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WO2012060272A1 - Métallo-siloxane liquide durcissable par addition - Google Patents

Métallo-siloxane liquide durcissable par addition Download PDF

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Publication number
WO2012060272A1
WO2012060272A1 PCT/JP2011/074760 JP2011074760W WO2012060272A1 WO 2012060272 A1 WO2012060272 A1 WO 2012060272A1 JP 2011074760 W JP2011074760 W JP 2011074760W WO 2012060272 A1 WO2012060272 A1 WO 2012060272A1
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silane
compound
group
compounds
vinyl
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江川智哉
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Daicel Corp
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Daicel Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/58—Metal-containing linkages

Definitions

  • the present invention relates to a metallosiloxane having addition curability, a curable resin composition having the metallosiloxane, and a cured product thereof.
  • 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.
  • 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.
  • 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.
  • 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.)
  • X 3 is an alkoxy group or a halogen atom
  • the metallosiloxane compound is preferably a liquid at any temperature of 0 to 90 ° C.
  • the present invention also provides a curable resin composition
  • 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).
  • this invention provides the hardened
  • 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.
  • 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.
  • 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.)
  • C 2-10 alkenyl groups include vinyl, allyl, 2-butenyl, 2-pentanyl, 2-hexynyl and the like.
  • a vinyl group and an allyl group are preferable.
  • 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. .
  • 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 is reacted with the metal compound (M).
  • a bifunctional silane compound (S1) is reacted with the metal compound (M).
  • M metal compound
  • 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).
  • 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.
  • 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.
  • 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. .
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • H-type dialkoxysilane compound examples 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, but
  • 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;
  • 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, dipheny
  • H-type dihalogenated silane compound examples 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.
  • 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, difluoropropylallylsi
  • 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
  • H-type dihydroxysilane compound examples 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.
  • 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
  • dihydroxysilane compounds examples include di-C 1-10 alkyl dihydroxysilane compounds such as dimethyldihydroxysilane, diethyldihydroxysilane, dipropyldihydroxysilane, and dibutyldihydroxysilane; di-C such as diphenyldihydroxysilane and dinaphthyldihydroxysilane.
  • 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.
  • X 1 and X 2 are 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.
  • silane compound (S1) examples 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.
  • 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.
  • R 1 in the above bifunctional silane compound examples of R 2 can be used.
  • 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.
  • H-type monoalkoxysilane compound examples 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
  • 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, methyldiallyl
  • vinyl-type monoalkoxysilane compound examples include, for example, dimethylvinylmethoxysilane, diethylvinylmethoxysilane, dipropylvinylmethoxysilane, dibutylvinylmethoxysilane, dimethylvinylethoxysilane, diethylvinylethoxysilane, dipropylvinylethoxysilane, Dibutylvinylethoxysilane, dimethylvinylpropoxysilane, diethylvinylpropoxysilane, dipropylvinylpropoxysilane, dibutylvinylpropoxysilane, dimethylvinylbutoxysilane, diethylvinylbutoxysilane, dipropylvinylbutoxysilane, dibutylvinylbutoxysilane, dimethylallylmethoxy Silane, diethylallylmethoxysilane, dipropylallylmethoxys
  • Examples of other monoalkoxysilane compounds include trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldiethylmethoxysilane, phenyldiethylethoxysilane, and diphenyl. Examples include methylmethoxysilane, diphenylmethylethoxysilane, diphenylethylmethoxysilane, and diphenylethylethoxysilane.
  • H-type monohalogenated silane compound examples 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,
  • 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,
  • vinyl monohalogenated silane compound examples 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, fluoro
  • 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
  • vinyl type monohalogenated silane compound examples 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 Dipropyl
  • 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.
  • 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 alky
  • vinyl-type monohydroxysilane compound examples 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 al
  • 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
  • Examples of other monohydroxysilane compounds include trimethylsilanol, triethylsilanol, triphenylsilanol, phenyldimethylsilanol, phenyldiethylsilanol, diphenylmethylsilanol, diphenylethylsilanol and the like.
  • silane compound (S2) the above-exemplified compounds can be used alone or in admixture of two or more.
  • the C 1-10 alkyl group as R 3 to R 5 is particularly preferably a C 1-5 alkyl group
  • 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.
  • 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.
  • 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.
  • 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.
  • a zirconium compound or a titanium compound represented by the above formula (2) and conventionally used for producing a polymetallosiloxane can be used.
  • 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
  • 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.
  • Bases include inorganic and organic bases.
  • 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.
  • the organic base examples 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-d
  • bases can be used alone or in combination of two or more.
  • tertiary amines such as triethylamine and 4-dimethylaminopyridine; nitrogen-containing aromatic heterocyclic compounds such as pyridine, lutidine and picoline are preferable.
  • the acid catalyst examples 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).
  • 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
  • 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.
  • halogenated organic acids halogenated carboxylic acids such as trifluoroacetic acid, trifluoromethane
  • Organic acids such as halogenated alkane sulfonic acids such as sulfonic acids
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the compound (B) include tetramethylsiloxane, tetramethyldivinylsiloxane, hexamethyltrisiloxane, hexamethyldivinyltrisiloxane, heptamethyltrisiloxane, heptamethylvinyltrisiloxane, octamethyltetrasiloxane, octamethyldivinyl.
  • Tetrasiloxane nonamethyltetrasiloxane, nonamethylvinyltetrasiloxane, nonamethyldivinyltetrasiloxane, decamethylpentasiloxane, decamethyldivinylpentasiloxane, undecamethylpentasiloxane, undecamethylvinylpentasiloxane, decamethyldivinylpentasiloxane, etc.
  • 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
  • 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)
  • 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.
  • the polysiloxane can be used alone or in combination of two or more.
  • 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.
  • hydrosilylation catalyst (C) examples include known hydrosilylation reaction catalysts such as platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts.
  • 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.
  • the curable resin composition of the present invention may contain a hydrosilylation reaction inhibitor to adjust the speed of the hydrosilylation reaction.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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; ⁇ -dicarbonyl compounds such as acetylacetone, 2,4-hexanedione, 3,5-heptanedione, acetoacetic acid and C 1 -C 4 alkylacetoacetic acids.
  • 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 ⁇ m, preferably 0.1 nm to 100 ⁇ m, particularly about 0.1 nm to 50 ⁇ m.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • the curable resin composition of the present invention can be obtained by uniformly mixing the above components.
  • 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.
  • the curable resin composition of the present invention can be cured by light or heat.
  • light irradiation of 1000 mJ / cm 2 or more can be performed with a mercury lamp or the like.
  • the temperature is 50 to 200 ° C., preferably 50 to 190 ° C., more preferably 50 to 180 ° C.
  • 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.
  • the resin component may be decomposed.
  • 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.
  • 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.
  • 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.
  • D3386 dimethoxymethylvinylsilane
  • Z0017 zirconium n-propoxide
  • Example 2 0.4 ⁇ l 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.
  • DMS-H03 hydrosilyl group-terminated silicone
  • 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.

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Abstract

L'invention concerne un composé métallo-siloxane obtenu au moyen d'une première étape de mise en réaction d'un composé silane bifonctionnel (S1), d'un composé métallique (M) de zirconium ou de titane et, si nécessaire, d'H2O ainsi que d'une deuxième étape de mise en réaction du produit de réaction de la première étape, d'un composé silane monofonctionnel (S2) et, si nécessaire, de H2O. Ce composé métallo-siloxane est obtenu par mise en réaction, selon un rapport molaire spécifique, du composé silane (S1), du composé métallique (M), du composé silane (S2), de H2O de la première étape, et de H2O de la deuxième étape, chaque molécule se caractéristant par le fait qu'elle possède au moins soit une liaison Si-H, soit un groupe alkéyle C2-10. Ce composé métallo-siloxane est un composé durcissable par addition et ne libère pas de gaz. En outre, lorsqu'il est dans une composition de résine durcissable et qu'il est durci, il présente une très bonne résistance au jaunissement à la chaleur.
PCT/JP2011/074760 2010-11-01 2011-10-27 Métallo-siloxane liquide durcissable par addition Ceased WO2012060272A1 (fr)

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CN112390820A (zh) * 2020-11-03 2021-02-23 吉林奥来德光电材料股份有限公司 一种可固化成膜的组合物单体及其组合物和该组合物的应用

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JP6327366B2 (ja) 2015-11-26 2018-05-23 東レ株式会社 ポリメタロキサン、その製造方法、その組成物、硬化膜およびその製造方法ならびにそれを備えた部材および電子部品
JP2023177815A (ja) * 2022-06-03 2023-12-14 Ｍｕアイオニックソリューションズ株式会社 非水系電解液、該非水系電解液を含む非水系電解液電池、及び化合物

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