WO2012060272A1 - Addition-curable liquid metallo-siloxane - Google Patents

Abstract

The disclosed metallo-siloxane compound is obtained by means of a first step of reacting a bifunctional silane compound (S1), a zirconium or titanium metal compound (M) and H₂O as necessary, and a second step of reacting the reaction product of said first step, a monofunctional silane compound (S2) and H₂O as necessary. The metallo-siloxane compound is produced by reactions in a specific molar ratio of said silane compound (S1) : said metal compound (M) : said silane compound (S2) : the H₂O of the first step : the H₂O of the second step, wherein each one molecule has at least one Si-H bond or C_2-10 alkenyl group. The metallo-siloxane compound is addition-curable and does not outgas, and, when included in a curable resin composition and cured, has excellent resistance to yellowing in heat.

Description

Liquid addition-curable metallosiloxane

The present invention relates to a metallosiloxane having addition curability, a curable resin composition having the metallosiloxane, and a cured product thereof.

In recent years, solid current devices such as semiconductor devices and optoelectronic devices have increased in current, and the amount of heat generation tends to increase accordingly. Therefore, high heat resistance and durability are required for package materials for sealing these devices. In addition to the above, the packaging material for optoelectronic devices is required to have transparency.

In order to meet the above requirements, resin compositions containing inorganic compounds have been used as resin materials having excellent heat resistance, heat stability (heat resistance coloration), transparency, and the like. Patent Document 1 describes a silylated polymetalloxane compound produced by hydrolysis and condensation of a reaction product obtained by reacting a polymetalloxane compound or a metal tetraalkoxide with an alkenyl group-containing monosilanol. Further, in Patent Document 2, an alkoxyzirconium compound or a mixture containing the same is added with an alkoxyzirconium compound or a mixture containing the same and water or a mixture of water and a water-soluble organic solvent. An organic solvent soluble zirconosiloxane produced by performing partial cohydrolytic condensation of a compound is described. However, these silylated polymetalloxane compounds and zirconosiloxanes are solids, and their heat-resistant non-yellowing has not been studied.

JP 2009-173910 A JP 2009-286986 A

An object of the present invention is to provide an addition-curable metallosiloxane compound which is excellent in heat-resistant non-yellowing property and does not emit outgas when contained in a curable resin composition and cured.
Another object of the present invention is to provide a curable resin composition that contains the metallosiloxane compound, does not generate outgas, and cures it to obtain a heat-resistant non-yellowing inorganic curable resin. It is in.
Another object of the present invention is to provide a heat-resistant non-yellowing cured product obtained by curing the curable resin composition.

As a result of intensive studies to solve the above problems, the present inventor obtained by reacting a bifunctional silane compound, a monofunctional silane compound, a metal compound, and, if necessary, H ₂ O at a specific molar ratio. The novel metallosiloxane compound produced has no outgassing during curing of the curable resin composition containing the metallosiloxane compound, and the cured product obtained by curing the curable resin composition has excellent heat-resistant non-yellowing And found the present invention.

That is, the present invention provides the following formula (1):

Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _6-14 aryl group, or a C _7-15 aralkyl group, X ¹ and X ² are the same or different and each represents a C _1-10 alkoxy group, a halogen atom, or a hydroxyl group.
And a silane compound (S1) represented by the following formula (2)

(In the formula, M represents zirconium or titanium, and Y ¹ to Y ⁴ are the same or different and represent a C _1-12 alkoxy group or a halogen atom.)
Or the first step of reacting the silane compound (S1) with the metal compound (M) and H ₂ O, the reaction product of the first step, and the following: Formula (3)

(Wherein R ³ to R ⁵ are the same or different and each represents a hydrogen atom, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _6-14 aryl group, or a C _7-15 aralkyl group, X ³ represents a C _1-10 alkoxy group, a halogen atom, or a hydroxyl group.)
Or a second step of reacting the reaction product of the first step with the silane compound (S2) and H ₂ O, and the silane compound (S2) represented by compound (S1): the metal compound (M): the silane compound (S2): H ₂ O in the first step: the second step _{H 2 O = m: n:} k: a: a molar ratio of b, and , M, n, k, a, b are reacted under conditions satisfying all of the following relationships (i) to (v), and at least one Si—H bond or C _2-10 alkenyl group is _{contained in} one molecule. A metallosiloxane compound characterized in that the metallosiloxane compound is provided.
(i) m> 0, n> 0, k> 0, a ≧ 0, b ≧ 0
(ii) n / m ≦ 3
_{(iii) (a + a m} ) / (m + n) = 0.03 ~ 0.8
(iv) k ≧ {a _h − (2a + a _m )}
(v) When X ³ is an alkoxy group or a halogen atom, b ≧ k, and when X ³ is a hydroxyl group, b = 0.
(In the above formula, a _m and a _h are a _m = 2 m and a _h = 4 n when X ¹ and X ² are both hydroxyl groups; only ^one of X ¹ and X ² is a hydroxyl group. A _m = m, a _h = m + 4n; if X ¹ and X ² are not hydroxyl groups, then a _m = 0 and a _h = 2m + 4n.)
The metallosiloxane compound is preferably a liquid at any temperature of 0 to 90 ° C.
The present invention also provides a curable resin composition comprising a compound having a Si—H bond and a compound having a C _2-10 alkenyl group, wherein at least the metallosiloxane compound (A) and the hydrosilylation catalyst (C). The curable resin composition characterized by containing these is provided.
The curable resin composition preferably further contains an inorganic filler (D).
The curable resin composition preferably further contains a silane coupling agent (E).
Furthermore, this invention provides the hardened | cured material formed by hardening | curing the said curable resin composition.

In the metallosiloxane compound according to the present invention, the curable resin composition containing the metallosiloxane compound has no outgassing during curing, and the cured product obtained by curing the curable resin composition has excellent heat-resistant non-yellowing properties. . Therefore, it is useful as a sealant or sealant for an electronic device such as an LED or a heat resistant hard coat.

[Metallosiloxane compound (A)]
The metallosiloxane compound (A) of the present invention has the following formula (1):

Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _6-14 aryl group, or a C _7-15 aralkyl group, X ¹ and X ² are the same or different and each represents a C _1-10 alkoxy group, a halogen atom, or a hydroxyl group.
And a silane compound (S1) represented by the following formula (2)

(In the formula, M represents zirconium or titanium, and Y ¹ to Y ⁴ are the same or different and represent a C _1-12 alkoxy group or a halogen atom.)
A first step of reacting the metal compound (M) represented by the formula ( ₂ ) with H ₂ O as necessary, the reaction product of the first step and the following formula (3)

(Wherein R ³ to R ⁵ are the same or different and each represents a hydrogen atom, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _6-14 aryl group, or a C _7-15 aralkyl group, X ³ represents a C _1-10 alkoxy group, a halogen atom, or a hydroxyl group.)
The silane compound (S1): the metal compound (M): the silane compound obtained through a second step of reacting H ₂ O with H ₂ O as necessary. (S2): H ₂ O in the first step: the second step _{H 2 O = m: n:} k: a: a molar ratio of b, and, m, n, k, a , b the following relation ( A compound produced by reacting under conditions satisfying all of i) to (v) and having at least one Si—H bond or C _2-10 alkenyl group in one molecule.
(i) m> 0, n> 0, k> 0, a ≧ 0, b ≧ 0
(ii) n / m ≦ 3
_{(iii) (a + a m} ) / (m + n) = 0.03 ~ 0.8
(iv) k ≧ {a _h − (2a + a _m )}
(v) When X ³ is an alkoxy group or a halogen atom, b ≧ k, and when X ³ is a hydroxyl group, b = 0.
(In the above formula, a _m and a _h are a _m = 2 m and a _h = 4 n when X ¹ and X ² are both hydroxyl groups; only ^one of X ¹ and X ² is a hydroxyl group. A _m = m, a _h = m + 4n; if X ¹ and X ² are not hydroxyl groups, then a _m = 0 and a _h = 2m + 4n.)
C _2-10 alkenyl groups include vinyl, allyl, 2-butenyl, 2-pentanyl, 2-hexynyl and the like. As the C _2-10 alkenyl group, a vinyl group and an allyl group are preferable. Note that m, n, and k are molar ratios of their total amounts when two or more silane compounds (S1), metal compounds (M), and silane compounds (S2) are used, as will be described later. .

In the present invention, in the first step, a so-called bifunctional silane having two functional groups (X ¹ , X ² ) of any one of a hydrolyzable group and a hydroxyl group which are alkoxy groups or halogen atoms in one molecule. The compound (S1) [hereinafter referred to as a bifunctional silane compound (S1)] is reacted with the metal compound (M). In the first step, it is considered that a main chain in which a silicon atom and a metal atom (Zr, Ti) of the bifunctional silane compound (S1) are bonded via an oxygen atom is formed.

The amount of the metal compound (M) used in the first step is not more than 3 times the mol of the bifunctional silane compound (S1) [formula (ii) above], “the above bifunctional silane compound (S1) and metal The ratio of “total use amount of H ₂ O and hydroxyl groups in the silane compound (S1)” to “total use amount with compound (M)” is set to 0.03 to 0.8 (molar ratio). Formula (iii)]. A metallosiloxane compound finally obtained by synthesizing the main chain by reacting the bifunctional silane compound (S1), the metal compound (M) and, if necessary, H ₂ O under the conditions as described above. It is considered that A) preferably becomes liquid at any temperature of 0 to 90 ° C. The molar ratio of “total amount used of H ₂ O and hydroxyl groups in silane compound (S1)” to “total amount used of bifunctional silane compound (S1) and metal compound (M)” is preferably It can be set in the range of 0.05 to 0.6, particularly preferably 0.1 to 0.45.

Subsequently, in the second step, one functional group (X ³ ) of one of the hydrolyzable group and hydroxyl group, which is an alkoxy group or a halogen atom, and one reaction group obtained in the first step is included in one molecule. A so-called monofunctional silane compound (S2) [hereinafter, referred to as a monofunctional silane compound (S2)] is reacted with H ₂ O as necessary. It is considered that a metallosiloxane compound in which a silyl group derived from the monofunctional silane compound (S2) is introduced into the side chain in the second step is obtained.

In the present invention, the amount of the monofunctional silane compound (S2) used is the same as or more than the number of moles of hydrolyzable groups remaining in the reaction solution obtained in the first step. [Formula (iv) above]. The number of moles of the monofunctional silane compound (S2) is preferably 1.5 times or more, more preferably 2 times or more of the number of moles of the hydrolyzable group remaining in the reaction solution obtained in the first step. . In the second step, the residual amount of hydrolyzable groups in the finally obtained metallosiloxane compound (A) is minimized by making the amount of the monofunctional silane compound (S2) used as described above. It is possible to obtain a metallosiloxane compound that does not generate outgas when cured and can obtain a heat-resistant non-yellowing cured product.

In the present invention, the amount of H ₂ O used in the first step depends on the number of functional groups X ¹ and X ² of the bifunctional silane compound (S1) when both or both are hydroxyl groups. It is not necessary to reduce or use H ₂ O. In the second step, when the functional group (X ³ ) of the monofunctional silane compound (S2) is a hydroxyl group, H ₂ O may not be used.

The reaction in the first step and the second step can be performed, for example, at 50 to 150 ° C., preferably 60 to 130 ° C., more preferably 60 to 100 ° C. However, the dropping of H ₂ O is preferably performed at a temperature of −30 ° C. or lower, for example. The reaction time in the first step and the second step varies depending on the reaction temperature and the type of silane compound and metal compound used, but can be, for example, 10 minutes to 10 hours, preferably 1 to 5 hours. .

The metallosiloxane compound (A) produced by the above production method is preferably a liquid at any temperature of 0 to 90 ° C., more preferably any temperature of 0 to 70 ° C., particularly preferably 0 to It is liquid at any temperature of 30 ° C.

[Bifunctional silane compound (S1)]
The bifunctional silane compound (S1) used in the reaction for producing the metallosiloxane compound (A) of the present invention is represented by the following formula (1).

Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _6-14 aryl group, or a C _7-15 aralkyl group, X ¹ and X ² are the same or different and each represents a C _1-10 alkoxy group, a halogen atom, or a hydroxyl group.
And known dialkoxysilane compounds, dihalogenated silane compounds, or dihydroxysilane compounds conventionally used for the production of polysiloxanes, polymetallosiloxanes, and the like.

_Examples of the C _1-10 alkyl group in R ¹ and R ² in the formula include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, decyl group, etc .; C _2-10 the alkenyl group, a vinyl group, an allyl group, a 2-butenyl group, 2-pentanyl group, 2-hexynyl group; the C _6-14 aryl group, a phenyl group, a naphthyl group; a C _7-15 aralkyl group Examples include benzyl group.

Examples of the C _1-12 alkoxy group in X ¹ and X ² in the above formula (1) include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Can be mentioned. In this specification, a silane compound containing one or more Si—H bonds is an “H-type” silane compound; a silane compound containing one or more C _2-10 alkenyl groups such as a vinyl group or an allyl group is “vinyl”. "Type" silane compounds; silane compounds containing neither Si-H bonds nor _C2-10 alkenyl groups are referred to as "other" silane compounds.

Examples of the H-type dialkoxysilane compound include diC _1-12 alkoxysilane compounds containing two hydrogen atoms such as dimethoxysilane, diethoxysilane, dipropoxysilane, and dibutoxysilane; methyldimethoxysilane, methyldiethoxysilane , Methyldipropoxysilane, methyldibutoxysilane, ethyldimethoxysilane, ethyldiethoxysilane, ethyldipropoxysilane, ethyldibutoxysilane, propyldimethoxysilane, propyldiethoxysilane, propyldipropoxysilane, propyldibutoxysilane, butyl Dimethoxysilane, Butyldiethoxysilane, Butyldipropoxysilane, Butyldibutoxysilane, Phenyldimethoxysilane, Phenyldiethoxysilane, Phenyldipropoxysilane, Phenyldibu Kishishiran, naphthyl dimethoxysilane, naphthyl diethoxy silane, naphthyl dipropoxy silane, naphthyl dibutoxy silane, benzyl dimethoxysilane, benzyl diethoxysilane, benzyl-di propoxysilane, benzyl dibutoxy di C ₁ to silane containing one hydrogen atom, such as _-12 alkoxysilane compounds and the like.

Examples of vinyl type dialkoxysilane compounds include divinyldimethoxysilane, diallyldimethoxysilane, di (2-butenyl) propyldimethoxysilane, di (2-pentanyl) dimethoxysilane, divinyldiethoxysilane, diallyldiethoxysilane, di ( 2-butenyl) propyldiethoxysilane, di (2-pentanyl) diethoxysilane, divinyldipropoxysilane, diallyldipropoxysilane, di (2-butenyl) propyldipropoxysilane, di (2-pentanyl) dipropoxysilane, DiC _2-10 alkenyl di C _1-12 alkoxysilane compounds such as divinyldibutoxysilane, diallyldibutoxysilane, di (2-butenyl) propyldibutoxysilane, di (2-pentanyl) dibutoxysilane; methylvinyldimethoxy Sisilane, ethylvinyldimethoxysilane, propylvinyldimethoxysilane, butylvinyldimethoxysilane, methylvinyldiethoxysilane, ethylvinyldiethoxysilane, propylvinyldiethoxysilane, butylvinyldiethoxysilane, methylallyldimethoxysilane, ethylallyldimethoxysilane C _1-10 alkyl C _2-10 alkenyl di C _1-12 such as propyl allyl dimethoxy silane, butyl allyl dimethoxy silane, methyl allyl diethoxy silane, ethyl allyl diethoxy silane, propyl allyl diethoxy silane, butyl allyl diethoxy silane Alkoxysilane compounds; phenylvinyldimethoxysilane, naphthylvinyldimethoxysilane, phenylvinyldiethoxysilane, naphthylvinyldiethoxysilane, pheny Vinyl dipropoxy silane, naphthyl vinyl dipropoxy silane, phenyl vinyl dibutoxy silane, naphthyl vinyl dibutoxy silane, phenyl allyl dimethoxy silane, naphthyl allyl dimethoxy silane, phenyl allyl diethoxy silane, naphthyl allyl diethoxy silane, phenyl allyl dipropoxy silane C _6-14 aryl C _2-10 alkenyl di C _1-12 alkoxy silane compounds such as naphthyl allyl dipropoxy silane, phenyl allyl dibutoxy silane, naphthyl allyl dibutoxy silane; benzyl vinyl dimethoxy silane, benzyl vinyl diethoxy silane, benzyl Vinyl dipropoxy silane, benzyl vinyl dibutoxy silane, benzyl allyl dimethoxy silane, benzyl allyl diethoxy silane, benzyl allyl dipropoxy Shishiran, C _7-15 aralkyl C _2-10 Arukeniruji C _1-12 alkoxysilane compounds such as benzyl allyl dibutoxy silane.

Other dialkoxysilane compounds include, for example, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, dibutyldiethoxysilane, dimethyl Di-C _1-10 alkyl di-C ₁ such as dipropoxy silane, diethyl dipropoxy silane, dipropyl dipropoxy silane, dibutyl dipropoxy silane, dimethyl dibutoxy silane, diethyl dibutoxy silane, dipropyl dibutoxy silane, dibutyl dibutoxy silane _-12 alkoxysilane compounds; diphenyldimethoxysilane, dinaphthyldimethoxysilane, diphenyldiethoxysilane, dinaphthyldiethoxysilane, diphenyldipropoxy DiC _6-14 aryl di C _1-12 alkoxysilane compounds such as silane, dinaphthyl dipropoxy silane, diphenyl dibutoxy silane, dinaphthyl dibutoxy silane; dibenzyl dimethoxy silane, dibenzyl diethoxy silane, dibenzyl dipropoxy silane , DiC _7-15 aralkyl di C _1-12 alkoxysilane compounds such as dibenzyldibutoxysilane; methylphenyldimethoxysilane, ethylphenyldimethoxysilane, propylphenyldimethoxysilane, butylphenyldimethoxysilane, methylphenyldiethoxysilane, ethylphenyl Diethoxysilane, propylphenyldiethoxysilane, butylphenyldiethoxysilane, methylnaphthyldimethoxysilane, ethylnaphthyldimethoxysilane, propylnaphthyldimethoxysilane , Butyl naphthyl dimethoxysilane, methyl naphthyl diethoxy silane, ethyl naphthyl diethoxy silane, propyl naphthyl diethoxy silane, C _1-10 alkyl C _6-14 aryldi C _1-12 alkoxysilane compounds such as butyl naphthyl diethoxy silane; methyl C _1-10 alkyl C such as benzyldimethoxysilane, ethylbenzyldimethoxysilane, propylbenzyldimethoxysilane, butylbenzyldimethoxysilane, methylbenzyldiethoxysilane, ethylbenzyldiethoxysilane, propylbenzyldiethoxysilane, butylbenzyldiethoxysilane Examples thereof include _7-15 aralkyldi C _1-12 alkoxysilane compounds.

Examples of the H-type dihalogenated silane compound include dihalogenated silane compounds containing two hydrogen atoms such as difluorosilane, dichlorosilane, and dibromosilane; difluoromethylsilane, dichloromethylsilane, dibromomethylsilane, difluoroethylsilane, and dichloroethyl. Silane, dibromoethylsilane, difluoropropylsilane, dichloropropylsilane, dibromopropylsilane, difluorobutylsilane, dichlorobutylsilane, dibromobutylsilane, difluorophenylsilane, dichlorophenylsilane, dibromophenylsilane, difluoronaphthylsilane, dichloronaphthylsilane, dibromo Contains one hydrogen atom such as naphthylsilane, fluorobenzylsilane, dichlorobenzylsilane, dibromobenzylsilane Halogenated silane compounds, and the like.

Examples of vinyl-type dihalogenated silane compounds include difluorodivinylsilane, dichlorodivinylsilane, dibromodivinylsilane, difluorodiallylsilane, dichlorodiallylsilane, dibromodiallylsilane, difluorodi (2-butenyl) silane, and dichlorodi (2-butenyl) silane. Dihalogenated diC _2-10 alkenylsilane compounds such as dibromodi (2-butenyl) silane, difluorodi (2-pentanyl) silane, dichlorodi (2-pentanyl) silane, dibromodi (2-pentanyl) silane; difluoromethylvinylsilane, difluoro Ethyl vinyl silane, difluoropropyl vinyl silane, difluorobutyl vinyl silane, dichloromethyl vinyl silane, dichloroethyl vinyl silane, dichloropropyl vinyl silane Dichlorobutylvinylsilane, dibromomethylvinylsilane, dibromoethylvinylsilane, dibromopropylvinylsilane, dibromobutylvinylsilane, difluoromethylallylsilane, difluoroethylallylsilane, difluoropropylallylsilane, difluorobutylallylsilane, dichloromethylallylsilane, dichloroethylallylsilane, dichloropropylallylsilane, dichlorobutyl allylsilanes, dibromomethyl allyl silane, dibromo ethyl allyl silanes, dibromopropyl allyl silane, dihalogenated C _1-10 alkyl C _2-10 alkenyl silane compound such as dibromo butyl allyl silane; difluorophenyl vinyl silane, difluoro-naphthyl vinyl silane, dichlorophenyl vinyl silane, dichloro-naphthyl vinyl Silane, dibromophenyl vinyl silane, dibromo-naphthyl vinyl silane, difluorophenyl allyl silane, difluoro naphthyl allyl silanes, dichlorophenyl allyl silane, dichloro naphthyl allyl silanes, dibromophenyl allyl silane, dihalogenated C _6-14 aryl C _2-10 alkenyl silane compounds such as dibromo naphthyl allyl silanes; difluoro Examples thereof include dihalogenated C _7-15 aralkyl C _2-10 alkenylsilane compounds such as benzylvinylsilane, dichlorobenzylvinylsilane, dibromobenzylvinylsilane, difluorobenzylallylsilane, dichlorobenzylallylsilane, and dibromobenzylallylsilane.

Examples of other dihalogenated silane compounds include difluorodimethylsilane, dichlorodimethylsilane, dibromodimethylsilane, difluorodiethylsilane, dichlorodiethylsilane, dibromodiethylsilane, difluorodipropylsilane, dichlorodipropylsilane, dibromodipropylsilane, Dihalogenated diC _1-10 alkylsilane compounds such as difluorodibutylsilane, dichlorodibutylsilane, dibromodibutylsilane; difluorodiphenylsilane, dichlorodiphenylsilane, dibromodiphenylsilane, difluorodinaphthylsilane, dichlorodinaphthylsilane, dibromodinaphthylsilane Dihalogenated di C _6-14 arylsilane compounds such as: difluorodibenzylsilane, dichlorodibenzylsilane, dibromodi Dihalogenated di-C _7-15 aralkylsilane compounds such as benzylsilane; difluoromethylphenylsilane, difluoroethylphenylsilane, difluoropropylphenylsilane, difluorobutylphenylsilane, dichloromethylphenylsilane, dichloroethylphenylsilane, dichloropropylphenylsilane, Dihalogenated C _1-10 alkyl C _6-14 arylsilane compounds such as dichlorobutylphenylsilane, dibromomethylnaphthylsilane, dibromoethylnaphthylsilane, dibromopropylnaphthylsilane, dibromobutylnaphthylsilane; difluoromethylbenzylsilane, difluoroethylbenzylsilane , Difluoropropylbenzylsilane, difluorobutylbenzylsilane, dichloromethylbenzylsilane, dichloroethyl Benzyl silane, dichloropropyl benzyl silane, dichlorosilane butyl benzyl silane, dibromomethyl benzyl silane, dibromo ethyl benzyl silane, dibromopropyl benzyl silane, dihalogenated such dibromo butylbenzyl silane C _1-10 alkyl C _7-15 aralkyl silane compounds, and the like Can be mentioned.

Examples of the H-type dihydroxysilane compound include dihydroxysilane (containing two hydrogen atoms); methyldihydroxysilane, ethyldihydroxysilane, propyldihydroxysilane, butyldihydroxysilane, phenyldihydroxysilane, naphthyldihydroxysilane, benzyldihydroxysilane, and the like. A dihydroxysilane compound containing one hydrogen atom is exemplified.

Examples of vinyl-type dihydroxysilane compounds include diC _2-10 alkenyldihydroxysilane compounds such as divinyldihydroxysilane, diallyldihydroxysilane, di (2-butenyl) dihydroxysilane, and di (2-pentanyl) dihydroxysilane; C _1-10 alkyl C _2-10 alkenyl dihydroxy silane such as silane, ethyl vinyl dihydroxy silane, propyl vinyl dihydroxy silane, butyl vinyl dihydroxy silane, methyl allyl dihydroxy silane, ethyl allyl dihydroxy silane, propyl allyl dihydroxy silane, butyl allyl dihydroxy silane Compound; phenyl vinyl dihydroxy silane, naphthyl vinyl dihydroxy silane, phenyl allyl dihydroxy silane, naphthyl allyl C _6-14 aryl C _2-10 alkenyl dihydroxy silane compounds such as hydroxy silane; benzyl vinyl dihydroxysilane, C _7-15 aralkyl C _2-10 alkenyl dihydroxysilane compounds such as benzyl allyl dihydroxy silane.

Examples of other dihydroxysilane compounds include di-C _1-10 alkyl dihydroxysilane compounds such as dimethyldihydroxysilane, diethyldihydroxysilane, dipropyldihydroxysilane, and dibutyldihydroxysilane; di-C such as diphenyldihydroxysilane and dinaphthyldihydroxysilane. _6-14 aryl dihydroxysilane compounds; di-C _7-15 aralkyl dihydroxysilane compounds such as dibenzyldihydroxysilane; methylphenyldihydroxysilane, ethylphenyldihydroxysilane, propylphenyldihydroxysilane, butylphenyldihydroxysilane, methylnaphthyldihydroxysilane, ethyl Naphthyl dihydroxy silane, propyl naphthyl dihydroxy silane, butyl naphthyl dihydroxy silane Which C _1-10 alkyl C _6-14 aryl dihydroxy silane compound; methylbenzyl dihydroxy silane, ethylbenzyl dihydroxy silane, propyl benzyl dihydroxy silane, C _1-10 alkyl C _7-15 aralkyl dihydroxy silane, such as butyl benzyl dihydroxy silane Can be mentioned. As the silane compound (S1), the compounds exemplified above can be used alone or in admixture of two or more.

In the silane compound (S1), the C _1-10 alkyl group as R ¹ and R ² in the above formula (1) is particularly preferably a C _1-5 alkyl group, and the C _2-10 alkenyl group is particularly preferably C _{2− 5-} Alkenyl groups are preferred. R ¹ and R ² are preferably a methyl group, an ethyl group, a phenyl group, a vinyl group, or an allyl group from the viewpoint of heat-resistant non-yellowing. Further, a phenyl group is more preferable from the viewpoint of hydrolysis resistance.

As the C _1-12 alkoxy group in X ¹ and X ² in the above formula (1), a C _1-6 alkoxy group is particularly preferable. X ¹ and X ² are preferably a methoxy group, an ethoxy group, a chlorine atom, a bromine atom and a hydroxyl group from the viewpoint of availability, and more preferably a methoxy group and an ethoxy group from the viewpoint of stability before the reaction.

Specific examples of the silane compound (S1) include di-C _1-10 alkyl di-C _1-12 alkoxy silane (and di-C _1-5 alkyl di-C _1-6 alkoxy silane) and di-C _{6- 14} aryldi C _1-12 alkoxysilanes (more preferably diphenyldiC _1-6 alkoxysilanes) are preferred, especially dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, divinyldimethoxysilane, diallyldimethoxysilane, dimethyldiethoxysilane, Diethyldiethoxysilane, diphenyldiethoxysilane, divinyldiethoxysilane, or diallyldiethoxysilane can be preferably used.

[Monofunctional silane compound (S2)]
The monofunctional silane compound (S2) used in the reaction for producing the metallosiloxane compound (A) of the present invention has the following formula (3):

(Wherein R ³ to R ⁵ are the same or different and each represents a hydrogen atom, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _6-14 aryl group, or a C _7-15 aralkyl group, X ³ represents a C _1-10 alkoxy group, a halogen atom, or a hydroxyl group.)
And known monoalkoxysilane compounds, monohalogenated silane compounds, or monohydroxysilane compounds conventionally used in the production of polysiloxanes, polymetallosiloxanes, and the like.

As the C _1-10 alkyl group, C _2-10 alkenyl group, C _6-14 aryl group, or C _7-15 aralkyl group in R ³ to R ⁵ in the formula, R ¹ in the above bifunctional silane compound, Examples of R ² can be used. As the C _1-10 alkoxy group and halogen atom in X ³ , those exemplified as X ¹ and X ² in the silane compound (S1) can be used.

Examples of the H-type monoalkoxysilane compound include C _1-12 alkoxysilane compounds containing three hydrogen atoms such as methoxysilane, ethoxysilane, propoxysilane, and butoxysilane; methylmethoxysilane, methylethoxysilane, methylpropoxysilane, Methylbutoxysilane, ethylmethoxysilane, ethylethoxysilane, ethylpropoxysilane, ethylbutoxysilane, propylmethoxysilane, propylethoxysilane, propylpropoxysilane, propylbutoxysilane, butylmethoxysilane, butylethoxysilane, butylpropoxysilane, butylbutoxy Silane, phenylmethoxysilane, phenylethoxysilane, phenylpropoxysilane, phenylbutoxysilane, naphthylmethoxysilane, naphthyl ester Kishishiran, naphthyl propoxysilane, naphthyl butoxysilane, benzyl trimethoxysilane, benzyl triethoxysilane, benzyl propoxysilane, C _1-12 alkoxysilane compound containing two hydrogen atoms, such as benzyl butoxysilane; dimethyl silane, diethyl silane, di Propylmethoxysilane, dibutylmethoxysilane, dimethylethoxysilane, diethylethoxysilane, dipropylethoxysilane, dibutylethoxysilane, dimethylpropoxysilane, diethylpropoxysilane, dipropylpropoxysilane, dibutylpropoxysilane, dimethylbutoxysilane, diethylbutoxysilane, DiC _1-10 alkyl C _1-12 alkoxysilane containing one hydrogen atom such as dipropylbutoxysilane, dibutylbutoxysilane Run; diC _6-14 containing one hydrogen atom such as diphenylmethoxysilane, dinaphthylmethoxysilane, diphenylethoxysilane, dinaphthylethoxysilane, diphenylpropoxysilane, dinaphthylpropoxysilane, diphenylbutoxysilane, dinaphthylbutoxysilane Aryl C _1-12 alkoxysilane; dibenzylmethoxysilane, dibenzylethoxysilane, dibenzylpropoxysilane, dibenzylbutoxysilane and the like containing a diC _7-15 aralkyl C _1-12 alkoxysilane and the like It is done.

Examples of vinyl monoalkoxysilane compounds include trivinylmethoxysilane, trivinylethoxysilane, trivinylpropoxysilane, trivinylbutoxysilane, triallylmethoxysilane, triallylethoxysilane, triallylpropoxysilane, triallylbutoxysilane. Tri C _2-10 alkenyl C _1-12 alkoxy silane compounds such as: methyl divinyl methoxy silane, methyl divinyl ethoxy silane, methyl divinyl propoxy silane, methyl divinyl butoxy silane, ethyl divinyl methoxy silane, ethyl divinyl ethoxy silane, ethyl divinyl propoxy silane , Ethyldivinylbutoxysilane, propyldivinylmethoxysilane, propyldivinylethoxysilane, propyldivinylpropoxysilane, propyl Divinylbutoxysilane, butyldivinylmethoxysilane, butyldivinylethoxysilane, butyldivinylpropoxysilane, butyldivinylbutoxysilane, methyldiallylmethoxysilane, methyldiallylethoxysilane, methyldiallylpropoxysilane, methyldiallylbutoxysilane, ethyldiallylmethoxysilane, ethyl Diallylethoxysilane, ethyldiallylpropoxysilane, ethyldiallylbutoxysilane, propyldiallylmethoxysilane, propyldiallylethoxysilane, propyldiallylpropoxysilane, propyldiallylbutoxysilane, butyldiallylmethoxysilane, butyldiallylethoxysilane, butyldiallylpropoxysilane, butyl C _1-10 alkyl di-C _2-10 such as diallyl butoxysilane Alkenyl C _1-12 alkoxysilane compounds; phenyldivinylmethoxysilane, phenyldivinylethoxysilane, phenyldivinylpropoxysilane, phenyldivinylbutoxysilane, naphthyldivinylmethoxysilane, naphthyldivinylethoxysilane, naphthyldivinylpropoxysilane, naphthyldivinylbutoxysilane, phenyl C _6-14 aryldi C _2-10 alkenyl such as diallylmethoxysilane, phenyldiallylethoxysilane, phenyldiallylpropoxysilane, phenyldiallylbutoxysilane, naphthyldiallylmethoxysilane, naphthyldiallylethoxysilane, naphthyldiallylpropoxysilane, naphthyldiallylbutoxysilane C _1-12 alkoxysilane; benzyl divinyl silane, benzyl divinyl Tokishishiran, benzyl divinyl propoxysilane, benzyl divinyl butoxysilane, benzyl diallyl silane, benzyl diallyl silane, benzyl diallyl propoxysilane, C _7-15 Ararukiruji C _2-10 alkenyl C _1-12 alkoxysilane compounds such as benzyl diallyl butoxysilane Etc.

Examples of the vinyl-type monoalkoxysilane compound include, for example, dimethylvinylmethoxysilane, diethylvinylmethoxysilane, dipropylvinylmethoxysilane, dibutylvinylmethoxysilane, dimethylvinylethoxysilane, diethylvinylethoxysilane, dipropylvinylethoxysilane, Dibutylvinylethoxysilane, dimethylvinylpropoxysilane, diethylvinylpropoxysilane, dipropylvinylpropoxysilane, dibutylvinylpropoxysilane, dimethylvinylbutoxysilane, diethylvinylbutoxysilane, dipropylvinylbutoxysilane, dibutylvinylbutoxysilane, dimethylallylmethoxy Silane, diethylallylmethoxysilane, dipropylallylmethoxysilane, dibutylallylmeth Sisilane, dimethylallylethoxysilane, diethylallylethoxysilane, dipropylallylethoxysilane, dibutylallylethoxysilane, dimethylallylpropoxysilane, diethylallylpropoxysilane, dipropylallylpropoxysilane, dibutylallylpropoxysilane, dimethylallylbutoxysilane, diethyl DiC _1-10 alkyl C _2-10 alkenyl C _1-12 alkoxysilane compounds such as allylbutoxysilane, dipropylallylbutoxysilane, dibutylallylbutoxysilane; diphenylvinylmethoxysilane, dinaphthylvinylmethoxysilane, diphenylvinylethoxysilane , Dinaphthyl vinyl ethoxysilane, diphenyl vinyl propoxy silane, dinaphthyl vinyl propoxy silane, diphenyl vinyl but Sisilane, dinaphthyl vinyl butoxy silane, diphenyl allyl methoxy silane, dinaphthyl allyl methoxy silane, diphenyl allyl ethoxy silane, dinaphthyl allyl ethoxy silane, diphenyl allyl propoxy silane, dinaphthyl allyl propoxy silane, diphenyl allyl butoxy silane, dinaphthyl allyl butoxy _{DiC 6-14} aryl C _2-10 alkenyl C _1-12 alkoxysilane compounds such as silane; dibenzylvinylmethoxysilane, dibenzylvinylethoxysilane, dibenzylvinylpropoxysilane, dibenzylvinylbutoxysilane, dibenzylallylmethoxy Di-C _7-15 aralkyl C _2-10 alkenyl C ₁ such as silane, dibenzylallylethoxysilane, dibenzylallylpropoxysilane, dibenzylallylbutoxysilane _-12 alkoxysilane compounds and the like.

Examples of other monoalkoxysilane compounds include trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldiethylmethoxysilane, phenyldiethylethoxysilane, and diphenyl. Examples include methylmethoxysilane, diphenylmethylethoxysilane, diphenylethylmethoxysilane, and diphenylethylethoxysilane.

Examples of the H-type monohalogenated silane compound include monohalogenated silane compounds containing three hydrogen atoms such as monofluorosilane, monochlorosilane, and monobromosilane; fluoromethylsilane, chloromethylsilane, bromomethylsilane, and fluoroethyl Silane, chloroethylsilane, bromoethylsilane, fluoropropylsilane, chloropropylsilane, bromopropylsilane, fluorobutylsilane, chlorobutylsilane, bromobutylsilane, fluorophenylsilane, chlorophenylsilane, bromophenylsilane, fluoronaphthylsilane, chloro Monohalogenated silane compounds containing two hydrogen atoms such as naphthylsilane, bromonaphthylsilane, fluorobenzylsilane, chlorobenzylsilane, bromobenzylsilane; Rhodimethylsilane, chlorodimethylsilane, bromodimethylsilane, fluorodiethylsilane, chlorodiethylsilane, bromodiethylsilane, fluorodipropylsilane, chlorodipropylsilane, bromodipropylsilane, fluorodibutylsilane, chlorodibutylsilane, bromodibutylsilane Monohalogenated di-C _1-10 alkylsilane compounds containing one hydrogen atom such as: hydrogen atoms such as fluorodiphenylsilane, chlorodiphenylsilane, bromodiphenylsilane, fluorodinaphthylsilane, chlorodinaphthylsilane, bromodinaphthylsilane Monohalogenated di-C _6-14 arylsilane compound containing one hydrogen atom; monohalogenated di-C containing one hydrogen atom such as fluorodibenzylsilane, chlorodibenzylsilane, bromodibenzylsilane, etc. _7-15 Aralkylsilane compounds; fluoromethylphenylsilane, fluoroethylphenylsilane, fluoropropylphenylsilane, fluorobutylphenylsilane, chloromethylphenylsilane, chloroethylphenylsilane, chloropropylphenylsilane, chlorobutylphenylsilane, bromomethylnaphthyl Monohalogenated C _1-10 alkyl C _6-14 arylsilane compounds containing one hydrogen atom, such as silane, bromoethylnaphthylsilane, bromopropylnaphthylsilane, bromobutylnaphthylsilane; fluoromethylbenzylsilane, fluoroethylbenzylsilane, Fluoropropylbenzylsilane, fluorobutylbenzylsilane, chloromethylbenzylsilane, chloroethylbenzylsilane, chloropropylbenzylsilane, chloropropylbenzylsilane Butyl benzyl silane, bromo methyl benzyl silane, bromoethyl benzyl silane, and bromopropyl benzyl silane, monohalogenated C _1-10 alkyl C _7-15 aralkyl silane compounds containing one hydrogen atom, such as bromo-butyl benzyl silane .

Examples of the vinyl monohalogenated silane compound include monohalogenated tri-C _2-10 alkenylsilane compounds such as fluorotrivinylsilane, chlorotrivinylsilane, bromotrivinylsilane, fluorotriallylsilane, chlorotriallylsilane, and bromotriallylsilane; Methyldivinylsilane, chloromethyldivinylsilane, bromomethyldivinylsilane, fluoroethyldivinylsilane, chloroethyldivinylsilane, bromoethyldivinylsilane, fluoropropyldivinylsilane, chloropropyldivinylsilane, bromopropyldivinylsilane, fluorobutyldivinylsilane, chloro Butyldivinylsilane, bromobutyldivinylsilane, fluoromethyldiallylsilane, chloromethyldiallylsilane, bromo Til diallylsilane, fluoroethyldiallylsilane, chloroethyldiallylsilane, bromoethyldiallylsilane, fluoropropyldiallylsilane, chloropropyldiallylsilane, bromopropyldiallylsilane, fluorobutyldiallylsilane, chlorobutyldiallylsilane, bromobutyldiallylsilane, etc. Monohalogenated C _1-10 alkyldiC _2-10 alkenylsilane compounds; fluorophenyldivinylsilane, chlorophenyldivinylsilane, bromophenyldivinylsilane, fluoronaphthyldivinylsilane, chloronaphthyldivinylsilane, bromonaphthyldivinylsilane, fluorophenyldiallylsilane, Chlorophenyldiallylsilane, bromophenyldiallylsilane, fluoronaphthyldiallylsilane, chloronaphth Rujiarirushiran, monohalogenated C _6-14 aryldi C _2-10 alkenyl silane compound such as bromo naphthyl diallyl silane; fluorobenzyl divinyl silane, chlorobenzyl divinyl silane, bromobenzyl divinyl silane, fluorobenzyl diallyl silane, chlorobenzyl diallyl silane, And monohalogenated C _7-15 aralkyldi C _2-10 alkenylsilane compounds such as bromobenzyldiallylsilane.

Examples of the vinyl type monohalogenated silane compound include, for example, fluorodimethylvinylsilane, chlorodimethylvinylsilane, bromodimethylvinylsilane, fluorodiethylvinylsilane, chlorodiethylvinylsilane, bromodiethylvinylsilane, fluorodipropylvinylsilane, chlorodipropylvinylsilane, bromodi Propyl vinyl silane, fluorodibutyl vinyl silane, chloro dibutyl vinyl silane, bromo dibutyl vinyl silane, fluoro dimethyl allyl silane, bromo dimethyl allyl silane, fluoro diethyl allyl silane, chloro diethyl allyl silane, bromo diethyl allyl silane, fluoro dipropyl allyl silane, chloro dipropyl allyl silane, bromo Dipropylallyl Orchids, fluoro dibutyl allyl silanes, chloro dibutyl allyl silanes, monohalogenated di C _1-10 alkyl C _2-10 alkenyl silane compound such as bromo-dibutyl allyl silane; fluoro diphenyl vinyl silane, chloro diphenyl vinyl silane, decabromodiphenyl vinyl silane, fluoro dinaphthyl vinyl silane, chloro Monohalogenated di-C _6-14 aryl C _2-10 such as dinaphthyl vinyl silane, bromo dinaphthyl vinyl silane, fluorodiphenyl allyl silane, chloro diphenyl allyl silane, bromo diphenyl allyl silane, fluoro dinaphthyl allyl silane, chloro dinaphthyl allyl silane, bromo dinaphthyl allyl silane Alkenylsilane compounds; fluorodibenzylvinylsilane, chlorodibenzylvinylsilane, bromodibenzylbi Monohalogenated di-C _7-15 aralkyl C _2-10 alkenylsilane compounds such as nylsilane, fluorodibenzylallylsilane, chlorodibenzylallylsilane, bromodibenzylallylsilane; fluoromethylphenylvinylsilane, fluoroethylphenylvinylsilane, fluoropropylphenylvinylsilane, Fluorobutylphenylvinylsilane, chloromethylphenylvinylsilane, chloroethylphenylvinylsilane, chloropropylphenylvinylsilane, chlorobutylphenylvinylsilane, bromomethylnaphthylvinylsilane, bromoethylnaphthylvinylsilane, bromopropylnaphthylvinylsilane, bromobutylnaphthylvinylsilane, fluoromethylphenylallylsilane, Fluoroethylphenylallylsilane, full Oropropylphenylallylsilane, fluorobutylphenylallylsilane, chloromethylphenylallylsilane, chloroethylphenylallylsilane, chloropropylphenylallylsilane, chlorobutylphenylallylsilane, bromomethylnaphthylallylsilane, bromoethylnaphthylallylsilane, bromopropylnaphthylallylsilane, bromobutylnaphthylallylsilane, etc. _{Monohalogenated} C _1-10 alkyl C _6-14 aryl C _2-10 alkenylsilane compound; fluoromethylbenzylvinylsilane, fluoroethylbenzylvinylsilane, fluoropropylbenzylvinylsilane, fluorobutylbenzylvinylsilane, chloromethylbenzylvinylsilane, chloroethylbenzyl Vinylsilane, chloropropylbenzyl vinylsila , Chlorobutylbenzylvinylsilane, bromomethylbenzylvinylsilane, bromoethylbenzylvinylsilane, bromopropylbenzylvinylsilane, bromobutylbenzylvinylsilane, fluoromethylbenzylallylsilane, fluoroethylbenzylallylsilane, fluoropropylbenzylallylsilane, fluorobutylbenzylallylsilane, chloromethylbenzylallylsilane Monohalogenated C _1-10 alkyl C _7-15 aralkyl such as chloroethylbenzyl allylsilane, chloropropylbenzyl allylsilane, chlorobutylbenzyl allylsilane, bromomethylbenzyl allylsilane, bromoethylbenzyl allylsilane, bromopropylbenzyl allylsilane, bromobutylbenzyl allylsilane C _2-10 alkenyl silane Compounds, and the like.

Examples of other monohalogenated silane compounds include fluorotrimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, fluorotriphenylsilane, chlorotriphenylsilane, bromotriphenylsilane, fluorophenyldimethylsilane, chlorophenyldimethylsilane, and bromophenyl. Examples include dimethylsilane, fluorophenyldiethylsilane, chlorophenyldiethylsilane, bromophenyldiethylsilane, fluorodiphenylmethylsilane, chlorodiphenylmethylsilane, bromodiphenylmethylsilane, fluorodiphenylethylsilane, chlorodiphenylethylsilane, and bromodiphenylethylsilane. .

Examples of H-type monohydroxysilane compounds include monohydroxysilane; two hydrogen atoms such as methylhydroxysilane, ethylhydroxysilane, propylhydroxysilane, butylhydroxysilane, phenylhydroxysilane, naphthylhydroxysilane, and benzylhydroxysilane. Hydroxysilane compounds; diC _1-10 alkylhydroxysilane compounds containing one hydrogen atom such as dimethylhydroxysilane, diethylhydroxysilane, dipropylhydroxysilane, dibutylhydroxysilane; hydrogen atoms such as diphenylhydroxysilane and dinaphthylhydroxysilane di C _6-14 aryl hydroxy silane compound containing one; di C _7-15 aralkyl hydroxy silane compound a hydrogen atom, such as dibenzyl hydroxy silane containing one Methylphenyl hydroxy silane, ethyl phenyl hydroxy silane, propyl phenyl hydroxy silane, butyl phenyl hydroxy silane, methyl naphthyl hydroxysilane, ethyl naphthyl hydroxypropyl silane, propyl naphthyl hydroxy silane, one hydrogen atom, such as butyl naphthyl hydroxysilane C _{1- 10} alkyl C _6-14 arylhydroxysilane compound; C _1-10 alkyl C _7-15 aralkyl hydroxysilane containing one hydrogen atom such as methylbenzylhydroxysilane, ethylbenzylhydroxysilane, propylbenzylhydroxysilane, butylbenzylhydroxysilane Compounds and the like.

Examples of the vinyl-type monohydroxysilane compound include tri-C _{2-10 alkenylhydroxysilane} compounds such as trivinylhydroxysilane and triallylhydroxysilane; methyldivinylhydroxysilane, ethyldivinylhydroxysilane, propyldivinylhydroxysilane, butyldivinylhydroxy C _1-10 alkyldi-C _2-10 alkenylhydroxysilane compounds such as silane, methyldiallylhydroxysilane, ethyldiallylhydroxysilane, propyldiallylhydroxysilane, butyldiallylhydroxysilane; phenyldivinylhydroxysilane, naphthyldivinylhydroxysilane, phenyldiallylhydroxy C _6-14 aryldi-C _2-10 alkenyl hydroxysilane compounds such as silane and naphthyl diallylhydroxysilane C _7-15 aralkyl C _1-10 alkyl diC _2-10 alkenyl hydroxysilane compounds such as benzyldivinylhydroxysilane and benzyldiallylhydroxysilane;

As the vinyl type monohydroxysilane compound, for example, dimethylvinylhydroxysilane, diethylvinylhydroxysilane, dipropylvinylhydroxysilane, dibutylvinylhydroxysilane, dimethylallylhydroxysilane, diethylallylhydroxysilane, dipropylallylhydroxysilane, DiC _1-10 alkyl C _2-10 alkenyl hydroxysilane compounds such as dibutylallylhydroxysilane; diC _6-14 aryl such as diphenylvinylhydroxysilane, dinaphthylvinylhydroxysilane, diphenylallylhydroxysilane, dinaphthylallylhydroxysilane C _2-10 alkenyl hydroxysilane compounds; di-C _7-15 aralkyl C _2- such as dibenzylvinylhydroxysilane and dibenzylallylhydroxysilane ₁₀ alkenyl hydroxysilane compounds; methyl phenyl vinyl hydroxy silane, ethyl phenyl vinyl hydroxy silane, propyl phenyl vinyl hydroxy silane, butyl phenyl vinyl hydroxy silane, methyl naphthyl vinyl hydroxy silane, ethyl naphthyl vinyl hydroxy silane, propyl naphthyl vinyl hydroxy silane, butyl naphthyl Vinyl hydroxy silane, methyl phenyl allyl hydroxy silane, ethyl phenyl allyl hydroxy silane, propyl phenyl allyl hydroxy silane, butyl phenyl allyl hydroxy silane, methyl naphthyl allyl hydroxy silane, ethyl naphthyl allyl hydroxy silane, propyl naphthyl allyl hydroxy silane, butyl naphthyl allyl hydroxy C _1-10 alkyl such as silane C _6-14 aryl C _2-10 alkenyl hydroxysilane compounds; methyl benzyl vinyl hydroxy silane, ethyl benzyl vinyl hydroxy silane, propyl benzyl vinyl hydroxy silane, butyl benzyl vinyl hydroxy silane, methyl benzyl allyl hydroxy silane, ethyl benzyl allyl hydroxy silane And C _1-10 alkyl C _7-15 aralkyl C _2-10 alkenyl hydroxysilane compounds such as propylbenzylallylhydroxysilane and butylbenzylallylhydroxysilane.

Examples of other monohydroxysilane compounds include trimethylsilanol, triethylsilanol, triphenylsilanol, phenyldimethylsilanol, phenyldiethylsilanol, diphenylmethylsilanol, diphenylethylsilanol and the like. As the silane compound (S2), the above-exemplified compounds can be used alone or in admixture of two or more.

In the above formula (2), the C _1-10 alkyl group as R ³ to R ⁵ is particularly preferably a C _1-5 alkyl group, and the C _2-10 alkenyl group is particularly preferably a C _2-5 alkenyl group. R ³ to R ⁵ are preferably a methyl group, an ethyl group, a phenyl group, a vinyl group, or an allyl group from the viewpoint of heat-resistant non-yellowing. From the viewpoint of hydrolysis resistance, a phenyl group is more preferable.

As the C _1-12 alkoxy group in X ³ in the above formula (2), a C _1-6 alkoxy group is particularly preferable. X ³ is preferably a methoxy group, an ethoxy group, a chlorine atom, a bromine atom or a hydroxyl group from the viewpoint of availability, and more preferably a hydroxyl group from the viewpoint of ease of reaction.

The monofunctional silane compound (S2) is preferably a monohydroxysilane compound, and specifically, for example, trimethylsilanol, triethylsilanol, triphenylsilanol, phenyldimethylsilanol, phenyldiethylsilanol, diphenylmethylsilanol, diphenylethylsilanol. Etc. can be preferably used.

Since the metallosiloxane compound of the present invention has at least one Si—H bond or C _2-10 alkenyl group capable of hydrosilylation in one molecule, silane used for the production of the metallosiloxane compound At least one of the compounds is an H-type silane compound having at least one Si—H bond in one molecule, or a vinyl-type silane compound having at least one C _2-10 alkenyl group in one molecule.

[Metal compound (M)]
The metal compound (M) used in the present invention has the following formula (2):

(In the formula, M represents zirconium or titanium, and Y ¹ to Y ⁴ are the same or different and represent a C _1-12 alkoxy group or a halogen atom.)
It is represented by _Examples of the C _1-12 alkoxy group in Y ¹ to Y ⁴ include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a C _1-6 alkoxy group is preferable. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

As the metal compound (M), a zirconium compound or a titanium compound represented by the above formula (2) and conventionally used for producing a polymetallosiloxane can be used. For example, zirconium alkoxide (zirconium tetraethoxide, Zirconium tetraisopropoxide, zirconium tetra n-propoxide, zirconium tetra t-butoxide, chlorozirconium triisopropoxide, dichlorozirconium diisopropoxide, trichlorozirconium isopropoxide, etc.), zirconium halide (zirconium tetrachloride, four odors) Zirconium-based Lewis acids such as zirconium fluoride; titanium-based Lewis acids corresponding to the zirconium-based Lewis acids (titanium tetraisopropoxide, titanium tetra-n-propoxide, etc.) Kishido, titanium tetrachloride, as the titanium tetrachloride halide bromide titanium and the like. Metal compound (M), the above-exemplified compounds may be used singly or in combination of two or more.

The C _1-12 alkoxy group or halogen atom in Y ¹ to Y ⁴ is preferably propoxy, butoxy, chlorine or bromine from the viewpoint of availability, and more preferably propoxy or butoxy from the viewpoint of stability before the reaction. Preferred metal compounds (M) include zirconium tetraisopropoxide, zirconium tetra n-propoxide, zirconium tetra t-butoxide, zirconium tetra n-butoxide, titanium tetraisopropoxide, titanium tetra n-propoxide, titanium tetra t -Butoxide, titanium tetra n-butoxide, etc., especially zirconium tetraisopropoxide, zirconium tetra n-propoxide and the like.

[catalyst]
The above reaction may proceed without a catalyst, but an acid catalyst and a base catalyst may be added as necessary. In general, the reaction rate is significantly increased by the presence of an acid catalyst or a base catalyst in the reaction system. Bases include inorganic and organic bases. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, and barium hydroxide. Alkaline metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; alkaline earth metal carbonates such as magnesium carbonate; alkali metal carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and cesium hydrogen carbonate Examples thereof include hydrogen salt.

Examples of the organic base include alkali metal organic acid salts (particularly alkali metal acetate) such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate; alkaline earth metal organic acid salts such as magnesium acetate; methyllithium, butyl Alkyllithium such as lithium (n-butyllithium, s-butyllithium, t-butyllithium, etc.); alkali metal alkoxide such as lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide; sodium Alkali metal phenoxides such as phenoxide; triethylamine, N-methylpiperidine, 4-dimethylaminopyridine (DMAP), 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), triethylenediamine (1,4-diazabicyclo [2.2.2] octane; DABCO), 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), hexamethylenetetramine, tetramethylethylenediamine, trioctylamine, Amines such as dimethylaniline, N-methylpyrrolidine, N-methylpiperidine, 4-methylmorpholine (tertiary amine, etc.); pyridine, lutidine, picoline, imidazole, 2,2'-bipyridyl, 1,10-phenanthroline And nitrogen-containing aromatic heterocyclic compounds. These bases can be used alone or in combination of two or more. Of these, tertiary amines such as triethylamine and 4-dimethylaminopyridine; nitrogen-containing aromatic heterocyclic compounds such as pyridine, lutidine and picoline are preferable.

Examples of the acid catalyst include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, carboxylic acids (such as C _1-10 saturated or unsaturated mono- or polycarboxylic acids such as acetic acid and propionic acid), and sulfonic acids (methanesulfone). Acids, C _1-6 alkanesulfonic acids such as ethanesulfonic acid, aromatic sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid), halogenated organic acids (halogenated carboxylic acids such as trifluoroacetic acid, trifluoromethane) Organic acids such as halogenated alkane sulfonic acids such as sulfonic acids), sulfates (calcium sulfate, etc.), metal oxides (SiO ₂ , Al ₂ O ₃ etc.), zeolites (Y type, X type having acidic OH, And solid acids such as ion exchange resins (cation exchange resins such as H type) and the like.

The amount of the acid catalyst or base catalyst used is not particularly limited, and is, for example, 0.01 to 5 mol, preferably 0.1 to 2 mol, and more preferably 0.8 to 1 mol of hydroxyl group in the reaction system. About 1.2 mol. When no acid catalyst or base catalyst is used, the reaction can be accelerated by heating or the like.

The reaction may be performed in the presence of a polymerization inhibitor. The reaction temperature can be appropriately selected depending on the reaction components and the type of catalyst. For example, when vinyl silane is used, it is about 20 to 200 ° C., preferably about 20 to 100 ° C., and more preferably about 40 to 60 ° C. When hydrosilane is used, the reaction temperature can be appropriately selected depending on the reaction components and the type of catalyst, and is, for example, −78 to 110 ° C., preferably −30 to 40 ° C., more preferably about −10 to 10 ° C. It is. The reaction may be carried out at normal pressure or under reduced pressure or pressure. The reaction atmosphere is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The reaction can be carried out by any method such as batch, semi-batch, and continuous methods.

After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these. The mixture after the reaction may be washed by adding an aqueous solvent such as water, 1 to 7% dilute hydrochloric acid, and 1 to 7% sodium bicarbonate water.

[Curable resin composition]
The curable resin composition of the present invention is a curable resin composition comprising a compound having a Si—H bond and a compound having a C _2-10 alkenyl group, and is hydrosilylated with at least the metallosiloxane compound (A). It contains a catalyst (C). The content of the metallosiloxane compound (A) in the curable resin composition is, for example, 30 to 99% by weight, preferably 50 to 80% by weight.

The curable resin composition of the present invention may contain a compound (B) having at least one Si—H bond or C _2-10 alkenyl group in one molecule other than the metallosiloxane compound (A). Good. When the metallosiloxane compound (A) is an H-type compound, the curable resin composition has a compound (B) [vinyl type compound (B)] having at least one C _2-10 alkenyl group in one molecule. Containing. When the metallosiloxane compound (A) is a vinyl type compound, the curable resin composition has a compound (B) having at least one Si—H bond in one molecule [H type compound (B)]. Containing.

[Compound (B) having at least one Si—H bond or C _2-10 alkenyl group in one molecule other than the metallosiloxane compound (A)]
The H-type or vinyl-type compound (B) includes a main chain composed of a siloxane bond (Si—O—Si) having at least one Si—H bond or C _2-10 alkenyl group in one molecule. H-type or vinyl-type polysiloxanes having the following can be used. The C _2-10 alkenyl group, examples are mentioned as a good C _2-10 alkenyl group which may be included in the silane compound. Specific examples of the polysiloxane include linear, branched or cyclic siloxane, and a crosslinked silicone resin having a three-dimensional structure.

Specific examples of the compound (B) include tetramethylsiloxane, tetramethyldivinylsiloxane, hexamethyltrisiloxane, hexamethyldivinyltrisiloxane, heptamethyltrisiloxane, heptamethylvinyltrisiloxane, octamethyltetrasiloxane, octamethyldivinyl. Tetrasiloxane, nonamethyltetrasiloxane, nonamethylvinyltetrasiloxane, nonamethyldivinyltetrasiloxane, decamethylpentasiloxane, decamethyldivinylpentasiloxane, undecamethylpentasiloxane, undecamethylvinylpentasiloxane, decamethyldivinylpentasiloxane, etc. A linear polydimethylsiloxane having 1 to 10 (preferably 2 to 5) (Si—O) units, a hydrosilyl group-containing Corn, having at least one linear polydialkylsiloxanes (preferably linear polydiene C _1-10 alkyl siloxane) the Si-H bonds or C _2-10 alkenyl groups in one molecule, such as a vinyl group-containing silicone, dimethyl 2 to 10 (Si—O) units such as cyclotrisiloxane, dimethyldivinylcyclotrisiloxane, tetramethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, trimethylcyclopentasiloxane, and trimethyltrivinylcyclopentasiloxane ( preferably 2 to 5) having, having at least one Si-H bond or a C _2-10 alkenyl groups per molecule, cyclic polydialkylsiloxanes such as cyclic polydimethylsiloxane (preferably cyclic polydiene C _1-10 alkyl Siloxane) The

Examples of the polysiloxane further include compounds in which all or part of alkyl groups such as methyl groups in the above exemplified compounds are substituted with aryl groups such as phenyl groups (preferably C _6-20 aryl groups), such as 1 A linear or cyclic polydiarylsiloxane such as polydiphenylsiloxane (preferably polydiC6-20 _arylsiloxane ) having at least one Si—H bond or C _2-10 alkenyl group in the molecule; A linear or cyclic polyalkylaryl siloxane such as polyphenylmethylsiloxane having at least one Si—H bond or C _2-10 alkenyl group (preferably a poly C _1-10 alkyl C _6-20 aryl siloxane) ); A copolymer composed of the above polyorganosiloxane units [dimethylsiloxane-methylvinylsiloxane copolymer) , Dimethylsiloxane-methylphenylsiloxane copolymer, dimethylsiloxane-methyl (3,3,3-trifluoropropyl) siloxane copolymer, dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymer, etc.] it can. The polysiloxane exemplified above may have a branched chain. Also, p-bis (dimethylsilyl) benzene, p-bis (dimethylvinylsilyl) benzene, and the like can be used.

The molecular weight of the polysiloxane may be, for example, from 100 to 800,000, preferably from 100 to 100,000. When the molecular weight of the polysiloxane is within this range, it is preferable that the polysiloxane is easily compatible.

As the compound (B), the polysiloxane can be used alone or in combination of two or more. Of these, tetramethyldisiloxane, hexamethyltrisiloxane, tetramethylcyclotetrasiloxane, hydrosilyl group-containing silicone, and p-bis (dimethylsilyl) benzene are preferred as the H-type compound (B), and the vinyl-type compound (B). Preferred are tetramethyldivinylsiloxane, hexamethyltrisiloxane, tetramethyltetravinylcyclotetrasiloxane, vinyl group-containing silicone, and p-bis (dimethylvinylsilyl) benzene.

Examples of the compound having a Si—H bond and the compound having a C _2-10 alkenyl group contained in the curable resin composition of the present invention include an H-type metallosiloxane compound (A) and a corresponding vinyl-type metallosiloxane compound ( A) can also be used.

The content of the compound (B) can be, for example, 0 to 100 parts by weight, preferably 5 to 60 parts by weight with respect to 100 parts by weight of the metallosiloxane compound (A). It is preferable that the content of the compound (B) is in this range because it is easily cured. When both the H-type metallosiloxane compound (A) and the vinyl-type metallosiloxane compound (A) are contained in the curable resin composition, the compound (B) may not be used.

The curable resin composition of the present invention contains other silane compounds that do not contain both Si—H bonds and alkenyl groups, corresponding to the H-type and vinyl-type compounds (B) exemplified above. Also good.

The silicon atom content in the curable resin composition of the present invention is, for example, 10 to 30% by weight, preferably 10 to 20% by weight. The content of zirconium or titanium atoms in the curable resin composition can be, for example, 1 to 10% by weight, preferably 1 to 5% by weight. By setting the content of silicon atoms and zirconium or titanium atoms in such a range, heat-resistant non-yellowing of a cured product obtained by curing the curable resin composition can be improved.

[Hydrosilylation catalyst (C)]
Examples of the hydrosilylation catalyst (C) contained in the curable resin composition of the present invention include known hydrosilylation reaction catalysts such as platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, complexes of chloroplatinic acid with alcohols, aldehydes, ketones, olefin complexes of platinum, platinum carbonyls such as platinum-carbonylvinylmethyl complexes Complexes, platinum-divinyltetramethyldisiloxane complexes, platinum-vinylmethylsiloxane complexes such as platinum-cyclovinylmethylsiloxane complexes, platinum-based catalysts such as platinum-phosphine complexes, platinum-phosphite complexes, and platinum atoms in the platinum-based catalysts Instead of palladium-based catalysts or palladium-containing catalysts containing palladium or rhodium atoms Um-based catalysts. These may be used alone or in combination of two or more. Of these, a platinum vinylmethylsiloxane complex is preferred because of its good reaction rate.

The content of the hydrosilylation catalyst (C) in the curable resin composition of the present invention is an amount such that platinum, palladium, or rhodium in the catalyst is in the range of 0.01 to 1,000 ppm by weight. Preferably, it is in the range of 0.1 to 500 ppm. The content of the hydrosilylation catalyst (C) is the total content of two or more when used in combination. When the content of the hydrosilylation catalyst (C) is in such a range, the crosslinking rate is not significantly slowed, and there is less possibility of causing problems such as coloring in the crosslinked product, which is preferable.

[Hydrosilylation reaction inhibitor]
The curable resin composition of the present invention may contain a hydrosilylation reaction inhibitor to adjust the speed of the hydrosilylation reaction. Examples of the hydrosilylation inhibitor include alkyne alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and phenylbutynol; 3-methyl-3-pentene Ene-in compounds such as 1-yne, 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1, Examples include 3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane and benzotriazole. The content of the hydrosilylation reaction inhibitor varies depending on the crosslinking conditions of the composition, but is practically within the range of 0.00001 to 5 parts by weight with respect to 100 parts by weight of the curable resin composition. Is preferred.

[solvent]
A conventionally known solvent such as toluene, hexane, isopropanol, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate may be used during the hydrosilylation reaction.

[Inorganic filler (D)]
The curable resin composition of the present invention may further contain an inorganic filler (D). The inorganic filler (D) is not particularly limited, but nano silica, nano titania, nano zirconia, carbon nanotube, silica, alumina, mica, synthetic mica, talc, calcium oxide, calcium carbonate, zirconium oxide, titanium oxide, titanium Barium acid, kaolin, bentonite, diatomaceous earth, boron nitride, aluminum nitride, silicon carbide, zinc oxide, cerium oxide, cesium oxide, magnesium oxide, glass beads, glass fiber, graphite, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, One or more types of cellulose can be used. These inorganic fillers (D) can be produced by a known method such as a flame hydrolysis method, a flame pyrolysis method, or a plasma method described in, for example, International Publication No. 96/31572.

As the preferred inorganic filler (D), nano-dispersed sols of stabilized colloidal inorganic particles such as nano silica, nano titania, nano zirconia, and carbon nanotube can be used, and commercially available products include silica sol manufactured by BAYER. SnO ₂ sols from Goldschmidt, TiO ₂ sols from MERCK, SiO ₂ , ZrO ₂ , A1 ₂ O ₃ and Sb ₂ O ₃ sols from Nissan Chemicals, Aerosil dispersions from DEGUSSA, etc. Are commercially available. The inorganic filler (D) needs not to block visible light.

The inorganic filler (D) can change the viscosity behavior by surface modification. The surface modification of the particles can be performed using a known surface modifier. As such a surface modifier, for example, a compound capable of interacting with a functional group present on the surface of the inorganic filler (D) such as a covalent bond or complex formation, or a compound capable of interacting with a polymer matrix. Can be used. Examples of such surface modifiers include carboxyl groups, (primary, secondary, and tertiary) amino groups, quaternary ammonium groups, carbonyl groups, glycidyl groups, vinyl groups, ) A compound having a functional group such as acryloxy group or mercapto group can be used. Such a surface modifier is usually a liquid under standard temperature and pressure conditions, and is composed of a low molecular organic compound having a carbon number in the molecule of, for example, 15 or less, preferably 10 or less, particularly preferably 8 or less. Is done. The molecular weight of the low molecular weight organic compound is, for example, 500 or less, preferably 350 or less, particularly 200 or less.

Preferred surface modifiers include, for example, formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, acrylic acid, methacrylic acid, crotonic acid, citric acid, adipic acid, succinic acid, glutaric acid, oxalic acid, malein C1-C12 saturated or unsaturated mono- and polycarboxylic acids (preferably monocarboxylic acids) such as acids and fumaric acids; and their esters (preferably C ₁ -C ₄ alkyl esters such as methyl methacrylate) Amides; β-dicarbonyl compounds such as acetylacetone, 2,4-hexanedione, 3,5-heptanedione, acetoacetic acid and C ₁ -C ₄ alkylacetoacetic acids. Moreover, although it does not specifically limit, a well-known and usual silane coupling agent can also be used as a surface modifier.

The particle size of the inorganic filler (D) is usually about 0.01 nm to 200 μm, preferably 0.1 nm to 100 μm, particularly about 0.1 nm to 50 μm.

The content of the inorganic filler (D) is preferably 1 to 2000 parts by weight, more preferably 10 to 1000 parts by weight, where the total content of the compound (A) and the compound (B) is 100 parts by weight. is there. Further, the content of the inorganic filler (D) with respect to the total amount of the low moisture-permeable resin composition for electronic devices is, for example, 5 to 95% by weight, preferably 10 to 90% by weight.

[Silane coupling agent (E)]
The curable resin composition of the present invention may further contain a silane coupling agent (E) in order to improve adhesion to an adherend such as a substrate. A silane coupling agent (E) is not specifically limited, A well-known and usual silane coupling agent can be used. Examples of the silane coupling agent (E) include tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris (methoxyethoxysilane). ), Phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltriacetoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxy Silane, γ- (meth) acryloxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxyp Pyrtriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, N- ( β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N -(Β-aminoethyl) -γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxy Silane, 3-mercaptopropyltrie Kishishiran, 3-mercaptopropyl methyl dimethoxy silane, bis (triethoxysilylpropyl) tetrasulfide, selected from the relatively stable ones in an aqueous solution, such as 3-isocyanate propyl triethoxysilane.

The amount of the silane coupling agent (E) used is preferably about 0.1 to 20% by weight in the curable resin composition, more preferably 0.3 to 8% by weight, and still more preferably 0. The range is from 5 to 5% by weight. If it is less than 0.1% by weight, the crosslinking effect of the resin by the silane coupling agent (E) is poor, so a dense film cannot be obtained, and the coupling effect to the metal substrate is poor and the adhesion is poor, which is desirable. Alkali resistance and rust resistance are difficult to obtain. When the content is more than 20% by weight, various performances such as water resistance and alkali resistance due to hydrolysis are remarkably deteriorated, resulting in a problem of film-forming property and easily disadvantageous in terms of economy.

[Other additives]
Furthermore, in the curable resin composition of the present invention, as other optional components, organic resin fine powders such as silicone resin, epoxy resin and fluororesin; filler such as conductive metal powder such as silver and copper, solvent, Stabilizers (antioxidants, UV absorbers, light stabilizers, heat stabilizers, etc.), flame retardants (phosphorous flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant aids, crosslinking agents , Reinforcing materials (other fillers, etc.), nucleating agents, coupling agents, agents, waxes, plasticizers, mold release agents, impact resistance improvers, hue improvers, fluidity improvers, colorants (dyes, pigments, etc.) ), Dispersants, antifoaming agents, defoaming agents, antibacterial agents, preservatives, viscosity modifiers, thickeners, leveling agents, ion adsorbers, phosphors and the like may be included. These additives can be used alone or in combination of two or more.

The curable resin composition of the present invention is preferably a liquid at any temperature of 0 to 90 ° C., more preferably 0 to 40 ° C., particularly preferably around room temperature (about 0 to 30 ° C.). Excellent workability during sealing, sealing and coating. Therefore, it can be used as a sealant, a sealant, and the like for an electronic component that requires a high refractive index and low moisture permeability, such as an organic electroluminescence device and an LED. It can also be used as a coating agent or an adhesive for an antireflection film of a display.

[Method for producing curable resin composition]
The curable resin composition of the present invention can be obtained by uniformly mixing the above components. In order to obtain the curable resin composition of the present invention, each component is preferably used by using generally known mixing equipment such as a revolving type stirring and defoaming device, a homogenizer, a planetary mixer, a three-roll mill, and a bead mill. It is desirable to perform stirring, dissolution, mixing, dispersion, etc. so as to be uniform.

[Cured product]
The curable resin composition of the present invention can be cured by light or heat. In the case of curing by light, light irradiation of 1000 mJ / cm ² or more can be performed with a mercury lamp or the like. In the case of curing by heat, the temperature is 50 to 200 ° C., preferably 50 to 190 ° C., more preferably 50 to 180 ° C., and the curing time is 10 to 600 minutes, preferably 10 to 480 minutes, more preferably. Can be cured in 15 to 360 minutes. If the curing temperature and the curing time are lower than the lower limit of the range, curing is insufficient. Conversely, if the curing temperature and the curing time are higher than the upper limit of the range, the resin component may be decomposed. Although the curing conditions depend on various conditions, when the curing temperature is high, the curing time is short, and when the curing temperature is low, the curing time is long and can be adjusted as appropriate. By curing the curable resin composition of the present invention, a cured product having few bubbles and excellent transparency and excellent heat-resistant non-yellowing can be obtained. The curable resin composition of the present invention can be used as a sealant, a sealant, or a coating agent for an organic electroluminescence device, LED, or display.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
In a glass flask equipped with a stirrer, a thermometer, a Dimroth cooling tank, and a dropping funnel, 3.30 g (25 mmol) of dimethoxymethylvinylsilane (D3386 manufactured by Tokyo Chemical Industry Co., Ltd.) and zirconium n-propoxide (Z0017 manufactured by Tokyo Chemical Industry Co., Ltd.) 23. 40 g (50 mmol 70 wt% n-propanol solution) and 300 g of n-propanol were mixed and cooled to −30 ° C. or lower in a dry methanol bath. Next, a solution obtained by mixing 0.54 g (30 mmol) of ion-exchanged water and 40 g of n-propanol was gradually added dropwise so that the internal temperature did not exceed −30 ° C. After completion of the dropwise addition, the internal temperature was returned to room temperature, and then the temperature was raised to 80 ° C. and stirred for 3 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, and unreacted and volatile components were distilled off by an evaporator. To the liquid after concentration, 100 g of toluene and 51.8 g (380 mmol) of triethylsilanol (Tokyo Chemical Industries, Ltd. T2017) were added and stirred at 80 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, and unreacted and volatile components were distilled off by an evaporator to obtain a liquid vinyl group-containing zirconosiloxane.

Example 2
0.4 μl of platinum catalyst was added to 0.2 g of the liquid vinyl group-containing zirconosiloxane obtained in Example 1, and then 0.084 g of hydrosilyl group-terminated silicone (DMS-H03, molecular weight 400-500, manufactured by Gelest) was added. , Mixed. The mixed solution was applied onto a glass plate and cured in an oven at 60 ° C. for 1 hour and 120 ° C. for 3 hours. No bubbles were observed in the cured product, and it remained colorless and transparent even when left in an oven at 180 ° C. for 500 hours or longer.

According to the metallosiloxane compound of the present invention, there is no outgassing when the curable resin composition containing the metallosiloxane compound is cured, and the cured product obtained by curing the curable resin composition is excellent. Since it has heat-resistant non-yellowing property, it is useful as a sealant or sealant for electronic devices such as LEDs, and a heat-resistant hard coat.

Claims (6)

1. Following formula (1)
   

   

   Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _6-14 aryl group, or a C _7-15 aralkyl group, X ¹ and X ² are the same or different and each represents a C _1-10 alkoxy group, a halogen atom, or a hydroxyl group.
   And a silane compound (S1) represented by the following formula (2)
   

   

   (In the formula, M represents zirconium or titanium, and Y ¹ to Y ⁴ are the same or different and represent a C _1-12 alkoxy group or a halogen atom.)
   Or the first step of reacting the silane compound (S1) with the metal compound (M) and H ₂ O, the reaction product of the first step, and the following: Formula (3)
   

   

   (Wherein R ³ to R ⁵ are the same or different and each represents a hydrogen atom, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _6-14 aryl group, or a C _7-15 aralkyl group, X ³ represents a C _1-10 alkoxy group, a halogen atom, or a hydroxyl group.)
   Or a second step of reacting the reaction product of the first step with the silane compound (S2) and H ₂ O, and the silane compound (S2) represented by compound (S1): the metal compound (M): the silane compound (S2): H ₂ O in the first step: the second step _{H 2 O = m: n:} k: a: a molar ratio of b, and , M, n, k, a, b are reacted under conditions satisfying all of the following relationships (i) to (v), and at least one Si—H bond or C _2-10 alkenyl group is _{contained in} one molecule. A metallosiloxane compound.
   (i) m> 0, n> 0, k> 0, a ≧ 0, b ≧ 0
   (ii) n / m ≦ 3
   _{(iii) (a + a m} ) / (m + n) = 0.03 ~ 0.8
   (iv) k ≧ {a _h − (2a + a _m )}
   (v) When X ³ is an alkoxy group or a halogen atom, b ≧ k, and when X ³ is a hydroxyl group, b = 0 (in the above formula, a _m and a _h are X ¹ , X ² are both hydroxyl groups, a _m = 2m, a _h = 4n; when only ^one of X ¹ and X ² is a hydroxyl group, a _m = m, a _h = m + 4n; X ¹ , X ² is not a hydroxyl group, a _m = 0 and a _h = 2m + 4n.)
2. The metallosiloxane compound according to claim 1, which is liquid at any temperature of 0 to 90 ° C.
3. A curable resin composition comprising a compound having a Si-H bond and a compound having a C _2-10 alkenyl group, wherein at least the metallosiloxane compound (A) and the hydrosilylation catalyst (C) according to claim 1 or 2 And a curable resin composition.
4. The curable resin composition according to claim 3, further comprising an inorganic filler (D).
5. The curable resin composition according to claim 3 or 4, further comprising a silane coupling agent (E).
6. A cured product obtained by curing the curable resin composition according to any one of claims 3 to 5.