JP5270059B2 - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve the curability of a curable composition containing triallyl isocyanurate (A), a compound (B) having at least two SiH groups in a molecule, and a hydrosilylation catalyst (C) as the essential components. <P>SOLUTION: The trially isocyanurate (A) used is the one whose content of 1,3-diallyl urea is &le;700 ppm. <P>COPYRIGHT: (C)2005,JPO&amp;NCIPI

Description

The present invention relates to a curable composition, and more particularly to a curable composition having excellent curability.

An organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, a compound having at least two SiH groups in one molecule, and a hydrosilylation catalyst as essential components In the curable composition, one using triallyl isocyanurate as an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule is known (Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5). Patent Document 3, Patent Document 4, and Patent Document 5 disclose that the cured product has high optical transparency and high light resistance and is useful as an optical material. However, the curable composition has a problem of low curability.

Examples of the method for producing triallyl isocyanurate include a method of reacting an alkali metal salt of cyanic acid with an allyl halide (for example, Patent Document 6), a method of reacting cyanuric acid or an alkali metal salt of cyanuric acid with an allyl halide. (For example, patent document 7, patent document 8), the method (for example, patent document 9) etc. which carry out an isomerization reaction after manufacturing triallyl cyanurate from cyanuric chloride and allyl alcohol can be illustrated.

Since it is not easy to produce high purity triallyl isocyanurate and triallyl isocyanurate is mixed with by-products that are not easily separated, a purification method has been developed (for example, Patent Document 10, Patent Document). 11, Patent Document 12, Patent Document 13, Patent Document 14, Patent Document 15, Patent Document 16).

As described above, triallyl isocyanurate tends to contain a nitrogen-containing compound that can be an activity reducing agent for the hydrosilylation catalyst due to its structure as an impurity. When a nitrogen-containing compound that can be an activity reducing agent is contained as an impurity, the curing rate of the curable composition is undesirably lowered.

Trial isocyanurate having a purity of 99.92% is disclosed in Patent Document 14, and 1,3-diallyl urea is one of by-products contained in triallyl isocyanurate in Patent Document 10, Patent Document 11 and Patent Document 15, and the like. Although described, there is no description regarding the amount of nitrogen-containing impurities such as 1,3-diallylurea contained in triallyl isocyanurate obtained by purification. Further, Patent Document 5 describes that triallyl isocyanurate may be purified as necessary, but there is no disclosure regarding the substance to be purified and its amount and the purpose of purification. There is no disclosure regarding the effect of the amount of 1,3-diallylurea contained in triallyl isocyanurate on the hydrosilylation reaction between triallyl isocyanurate and a compound having a SiH group.

JP 50-100 JP-A-9-291214 JP 2002-80733 A JP2002-317048 JP 2003-34743 A Japanese Patent Publication 36-3985 Shoko 38-21910 US2984950 JP 58-85874 A Shoko 40-2556 Japanese Patent Publication No.42-9345 Japanese Patent Publication 47-14395 Shoko 47-22588 JP-A 57-200371 Shoko 58-22118 JP-A-11-255753

The problem to be solved by the present invention is a means for improving the curability of a curable composition containing triallyl isocyanurate, a compound having at least two SiH groups in one molecule and a hydrosilylation catalyst as essential components. Is to provide.

As a result of intensive studies to solve such problems, the present inventor uses triallyl isocyanurate having a content of 1,3-diallyl urea of 700 ppm or less as triallyl isocyanurate as component (A). The present inventors have found that the above problems can be solved and have reached the present invention.

That is, the present invention
(A) triallyl isocyanurate, (B) a compound having at least two SiH groups in one molecule, (C) a curable composition containing a hydrosilylation catalyst as an essential component, It is a curable composition (Claim 1) in which the content of 1,3-diallylurea in a certain triallyl isocyanurate is 700 ppm or less,
(A) The curable composition (Claim 2) according to claim 1, wherein the component (A) is triallyl isocyanurate in which the content of 1,3-diallyl urea exceeding 700 ppm is reduced to 700 ppm or less by purification treatment. ,
The curable composition (claim 3) according to claim 2, wherein the purification treatment of triallyl isocyanurate is a treatment using a treating agent capable of removing a basic substance.
The curable composition according to any one of claims 1 to 3, wherein the content of 1,3-diallylurea in triallyl isocyanurate as component (A) is 100 ppm or less. ,
The curable composition according to any one of claims 1 to 3, wherein the content of 1,3-diallylurea in triallyl isocyanurate as component (A) is 50 ppm or less. ,
The curable composition according to any one of claims 1 to 3, wherein the content of 1,3-diallylurea in triallyl isocyanurate as component (A) is 10 ppm or less. .

According to the present invention, the curability of a curable composition containing triallyl isocyanurate (A), a compound (B) having at least two SiH groups in one molecule, and a hydrosilylation catalyst (C) as essential components is improved. Can be made.

Hereinafter, the present invention will be described in detail.
((A) component)
(A) component of this invention is triallyl isocyanurate whose content of 1, 3- diallyl urea in triallyl isocyanurate is 700 ppm or less. The content can be measured by an internal standard method using gas chromatography.

When the content of 1,3-diallyl urea in triallyl isocyanurate exceeds 700 ppm, triallyl isocyanurate (A), compound (B) having at least two SiH groups in one molecule, and hydrosilylation catalyst ( The curability of the curable composition containing C) as an essential component is low, and in order to supplement the curability, it is necessary to use a large amount of the expensive hydrosilation catalyst (C). Moreover, the storage stability of a curable composition falls by using a hydrosilylation catalyst in large quantities, and the fall of the product quality by coloring of hardened | cured material becomes a problem. The amount of 1,3-diallylurea contained in triallyl isocyanurate is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less.

The method for producing triallyl isocyanurate in which the content of 1,3-diallyl urea in triallyl isocyanurate is 700 ppm or less is not particularly limited.
The content of 1,3-diallyl urea can be reduced to 700 ppm or less by selecting raw materials and reaction conditions that eliminate as much impurities as possible by-produce 1,3-diallyl urea during triallyl isocyanurate production. Certain triallyl isocyanurates can be produced.

In addition, it is not easy to avoid 1,3-diallyl urea as a by-product during the production of triallyl isocyanurate, and if the content of 1,3-diallyl urea exceeds 700 ppm, 1,3-diallyl can be obtained by carrying out a purification treatment. A triallyl isocyanurate having a urea content of 700 ppm or less can be produced. There are no particular limitations on the method of purification treatment, distillation under reduced pressure or recrystallization, acidic water such as hydrochloric acid or sulfuric acid aqueous solution, aqueous solution of sodium hydroxide, alkaline water such as sodium carbonate or potassium carbonate, and neutral water such as pure water. Examples include cleaning by combination, adsorption treatment with an adsorbent such as silica, aluminum silicate, magnesium silicate, activated clay, activated carbon, and the like. If triallyl isocyanurate purification is repeated if necessary, and if necessary, a plurality of purification methods may be combined until the content of 1,3-diallyl urea in triallyl isocyanurate is 700 ppm or less. good. Treatment using a treatment agent capable of removing basic substances among these purification treatment methods (for example, acidic water such as hydrochloric acid and sulfuric acid aqueous solution, silica, aluminum silicate, activated clay, activated carbon, etc.) Is preferred. In the purification treatment, a solvent may or may not be used.

((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 (I)

(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 (I) 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 (I) 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.

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, as the component (α), an organic compound (α1) containing at least two carbon-carbon double bonds having reactivity with the SiH group can be used. 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.

((Α1) component)
The (α1) component is not particularly limited as long as it is an organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule.
Organic compounds do not contain siloxane units (Si-O-Si) such as polysiloxane-organic block copolymers and polysiloxane-organic graft copolymers, but other than C, H, N, O, S and halogen as constituent elements A compound containing no element is more preferable. Those containing siloxane units have gas permeability and repelling problems.

The bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and may be present anywhere in the molecule.
The organic compound containing at least two carbon-carbon double bonds reactive with the SiH group of the component (α1) in one molecule can be classified into an organic polymer compound and an organic monomer compound.

Organic polymer compounds include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, phenol-formaldehyde (phenolic resin) And polyimide compounds.

Examples of organic monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene and naphthalene, aliphatic hydrocarbons such as straight chain and alicyclic, ethers, and heterocyclic compounds. These mixtures can be exemplified.

Specific examples of the component (α1) include butadiene, isoprene, octadiene, decadiene, cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene, norbornadiene, diallyl phthalate, triallyl trimellitate, diethylene glycol. Bisallyl carbonate, trimethylolpropane diallyl ether, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, pentaerythritol triallyl ether, 1,1,2,2, -tetraallyloxyethane, diarylidenepenta Erythlit, 1,2,4-trivinylcyclohexane, divinylbenzenes (having a purity of 50 to 100%, preferably having a purity of 80 to 100%), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio of 50 to 100%) ), Novolak phenol allyl ether, allylated polyphenylene oxide,

Triallyl cyanurate, triallyl isocyanurate,

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.

From the viewpoint that the obtained cured product is less colored, has high optical transparency, and has high light resistance, the component (α1) includes vinylcyclohexene, dicyclopentadiene, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, 2 , 2-bis (4-hydroxycyclohexyl) propane diallyl ether, 1,2,4-trivinylcyclohexane are preferred, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, 2,2-bis (4-hydroxycyclohexyl) propane Of these, diallyl ether and 1,2,4-trivinylcyclohexane are particularly preferred.
The component (α1) can be used alone or in combination of two or more.

((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 (Α). 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.

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, Linearene (registered trademark, manufactured by Idemitsu Petrochemical Co., Ltd.), 4,4-dimethyl-1-pentene, 2-methyl-1-hexene, 2,3,3-trimethyl-1-butene, 2,4,4-trimethyl-1 -Chain aliphatic hydrocarbon compounds such as pentene, cyclohexene, methylcyclohexene, methylenecyclohexane, norbornylene, ethylidenecyclohexane, vinylcyclohexane, camphene, carene, α-pinene, β-pinene, etc. Compounds, styrene, α-methylstyrene, indene, phenylacetylene, 4-ethynyltoluene, allylbenzene , Aromatic hydrocarbon compounds such as 4-phenyl-1-butene, allyl ethers such as alkyl allyl ether and allyl phenyl ether, glycerin monoallyl ether, ethylene glycol monoallyl ether, 4-vinyl-1, Aliphatic compounds such as 3-dioxolan-2-one, aromatic compounds such as 1,2-dimethoxy-4-allylbenzene and o-allylphenol, monoallyl dibenzyl isocyanurate, monoallyl diglycidyl isocyanate Substituted isocyanurates such as nurate, silicon compounds such as vinyltrimethylsilane and vinyltriphenylsilane, monoallyl diglycidyl isocyanurate, allyl glycidyl ether, allyloxyethyl methacrylate, allyloxyethyl acrylate, vinyltrimethoxy Carbon reactive with a SiH group of the silane, such as - compounds like having a carbon-carbon double bond and the other reactive groups. Furthermore, polyether resins such as one-end allylated polyethylene oxide and one-end allylated polypropylene oxide, hydrocarbon resins such as one-end allylated polyisobutylene, one-end allylated polybutyl acrylate, one-end allylated polymethyl methacrylate Examples thereof also include polymers or oligomers having a vinyl group at one end, such as acrylic resins.

The structure may be linear or branched, and the molecular weight is not particularly limited, and various types can be used. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, and more preferably 1.5 or less in that the viscosity of the mixture is low and the moldability is likely to be good. More preferably it is.
As the above (α2) component, a single component may be used, or a plurality of components may be used in combination.

((Β) component)
The component (β) is a linear and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule.
Specifically, for example

Is mentioned.
Here, from the viewpoint of easy compatibility with the component (α), the following general formula (I)

(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 3 SiH groups in one molecule. Is preferred.
The substituent R ¹ in the compound represented by the general formula (I) 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. In view of the strength of the cured product due to the above, since it is preferable that the component (B) has a larger 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 ), a platinum-phosphine complex (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), a platinum-phosphite complex (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.), Jikaruboni Dichloroplatinum, Karstedt catalyst, and platinum-hydrocarbon complexes described in Ashby US Pat. Nos. 3,159,601 and 3,159,622, and Lamoreaux, US Pat. No. 3,220,972. Examples include platinum alcoholate catalysts described in the text. 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 ⁻⁷ mol, and the upper limit of the preferable addition amount is 10 ⁻¹ mol, more preferably 10 ⁻² mol, per 1 mol of SiH group of the component (β).

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 relative to 1 mol of the hydrosilylation catalyst is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.

Various methods can be used for mixing the (α) component, the (β) component, and the catalyst in the reaction, and the (α) component mixed with the catalyst is mixed with the (β) component. The method is preferred. If the catalyst is mixed with the mixture of the (α) component and the (β) component, it is difficult to control the reaction. When the method of mixing the (α) component with the mixture of the (β) component and the catalyst is taken, the time for heating only the (β) component in the presence of the catalyst becomes longer, so the quality deteriorates due to side reactions. Become easier

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.

The mixing ratio of the component (A) and the component (B) is not particularly limited as long as the strength required for the cured product is not lost. When the organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in the curable composition of the present invention is only triallyl isocyanurate as component (A), In the ratio of the total number of SiH groups in the component B) to the total number of allyl groups in the component (A) (X), the lower limit of the preferred range is Y / X ≧ 0.3, more preferably Y / X ≧ 0.5, more preferably Y / X ≧ 0.7, and the upper limit of the preferable range is 3 ≧ Y / X, more preferably 2 ≧ Y / X, still 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.

The curable composition of the present invention may contain an organic compound containing a carbon-carbon double bond having reactivity with the SiH group in addition to the triallyl isocyanurate as the component (A). As such an organic compound containing a carbon-carbon double bond having reactivity with the SiH group, those described in the above component (α) and excluding triallyl isocyanurate can be used. When there is an organic compound containing a carbon-carbon double bond reactive with SiH groups in addition to the triallyl isocyanurate component (A), the number of SiH groups (Y) in component (B) In the ratio to the number of carbon-carbon double bonds (X ′) having reactivity with SiH groups, the lower limit of the preferred range is Y / X ′ ≧ 0.3, more preferably Y / X ′ ≧ 0.5, Preferably, Y / X ′ ≧ 0.7, and the upper limit of the preferable range is 3 ≧ Y / X ′, more preferably 2 ≧ Y / X ′, and further 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, B Represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer.), Dicarbonyldichloroplatinum, a Karlstedt catalyst, and Ashby US Pat. No. 3,159,601. And platinum-hydrocarbon complexes described in US Pat. No. 3,159,662, and platinum alcoholate catalysts described in US Pat. No. 3,220,972 to Lamoreaux. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

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

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

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 mol, and the upper limit of the preferable addition amount is 10 ⁻¹ mol, more preferably 10 ⁻² mol, relative to 1 mol of the SiH group of the component (B).

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 relative to 1 mol of the hydrosilylation catalyst is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.

In the composition of the present invention, a curing retarder can be used for the purpose of improving 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, ene-yne compounds, maleate esters and the like. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, 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.

The addition amount of the curing retarder can be selected at various levels, the preferred amount of the lower limit is 10 ^-1 moles with respect to hydrosilylation catalyst 1mol used, more preferably 1 mol, the upper limit of the preferable 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.

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

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

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

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

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

Although the addition amount of the epoxy compound can be variously set, the lower limit of the preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] is preferably 1 part by weight, more preferably 3 parts by weight. The upper limit of the addition amount is 50 parts by weight, more preferably 25 parts by weight. If the addition amount is small, the effect of improving adhesiveness does not appear.
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 an organoaluminum compound and / or a borate ester and / or a titanium-based compound is preferable. Boric acid esters are preferred from the viewpoint of low colorability at curing and at high temperatures.

The amount used in the case of using a silanol condensation catalyst can be variously set, but the lower limit of the preferable addition amount with respect to 100 parts by weight of the coupling agent is 0.1 part by weight, more preferably 1 part by weight. The upper limit 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.

The organoaluminum compound used in the present invention can be used as a silanol condensation catalyst to improve adhesion and / or stabilization.
Examples of the organoaluminum compound used in the present invention include aluminum alcoholate compounds such as trimethoxyaluminum, triethoxyaluminum, triisopropylaluminum and trinormalpropylaluminum; aluminum organic acid salts such as naphthenic acid, stearic acid, octylic acid and benzoic acid Aluminum chelate compounds such as aluminum ethyl acetoacetoacetate diisopropylate, aluminum ethyl acetoacetoacetate diisobutyrate, aluminum tris (ethyl acetoacetate), aluminum bisethyl acetoacetate monoacetylacetonate, aluminum tris (acetylacetonate), etc. From the viewpoint of reactivity, adhesion to the substrate and adhesion, aluminum chelate and aluminum Muarukorato are preferred, and aluminum tris (ethylacetoacetate) from compatibility with the hydrosilylation curing reaction are preferred. These may be used in combination.

The boric acid ester used in the present invention can be used as a silanol condensation catalyst to improve adhesion and / or stabilize.
Examples of the boric acid ester used in the present invention include tri-2-ethylhexyl borate, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, trinormal butyl borate, tri-sec borate. -Butyl, tri-tert-butyl borate, triisopropyl borate, trinormalpropyl borate, triallyl borate, triethyl borate, trimethyl borate, boron methoxyethoxide and the like. As the borate ester, only one type may be used, or two or more types may be mixed and used. Mixing may be performed in advance or may be performed at the time of producing a cured product.

From the viewpoint of suppression of volatility and 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, triethyl borate is preferred, and trimethyl borate is more preferred.

The titanium-based compound used in the present invention is used as a silanol condensation catalyst, and can improve and / or stabilize the adhesion.
Titanium compounds used in the present invention include tetraalkoxy titaniums such as tetraisopropoxy titanium and tetrabutoxy titanium: titanium chelates such as titanium tetraacetylacetonate: general residues having residues such as oxyacetic acid and ethylene glycol And titanate coupling agents.
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 a silanol source 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. If the addition amount is small, the effect of improving adhesiveness does not appear.
These silanol source compounds may be used alone or in combination of two or more.

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

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

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. If the addition amount is small, the effect of improving adhesiveness does not appear.
Moreover, these carboxylic acids or / and acid anhydrides may be used alone or in combination of two or more.

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

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

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

The thermosetting resin may be a resin raw material 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.

Various thermoplastic resins may be added to the composition of the present invention for the purpose of modifying the properties. Various thermoplastic resins can be used. For example, a homopolymer of methyl methacrylate or a polymethyl methacrylate resin such as a random, block or graft polymer of methyl methacrylate and other monomers (for example, Hitachi Chemical) Optretz, etc.), acrylic resins represented by polybutyl acrylate resins such as butyl acrylate homopolymers or random, block or graft polymers of butyl acrylate and other monomers, bisphenol A, 3, A polycarbonate resin such as a polycarbonate resin containing 3,5-trimethylcyclohexylidenebisphenol or the like as a monomer structure (for example, APEC manufactured by Teijin Limited), a norbornene derivative, a vinyl monomer, or the like is copolymerized alone or copolymerized. Cycloolefin resins such as resins obtained by ring-opening metathesis polymerization of fats and norbornene derivatives, or hydrogenated products thereof (for example, APEL (registered trademark) manufactured by Mitsui Chemicals, ZEONOR (registered trademark), ZEONEEX (registered trademark) manufactured by Nippon Zeon Co., Ltd.) Trademark), ARTON (registered trademark) manufactured by JSR, etc.), olefin-maleimide resins such as copolymers of ethylene and maleimide (for example, TI-PAS (registered trademark) manufactured by Tosoh Corporation), bisphenol A, bis (4- Polyester resins such as polyesters obtained by polycondensation of bisphenols such as (2-hydroxyethoxy) phenyl) fluorene and diols such as diethylene glycol with phthalic acids such as terephthalic acid and isophthalic acid and aliphatic dicarboxylic acids (for example, Kanebo) O-PET (registered trademark), etc.), polyethersulfur Examples include, but are not limited to, rubber resins such as natural rubber and EPDM, as well as polyethylene resins, polyarylate resins, polyvinyl acetal resins, polyethylene resins, polypropylene resins, polystyrene resins, polyamide resins, silicone resins, and fluororesins. It is not a thing.

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. It is good also as a state or / and a mixed state.

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

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

The filler is preferably low radiation from the viewpoint of hardly damaging the semiconductor or electronic material to be sealed.
The 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, there is a method of adding a filler. 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 composition of the present invention. There can also be mentioned a method in which a filler is produced in the composition by reacting in a partial reactant in the composition or in the composition.

Among the fillers as described above, a silica-based filler is preferable from the viewpoint that the curing reaction is hardly inhibited and the effect of reducing the linear expansion coefficient is large.

The average particle diameter of the filler is preferably 10 μm or less and more preferably 5 μm or less in terms of easy penetration into a narrow gap of the sealing material.
The ratio of the particles having a particle diameter of 50 μm or more of the filler is preferably 1% by weight or less, and preferably 0.1% by weight or less in terms of easy penetration into the narrow gap of the sealing material. More preferably.

The particle size distribution of the filler can be variously set, including those used and / or proposed as fillers for conventional sealing materials such as epoxy. For example, particles of 24 μm or more may be 15% by weight or more and particles of 1 μm or less may be 3% by weight or more.
The average particle diameter of the filler and the ratio of particles having a particle diameter of 50 μm or more can be measured using a laser microtrack particle size analyzer.

The specific surface area of the filler can also be set in various ways including those used and / or proposed as fillers for conventional sealing materials such as epoxy. For example, 4 m ² / g or more, 4 m ² / g or less, 10 m ² / g or less can be arbitrarily set.
The specific surface area can be measured with a BET method monosorb specific surface area measuring device.

The vitrification rate of the filler can also be variously set, including those used and / or proposed as fillers for conventional sealing materials such as epoxy. For example, it can be set arbitrarily such as 97% or more.

The shape of the filler is preferably a spherical filler from the viewpoint of easily reducing the viscosity of the sealing material.
A filler may be used independently and may be used together 2 or more types.

The addition amount of the 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 is good, the preferred lower limit of the addition amount is 30% by weight in the total composition, More preferably, it is 50% by weight, and the upper limit of the preferable addition amount is 80% by weight in the total composition, more preferably 70% by weight.

As a method of mixing the filler, various methods can be used. However, in the point that the storage stability of the intermediate raw material of the composition tends to be good, the component (A) and the filler (C) are added to the component (A). A method of mixing the mixture and the component (B) is preferable. When the method of mixing the component (A) with the component (B) mixed with the component (B) and / or the filler, the component (B) is added in the presence or absence of the component (C). Since it has reactivity with moisture and / or fillers in the environment, it may be altered during storage.

An antioxidant may be added to the composition of the present invention. Examples of the anti-aging agent include commonly used anti-aging agents such as citric acid, phosphoric acid, and sulfur-based anti-aging agents. Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylic acid esters, 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.

A radical inhibitor may be added to the composition of the present 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.

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

The composition of the present invention includes, in addition to those used or / and proposed as a filler for conventional sealing materials such as epoxy, colorants, mold release agents, flame retardants, flame retardant aids, Surfactant, antifoaming agent, emulsifier, leveling agent, anti-repellent agent, ion trap agent, thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plastic Agent, reactive diluent, antioxidant, heat stabilizer, conductivity enhancer, antistatic agent, radiation blocking agent, nucleating agent, phosphorus peroxide decomposer, lubricant, pigment, metal deactivator, Thermal conductivity-imparting agents, physical property modifiers, and the like can be added within a range that does not impair the object and effect of the present invention.

The composition of 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 with respect to 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.

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

The optical material referred to in the present invention refers to general materials used for applications in which light such as visible light, infrared light, ultraviolet light, X-rays, and laser passes through the material.
Examples thereof include materials used for liquid crystal display devices such as color filter protective films, TFT flattening films, and substrate materials, and materials used for light emitting diodes (LEDs) such as sealants and die bond agents.

Furthermore, substrate materials, light guide plates, prism sheets, deflector plates, retardation plates, viewing angle correction films, polarizer protective films, color filters, etc., and various coating agents, protective films, sealants used in them in the liquid crystal display field Also, an adhesive and the like can be mentioned.

Also, LED element molding agents used in LED display devices, LED sealants, front glass protective films, front glass substitute materials and various coating agents, protective films, sealants, adhesives, etc. used therefor Also mentioned.

Also, color PDP (plasma display) anti-reflection film, optical correction film, housing material, front glass protective film, front glass substitute material and various coating agents, protective film, sealant, adhesive, etc. Also mentioned. In addition, substrate materials, light guide plates, prism sheets, deflector plates, retardation plates, viewing angle correction films, polarizer protective films and various coating agents, protective films, and sealants used in plasma addressed liquid crystal (PALC) displays Also, an adhesive and the like can be mentioned. Moreover, the protective film of the front glass in an organic EL (electroluminescence) display, a front glass substitute material, various coating agents used for them, a protective film, a sealing agent, an adhesive agent, etc. are mentioned. Moreover, various film substrates in a field emission display (FED), a front glass protective film, a front glass substitute material, and various coating agents, protective films, sealants, adhesives and the like used therefor.

In addition, in the optical recording field, VD (video disk), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disk), disk substrate for optical cards. Examples include materials, pickup lenses, protective films, and various coating agents, protective films, sealants, adhesives and the like used for them.

In the field of optical equipment, a steel camera lens material, a finder prism, a target prism, a finder cover, a light receiving sensor unit, and various coating agents, protective films, sealants, adhesives, and the like used for them. In addition, a video camera photographing lens, a finder, and various coating agents, protective films, sealants, adhesives and the like used for them can also be used. Moreover, the projection lens of a projection television, a protective film, the various coating agent used for them, a protective film, a sealing agent, an adhesive agent, etc. are mentioned. Examples of the lens materials for optical sensing devices, various films, and various coating agents, protective films, sealants, adhesives and the like used therefor.

In the field of optical components, fiber materials, lenses, waveguides, elements and various coating agents, protective films, sealants, adhesives and the like used in the vicinity of optical switches in optical communication systems are also included. Examples also include optical fiber materials around the optical connector, ferrules, various coating agents used for them, protective films, sealing agents, and adhesives. In the case of optical passive components and optical circuit components, lenses, waveguides, various coating agents, protective films, sealants, adhesives and the like used for them are also included. Examples also include substrate materials around the optoelectronic integrated circuit (OEIC), fiber materials, and various coating agents, protective films, sealants, adhesives and the like used for them.

In the field of optical fibers, illuminations and light guides for decorative displays, sensors for industrial use, displays and signs, etc., optical fibers for communication infrastructure and home use, and various coating agents and protective films used for them. , Sealants, adhesives and the like.

Examples of peripheral materials for semiconductor integrated circuits include resist materials for microlithography for LSI and VLSI materials.

In the field of automobiles and transport equipment, lamp materials such as automotive headlamps, tail lamps, and interior lamps, lamp reflectors, lamp lenses, exterior and interior products such as exterior panels and interior panels, glass substitutes, and various coating agents used for them , Protective film, sealant, adhesive and the like. Moreover, exterior parts for railway vehicles, glass substitutes, and various coating agents, protective films, sealants, adhesives and the like used for them are also included. In addition, aircraft exterior parts, glass substitutes, and various coating agents, protective films, sealants, adhesives and the like used for them are also included.

In the construction field, glass intermediate films, glass substitutes, solar cell peripheral materials, various coating agents used for them, protective films, sealants, adhesives, and the like are also included.
For agriculture, a house covering film is also included.

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 And various coating agents, protective films, sealants, adhesives and the like used therefor.

The electronic material referred to in the present invention is a material generally used for electrical and electronic applications. For example, in addition to peripheral materials for semiconductors, peripheral materials for circuit boards, peripheral materials for display devices such as liquid crystals, various peripheral materials for batteries, organic EL ( Electroluminescent) peripheral materials, optical communications, optical circuit peripheral materials, optical recording peripheral materials, and the like.

Peripheral materials for semiconductors include interlayer insulation films, resists, passivation films, junction coat films, buffer coat films, and other protective films used in semiconductor pre-processes, die bond agents, die bond films, and underfills used in semiconductor post-processes. , Anisotropic conductive adhesives (ACP), anisotropic conductive films (ACF), conductive adhesives used for connecting diodes, crystal resonators, etc., thermal conductive adhesives, sealing agents, Examples thereof include a fixing film and a fixing film. In this case, the semiconductor includes various types, for example, elements such as transistors and diodes, light emitting elements such as semiconductor lasers and light emitting diodes, light receiving elements such as optical sensors, ICs such as solar cells, memories, and logic circuits, LSIs, etc. Is mentioned. Specifically, die bonding agents for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, sensors, etc., sealing agents by potting, dipping, transfer molding, coating, screen printing, etc., COBs, COFs of ICs, LSIs, Potting sealant such as TAB, underfill such as flip chip, sealant for mounting IC packages such as BGA and CSP (reinforcing underfill), die bond film for stacked IC, sealing for wafer level CSP Agents, solder substitute connection materials, and the like.

Circuit board peripheral materials include, for example, single-sided / double-sided / multi-layer rigid printed circuit board materials / flexible printed circuit board materials / build-up boards and interlayer insulation materials for copper foil with resin, adhesives between board and copper foil, resist, filling via holes Agents, protective coating agents for substrates, contact protection (coating) agents for substrates and elements, substrates and substrates, substrates and cables, solder resists, and the like. The use of the substrate includes peripheral parts for connecting a movable part and liquid crystal as well as for a mother board and an interposer such as BGA / CSP / MCM. Moreover, the electrically conductive paste used for a membrane switch etc. is also mentioned.

Examples of peripheral materials for display devices such as liquid crystal include substrate materials, light guide plates, prism sheets, deflection plates, retardation plates, viewing angle correction films, adhesives, polarizer protective films, antireflection films, color filters, and black matrices. And a liquid crystal film such as a color filter protective film (flattening film) and a TFT protective film (flattening film), a coating agent, and an adhesive. Moreover, the sealing agent of color PDP (plasma display) anticipated as a next-generation flat panel display, an antireflection film, an optical correction film, a housing material, a front glass protective film, a front glass substitute material, and an adhesive may be mentioned. Furthermore, the molding material of the light emitting element used for a light emitting diode display apparatus, the protective film of a front glass, a front glass substitute material, an adhesive agent, etc. are mentioned. Other substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflector plates, retardation plates, viewing angle correction films, adhesives, polarizer protective films, various film substrates for field emission displays (FED), Examples include a front glass protective film, a front glass substitute material, and an adhesive.

Examples of various battery peripheral materials include substrate materials for solar cells, protective coating agents, sealing agents, separators for lithium ion batteries, fuel cells, sealing agents, protective agents, and the like.

Examples of organic EL (electroluminescence) peripheral materials include substrate materials, various protective coating agents, protective films, and adhesives.

Examples of optical communication and optical circuit peripheral materials include substrate materials, fiber materials, lenses, waveguides, sealants, adhesives, ferrules and the like used for optoelectronic integrated circuits, optical switches, optical connectors, and the like.

Optical recording peripheral materials include VD (video disk), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disk), optical card, etc. Examples include substrate materials, pickup lenses, protective films, sealants, and adhesives.

In addition, as next-generation optical / electronic functional organic materials, 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, The sealing agent of an element, an adhesive agent, etc. are mentioned.
Further, a protective agent, a coating agent, a sealant, an adhesive, etc. around the electronic component of the automobile can be mentioned.
In addition, the additive etc. to other resin etc. which are used for the said use are also mentioned.

A semiconductor, an electronic component, an electronic circuit, or an electrical contact can be sealed using the sealant of the present invention.
Semiconductors include not only those based on normal silicon but also those based on various metals such as gallium, indium, germanium, and zinc. In addition, organic semiconductors are also included. In addition to transistors, resistors, and diodes, the elements include light emitting elements such as light emitting diodes and semiconductor lasers, light receiving elements such as various sensors, and solar cells. Also included are various ICs such as memories and logic circuits, LSIs, and the like. The shape of the semiconductor includes not only a normal flat plate shape and block shape but also a thin film shape and a ball shape (ball semiconductor). Various sizes of semiconductors can be applied. For example, the semiconductor size may be as small as 0.3 mm square or as large as 25 mm square or 100 mm square. In addition, a protective film such as a passivation film provided on a semiconductor, a connection portion such as a solder bump, a gold bump, and an aluminum pad can be set as appropriate.

Examples of the electronic components include a live-back transformer and a capacitor, as well as an automobile peripheral electronic component, a liquid crystal peripheral electronic component, a battery peripheral electronic component, an organic EL (electroluminescence) peripheral electronic component, and an optical recording peripheral electronic component. Examples of automobile peripheral electronic components include ignition coils, electronic components for various electronic controls such as fuel supply, instrument components, lighting components, and the like. Examples of the liquid crystal peripheral electronic component include a polarizer, a color filter, a TFT transistor, a transparent conductive film, a liquid crystal, and a liquid crystal display device. Examples of the battery peripheral electronic component include a solar cell substrate, a lithium ion battery, and a fuel cell. Examples of the organic EL (electroluminescence) peripheral electronic component include an organic EL substrate. Optical recording peripheral electronic components include VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), optical card, etc. Examples include a disk substrate, a light emitting component, a pickup lens, and a light receiving component.

Examples of the electric circuit include a rigid printed board, a flexible printed board, a build-up board, and an optoelectronic circuit.
Examples of the electrical contact include a connection point between the board and the cable, a connection point between the cable and the cable or a connection point between the boards, a connection point between the board and the element, and a connection point between the cable and the element.

Various sealing methods can be used including those used or / and proposed as sealing methods for conventional sealing materials such as epoxy. For example, sealing can be performed by casting, potting, dipping, pressing, coating, or screen printing, or molding sealing such as transfer molding can be performed. Moreover, it can seal also by the method (underfill) which osmose | permeates a clearance gap after dispensing.

Various treatments can be performed as necessary at the time of sealing. For example, a treatment for defoaming a sealant or a partially reacted sealant by centrifugation, decompression, or the like can be applied to suppress voids generated at the time of sealing. You can also

Various pressure conditions for sealing can be set, and any of normal pressure, reduced pressure, and pressurized methods can be applied. In some cases, it is effective to reduce the pressure when infiltrating into a gap such as underfill or when it is desired to increase the permeability to a fine part. The pressure may be constant, or may be changed continuously or stepwise over time as necessary.

Various temperatures can be set for sealing. It may be effective to carry out in a warmed state when it penetrates into gaps, such as underfill, or when it is desired to increase the permeability to fine parts. In this case, for example, a temperature of 50 ° C. to 200 ° C. can be applied. The temperature may be constant, or may be changed continuously or stepwise over time as necessary.

Although the specific example of a sealing agent is given below, the sealing agent of this invention is not limited to this.
Examples of semiconductor sealants include sealants for sealing capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, sensors, etc. by casting, potting, dipping, transfer molding, coating, screen printing, etc. More specifically, light emitting diodes, ICs, LSIs, sensors and other potting sealants such as COB, COF, TAB, flip chip underfill (capillary flow type and compression flow type), IC packages such as BGA, CSP, etc. Examples of the sealing agent for mounting (reinforcing underfill), a sealing agent for stacked IC, and a sealing agent for wafer level CSP can be given. In addition, various protective films such as a passivation film, a junction coat film, and a buffer coat film used in the semiconductor pre-process are also examples of semiconductor sealing agents.

Sealing agents for electronic components include polarizing plates, color filters, TFT transistors, transparent conductive films, protective coating agents for liquid crystal display devices, liquid crystal sealing agents filled in cells, solar cell protective coating agents, lithium Sealing agent for ion batteries and fuel cells, protective coating agent for organic EL (electroluminescence), light source for optical recording, coating agent and sealing agent for light receiving element, protective coating agent and sealing agent for electronic parts around automobiles Also mentioned.

Examples of the sealing agent for electronic circuits include rigid printed circuit boards, flexible printed circuit board materials, solder resists for build-up boards, and protective coating agents.

Examples of the electrical contact sealing agent include contact protection (coating) agents such as substrates and elements, substrates and substrates, substrates and cables, and junction coating agents.

A semiconductor device can be manufactured by sealing a semiconductor by the above-described method using the sealing agent of the present invention. In this case, the sealing agent of the present invention may be used for the above-described applications and a semiconductor device may be manufactured by a normal method.

The semiconductor device is a device including various semiconductors, for example, generally, DIP, QFP, SOP, TSOP, PGA, CSP, BGA, PI resin, ceramic, BT resin, FR4 using various substrates such as FR4, QFN, Examples include various IC packages called COB, COF, TAB, wafer level CSP, stacked package, BCC, MCM, SIP, etc., light emitting diode components, optical sensor components, and substrates and modules on which they are mounted. It is done.

Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.
(Production Example 1)
A filter paper was mounted on a funnel having an inner diameter of 95 mm that can be sucked under reduced pressure, and 80 g of silica (Wakogel C-200 (registered trademark) manufactured by Wako Pure Chemical Industries, Ltd.) was filled. The rate of about 1 drop / second is adjusted by adjusting the degree of decompression of 300 g of triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd., which contains 2,800 ppm of 1,3-diallylurea determined by an internal standard method by gas chromatography. The adsorption filtration treatment was performed for 2 cycles. The recovered silica-treated triallyl isocyanurate was 250 g, and the content of 1,3-diallylurea determined by an internal standard method by gas chromatography was 90 ppm.

(Production Example 2)
A filter paper was mounted on a funnel having an inner diameter of 60 mm and which can be sucked under reduced pressure, and 20 g of synthetic aluminum silicate (Kyoward (registered trademark) 700, manufactured by Kyowa Chemical Industry Co., Ltd.) was charged. The rate of about 1 drop / second is adjusted by adjusting the degree of decompression of 130 g of triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd., whose content of 1,3-diallylurea determined by an internal standard method by gas chromatography is 2,800 ppm. The adsorption filtration treatment was performed for 2 cycles. The recovered synthetic aluminum silicate-treated triallyl isocyanurate was 110 g, and the content of 1,3-diallylurea determined by an internal standard method by gas chromatography was 530 ppm.

(Production Example 3)
A filter paper was mounted on a funnel having an inner diameter of 60 mm and capable of being sucked under reduced pressure, and 20 g of activated clay (Galeon Earth (registered trademark) manufactured by Mizusawa Chemical Co., Ltd.) was filled. An activated white clay-treated triallyl was subjected to adsorption filtration while reducing pressure of 157 g of triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd. with a 1,3-diallylurea content of 2,800 ppm determined by an internal standard method by gas chromatography. 60 g of isocyanurate was obtained. The content of 1,3-diallylurea determined by an internal standard method by gas chromatography was 520 ppm.

(Production Example 4)
200 g of 0.1N sulfuric acid aqueous solution and 200 g of triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd., having a content of 1,3-diallylurea of 2,800 ppm determined by an internal standard method by gas chromatography, are placed in a 500 ml Erlenmeyer flask. Magnetic stirring was performed at room temperature for 2 hours. The triallyl isocyanurate layer and the aqueous layer were separated with a separatory funnel, and the triallyl isocyanurate layer was washed 3 times with 200 g of pure water to confirm that the aqueous layer showed neutrality. Anhydrous sodium sulfate was added as a desiccant and left overnight. On the next day, sodium sulfate was removed by filtration to obtain 165 g of sulfuric acid-treated triallyl isocyanurate. The content of 1,3-diallylurea determined by an internal standard method by gas chromatography was 190 ppm.

(Production Example 5)
A membrane filter was attached to a pressure filter with an inner diameter of 35 mm, and 80 g of silica (Wakogel C-200 (registered trademark) manufactured by Wako Pure Chemical Industries, Ltd.) was filled. 300 g of triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd., whose content of 1,3-diallylurea determined by an internal standard method by gas chromatography was 2,800 ppm was filtered under a nitrogen pressure of about 0.1 MPa. The silica-treated triallyl isocyanurate obtained by the first pressure filtration treatment was 180 g, and the content of 1,3-diallylurea determined by an internal standard method by gas chromatography was 450 ppm. A membrane filter is newly attached to a pressure filter having an inner diameter of 35 mm, 40 g of silica (Wakogel C-200 (registered trademark) manufactured by Wako Pure Chemical Industries, Ltd.) is filled, and silica having a 1,3-diallyl urea content of 450 ppm is filled. 150 g of treated triallyl isocyanurate was subjected to pressure filtration at a nitrogen pressure of about 0.2 MPa. The silica-treated triallyl isocyanurate obtained by the second pressure filtration treatment was 85 g, and the content of 1,3-diallylurea determined by an internal standard method by gas chromatography was 90 ppm.

(Production Example 6)
A membrane filter was attached to a pressure filter having an inner diameter of 35 mm, and 40 g of silica (Wakogel C-200 (registered trademark) manufactured by Wako Pure Chemical Industries, Ltd.) was filled. 370 g of triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd., whose content of 1,3-diallylurea quantified by an internal standard method by gas chromatography was 2,800 ppm was filtered under a nitrogen pressure of about 0.2 MPa. The silica-treated triallyl isocyanurate obtained by the first pressure filtration treatment was 300 g, and the content of 1,3-diallylurea determined by an internal standard method by gas chromatography was 520 ppm. A membrane filter is newly attached to a pressure filter having an inner diameter of 35 mm, 40 g of silica (Wakogel C-200 (registered trademark) manufactured by Wako Pure Chemical Industries, Ltd.) is filled, and silica having a 1,3-diallyl urea content of 520 ppm is filled. 290 g of treated triallyl isocyanurate was subjected to pressure filtration at a nitrogen pressure of about 0.2 MPa. The silica-treated triallyl isocyanurate obtained by the second pressure filtration treatment was 230 g, and the content of 1,3-diallylurea determined by an internal standard method by gas chromatography was 140 ppm. Similarly, a new silica was filled and pressure filtration was performed to obtain 160 g of triaryl isocyanurate treated with 3 times of silica having a content of 1,3-diallyl urea of 30 ppm. In the same manner, new silica was filled and pressure filtration was performed to obtain 80 g of triallyl isocyanurate treated with 4 times of silica. No 1,3-diallylurea was detected from this silica 4-treated triallyl isocyanurate by gas chromatography. This corresponds to a 1,3-diallylurea content of 10 ppm or less from the detection sensitivity.

(Comparative Production Example 1)
A filter paper was mounted on a funnel having an inner diameter of 60 mm and capable of being sucked under reduced pressure, and 20 g of magnesium oxide (Kyowa Chemical Co., Ltd. Kyowa Mag (registered trademark) 150) was filled. The rate of about 1 drop / second is adjusted by adjusting the degree of decompression of 130 g of triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd., whose content of 1,3-diallylurea determined by an internal standard method by gas chromatography is 2,800 ppm. The adsorption filtration treatment was performed for 2 cycles. The recovered magnesium oxide-treated triallyl isocyanurate was 70 g, and the content of 1,3-diallylurea determined by an internal standard method by gas chromatography was 2700 ppm.

(Comparative Production Example 2)
160 g of triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd., which has a content of 1,3-diallylurea determined by an internal standard method by gas chromatography and 2,800 ppm, is placed in a 500 ml Erlenmeyer flask, and 2. Magnetic stirring was performed for 5 hours. The triallyl isocyanurate layer and the aqueous layer were separated with a separatory funnel, anhydrous sodium sulfate was added as a desiccant and left overnight. The next day, sodium sulfate was removed by filtration to obtain 130 g of sulfuric acid-treated triallyl isocyanurate. The content of 1,3-diallylurea determined by an internal standard method by gas chromatography was 1100 ppm.

(Production Example 7)
(Production of a compound having at least two SiH groups in one molecule)
To a 2 L autoclave, 510 g of toluene and 432 g of 1,3,5,7-tetramethylcyclotetrasiloxane (KF9902 manufactured by Shin-Etsu Chemical Co., Ltd.) were added and heated and stirred at a liquid temperature of 107 ° C. After replacing the gas phase with a nitrogen mixed gas having an oxygen content of 3%, triallyl isocyanurate (containing 2,800 ppm 1,3-diallylurea manufactured by Nippon Kasei Co., Ltd.), 90 g of toluene and a xylene solution of a platinum vinylsiloxane complex ( A mixed solution of 0.38 g (containing 3 wt% as platinum) was dropped over 25 minutes. Immediately after the dropping and at 30-minute intervals thereafter, the gas phase portion was replaced with a nitrogen mixed gas having an oxygen content of 3%, and the reaction was continued by pressurizing 0.1 MPa. 5.5 hours after the completion of dropping, ¹ H-NMR confirmed that the allyl group reaction rate was 95% or more, and the reaction was terminated by cooling. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure.

The viscosity of this product was 2.2 Pa · s. When this product was subjected to GPC measurement, a multimodal chromatogram was obtained, suggesting that it was a mixture. From the measurement of ¹ H-NMR, this product was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with the allyl group of triallyl isocyanurate, and 8.6 mmol. / G SiH group (1,2-dibromomethane as internal standard) was found. Moreover, although this product (it is set as the partial reaction material B) is a mixture, it contains (B) component of this invention which has the following structural formula from GC / MS as a main component. Moreover, the platinum vinylsiloxane complex which is (C) component of this invention is contained.

Example 1
1.0 g of the silica-treated triallyl isocyanurate obtained in Production Example 1 and 1.5 g of the partial reaction product B obtained in Production Example 7 were sufficiently mixed. One drop was dropped on a hot plate adjusted to a surface temperature of 135 ° C., and stirring with a spatula was continued until the liquid changed into a solid (gelation time), which was 93 seconds.

(Examples 2-6, Comparative Examples 1-3)
Gelation time was measured in the same manner as in Example 1 using the treated triallyl isocyanurate obtained in Production Examples 2 to 6 instead of the treated triisocyanurate obtained in Production Example 1. The results are shown as Examples 2 to 6 and shown in Table 1 together with Example 1.
Instead of the treated triisocyanurate obtained in Production Example 1, triallyl isocyanurate obtained by the treatment of Comparative Synthesis Examples 1 and 2 and gas chromatography used as a raw material for the above Production Examples and Comparative Production Examples The gelation time was measured in the same manner as in Example 1 using triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd., having a content of 1,3-diallylurea determined by the internal standard method of 2,800 ppm. The results are shown in Table 1 as Comparative Examples 1 to 3, respectively.

(Example 7)
To a silica-treated triallyl isocyanurate having a content of 90 ppm of 1,3-diallylurea obtained in Production Example 1, a toluene solution of 5% by weight of 1,3-diallylurea (Aldrich reagent, purity 98%) was added to 1,3 -500 ppm was added as diallylurea (the content of 1,3-diallylurea was 590 ppm). 1.0 g of silica-treated triallyl isocyanurate having a 1,3-diallylurea content of 590 ppm excluding toluene and 1.5 g of the partial reaction product B obtained in Production Example 7 were sufficiently mixed. One drop was dropped on a hot plate adjusted to a surface temperature of 135 ° C. and stirring with a spatula continued until the liquid changed to a solid (gelation time), which was 101 seconds.

(Example 8)
To a silica-treated triallyl isocyanurate having a content of 90 ppm of 1,3-diallylurea obtained in Production Example 1, a toluene solution of 5% by weight of 1,3-diallylurea (Aldrich reagent, purity 98%) was added to 1,3 -100 ppm was added as diallylurea (the content of 1,3-diallylurea was 190 ppm). 1.0 g of silica-treated triallyl isocyanurate having a 1,3-diallyl urea content of 190 ppm excluding toluene and 1.5 g of the partial reaction product B obtained in Production Example 7 were sufficiently mixed. One drop was dropped on a hot plate adjusted to a surface temperature of 135 ° C., stirring with a spatula was continued, and the time taken for the liquid to change to a solid (gel time) was 98 seconds.

Example 9
0.4 g of diallyl monoglycidyl isocyanurate (manufactured by Shikoku Kasei Co., Ltd.), 0.6 g of triallyl isocyanurate obtained in Production Example 6 and having a 1,3-diallyl urea content of 10 ppm or less, and partial reaction obtained in Production Example 7 The product B 1.2g was mixed well. One drop was dropped on a hot plate adjusted to a surface temperature of 135 ° C., and stirring with a spatula was continued until the time when the liquid changed to a solid (gelation time) was 88 seconds.

(Comparative Example 4)
Obtained in 0.4 g of diallyl monoglycidyl isocyanurate (manufactured by Shikoku Kasei Co., Ltd.), 0.4 g of triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd., which has a 1,3-diallyl urea content of 2,800 ppm, Further, 0.2 g of triallyl isocyanurate having a content of 1,3-diallyl urea of 10 ppm or less and 1.2 g of the partial reaction product B obtained in Production Example 7 were sufficiently mixed. One drop was dropped on a hot plate adjusted to a surface temperature of 135 ° C., and stirring with a spatula continued until the liquid changed to a solid (gel time), which was 110 seconds.

Claims (4)

(A) triallyl isocyanurate, (B) a compound having at least two SiH groups in one molecule, (C) a curable composition containing a hydrosilylation catalyst as an essential component, A curable composition having a content of 1,3-diallyl urea in a triallyl isocyanurate of 50 ppm or less,
Compound (B) is a chain and / or cyclic organopolysiloxane having at least two SiH groups in the molecule, or one or more carbon-carbon double bonds reactive with SiH groups in one molecule. Curability that is a compound that can be obtained by hydrosilylation reaction of the organic compound (α) contained and a linear and / or cyclic polyorganosiloxane (β) having at least two SiH groups in one molecule. Composition. The curable composition according to claim 1, wherein the component (A) is triallyl isocyanurate in which the content of 1,3-diallyl urea exceeding 700 ppm is reduced to 50 ppm or less by a purification treatment. The curable composition according to claim 2, wherein the purification treatment of triallyl isocyanurate is a treatment using a treating agent capable of removing a basic substance. The curable composition according to any one of claims 1 to 3, wherein the content of 1,3-diallylurea in triallyl isocyanurate as component (A) is 10 ppm or less.