilylation reaction between an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule and the (β) component in the case of using a compound capable of reacting with SiH will be described.

  A hydrosilylation reaction of an organic compound containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule and the (β) component results in a plurality of compounds containing the component (A) of the present invention. However, the curable composition of the present invention can be prepared by using the mixture as it is without separating the component (A).

  Carbon-carbon double having reactivity with SiH group when hydrosilylation reaction of organic compound containing at least two carbon-carbon double bonds reactive with SiH group in one molecule and (β) component The mixing ratio of the organic compound containing at least two bonds in one molecule and the (β) component is not particularly limited, but generally is reactive with the SiH group to be mixed in that gelation during the reaction can be suppressed. In the (β) component to be mixed with the total number (X) of carbon-carbon double bonds having reactivity with SiH groups in an organic compound containing at least two carbon-carbon double bonds in one molecule The ratio of the total number of SiH groups (Y) is preferably X / Y ≧ 2, more preferably X / Y ≧ 3. Moreover, it is preferable that it is 10> = X / Y from the point that compatibility with (B) component of (A) component becomes easy, and it is more preferable that it is 5> = X / Y.

In the case of hydrosilylation reaction of an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH group in one molecule and the (β) component, 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 _{(e.g., Pt (ViMe 2 SiOSiMe 2 Vi} ) n, Pt [(MeViSiO) 4] _m ), platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phosphite complexes (eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄₎ (in the formula, Me represents a methyl group, Bu a butyl group, Vi is vinyl group, Ph represents a phenyl group, n, m is an integer.), dicarbonyl dichloroplatinum, Karushuteto Karstedt catalyst, as well as the platinum-hydrocarbon complexes described in Ashby US Pat. Nos. 3,159,601 and 3,159,622, and Lamoreaux, US Pat. No. 3,220,972. And platinum alcoholate catalysts. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

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

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

The addition amount of the catalyst is not particularly limited, but the lower limit of the preferred addition amount is sufficient with respect to 1 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 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, amine compounds such as triethylamine, and the like. 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 as a method of mixing the organic compound containing at least two carbon-carbon double bonds reactive with the SiH group in the case of reaction, the (β) component, and the catalyst. However, a method in which a catalyst is mixed with an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule and (β) component is mixed. If the catalyst is mixed with a mixture of an organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule and the (β) component, it is difficult to control the reaction. In the case of adopting a method of mixing an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups into a mixture of component (β) and a catalyst, in the presence of the catalyst ( Since β) is reactive with moisture mixed therein, it may be altered.

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

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

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

  In addition, various additives may be used for the purpose of controlling reactivity.

  After reacting (β) component with an organic compound containing at least two carbon-carbon double bonds reactive with SiH group in one molecule, it has reactivity with solvent and / or unreacted SiH group Organic compounds containing at least two carbon-carbon double bonds per molecule and / or (β) component can also be removed. By removing these volatile components, the obtained component (A) does not have a volatile component, so that in the case of curing with the component (B), problems of voids and cracks due to the volatilization of the volatile components are less likely to occur. 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 60 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

Examples of the component (A) which is a reaction product of the organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule and the component (β) are bisphenol. A reaction product of diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of vinylcyclohexene and 1,3,5,7-tetramethylcyclotetrasiloxane, divinylbenzene and 1,3,5, Reaction product of 7-tetramethylcyclotetrasiloxane, reaction product of dicyclopentadiene and 1,3,5,7-tetramethylcyclotetrasiloxane, triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane Reaction of diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane Applied Physics, etc. can be mentioned.
(Other reactive groups of component (A))
(A) As a component, you may have another reactive group. Examples of the reactive group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When it has these functional groups, the adhesiveness of the resulting curable composition tends to be high, and the strength of the resulting cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the obtained cured product tends to be high.
(Mixing of component (A))
(A) component can be used individually or in mixture of 2 or more types.
(B component)
Next, the compound which has SiH group which is (B) component is demonstrated.

  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, the compound described in International Publication WO 96/15194 is 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、Ｒ¹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 ¹ 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 ¹ 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, but a low molecular weight is preferably used from the viewpoint of easier expression of fluidity. In this case, the lower limit of the preferred molecular weight is 50, and the upper limit of the preferred molecular weight is 100,000, more preferably 1,000, and still more preferably 700.

Component (B) can be used alone or in combination of two or more.
(Preferred structure of component (B))
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.
((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 component (α2), the following general formula (II)

（式中Ｒ²は水素原子あるいはメチル基を表す。）で示される脂環式の基が、硬化物の耐熱性が高いという点から好適である。また、原料の入手の容易さからは、

An alicyclic group represented by the formula (wherein R ² represents a hydrogen atom or a methyl group) is preferred from the viewpoint that the heat resistance of the cured product is high. In addition, from the availability of raw materials,

示される脂環式の基が特に好ましい。

The alicyclic groups shown are particularly preferred.

  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 of the (α2) component 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.

  In the case where the glass transition temperature of the component (α2) is present, there is no particular limitation on this, and various materials are used. However, the glass point transfer temperature is 100 ° C. or lower in that the obtained cured product tends to be tough. Preferably, it is 50 ° C. or lower, and 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 component (α2) is preferably a 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 include monoallyl diglycidyl isocyanurate, allyl glycidyl ether, allyloxyethyl methacrylate, allyloxyethyl acrylate, vinyltrimethoxysilane, and the like.

As the above (α1) component and / or (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 (V)

（式中、Ｒ¹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 ¹ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10). Cyclic polyorganosiloxane having at least three SiH groups in one molecule. Is preferred.

The substituent R ¹ in the compound represented by the general formula (V) 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 be prepared 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, 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 _{(e.g., Pt (ViMe 2 SiOSiMe 2 Vi} ) n, Pt [(MeViSiO) 4] _m ), platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phosphite complexes (eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄₎ (in the formula, Me represents a methyl group, Bu a butyl group, Vi is vinyl group, Ph represents a phenyl group, n, m is an integer.), dicarbonyl dichloroplatinum, Karushuteto Karstedt catalyst, as well as the platinum-hydrocarbon complexes described in Ashby US Pat. Nos. 3,159,601 and 3,159,622, and Lamoreaux, US Pat. No. 3,220,972. And platinum alcoholate catalysts. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

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

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

The addition amount of the catalyst is not particularly limited, but the lower limit of the preferred addition amount is sufficient with respect to 1 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 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, amine compounds such as triethylamine, and the like. 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 to mix the (α) component, (β) component, and catalyst in the reaction, but the (α) component mixed with the catalyst is mixed with the (β) component. Is preferred. If the catalyst is mixed with the mixture of the (α) component and the (β) component, it is difficult to control the reaction. 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. .

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

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

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

  In addition, various additives may be used for the purpose of controlling reactivity.

  After reacting the (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 60 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

Examples of the component (B) that is a reaction product of the component (α) and the component (β) as described above include a reaction product of bisphenol A diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, Reaction product of vinylcyclohexene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane, dicyclopentadiene and 1,3,5, Reaction product of 7-tetramethylcyclotetrasiloxane, reaction product of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylcyclo Reactant of tetrasiloxane, allyl glycidyl ether and 1,3,5,7-tetramethylcyclotetrasilo A reaction product of xane, a reaction product of α-methylstyrene and 1,3,5,7-tetramethylcyclotetrasiloxane, a reaction product of monoallyldiglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, Etc.
(Mixing of component (A) and component (B))
Regarding combinations of component (A) and component (B), various combinations of those listed as examples of component (A) and their various mixtures / examples of component (B) and their various mixtures are listed. be able to.

The mixing ratio of the component (A) and the component (B) is not particularly limited as long as the necessary strength is not lost, but the number of SiH groups in the component (B) (Y) is the carbon-carbon in the component (A). In the ratio to the number of double bonds (X), the lower limit of the preferred range is Y / X ≧ 0.3, more preferably Y / X ≧ 0.5, and even more preferably Y / X ≧ 0.7, which is preferable. The upper limit of the range is 3 ≧ Y / X, more preferably 2 ≧ Y / X, and even more preferably 1.5 ≧ Y / X. When it deviates from the preferred range, sufficient strength may not be obtained or thermal deterioration may easily occur.
((C) component)
Next, the hydrosilylation catalyst as component (C) will be described.

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

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

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

Although the addition amount of the catalyst is not particularly limited, the lower limit of the preferable addition amount is sufficient with respect to 1 mol of SiH groups of the component (B) in order to have sufficient curability and keep the cost of the curable composition relatively low. 10 ^-8 mol, more preferably 10 ^-6 mole, preferable amount of the upper limit 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 simple sulfur, amine compounds such as triethylamine, and the like. 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.
((D) component)
The component (D) of the present invention is an inorganic filler.

  Various inorganic fillers are used. For example, silica-based inorganic fillers such as quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, and ultrafine powder amorphous silica, alumina, zircon , Titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, alumina fiber, carbon fiber, mica, graphite, carbon black, graphite, diatomaceous earth, white clay, clay, talc, aluminum hydroxide, calcium carbonate, Inorganic fillers generally used and / or proposed as fillers for conventional sealing materials such as epoxy-based materials, including inorganic fillers such as magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloons, silver powder, etc. Etc. The inorganic filler is preferably low radiation from the viewpoint of hardly damaging the semiconductor element.

  The inorganic filler may be appropriately surface treated. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a coupling agent, and the like.

  Examples of the coupling agent in this case include 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.

  In addition, the method of adding an inorganic filler is mentioned. For example, a hydrolyzable silane monomer or oligomer such as alkoxysilane, acyloxysilane, or halogenated silane, or an alkoxide, acyloxide, or halide of a metal such as titanium or aluminum is added to the curable composition obtained in the present invention. In addition, a method of reacting in the composition or a partial reaction product of the composition to form an inorganic filler in the composition can also be mentioned.

  Of the inorganic fillers as described above, a silica-based inorganic filler is preferable from the viewpoint that it is difficult to inhibit the curing reaction, has a large effect of reducing the linear expansion coefficient, and tends to have high adhesion to other inorganic materials. Furthermore, fused silica is preferable in terms of a good balance of physical properties such as moldability and electrical characteristics, and crystalline silica is preferable in terms of high thermal conductivity and high heat dissipation. Alumina is preferable in that heat dissipation tends to be higher. In addition, titanium oxide is preferable in that the reflectance of light tends to be high. In addition, glass fiber, potassium titanate, and calcium silicate are preferable in terms of high reinforcing effect and high strength.

  As the average particle size and particle size distribution of the inorganic filler, various types are used without particular limitation, including those used or / and proposed as fillers for conventional sealing materials such as epoxy-based materials. The lower limit of the average particle size used is 0.1 μm, preferably 0.5 μm from the viewpoint that the fluidity tends to be good, and the upper limit of the average particle size usually used is 120 μm, the fluidity tends to be good. To preferably 60 μm, more preferably 15 μm.

  The specific surface area of the inorganic filler can also be variously set, including those used and / or proposed as fillers for conventional sealing materials such as epoxy-based fillers.

  As the shape of the inorganic filler, various types such as a crushed shape, a piece shape, a spherical shape, and a rod shape are used. Various aspect ratios are used. The aspect ratio of 10 or more is preferable in that the strength of the obtained cured product tends to increase. From the viewpoint of isotropic shrinkage of the resin, a powder form is preferable to a fiber form. Or the spherical thing is preferable at the point that the fluidity | liquidity at the time of shaping | molding becomes easy also at the time of high filling.

  These inorganic fillers may be used alone or in combination of two or more.

  The addition amount of the inorganic filler is not particularly limited, but from the viewpoint that the effect of reducing the linear expansion coefficient is high and the fluidity of the composition at the time of molding is good, the preferred lower limit of the addition amount is in the total composition It is 30% by weight, more preferably 50% by weight, still more preferably 75% by weight, and the upper limit of the preferable addition amount is 95% by weight in the total composition, more preferably 85% by weight.

  As the order of mixing the inorganic filler, various methods can be used. However, in the point that the storage stability of the intermediate raw material of the composition is likely to be good, the component (A) is combined with the component (C) and the inorganic filler. A method of mixing the mixture and the component (B) is preferable. When the method of mixing the component (A) into the component (B) mixed with the component (C) or / and the inorganic filler, the component (B) is added in the presence or absence of the component (C). Since it has reactivity with moisture or / and inorganic fillers in the environment, it may be altered during storage. In addition, (A) component, (B) component, (C) in that (A) component, (B) component, and (C) component which are reaction components are well mixed and a stable molded product is easily obtained. It is preferable to mix an inorganic filler with a mixture of components.

As means for mixing these inorganic fillers, various means conventionally used for epoxy resins or / and proposed can be used. Examples thereof include a two-roll or three-roll, a planetary stirring and deaerator, a stirrer such as a homogenizer, a dissolver, and a planetary mixer, and a melt kneader such as a plast mill. Of these, a three-roller and a melt kneader are preferred in that sufficient dispersibility of the inorganic filler is easily obtained even with high filling. The mixing of the inorganic filler may be performed at normal temperature or may be performed by heating. Moreover, you may carry out under a normal pressure and may carry out in a pressure-reduced state. In view that sufficient dispersibility of the inorganic filler is easily obtained even at high filling, it is preferable to mix in a heated state, and it is easy to obtain sufficient dispersibility by improving the wettability of the inorganic filler surface. Is preferably mixed under reduced pressure.
(Additive)
(Curing retarder)
In the curable composition obtained in the present invention, a curing retarder can be used for the purpose of improving the storage stability or adjusting the reactivity of the hydrosilylation reaction during the production process. 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 the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine 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 curable composition obtained in 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.

  Examples of coupling agents include silane coupling agents and titanate coupling agents.

  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 / or hydrolyzable silicon group in the molecule. The group reactive with the organic group includes 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, a carbamate group, and a ureido group from the viewpoint of handleability. From the viewpoint of curability 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) silanes having an epoxy functional group such as ethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltri Silica having methacrylic group or acrylic group such as ethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane , Vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane and other silanes having a vinyl group, γ-mercaptopropyltrimethoxysilane, γ-mercapto Mercaptosilanes such as propylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxy Silane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, N-β- (N-vinylbenzylamino) Til) -γ-aminopropyltrimethoxysilane and other silanes having an amino group, methyltrimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, dimethyldimethoxysilane, Examples thereof include silanes such as dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane.

  Titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2 , 2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate , Isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate DOO, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate.

  The addition amount of the coupling agent can be variously set, but the lower limit of the preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] is 0.1 parts by weight, more preferably 0.5 parts 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.

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

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

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

  In the present invention, a silanol condensation catalyst can be further used to enhance the effect of the coupling agent or the epoxy compound, and the adhesion can be improved and / or stabilized. Such a silanol condensation catalyst is not particularly limited, but is preferably a boron compound or / and an aluminum compound or / and a titanium compound. Examples of the aluminum compound used as a silanol condensation catalyst 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 as silanol condensation catalysts 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.

  Examples of the boron compound that serves as a silanol condensation catalyst include boric acid esters. As the borate ester, those represented by the following general formulas (VII) and (VIII) can be preferably used.

（式中Ｒ¹は炭素数１〜４８の有機基を表す。）
ほう酸エステルの具体例として、ほう酸トリ−２−エチルヘキシル、ほう酸ノルマルトリオクタデシル、ほう酸トリノルマルオクチル、ほう酸トリフェニル、トリメチレンボレート、トリス（トリメチルシリル）ボレート、ほう酸トリノルマルブチル、ほう酸トリ−ｓｅｃ−ブチル、ほう酸トリ−ｔｅｒｔ−ブチル、ほう酸トリイソプロピル、ほう酸トリノルマルプロピル、ほう酸トリアリル、ほう酸トリエチル、ほう酸トリメチル、ほう素メトキシエトキサイドを好適に用いることができる。

(In the formula, R ¹ represents an organic group having 1 to 48 carbon atoms.)
Specific examples of boric acid esters include tri-2-ethylhexyl borate, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, trinormal butyl borate, tri-sec-butyl borate, Tri-tert-butyl borate, triisopropyl borate, trinormalpropyl borate, triallyl borate, triethyl borate, trimethyl borate, and boron methoxyethoxide can be preferably used.

  These borate 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 borate 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 practicality.

  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.

  The amount used in the case of using a silanol condensation catalyst 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 / and 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.

  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 preferable addition amount with respect to 100 parts by weight of the coupling agent and / or 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 addition amount with respect to 100 parts by weight of the coupling agent or / and epoxy compound epoxy compound is 0.1 parts by weight, More preferably, it is 1 part by weight, and the upper limit of the preferable addition amount is 50 parts by weight, more preferably 10 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

Moreover, these carboxylic acids or / and acid anhydrides may be used alone or in combination of two or more.
(Thermosetting resin)
Various thermosetting resins can be added to the curable composition obtained in the present invention for the purpose of modifying the properties. Examples of the thermosetting resin include, but are not limited to, epoxy resins, cyanate ester resins, phenol resins, polyimide resins, urethane resins, bismaleimide resins, and the like. Among these, an epoxy resin is preferable from the viewpoint of excellent practical properties such as adhesiveness.

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

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

  These thermosetting resins may be used alone or in combination.

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

When the thermosetting resin is used in a dispersed state, the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. There may be a distribution of the particle system, which may be monodispersed or have a plurality of peak particle diameters, but from the viewpoint that the viscosity of the curable composition is low and the moldability tends to be good. The coefficient of variation is preferably 10% or less.
(Thermoplastic resin)
Various thermoplastic resins can be added to the curable composition obtained in 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.
(Anti-aging agent)
You may add antioxidant to the curable composition obtained by this invention. Examples of the anti-aging agent include citric acid, phosphoric acid, sulfur-based anti-aging agent and the like in addition to the anti-aging agents generally used such as hindered phenol type.

  As the hindered phenol-based anti-aging agent, various types such as Irganox 1010 available from Ciba Specialty Chemicals are used.

  Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylates, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.

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

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

Moreover, these ultraviolet absorbers may be used independently and may be used together 2 or more types.
(Other additives)
In addition, the curable composition obtained in the present invention includes a colorant, a release agent, a flame retardant, a flame retardant aid, a surfactant, an antifoaming agent, an emulsifier, a leveling agent, a repellent, an antimony-bismuth, and the like. Ion trapping agent, thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, The purpose of the present invention is to provide a conductivity 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, a physical property modifier, and the like. It can add in the range which does not impair an effect.
(solvent)
The curable composition obtained in the present invention can be used by dissolving in a solvent. Solvents that can be used are not particularly limited. Specific examples include hydrocarbon solvents such as benzene, toluene, hexane, and heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, and the like. An ether solvent, a ketone solvent such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and a halogen solvent such as chloroform, methylene chloride, and 1,2-dichloroethane can be preferably used.

  As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable.

  Although the amount of solvent to be used can be set as appropriate, the lower limit of the 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.
(Release agent)
Various releasing agents may be added to the curable composition obtained in the present invention in order to improve the releasing property at the time of molding.

  Various conventionally used release agents are used. For example, metal soap, waxes and the like can be mentioned. The metal soap here is generally a combination of long-chain fatty acids and metal ions. The nonpolar or low polarity part based on the fatty acid and the polar part based on the metal binding part are combined in one molecule. Can be used. Examples of the long chain fatty acid include saturated fatty acids having 1 to 18 carbon atoms, unsaturated fatty acids having 3 to 18 carbon atoms, and aliphatic dicarboxylic acids. Among these, saturated fatty acids having 1 to 18 carbon atoms are preferable from the viewpoint of easy availability and high industrial feasibility, and 6 to 18 carbon atoms from the viewpoint of high effect of releasability. The saturated fatty acid is more preferable. Examples of metal ions include zinc, cobalt, aluminum, strontium, and the like in addition to alkali metals and alkaline earth metals. Specific examples of metal soaps include lithium stearate, lithium 12-hydroxystearate, lithium laurate, lithium oleate, lithium 2-ethylhexanoate, sodium stearate, sodium 12-hydroxystearate, lauric acid Sodium, sodium oleate, sodium 2-ethylhexanoate, potassium stearate, potassium 12-hydroxystearate, potassium laurate, potassium oleate, potassium 2-ethylhexanoate, magnesium stearate, magnesium 12-hydroxystearate, Magnesium laurate, magnesium oleate, magnesium 2-ethylhexanoate, calcium stearate, calcium 12-hydroxystearate, calcium laurate , Calcium oleate, calcium 2-ethylhexanoate, barium stearate, barium 12-hydroxystearate, barium laurate, zinc stearate, zinc 12-hydroxystearate, zinc laurate, zinc oleate, 2-ethylhexane Examples include zinc acid, lead stearate, lead 12-hydroxystearate, cobalt stearate, aluminum stearate, manganese oleate, barium ricinoleate, and the like. Among these metal soaps, metal stearates are preferred from the viewpoint of easy availability, safety and industrial feasibility, and calcium stearate, magnesium stearate, stearin are particularly preferred from the viewpoint of economy. Most preferred is one or more selected from the group consisting of zinc acid.

  Although there is no restriction | limiting in particular as addition amount of this metal soap, The minimum of a preferable amount is 0.025 with respect to 100 weight part of the whole composition, More preferably, it is 0.05 weight part, The upper limit of a preferable amount is a composition. The amount is 5 parts by weight, more preferably 4 parts by weight with respect to 100 parts by weight as a whole. When the addition amount is too large, the physical properties of the cured product are deteriorated. When the addition amount is too small, mold releasability may not be obtained.

  Examples of waxes include natural wax, synthetic wax, oxidized or non-oxidized polyolefin, and polyethylene wax.

In addition, it is better not to use a release agent when sufficient release properties can be obtained without adding a release agent.
(Method for producing curable composition)
First, (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, (B) a compound containing at least two SiH groups in one molecule, (C ) Prepare a hydrosilylation catalyst, (D) an essential component of the inorganic filler, and other components as necessary, and mix them uniformly by an appropriate method. There is no restriction | limiting in particular in the order of mixing. For mixing, hand mixing with a spatula, etc., various extruders such as rolls, kneaders, dissolvers, plast mills, single screw extruders, twin screw extruders, planetary stirring deaerators, etc. may be used as appropriate. . Next, the carbon-carbon double bond having reactivity with the SiH group of the component (A) in the mixture obtained by the above method and the SiH group of (B) are mixed at a temperature of 10 ° C. from the ambient temperature. A curable composition having fluidity at 150 ° C. is produced by a hydrosilylation reaction within a theoretical range of 10 to 60% while keeping it not higher. In this case, since the hydrosilylation reaction is an exothermic reaction, once the reaction starts, if the heat release is not sufficient, the temperature of the mixture rapidly rises due to self-heating, and the rapid curing progresses and the composition has fluidity. Can't get. Therefore, it is necessary to carry out the reaction while controlling the temperature of the mixture so as not to be higher by 10 ° C. than the ambient temperature. It is preferably controlled so as not to increase by 5 ° C., more preferably by 3 ° C., particularly preferably by 2 ° C. or more. The temperature of the mixture can be controlled by various methods. For example, you may use the apparatus which can stir so that this mixture may not become a thick state, such as a hot roll, a kneader, a plast mill, an extruder. Alternatively, it may be sandwiched between a press machine or two plates and kept at a thickness of 3 mm or less, preferably 2 mm or less, more preferably 1 mm or less, and processed at a predetermined temperature for a predetermined time. The treatment temperature depends on the reactivity of the carbon-carbon double bond having reactivity with the SiH group of the component (A) in the mixture to be treated and the SiH group of (B), but generally the range of 30 to 150 ° C. Just do it. Preferably it is 50-130 degreeC, More preferably, it is 60-120 degreeC. The treatment time is set so that the reaction rate between the functional groups falls within the theoretical range of 10-60% and fluidity can be secured at 150 ° C. The fluidity at 150 ° C. is at a level that can secure the time required for molding the curable composition obtained in the present invention. For example, when applied to transfer molding, fluidity of about 1-3 minutes is required. An appropriate processing time can be set, for example, by sampling a small amount from the mixture being processed over time and measuring the gelation time. The gelation time in this case is examined as follows. An aluminum foil having a thickness of 50 μm is placed on a hot plate adjusted to a preset temperature, and 100 mg of the composition is placed thereon to measure the time until gelation is taken as the gelation time. More simply, a small amount of sampled material can be sandwiched between the thumb and forefinger, and the fluidity can be determined in a sticky state. A moderately reacted curable composition extends for example 3 mm or more when the thumb / index finger is released. Use other equipment generally known for measuring the curable behavior of thermosetting resins, such as a curast meter, disc cure tester, pendulum viscoelasticity device, Koka flow tester, etc. Processing time can also be determined.
(Curing)
The curable composition obtained by the method of the present invention can be cured by further reacting a SiH group with a reactive carbon-carbon double bond and a SiH group remaining in the composition.

  Although the curing temperature can be variously set, the lower limit of the preferable temperature is 30 ° C., more preferably 100 ° C., and the upper limit of the preferable temperature is 300 ° C., more preferably 200 ° C. 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 uniform cured product without distortion can be easily obtained. Moreover, it is preferable to perform at a constant temperature in that the molding cycle can be shortened.

  Although various curing times can be set, it is preferable to react at a relatively low temperature for a long time rather than reacting at a high temperature for a short time because a uniform cured product without distortion can be easily obtained. Conversely, the reaction at a high temperature in a short time is preferable in that the molding cycle can be shortened.

  The pressure during the reaction can be variously set as required, and the reaction can be carried out under normal pressure, high pressure, or reduced pressure. In view of easy removal of volatile matter generated in some cases, it is preferable to cure under reduced pressure. In terms of preventing cracks in the molded body, it is preferable to cure under pressure.

  In the manufacturing process in which the composition is used, the weight loss during curing is 5% by weight or less from the viewpoint that generation of voids in the composition and process problems due to outgas from the composition hardly occur. Is preferably 3% by weight or less, more preferably 1% or less.

  The weight loss during curing is examined as follows. Using a thermogravimetric analyzer, 10 mg of the sealant is heated from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, and can be determined as a ratio of the initial weight of the reduced weight.

In addition, when used as an electronic material or the like, it is preferable that the content of Si atoms in the volatile component in this case is 1% or less in that the problem of silicone contamination hardly occurs.
(Molding method)
Various methods are used as a molding method of the curable composition obtained in the present invention. For example, various molding methods generally used for thermosetting resins such as thermoplastic resins and epoxy resins, such as injection molding, transfer molding, RIM molding, casting molding, and press molding, are used. Of these, transfer molding is preferred in that the molding cycle is short and the moldability is good. The molding conditions can be arbitrarily set, for example, the molding temperature is also arbitrary. However, in terms of fast curing and a short molding cycle, the moldability tends to be good, more preferably 100 ° C. or higher, more preferably 120 ° C. or higher. A temperature of 150 ° C. or higher is preferable. After molding by the various methods as described above, post-curing (after-curing) is optional as required. Post-curing tends to increase the heat resistance.
(Use of curable composition obtained in the present invention)
Examples of the use of the curable composition obtained in the present invention are substrate materials in the liquid crystal display field, peripheral materials for liquid crystal display devices such as liquid crystal films such as adhesives, and color PDPs expected as next-generation flat panel displays. (Plasma Display) Sealant, Housing Material, Substrate Material in Plasma Addressed Liquid Crystal (PALC) Display, Adhesive, Adhesive in Organic EL (Electroluminescence) Display, Adhesive in Field Emission Display (FED) Etc.

  In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Sealing agents, adhesives and the like. Projection televisions, sealing agents for optical sensing devices, adhesives, etc.

  In the field of optical components, it is a sealant and an adhesive around an optical switch in an optical communication system. Optical fiber material, ferrule, sealant, adhesive, etc. around the optical connector. For optical passive components and optical circuit components, they are lenses, waveguides, sealing agents for light emitting elements, adhesives, and the like. These are substrate materials, fiber materials, device sealants, adhesives, etc. around an optoelectronic integrated circuit (OEIC).

  In the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and VLSI material.

  In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, and automotive defenses Rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, glass replacements. In addition, it is a multilayer glass for railway vehicles. Further, they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wireness, and corrosion-resistant coatings.

  In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film.

  Next-generation optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing agent, adhesive and the like.

  Furthermore, as a use other than the optical material, a general use in which a thermosetting resin such as an epoxy resin is used, for example, an adhesive, a paint, a coating agent, a molding material (sheet, film, FRP, etc.) ), Insulating materials (including printed circuit boards, wire coatings, etc.), sealants, additives to other resins, and the like.

  Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for sealing, and sealing (reinforcing underfill) when mounting IC packages such as BGA and CSP.

Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.
(Synthesis Example 1)
After placing 1745 g of toluene and 1495 g of 1,3,5,7-tetramethylcyclotetrasiloxane in a stainless steel 5 L separable flask, a dropping funnel with a 500 mL uniform tube and a cooling tube with a three-way cock were provided. Under a nitrogen atmosphere, the bath temperature was set to 50 ° C., and the mixture was stirred at 80 rpm. After adjusting the temperature, 156 g of divinylbenzene manufactured by Nippon Steel Chemical Co., Ltd., 0.1948 g of a platinum vinylsiloxane complex xylene solution (containing 3 wt% as platinum), and 144 g of toluene are weighed and mixed well in a 500 mL Erlenmeyer flask to prepare a uniform solution. Thereafter, a 500 mL dropping funnel was charged under a nitrogen atmosphere. A divinylbenzene solution was dropped from the funnel. The dropping speed was 300 g / 60 minutes. When 50 cc was dropped, the temperature increased to about 2 ° C., and the progress of the hydrosilylation reaction could be confirmed. The dropping was continued and the dropping was completed in about 1 hour. At this time, the temperature of the reaction solution was about 10 ° C. The conversion of vinyl was confirmed by ¹ H-NMR, and the reaction was continued for 2 hours. The mixture was allowed to cool for 1 hour under a nitrogen atmosphere. To 3440 g of the reaction solution, 0.3619 g of 1-ethynylcyclohexanol and 0.2363 g of benzothiazole were diluted with about 4 g of toluene, stirred for 30 minutes, and then left overnight. The reaction solution was subjected to suction filtration (Kiriyama filter paper No. 5B) and then evaporated at 50 ° C. for about 5 hours (direct draw 2 hours, 1.1 Torr). 648 g of product was obtained. The ratio of SiH value and α and β addition of SiH was examined by ¹ H-NMR (a quantitative method using 1,2-dibromoethane as an internal standard). The SiH value was 9.63 mmol / g, α addition 0.50, and β addition 0.50. The viscosity was measured with an E-type viscometer. 0.042 Pa · s. Although the product is a mixture, it contains as a main component the following component (B) of the present invention. Moreover, the platinum vinylsiloxane complex which is (C) component of this invention is contained.

（配合例１）
１Ｌプラスチック製ディスポーザブルカップに、トリアリルイソシアヌレート２６６．７ｇ（本発明の（Ａ）成分）、合成例１で合成したＳｉＨ含有化合物（本発明の（Ｂ）成分）３３３．３ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０．９００ｇ（本発明の（Ｃ）成分）、酸化チタンＲ−８２０（石原産業（株））製）２７．０６ｇ及びアエロジルＲ９７２（日本アエルジル社（株）製）５４．１２ｇ（本発明の（Ｄ）成分）、ホウ酸トリメチル３．００ｇ、１−エチニル−１−シクロヘキサノール１．８０ｇ、３−グリシドキシプロピルトリメトキシシラン１５．００ｇを秤り取り、スパ−テルにて十分混合したのち、さらにあわとり練太郎ＡＲ−２５０型(（株）シンキー製)にて混合（攪拌モード１分／脱泡モード３分）し、白色で流動性を有するペースト状の均質な混合物を得た。少量を１２０℃に加熱した熱板上に置くと一旦低粘度化して流動状態となり２分４５秒後にゲル化した。
（参考例１）
配合例１で得られた混合物約５０ｇを大きさ３０ｘ３０ｃｍのＰＥＴフィルムに挟み込み、厚み２ｍｍのスペーサーを用いて、ＰＥＴフィルムとほぼ同じサイズのガラス板で侠圧し引き伸ばしガラス板周囲をクリップで固定した後、８０℃に設定した箱型オーブン内に水平になるように置いて加熱し、該混合物の挙動を観察した。加熱後３０分頃から表面にクレーター状の小さな気泡が多数発生してきた。４５分後にはクレーター部分からクラックが進行した。該混合物の外形寸法が膨張し始めた。１時間経過後、クラックが成長、材料の外形寸法がさらに膨張した。ただし、この時点では該混合物は初期と同等の流動性を有していた。流動性は該混合物を少量サンプリングして親指と人差し指に挟み軽く引き伸ばしたときの粘り気の程度で定性的に判断することができる。この場合はペーストの伸びがなく引き伸ばしたときにすぐに切れ粘り気がない状態であった。１時間３０分経過後クラックの成長は止まったように見られた。未硬化であった。１時間４５分経過後、先と同様の指触検査で粘度が上昇している(ペーストを触った感じが初期より硬く、軽く引き伸ばしたときにある程度追随して伸びる)ことが確認できた。流動性はまだ有していた。２時間１５経過後に再度チェックしたところ、既にゴム状態にゲル化し流動性は有していなかった。この一連の挙動観察から、粘度が上昇し始めてからゲル化前の適当な時点で加熱処理を中止すれば、本発明の硬化性組成物が得られることが明らかとなった。
（実施例２）
参考例１と同様に配合例１で得られた混合物を加熱処理した。だたし１時間４５分経過後に加熱処理を中止した。ＰＥＴフィルム状の増粘した混合物（本発明の硬化性組成物）をスパテールでこそぎ取り、あわとり練太郎ＡＲ−２５０型(（株）シンキー製)用のプラスチック容器に入れ、攪拌（３０秒）／脱泡（１分）した。該組成物をステンレス板上にＰＥＴフィルムを敷いた上に置いたＳＵＳ製型枠（６７ｘ６７ｘ３ｍｍでダイフリーで離型処理したもの）内にできるだけ泡が噛まないよう中央部１ヶ所に約４０ｇチャージした。上部から下部と同じＰＥＴフィルム及び鏡面ステンレス板で挟み、さらに上下にステンレス板を各１枚用いて８３〜８５℃で１時間圧縮成形した。圧力５３ｋｇ／ｃｍ^２。得られた成形品は良好な外観を示していた。ただし表面にわずかにあばたが見られるが、離型に使用したＰＥＴフィルムの影響と考えられ、型盤に鏡面金属板を用いれば、平滑面が得られるものと考えられた。
（実施例３）
配合例１で得られた混合物約１８０ｇを参考例１と同様に２ｍｍ厚に引き伸ばした後、加熱処理した。ただし加熱は１時間５０分経過した時点で中止した。得られた増粘した混合物（本発明の硬化性組成物）を実施例２と同様の操作にてこそぎ取り、攪拌脱泡した。該組成物をＳＵＳ製型枠（７２ｘ１００ｘ９ｍｍ）内に実施例２と同様にチャージし実施例２と同様の要領で８３〜８５℃にて圧縮成形した。さらに継続して１２０℃／１時間３０分、１５０℃／１時間処理した。脱型するとクラックのない良好な外観をもつ白色成形体が得られた。後で本成形体を横方向にダイヤモンドカッターにて切断し切断面を観察したがボイド・クラックは全く見られなかった。
（比較例１）
配合例１で得られた混合物約５０ｇを攪拌脱泡用の２００ｃｃプラスチック容器にいれ、参考例１と同様に８０℃の加熱処理を行なった。３０分経過後、急激な発熱とともに内容物がゲル化しプラスチック容器が溶けてしまった。再度同様の検討を行なったが、発熱・ゲル化・容器が解ける挙動は同じであった。本比較例と実施例との比較から、混合物のヒドロシリル化反応による発熱と混合物周囲への放熱がバランスされた状態で反応を進行させないと本発明の硬化性組成物は得られないことが示唆される。
（実施例４）
配合例１で得られた混合物約３０ｇを３００ｘ２００ｘ０．０２５ｍｍサイズのＰＥＴフィルム中央部に乗せ、上から同じサイズのＰＥＴフィルムで挟んだ後、厚さ２ｍｍのスペーサーを挟んで、上下から３００ｘ２００ｘ２ｍｍのステンレス板で挟み周囲をダブルクリップで固定し８０℃設定のパーフェクトオーブンに入れた。約７０分経過後オーブンから１０〜１５分毎に取出してステンレス板をあけ様子を観察した。３０分経過後から徐々に粘度上昇がみられ、合計３時間１８分で熱処理を終了した。部分的に反応したと思われる粘ちょうな本発明の硬化性組成物が得られた。予めダイフリーで離型処理したアルミ製オープン型枠（６０ｘ７０ｘ３ｍｍ）をＰＥＴフィルム（１５０ｘ１５０ｘ０．０２５ｍｍ）に置いた物を別途用意し、ＰＥＴフィルムからこそぎ取った該硬化性組成物をできるだけ空気が噛まないようにチャージしてある程度手で伸ばした後、上下をステンレス板で挟み、８０℃／２時間、１２０℃／１時間、１５０℃／１時間、圧力６０ｋｇ／ｃｍ^２で、圧縮成形した。成形を直ちに型枠を外し、わずかなシンクマークはあるが外観良好な白色成形体を得た。
（測定例１）
実施例４の８０℃加熱処理にて得られた本発明の硬化性組成物約１ｇをＣＤＣｌ_３２ｍｌに分散させ液層部分の^１Ｈ−ＮＭＲ（１，２−ジブロモエタンを内部標準とする定量方法）を測定した。本発明の（Ｂ）成分である合成例１の化合物に含まれていたＳｉＨ基のうち約４０％が反応していることがわかった。
（測定例２）
実施例４の８０℃加熱処理にて得られた本発明の硬化性組成物約１ｇをトルエン１０ｍｌに分散させ液層部分をＧＰＣ測定した。Ｍｎ５８７００以上の領域が１０％、１６８００以上の領域が２３％、５５００以上の領域が４４％以上であった。一方加熱前の配合例１で得られた混合物のＧＰＣ測定では、Ｍｎ１５１００以上の領域が０％、１１００以上の領域が１１％、６１０以上の領域が５９％であった。以上から本発明の硬化性組成物は、制御された条件下で分子鎖延長のヒドロシリル化反応が選択的に進行した結果、増粘はするが流動性は失わない特性を保持した組成物として得られたことが分かる。
（配合例２）
１Ｌプラスチック製ディスポーザブルカップに、トリアリルイソシアヌレート１５５．５７ｇ（本発明の（Ａ）成分）、合成例１で合成したＳｉＨ含有化合物（本発明の（Ｂ）成分）１９４．４３ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０．５２５ｇ（本発明の（Ｃ）成分）、酸化チタンＲ−８２０（石原産業（株）製）１５．７８ｇ及びアエロジルＲ９７２（日本アエロジル（株）製）３１．５７ｇ（本発明の（Ｄ）成分）、ホウ酸トリメチル１．７５ｇ、１−エチニル−１−シクロヘキサノール１．０５ｇ、３−グリシドキシプロピルトリメトキシシラン８．７５ｇを秤り取り、スパ−テルにて十分混合したのち、さらにあわとり練太郎ＡＲ−２５０型(（株）シンキー製）にて混合（攪拌モード１分／脱泡モード３分）し、白色で流動性を有するペースト状の均質な混合物を得た。少量を１２０℃に加熱した熱板上に置くと一旦低粘度化して流動状態となり４分１３秒後にゲル化した。
（実施例５）
配合例２で得られた混合物をＰＥＴフィルムに挟み、厚さ２ｍｍで８０℃の箱型オーブンで加熱処理した。粘度の上昇を触指によりモニターしながら追ったが、３時間４５分で増粘した良好なＢステージ化物が得られた。あわとり練太郎で脱泡し、１００ｘ１００ｘ３ｍｍの額縁型にチャージし両面研磨のステンレス板に挟み圧縮成形した。８３℃／１時間（５〜１０分後にゲル化）、１２０℃／１時間、１５０℃／１時間、１７０℃／１時間。すぐに脱型したが、割れることなく取出せた。わずかなシンクマークはあるが外観良好な白色成形体が得られた。ポジティブ型を用いればシンクマークは防げるものと考えられる。該成形体から所定サイズの試験片をダイヤモンドカッターを用いて切り取り、各試験に供した。曲げ試験：弾性率２．４８ＧＰａ、最大強度７０ＭＰａ、最大歪５．０％。ＴＭＡ：Ｔｇ１１５℃、α１＝１１４ｐｐｍ（８０℃）、α２＝１３９ｐｐｍ（１４０℃）。ＤＭＡ：Ｔｇ（ｔａｎδ）１４５℃。吸水率：０．２０％。
（配合例３）
１００ｍｌプラスチック製ディスポーザブルカップに、トリアリルイソシアヌレート８．８１２４ｇ（本発明の（Ａ）成分）、合成例１で合成したＳｉＨ含有化合物（本発明の（Ｂ）成分）１１．１８７６ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０．０３０ｇ（本発明の（Ｃ）成分）、酸化チタンＲ−８２０（石原産業（株）製）０．８８３６ｇ及びアエロジルＲ９７２（日本アエロジル（株）製）１．７８８４ｇ（本発明の（Ｄ）成分）、ホウ酸トリメチル０．１００ｇ、１−エチニル−１−シクロヘキサノール０．０６０ｇ、３−グリシドキシプロピルトリメトキシシラン０．５００ｇを秤り取り、スパ−テルにて十分混合したのち、さらにあわとり練太郎ＡＲ−２５０型（(株)シンキー製）にて混合（攪拌モード１分／脱泡モード３分）し、白色で流動性を有するペースト状の均質な混合物を得た。
（参考例６）
配合例３で得られた混合物３．３５７４ｇをマルエムサンプル管Ｎｏ．６に入れ、該混合物温度を熱電対でモニターするとともに、オイルバスを用意し８５℃設定した。サンプル管をバスに浸漬し１２０分反応させてやることにより、１００−１２０分処理段階で安定な増粘状態（Ｂステージ化状態：本発明の硬化性組成物の状態）を明確に確認できた。その後段階的に昇温（１２０℃／１５分→１５０℃／１５分→１８０℃／１５分）すると１２０℃への昇温段階で１３０℃程度の発熱が１分程度みられたがすぐにバス温１２０℃と平衡となり、その後の昇温では発熱は見られなかった。最終的に外観良好で均質な硬化物が得られた。
（比較例２）
配合例３で得られた混合物３．３３２５ｇを使用し、オイルバスを１２６℃に設定した以外は参考例６と同様の操作をした。内温が９８℃になった時に急激に発熱し２秒後に２５０℃、さらに２０秒後に２８８℃に達した後、徐々に降温した。表面が波打ち、内部に少し着色が見られる硬化物が得られた。
（比較例３）
配合例３で得られた混合物３．３７２３ｇを使用し、オイルバスを９４℃に設定した以外は参考例６と同様の操作をした。内温はサンプル管をオイルバスに浸漬後１分でバス温と平衡に達したが、その後徐々に上昇し９分で１０２℃に達した。その瞬間急激な発熱が起こり内温は２秒で２１５℃に達した後、徐々に降温した。内部にクラックが多数ある硬化物が得られた。
（合成例２）
５Ｌの四つ口フラスコに、攪拌装置、滴下漏斗、冷却管をセットした。このフラスコにトルエン１８００ｇ、１，３，５，７−テトラメチルシクロテトラシロキサン１４４０ｇを入れ、１２０℃のオイルバス中で加熱、攪拌した。トリアリルイソシアヌレート２００ｇ、トルエン２００ｇ及び白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）１．４４ｍｌの混合液を５０分かけて滴下した。得られた溶液をそのまま６時間加温、攪拌した後、未反応の１，３，５，７−テトラメチルシクロテトラシロキサン及びトルエンを減圧留去した。^１Ｈ−ＮＭＲによりこのものは１，３，５，７−テトラメチルシクロテトラシロキサンのＳｉＨ基の一部がトリアリルイソシアヌレートと反応したものであることがわかった。また、１，２−ジブロモメタンを内部標準に用いて^１Ｈ−ＮＭＲによりＳｉＨ基の含有量を求めたところ、８．０８ｍｍｏｌ／ｇのＳｉＨ基を含有していることがわかった。生成物は混合物であるが、本発明の（Ｂ）成分である下記のものを主成分として含有している。また、本発明の（Ｃ）成分である白金ビニルシロキサン錯体を含有している。

(Formulation example 1)
Disposable cup made of 1 L plastic, 266.7 g triallyl isocyanurate (component (A) of the present invention), SiH-containing compound synthesized in Synthesis Example 1 (component (B) of the present invention) 333.3 g, platinum vinylsiloxane complex Xylene solution (containing 3 wt% as platinum) 0.900 g (component (C) of the present invention), titanium oxide R-820 (manufactured by Ishihara Sangyo Co., Ltd.) 27.06 g and Aerosil R972 (Nippon Aerosil Co., Ltd.) Manufactured) 54.12 g (component (D) of the present invention), trimethyl borate 3.00 g, 1-ethynyl-1-cyclohexanol 1.80 g, 3-glycidoxypropyltrimethoxysilane 15.00 g Then, mix thoroughly with a spatula, and then mix with Awatori Nertaro AR-250 (made by Shinky Co., Ltd.) (stirring mode 1 minute) Defoamed mode 3 minutes), to obtain a pasty homogeneous mixture having a white flowable. When a small amount was placed on a hot plate heated to 120 ° C., the viscosity was once reduced to a fluid state and gelled after 2 minutes and 45 seconds.
( Reference Example 1)
After about 50 g of the mixture obtained in Formulation Example 1 was sandwiched between PET films having a size of 30 × 30 cm, and using a spacer with a thickness of 2 mm, it was pressed and stretched with a glass plate of approximately the same size as the PET film, and the periphery of the glass plate was fixed with clips. And placed in a box oven set at 80 ° C. so as to be horizontal, and the behavior of the mixture was observed. Many crater-like bubbles have been generated on the surface about 30 minutes after heating. After 45 minutes, cracks progressed from the crater portion. The outer dimensions of the mixture began to expand. After 1 hour, the crack grew and the outer dimensions of the material further expanded. However, at this point, the mixture had a fluidity equivalent to that in the initial stage. The fluidity can be qualitatively determined by the degree of stickiness when a small amount of the mixture is sampled and sandwiched between the thumb and forefinger and lightly stretched. In this case, there was no elongation of the paste, and when it was stretched, it was immediately cut and not sticky. The crack growth seemed to stop after 1 hour 30 minutes. Uncured. After 1 hour and 45 minutes, it was confirmed that the viscosity was increased by the same finger touch test as before (the feeling of touching the paste was harder than the initial stage and extended to some extent when lightly stretched). It still had liquidity. When checked again after the lapse of 2 hours and 15 hours, it had already gelled into a rubber state and did not have fluidity. From this series of behavioral observations, it became clear that the curable composition of the present invention can be obtained by stopping the heat treatment at an appropriate time before gelation after the viscosity starts to increase.
(Example 2)
In the same manner as in Reference Example 1, the mixture obtained in Formulation Example 1 was heat-treated. However, the heat treatment was stopped after 1 hour 45 minutes. A PET film-like thickened mixture (the curable composition of the present invention) is scraped with a spatula and placed in a plastic container for Awatori Nertaro AR-250 (manufactured by Sinky Corporation) and stirred (30 seconds) ) / Defoaming (1 minute). About 40 g of the composition was charged in one central portion so that bubbles would not bite as much as possible in a SUS mold frame (67 × 67 × 3 mm die-free mold release processing) placed on a stainless steel plate with a PET film spread on it. . The upper part and the lower part were sandwiched between the same PET film and a mirror stainless steel plate, and compression molding was performed at 83 to 85 ° C. for 1 hour using one stainless plate above and below. Pressure 53 kg / cm ² . The obtained molded product showed a good appearance. However, although slight fluttering was observed on the surface, it was considered that this was due to the influence of the PET film used for mold release, and it was considered that a smooth surface could be obtained by using a mirror metal plate for the mold platen.
(Example 3)
About 180 g of the mixture obtained in Formulation Example 1 was stretched to a thickness of 2 mm as in Reference Example 1, and then heat-treated. However, heating was stopped when 1 hour and 50 minutes had elapsed. The resulting thickened mixture (the curable composition of the present invention) was scraped by the same operation as in Example 2 and stirred and degassed. The composition was charged in a SUS mold (72 × 100 × 9 mm) in the same manner as in Example 2 and compression molded at 83 to 85 ° C. in the same manner as in Example 2. Further, the treatment was continued at 120 ° C./1 hour 30 minutes and 150 ° C./1 hour. When demolded, a white molded body having a good appearance without cracks was obtained. Later, the molded body was cut in a transverse direction with a diamond cutter and the cut surface was observed, but no voids or cracks were observed.
(Comparative Example 1)
About 50 g of the mixture obtained in Formulation Example 1 was placed in a 200 cc plastic container for stirring and defoaming, and heat treatment at 80 ° C. was performed in the same manner as in Reference Example 1. After 30 minutes, the contents gelled with sudden heat generation and the plastic container was melted. The same investigation was performed again, but the behavior of heat generation, gelation, and dissolution of the container was the same. The comparison between this comparative example and the example suggests that the curable composition of the present invention cannot be obtained unless the reaction is allowed to proceed in a state where the heat generated by the hydrosilylation reaction of the mixture and the heat release to the periphery of the mixture are balanced. The
Example 4
About 30 g of the mixture obtained in Formulation Example 1 was placed on the center of a 300 x 200 x 0.025 mm size PET film, sandwiched by the same size PET film from above, and then sandwiched by a 2 mm thick spacer, 300 x 200 x 2 mm stainless steel plate from above and below The surrounding area was fixed with a double clip and placed in a perfect oven set at 80 ° C. After about 70 minutes, the steel plate was taken out from the oven every 10 to 15 minutes and the state of opening the stainless steel plate was observed. After 30 minutes, the viscosity gradually increased and the heat treatment was completed in 3 hours and 18 minutes. A viscous curable composition of the present invention that was thought to have partially reacted was obtained. Separately prepare a die-free aluminum open mold (60x70x3mm) placed on a PET film (150x150x0.025mm) and let the air bite the curable composition scraped from the PET film as much as possible. After charging to a certain extent and stretching by hand to some extent, the upper and lower parts were sandwiched between stainless steel plates and compression molded at 80 ° C./2 hours, 120 ° C./1 hour, 150 ° C./1 hour, and a pressure of 60 kg / cm ² . Immediately after molding, the mold was removed, and a white molded article having a good appearance although having a slight sync mark was obtained.
(Measurement Example 1)
About 1 g of the curable composition of the present invention obtained by heat treatment at 80 ° C. in Example 4 was dispersed in 2 ml of CDCl ₃ and ¹ H-NMR (quantitative determination using 1,2-dibromoethane as an internal standard) of the liquid layer portion. Method). About 40% of (B) SiH groups contained in the compound of Synthesis Example 1, a component of the present invention was found to react.
(Measurement example 2)
About 1 g of the curable composition of the present invention obtained by heat treatment at 80 ° C. in Example 4 was dispersed in 10 ml of toluene, and the liquid layer portion was subjected to GPC measurement. The region of Mn 58700 or more was 10%, the region of 16800 or more was 23%, and the region of 5500 or more was 44% or more. On the other hand, in the GPC measurement of the mixture obtained in Formulation Example 1 before heating, the region of Mn 15100 or higher was 0%, the region of 1100 or higher was 11%, and the region of 610 or higher was 59%. As described above, the curable composition of the present invention is obtained as a composition having the property of increasing the viscosity but not losing the fluidity as a result of the selective hydrosilylation reaction of molecular chain extension under controlled conditions. You can see that
(Formulation example 2)
Disposable cup made of 1 L plastic, 155.57 g of triallyl isocyanurate (component (A) of the present invention), 194.43 g of SiH-containing compound synthesized in Synthesis Example 1 (component (B) of the present invention), platinum vinylsiloxane complex Xylene solution (containing 3 wt% as platinum) 0.525 g (component (C) of the present invention), titanium oxide R-820 (Ishihara Sangyo Co., Ltd.) 15.78 g and Aerosil R972 (Nihon Aerosil Co., Ltd.) 31.57 g (component (D) of the present invention), 1.75 g of trimethyl borate, 1.05 g of 1-ethynyl-1-cyclohexanol, and 8.75 g of 3-glycidoxypropyltrimethoxysilane were weighed, and the spa -Mix well with Tell, then mix with Awatori Nertaro AR-250 (made by Shinky Co., Ltd. ) (stirring mode 1 min / The defoaming mode was 3 minutes, and a white paste-like homogeneous mixture having fluidity was obtained. When a small amount was placed on a hot plate heated to 120 ° C., the viscosity was once reduced to a fluid state and gelled after 4 minutes and 13 seconds.
(Example 5)
The mixture obtained in Formulation Example 2 was sandwiched between PET films and heat-treated in a box oven having a thickness of 2 mm and 80 ° C. The increase in viscosity was followed while monitoring with a finger, but a good B-staged product having increased viscosity in 3 hours and 45 minutes was obtained. It was defoamed with Nawataro Awatori, charged into a frame shape of 100 × 100 × 3 mm, and sandwiched between double-side polished stainless plates and compression molded. 83 ° C./1 hour (gelation after 5 to 10 minutes), 120 ° C./1 hour, 150 ° C./1 hour, 170 ° C./1 hour. Although it was immediately removed from the mold, it could be removed without cracking. A white molded article with a good appearance was obtained although there were slight sync marks. If the positive type is used, the sync mark can be prevented. A test piece of a predetermined size was cut out from the molded body using a diamond cutter and subjected to each test. Bending test: elastic modulus 2.48 GPa, maximum strength 70 MPa, maximum strain 5.0%. TMA: Tg 115 ° C., α1 = 114 ppm (80 ° C.), α2 = 139 ppm (140 ° C.). DMA: Tg (tan δ) 145 ° C. Water absorption: 0.20%.
(Formulation example 3)
In a disposable cup made of 100 ml plastic, 8.8124 g of triallyl isocyanurate (component (A) of the present invention), 11.1876 g of SiH-containing compound synthesized in Synthesis Example 1 (component (B) of the present invention), platinum vinylsiloxane complex Xylene solution (containing 3 wt% as platinum) 0.030 g (component (C) of the present invention), titanium oxide R-820 (Ishihara Sangyo Co., Ltd.) 0.8836 g and Aerosil R972 (Nihon Aerosil Co., Ltd.) 1.7884 g (component (D) of the present invention), trimethyl borate 0.100 g, 1-ethynyl-1-cyclohexanol 0.060 g, 3-glycidoxypropyltrimethoxysilane 0.500 g were weighed and spa -Mix well with Tell, then mix with Awatori Nertaro AR-250 (Sinky Co., Ltd.) Stirring Mode 1 minute / defoaming mode 3 minutes) to obtain a paste-like homogeneous mixture having a white flowable.
( Reference Example 6)
3.3574 g of the mixture obtained in Formulation Example 3 was added to Maruemu Sample Tube No. The temperature of the mixture was monitored with a thermocouple, and an oil bath was prepared and set at 85 ° C. By immersing the sample tube in the bath and allowing it to react for 120 minutes, a stable thickened state (B-staged state: state of the curable composition of the present invention) could be clearly confirmed in the treatment stage for 100 to 120 minutes. . After that, when the temperature was raised stepwise (120 ° C / 15 minutes → 150 ° C / 15 minutes → 180 ° C / 15 minutes), a heat generation of about 130 ° C was observed for about 1 minute at the temperature rising stage to 120 ° C. The temperature reached equilibrium at 120 ° C., and no exotherm was observed at the subsequent temperature increase. Finally, a uniform cured product having a good appearance was obtained.
(Comparative Example 2)
The same operation as in Reference Example 6 was performed except that 3.3325 g of the mixture obtained in Formulation Example 3 was used and the oil bath was set to 126 ° C. When the internal temperature reached 98 ° C., heat was suddenly generated, and after 2 seconds, 250 ° C. was reached, and after 20 seconds, 288 ° C. was reached. A cured product having a waved surface and slightly colored inside was obtained.
(Comparative Example 3)
The same operation as in Reference Example 6 was performed except that 3.3723 g of the mixture obtained in Formulation Example 3 was used and the oil bath was set at 94 ° C. The internal temperature reached equilibrium with the bath temperature in 1 minute after immersing the sample tube in the oil bath, but then gradually increased and reached 102 ° C. in 9 minutes. At that moment, sudden heat generation occurred and the internal temperature reached 215 ° C. in 2 seconds, and then the temperature gradually decreased. A cured product having many cracks inside was obtained.
(Synthesis Example 2)
A stirrer, a dropping funnel, and a condenser tube were set in a 5 L four-necked flask. Into this flask, 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, heated and stirred in an oil bath at 120 ° C. A mixed solution of 200 g of triallyl isocyanurate, 200 g of toluene and 1.44 ml of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 50 minutes. The resulting solution was heated and stirred as it was for 6 hours, and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ^{By 1} H-NMR, it was found that a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane reacted with triallyl isocyanurate. Further, when the content of SiH groups was determined by ¹ H-NMR using 1,2-dibromomethane as an internal standard, it was found to contain 8.08 mmol / g SiH groups. Although the product is a mixture, it contains as a main component the following component (B) of the present invention. Moreover, the platinum vinylsiloxane complex which is (C) component of this invention is contained.

（配合例４）
１００ｍｌプラスチック製ディスポーザブルカップに、トリアリルイソシアヌレート４０ｇ（本発明の（Ａ）成分）、合成例２で合成したＳｉＨ含有化合物（本発明の（Ｂ）成分）２３ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０．０９４ｇ（本発明の（Ｃ）成分）、球状シリカ シルスターＬＥ０５Ｓ（日本化学（株）製）３０ｇ及びカーボンブラック 旭＃６６（旭カーボン（株）製）３ｇ（本発明の（Ｄ）成分）、１−エチニル−１−シクロヘキサノール０．３０ｇを秤取る。内容物を十分に手混ぜ攪拌する。さらにあわとり練太郎ＡＲ−２５０型(（株）シンキー製)にて混合（攪拌モード１分／脱泡モード３分）すると、黒色で流動性を有するペースト状の均質な混合物が得られる。
（参考例７）
配合例４で得られた混合物約３．４ｇマルエムサンプル管Ｎｏ．６に入れ、混合物の温度が計れる様に熱電対をセットする。１００℃に設定したオイルバスに該サンプル管を浸漬すると、徐々に増粘し約１〜５時間の範囲で良好な成形性を有する粘ちょうな硬化性組成物を確認できる。この時間範囲は用いる（Ｂ）成分のヒドロシリル化反応活性に大きく左右されることがある。得られた本発明の硬化性組成物をさらに１００℃／１ｈ，１２０℃／１ｈ，１５０℃／１ｈの条件で熱処理することにより円盤状の均質な硬化物を得ることができる。

(Formulation example 4)
In a 100 ml plastic disposable cup, 40 g of triallyl isocyanurate (component (A) of the present invention), 23 g of the SiH-containing compound synthesized in Synthesis Example 2 (component (B) of the present invention), a xylene solution of a platinum vinylsiloxane complex ( 0.094 g (containing (C) component of the present invention) as platinum, 30 g of spherical silica Silstar LE05S (manufactured by Nippon Chemical Co., Ltd.) and 3 g of carbon black Asahi # 66 (manufactured by Asahi Carbon Co., Ltd.) (D) component), 0.30 g of 1-ethynyl-1-cyclohexanol is weighed. Thoroughly mix and stir the contents. Further, when mixed (stirring mode 1 minute / defoaming mode 3 minutes) with Awatori Nertaro AR-250 type (manufactured by Shinky Co., Ltd.), a black paste-like homogeneous mixture having fluidity is obtained.
( Reference Example 7)
About 3.4 g of the mixture obtained in Formulation Example 4 6. Set thermocouple so that the temperature of the mixture can be measured. When the sample tube is immersed in an oil bath set at 100 ° C., a thick curable composition having a gradually increased viscosity and having good moldability in a range of about 1 to 5 hours can be confirmed. This time range may greatly depend on the hydrosilylation reaction activity of the component (B) used. The obtained curable composition of the present invention is further heat-treated at 100 ° C./1 h, 120 ° C./1 h, 150 ° C./1 h to obtain a disk-like homogeneous cured product.

Claims (2)

(A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, (B) a compound containing at least two SiH groups in one molecule, (C) A hydrosilylation catalyst, (D) a mixture containing an inorganic filler as an essential component is prepared, a carbon-carbon double bond having reactivity with the SiH group of component (A) in the mixture, and the SiH group of (B) Is obtained by reacting in the range of 10-60% theoretically while maintaining the temperature of the mixture so as not to be higher than the ambient temperature by more than 10 ° C. , transfer molding, RIM formed Katachima other is a method for producing a press-molding the curable composition,
(A) When reacting the SiH group of the component and the reactive carbon-carbon double bond with the SiH group of (B), the thickness of the mixture is maintained at 3 mm or less. The method according to claim 1, wherein the inorganic filler of component (D) is titanium oxide and / or silica.