TWI526467B - And a silicon-containing hardening resin composition - Google Patents

Description

Antimony-containing curable resin composition

The present invention relates to a cerium-containing curable resin composition containing an oxime compound having an epoxy group, an epoxy curing agent or an epoxy curing catalyst, and a cured product thereof.

It is known that compared with an epoxy compound of an organic resin skeleton such as a bisphenol A type epoxy resin or a 3,4-epoxycyclohexylcarboxylic acid-(3',4'-epoxycyclohexyl)methyl ester which has been used in the past. A compound having an anthracene group as a repeating unit and having an epoxy group in an organic group can obtain a cured product excellent in heat resistance, light resistance, and oxidation resistance, and a cyclic oxiranyl group having an epoxy group is A compound obtained by linking a linear polyoxyalkylene group (see, for example, Patent Documents 1 to 3) is excellent in flexibility, and is suitable as a sealing material for an optical semiconductor element such as a light-emitting diode or a photodiode (for example, Refer to Patent Documents 1 to 3). However, the cured product obtained from such a compound has a drawback that the surface is liable to be sticky and cannot be used for the surface coating.

In view of this, Patent Document 4 discloses a composition comprising a cyclic oxirane compound having an epoxy group, a cyclic oxiranyl group having an epoxy group, and a linear polyoxyalkylene group. An epoxy oxirane compound obtained by crosslinking a compound and a cyclic siloxane structure in a ring-like (poly)phosphonoalkyl group in a ring (refer to Patent Document 4), and Patent Document 4 The viscosity of the surface of the cured product obtained by the disclosed composition is improved, and the heat resistance is insufficient. When used for the use of the surface coating, there is a problem that cracks are likely to occur at a high temperature for a long period of time.

Prior technical literature Patent literature

Patent Document 1: US Patent No. 6313255

Patent Document 2: International Publication No. 2007/046399

Patent Document 3: Japanese Patent Laid-Open Publication No. 2008-266485

Patent Document 4: International Publication No. 2008/133108

An object of the present invention is to provide a curable composition which is excellent in heat resistance without surface tackiness and heat resistance and which is less likely to cause cracks even when used at a high temperature for a long period of time.

The present invention achieves the above object by providing a cerium-containing curable resin composition characterized by containing at least two epoxy group-containing groups in one molecule, and An epoxy oxirane compound having a group represented by the formula (1) as the component (A); an epoxy oxirane compound having 1 to 10 germanium atoms and at least 2 epoxy group-containing groups in one molecule (B) component; and an epoxy hardening compound as (C) component.

(wherein R ¹ to R ⁴ represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, and a represents a number of 20 to 10,000).

According to the present invention, it is possible to provide a curable composition which is excellent in heat resistance and excellent in heat resistance, and which is hard to be cracked even when used at a high temperature for a long period of time.

The component (A) of the cerium-containing curable resin composition of the present invention is an epoxy oxirane compound having at least two epoxy group-containing groups and a group represented by the above formula (1) in one molecule.

In the formula (1), R ¹ to R ^{4 each} represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, an isobutyl group, and a third butyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, an ethylphenyl group, a tolylmethyl group, a cumyl group, a xylyl group, and a pseudocumyl group. Base, tert-butylphenyl, phenethyl and the like. R ¹ to R ⁴ are preferably a methyl group, an ethyl group or a phenyl group in terms of heat resistance, more preferably a methyl group or a phenyl group, and most preferably a phenyl group. In terms of low viscosity and difficulty in crystallization, a methyl group, an ethyl group, a propyl group, and a butyl group are preferred, and a methyl group or an ethyl group is more preferred, and a methyl group is preferred. Therefore, R ¹ to R ^{4 are} preferably a combination of a methyl group and a phenyl group, and the ratio of methyl group to phenyl group in R ¹ to R ⁴ contained in the group represented by the formula (1) is methyl group and The ratio of the phenyl group to the molar ratio is preferably 40:60 to 100:0, more preferably 60:40 to 97:3, and most preferably 65:35 to 95:5.

In the formula (1), a represents a number from 20 to 10,000. When the ratio of a is less than 20, the heat resistance of the cured product is insufficient, and when it is more than 10,000, the viscosity becomes large, which causes an obstacle to the operation. a is preferably from 100 to 5,000, more preferably from 200 to 2,000.

The one molecule of the component (A) has at least two groups containing an epoxy group. The number of epoxy groups in the component (A) is preferably at least 3, more preferably at least 4, in terms of crack resistance. When the content of the epoxy group in the component (A) is too small, the cured product tends to be sticky, and when it is too large, the crack resistance is lowered. Therefore, the epoxy equivalent of the component (A) is preferably 500. ~50000, more preferably 700~20000, the best is 1000~10000. In addition, the epoxy equivalent means the mass (grams) of the epoxy compound containing one equivalent of the epoxy group.

The epoxy group-containing group of the component (A) is exemplified by the following formulas (5) to (24), and is preferably in the form of (10) in terms of excellent reactivity and easy industrial availability of the raw material. 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl)ethyl of formula (16), 2-(3,4-epoxy-4-methyl of formula (17) Cyclohexyl)propyl, more preferably 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl)ethyl.

The epoxy group-containing group may be directly bonded to the group represented by the formula (1), and it is preferred to increase the number of the epoxy group-containing groups in the component (A). The linking group is bonded to the group represented by the formula (1). Examples of the linking group include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group-containing group, a decyl group, a linear decyloxy group, and a cyclic oxiranyl group. The heat resistance is preferably improved. It is a cyclic oxiranyl group. In the case where the component (A) is a compound in which an epoxy group-containing group is bonded to a group represented by the formula (1) via a cyclic oxiranyl group, in terms of particularly good heat resistance, It is preferable that the groups represented by the following formula (2) or the group represented by the following formula (2) and the group represented by the following formula (3) are groups represented by the above formula (1) A linked epoxy oxirane compound.

(wherein R ⁵ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, E ¹ represents an epoxy group-containing group, and b represents a number of 2 to 5).

(wherein c represents a number of 2 to 6 such that b-c+1 is 0 to 4, and R ⁵ , E ¹ and b are synonymous with the general formula (2)).

In the formula (2), R ⁵ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ to R ^{4 of} the formula (1). R ⁵ is preferably a methyl group or a phenyl group in terms of improvement in heat resistance, and is preferably a methyl group.

In the formula (2), b represents a number of 2 to 5, and in terms of easily obtaining industrial raw materials, b is preferably 2 to 4, more preferably 2 to 3, most preferably 3. Further, E ¹ represents an epoxy group-containing group, and specific examples thereof include the above formulas (5) to (24).

In the formula (3), c represents a number of 2 to 6 in which b-c+1 is a number from 0 to 4, and R ¹ , E and a are synonymous with the formula (1).

An epoxy oxirane obtained by linking the groups represented by the formula (2) or the group represented by the formula (2) and the group represented by the formula (3) to a group represented by the formula (1) The compound can be obtained by subjecting a vinyl group of a chain siloxane compound represented by the following formula (1a) to a SiH group of a cyclic siloxane compound represented by the following formula (2a). After the reaction, an epoxy compound containing a carbon-carbon double bond reactive with an SiH group is further subjected to a hydrazine hydrogenation reaction.

(wherein R ¹ to R ⁴ and a are synonymous with the general formula (1)).

(wherein R ⁵ and b are synonymous with the formula (2)).

Among the compounds represented by the formula (2a), preferred examples of the compound include 2,4,6-trimethylcyclotrioxane and 2,4,6-triethylcyclotrioxane. 2,4,6-triphenylcyclotrioxane, 2,4-dimethyl-6-phenylcyclotrioxane, 2,4,6,8-tetramethylcyclotrioxane, 2,4,6,8-tetraethylcyclotetraoxane, 2,4,6,8-tetraphenylcyclotetraoxane, 2,4,6-trimethyl-8-phenyl ring Alkoxyoxane, 2,4-dimethyl-6,8-diphenylcyclotetraoxane, 2,4,6,8,10-pentamethylcyclopentaoxane, and the like.

The hydrogenation reaction of the chain siloxane compound represented by the formula (1a) with the cyclic siloxane compound represented by the formula (2a) is preferably carried out using a catalyst, and as a ruthenium hydrogenation catalyst, for example, Platinum-based catalysts, palladium-based catalysts, and ruthenium-based catalysts are listed. Examples of the platinum-based catalyst include chloroplatinic acid, a complex of chloroplatinic acid with an alcohol, an aldehyde, a ketone, etc., a platinum-olefin complex, and a platinum-carbonylvinylmethyl complex (Ossko catalyst). ), platinum-divinyltetramethyldioxane complex (Karstedt catalyst), platinum-cyclovinylmethyl oxime complex, platinum-octanal complex, platinum-phosphine complex (for example, Pt[P(C ₆ H ₅ ) ₃ ] ₄ , PtCl[P(C ₆ H ₅ ) ₃ ] ₃ , Pt[P(C ₄ H ₉ ) ₃ ) ₄ ]), platinum-phosphite A complex (for example, Pt[P(OC ₆ H ₅ ) ₃ ] ₄ , Pt[P(OC ₄ H ₉ ) ₃ ] ₄ ), dicarbonyldichloroplatinum or the like. Examples of the palladium-based catalyst or the ruthenium-based catalyst include a compound containing a palladium atom or a ruthenium atom in place of the platinum atom of the platinum-based catalyst. These may be used alone or in combination of two or more. As the rhodium hydrogenation catalyst, in terms of reactivity, a platinum-based catalyst is preferred, and a platinum-divinyltetramethyldioxane complex and a platinum-carbonylvinylmethyl complex are more preferred. Most preferred is a platinum-carbonylvinylmethyl complex. In addition, the amount of the catalyst to be used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, and most preferably 0.001 to 0.1% by mass, based on the total amount of each raw material. The reaction conditions for the hydrogenation of hydrazine are not particularly limited, and the above-mentioned catalyst may be used under previously known conditions. However, in terms of reaction rate, it is preferably carried out at room temperature (25 ° C) to 130 ° C. A previously known solvent such as toluene, hexane, methyl isobutyl ketone, cyclopentanone or propylene glycol monomethyl ether acetate can also be used.

a reaction product of a chain siloxane compound represented by the formula (1a) with a cyclic siloxane compound represented by the formula (2a), and an epoxy group having a carbon-carbon double bond reactive with a SiH group The hydrogenation reaction of the compound may be carried out under the same conditions as the hydrogenation reaction of the chain oxirane compound represented by the formula (1a) and the cyclic oxirane compound represented by the formula (2a). Preferably, after the hydrogenation reaction of the hydrazine, the reaction is continued without isolation and purification.

Examples of the epoxy compound containing a carbon-carbon double bond reactive with an SiH group include compounds of the following formulas (5a) to (20a) and (22a) to (24a), and by using such a compound, The epoxy group-containing groups of the above formulae (5) to (20) and (22) to (24) are introduced, respectively.

After reacting the cyclic oxirane compound represented by the formula (2a) with the chain oxirane compound represented by the formula (1a), an epoxy having a carbon-carbon double bond reactive with the SiH group is obtained. When the compound is reacted, an epoxy oxirane compound in which the groups represented by the formula (2) are bonded to each other by the group represented by the formula (1), and a group represented by the formula (2) and A mixture of an epoxy oxirane compound in which a group represented by the formula (3) is bonded to a group represented by the formula (1). When the epoxy oxirane compound in which the groups represented by the formula (2) are bonded to each other by the group represented by the formula (1) is selectively obtained, it is only as shown in the formula (1a). The chain oxirane compound is largely subjected to a hydrazine hydrogenation reaction using a cyclic siloxane compound represented by the formula (2a), and after the reaction is completed, the unreacted cyclic oxirane represented by the formula (2a) is removed. The compound is then reacted with an epoxy compound containing a carbon-carbon double bond reactive with the SiH group.

The component (B) of the cerium-containing curable resin composition of the present invention is an epoxy oxirane compound having 1 to 10 germanium atoms and at least two epoxy group-containing groups in one molecule. The component (B) is preferably a compound represented by the following formula (4) in terms of improving heat resistance. In addition, the component (B) can be listed, for example. The compounds represented by the following formulas (25) to (27) and the like are given.

(wherein R ⁶ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, E ² represents an epoxy group-containing group, and d represents a number of 3 to 6).

(wherein R ⁷ to R ⁹ each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, E ² represents an epoxy group-containing group, and e represents a number of 1 to 3, f And g respectively represent the number of 0 to 6. The total of the germanium atoms is 1 to 10).

(wherein R ¹⁰ to R ¹² each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and E ² represents an epoxy group-containing group, and h represents a number of 0 to 8).

(wherein R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and E ² represents an epoxy group-containing group).

In the general formulae (4) and (25) to (27), E ² represents an epoxy group-containing group. Examples of the epoxy group-containing group include the above formulas (5) to (24). The epoxy group-containing group as the component (B) has the same reactivity as the epoxy group-containing group of the component (A), and is preferably the same group as the epoxy group-containing group of the component (A). .

In the formula (4), R ⁶ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ to R ^{4 of} the formula (1). R ⁵ is preferably a methyl group or a phenyl group in terms of improving heat resistance, and is preferably a methyl group. d represents the number of 3 to 6, and it is easy to obtain the raw material in the industry. d is preferably 3 to 5, more preferably 3 to 4, and most preferably 4.

In the formula (25), R ⁷ to R ⁹ each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ to R ^{4 of} the formula (1). R ⁵ is preferably a methyl group or a phenyl group in terms of improving heat resistance, and is preferably a methyl group. e represents the number of 1~3, and f and g respectively represent the number of 0~6. Among them, the total number of germanium atoms is 1 to 10. In terms of improving the heat resistance of the cured product, e is preferably from 2 to 3. Further, for the same reason, f and g are preferably 0 to 2, more preferably 0 to 1.

In the formula (26), R ¹⁰ to R ¹² each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ to R ^{4 of} the formula (1). R ⁵ is preferably a methyl group or a phenyl group in terms of improving heat resistance, and is preferably a methyl group. h represents a number of 0 to 8, and in terms of improving the heat resistance of the cured product, it is preferably 0 to 3, more preferably 0 to 1, and most preferably 0.

In the formula (27), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ to R ^{4 of} the formula (1). R ⁵ is preferably a methyl group or a phenyl group in terms of improving heat resistance, and is preferably a methyl group.

The compound represented by the formulae (4) and (25) to (27) can be obtained by an epoxy compound containing a carbon-carbon double bond reactive with an SiH group, and the following formula (4a), ( The SiH groups of the compounds represented by 25a) to (27a) are respectively obtained by a hydrogen halide reaction, and the hydrogen halide reaction is carried out as shown in the formula (2a) with the chain oxyalkylene compound represented by the formula (1a). The reaction may be carried out under the same conditions as the hydrogen evolution reaction of the cyclic siloxane compound.

(wherein R ⁶ and d are synonymous with the formula (4)).

(wherein R ⁷ to R ⁹ , e, f and g are synonymous with the formula (25)).

(wherein R ¹⁰ to R ¹² and h are synonymous with the formula (26)).

(wherein R ¹³ to R ^{14 are} synonymous with the formula (27)).

As an epoxidation containing a carbon-carbon double bond reactive with a SiH group The compounds of the formulae (5a) to (20a) and (22a) to (24a) can be introduced into the formulas (5) to (20) and (22) to (24), respectively. An epoxy group-containing group.

In the cerium-containing curable resin composition of the present invention, when the ratio of the component (B) to the component (A) is too small, the cured product is excessively soft and the surface tends to be sticky, and in the case of excessively, the cured product The content of the component (B) is preferably from 3 to 50 parts by mass, more preferably from 5 to 40 parts by mass, even more preferably from 7 to 40 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). ~35 parts by mass.

The component (C) of the cerium-containing curable resin composition of the present invention is an epoxy curable compound. Examples of the epoxy curable compound include an epoxy curing agent and an epoxy curing catalyst. In the present invention, the term "epoxy hardener" means a compound which can cure an epoxy composition by reacting with an epoxy group, and the term "epoxy hardening catalyst" means the action by heat or energy rays or the like. A compound which produces an acidic substance or a basic substance which reacts epoxy groups with each other to harden an epoxy resin.

Examples of the epoxy curing agent include a phenolic novolac resin, a bisphenol novolak resin, and a phenolic curing agent such as poly(p-vinylphenol); diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and dicyandiamide. , polyamine amine (polyamide resin), ketimine compound, isophorone diamine, m-xylylenediamine, m-phenylenediamine, 1,3-bis(aminomethyl)cyclohexane, N -Aminoethyl a polyamine curing agent such as 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane or diaminodiphenylanthracene; Phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, A polycarboxylic acid-based curing agent such as hexachloro-methylenetetrahydrophthalic anhydride or methyl-3,6-endomylenetetrahydrophthalic anhydride can obtain hardening with high heat resistance. In terms of the object, a phenol-based curing agent or a polycarboxylic acid-based curing agent is preferred, and a polycarboxylic acid-based curing agent is more preferred.

When an epoxy curing agent is used as the epoxy curing compound of the component (C), the amount of the epoxy curing agent used is preferably relative to the component (A) and (B) in terms of obtaining a good cured product. The epoxy group contained in the component is 1 mol, and the epoxy reactive group contained in the epoxy hardener is 0.4 to 1.2 mol, more preferably the epoxy reactive group is 0.5 to 0.9 mol. . In the case of using an epoxy curing agent, it is preferred that the amount of the epoxy curing agent used is 100 parts by mass based on the total amount of the component (A) and the component (B), from the viewpoint of the effect of the present invention. 10 to 50 parts by mass, more preferably 15 to 40 parts by mass.

As the epoxy curing catalyst, an epoxy curing catalyst of an acidic substance type is preferable in terms of a reaction at a relatively low temperature, and in terms of storage stability and reactivity, Jia is an organic bismuth salt hardening catalyst. Examples of the organic cerium salt-based curing catalyst include a diazonium salt-based catalyst, an iodonium-based catalyst, and a sulfonium salt catalyst. These may be thermosetting or energy ray-curing. . In general, an aliphatic sulfonium salt is used for thermosetting, and an aromatic sulfonium salt is used for energy ray hardening. The organic cerium salt-based hardening catalyst can obtain good hardening with a small amount of use, and when it is hardened by an energy ray, the (C) component is good in compatibility with the component (A). Preferred are aromatic iodonium salts and aromatic sulfonium salts. Also, when it is hardened by heat, it is compatible with the component (A). In terms of good properties, the component (C) is preferably an aliphatic sulfonium salt.

In the present invention, the aromatic iodonium salt refers to an iodonium salt in which at least one of the substituents of iodonium is an aryl group. Examples of the aromatic iodonium salt include 4-isopropoxy-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate and 4-isopropoxy-4'-methyl-2. Phenyl iodonium hexafluorophosphate, 4-isopropoxy-4'-methyldiphenyliodonium hexafluoroantimonate, (tolylisopropylphenyl) iodonium hexafluorophosphate, (tolyl Phenylphenyl)iodonium hexafluoroantimonate, (tolylcumyl)iodonium tetrakis(pentafluorophenyl)borate, bis(t-butylphenyl)iodonium hexafluorophosphate, double (Third butylphenyl) iodonium hexafluoroantimonate, bis(t-butylphenyl)iodonium tetrakis(pentafluorophenyl)borate, and the like.

In the present invention, the term "aromatic sulfonium salt" means a sulfonium salt in which at least one of the substituents of thioindigo is an aryl group. Examples of the aromatic sulfonium salt include 4,4′-bis[bis(4-heptyloxyphenyl)sulfonylphenyl]thioether-bishexafluoroantimonate, 4,4′-bis[ (4-heptyloxyphenyl)phosphonium phenyl] thioether-bis hexafluorophosphate, 4-(4-benzylidene-phenylthio)phenyl-di-(4-fluorophenyl)sulfide Hexafluorophosphate, 4,4'-bis[bis((β-hydroxyethoxy)phenyl)thiol]phenyl sulfide dihexafluorophosphate, 4,4'-double [double ( β-Hydroxyethoxy)phenyl)thiol]phenylsulfate dihexafluoroantimonate, 4,4′-bis[bis(fluorophenyl)thioindolyl]phenyl sulfide dihexafluorophosphate Salt, 4,4'-bis[bis(fluorophenyl)thiol]phenyl sulfide dihexafluoroantimonate, 4,4'-bis(diphenylsulfanyl)phenyl sulfide double six Fluorophosphate, 4,4'-bis(diphenylsulfanyl)phenyl sulfide dihexafluoroantimonate, 4-(4-benzylidenephenylthio)phenyl-di-(4- (β-hydroxyethoxy)phenyl)phosphonium hexafluorophosphate, 4-(4-benzylidenephenylthio)phenyl-di-(4-(β-hydroxyethoxy)phenyl) Thiosulfonium hexafluoroantimonate, 4-(4-benzylidenephenylthio)phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate, 4-(4-benzylidenephenylthio)phenyl-di-(4-fluorophenyl)thioindole hexafluoroantimonate, 4-( 4-Benzylmercaptophenylthio)phenyl-diphenylsulfonium hexafluorophosphate, 4-(4-benzylidenephenylthio)phenyl-diphenylsulfonium hexafluoroantimonate, 4-(phenylthio)phenyl-bis-(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluorophosphate, 4-(phenylthio)phenyl-di-(4-(β -hydroxyethoxy)phenyl)thioindole hexafluoroantimonate, 4-(phenylthio)phenyl-di-(4-fluorophenyl)phosphonium hexafluorophosphate, 4-(phenylthio) Phenyl-bis-(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(phenylthio)phenyl-diphenylsulfonium hexafluorophosphate, 4-(phenylthio)phenyl- Diphenylsulfonium hexafluoroantimonate, 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluorophosphate, 4-(2- Chloro-4-benzylidene phenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-benzylidenephenylthio)phenyl double (4-fluorophenyl) sulfonium hexafluorophosphate, 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)thioindole hexafluoroantimonate, 4 -(2-chloro-4-benzylidenephenylthio)phenyldiphenylsulfonium Hexafluorophosphate, 4-(2-chloro-4-benzylidenephenylthio)phenyldiphenylsulfonium hexafluoroantimonate, 4-(2-chloro-4-benzylidenesulfonate) Phenyl bis(4-hydroxyphenyl)phosphonium hexafluorophosphate, 4-(2-chloro-4-benzylidenephenylthio)phenyl bis(4-hydroxyphenyl)phosphonium hexafluoro Citrate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, 4-ethyloxyphenyl dimethyl sulfonium hexafluorophosphate, 4-ethenyloxybenzene Methyl dimethyl sulfonium hexafluoroantimonate, 4-methoxycarbonyloxyphenyl dimethyl sulfonium hexafluorophosphate, 4-methoxycarbonyloxyphenyl dimethyl sulfonium hexafluoroantimony An acid salt, 4-ethoxycarbonyloxyphenyl dimethyl sulfonium hexafluorophosphate, 4-ethoxycarbonyloxyphenyl dimethyl sulfonium hexafluoroantimonate or the like.

In the present invention, the aliphatic sulfonium salt refers to a sulfonium salt of an aliphatic hydrocarbon having a substituent of all of an aliphatic hydrocarbon group or a substituent. Examples of the aliphatic sulfonium salt include dimethylbenzylsulfonium hexafluoroantimonate, tribenzylsulfonium hexafluoroantimonate, and dimethylbenzimidiummethylsulfonium hexafluoroantimonate. (3-methyl-2-butenyl) dimethylsulfonium hexafluoroantimonate, benzyl tetrahydrothiophene hexafluoroantimonate, phenylallyldimethylsulfonium hexafluoroantimonate, 1-(α-naphthylmethyl)tetrahydrothiophene hexafluoroantimonate, 1-(α-naphthylmethyl)tetrahydrothiophene hexafluorophosphate, 1-(phenylallyl)tetrahydrothiophene hexa Fluoride, 1-(phenylallyl)tetrahydrothiophene hexafluorophosphate, and the like.

When an epoxy curing catalyst is used as the (C) component epoxy curable compound, if the epoxy curing catalyst is too small, the curing is insufficient, and when it is too large, the heat resistance of the cured product may be poor. In the case of the influence, the content of the epoxy curing catalyst is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). It is 0.1 to 1 part by mass.

The cerium-containing curable resin composition of the present invention can be selected from the group consisting of (C) component epoxy curable compounds, and thermosetting, photocuring, or curing using both light and heat as the type of curing. The hardening temperature in the case of heat hardening is preferably 60 to 200 ° C, more preferably 80 to 150 ° C. The hardening time is preferably from 0.1 to 10 hours, more preferably from 1 to 6 hours. In the case of photohardening, as the active energy ray that can be used, there are ultraviolet rays, electron beams, X-rays, radiation, high-frequency waves, and the like, and ultraviolet rays are economically optimal. As a light source of ultraviolet rays, there are ultraviolet lasers, mercury lamps, high-pressure mercury lamps, xenon lamps, sodium lamps, alkali metal lamps, and the like. The ultraviolet light source used herein is preferably a high pressure mercury lamp. The most suitable conditions for the irradiation energy vary depending on the film thickness to be applied, and are usually in the range of 100 to 10,000 mJ/cm ² . Further, in the case where the glass is thermally cured after photohardening, it is usually heated in the range of 60 to 150 °C.

The cerium-containing curable resin composition of the present invention may contain other epoxy compounds, hardening accelerators, sensitizers, metal oxide fine powders, and weathering resistance insofar as the performance of the cerium-containing curable resin of the present invention is not lowered. Any additive such as a sex imparting agent. In addition, in the case of containing the additive other than the metal oxide fine powder, it is preferable to use the component (A), the component (B), and the component (C) from the viewpoint of ensuring the effect of the present invention. The total amount of the metal oxide fine powder after removing the content of the metal oxide fine powder from the cerium-containing curable resin composition of the present invention is 90% by mass or more, and the like.

In the present invention, the above-mentioned other epoxy resin means a compound other than the component (A) and the component (B) of the present invention having at least one epoxy group in the molecule. Preferred other epoxy resins include 2,2-bis(3,4-epoxycyclohexyl)propane and (3,4-epoxy)cyclohexanecarboxylic acid-3',4'-epoxy rings. Hexylmethyl ester, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl Alkane, bis[(3,4-epoxycyclohexyl)methyl]adipate, 6-(3,4-epoxycyclohexylcarbonyloxy)hexanoic acid (3,4-epoxycyclohexyl) An alicyclic epoxy compound such as an ester; a bisphenol type epoxy resin such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether; phenol novolac epoxy resin; Cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac epoxy resin and other novolak type epoxy resin; glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, epoxidized poly An aromatic epoxy resin such as a polyfunctional epoxy resin such as ethylene phenol; a polyglycidyl ether of an aliphatic polyol; a polyglycidyl ether of a polyester polyol of an aliphatic polyol and an aliphatic polycarboxylic acid; Polyglycidyl ester of polycarboxylic acid; polyglycidyl ester of polyester polycarboxylic acid of aliphatic polyhydric alcohol and aliphatic polycarboxylic acid; obtained by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate Dimer, oligomer, polymer; by glycidyl acrylate or methacryl An oligomer or a polymer obtained by polymerizing a vinyl glycidyl ester with another vinyl monomer; an epoxidized polybutadiene; an epoxy oxirane compound represented by the following formula (28).

(wherein R ¹⁵ to R ¹⁹ each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, E ³ represents an epoxy group-containing group, and X represents an alkyl group having 1 to 4 carbon atoms. The base, the aryl group having 6 to 10 carbon atoms or the group containing an epoxy group, and j and k represent the number of 0 to 1000 in which j+k is 9 to 1000. Wherein, when j is a number 0, X represents The base of the epoxy group).

As the other epoxy compound, a molecular weight of 100 to 1,000 is preferable because the mechanical strength of the obtained cured product is remarkably improved, and the epoxy equivalent is preferably from 100 to 600. When the amount of the other epoxy compound is too large, the heat resistance of the obtained cured product may be lowered. Therefore, the blending amount is preferably 100 parts by mass based on the total amount of the component (A) and the component (B). 1 to 30 parts by mass, more preferably 1 to 20 parts by mass. Further, in the case of blending other epoxy compounds, it is preferred that when the component (C) is an epoxy curing agent, the total content of the epoxy groups of the component (A), the component (B) and other epoxy compounds is preferably When the amount of the component (C) is appropriately changed, when it is an epoxy curing catalyst, the amount of the component (C) is appropriately changed depending on the total content of the component (A), the component (B), and other epoxy compounds.

The hardening accelerator is a compound for promoting the reaction between an epoxy group and an epoxy curing agent, and in particular, when the epoxy curing agent is a phenolic curing agent or a polycarboxylic acid curing agent, the curing accelerator is formulated. good. Examples of the hardening accelerator include 1,8-diazabicyclo[5.4.0]undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and trisole. A tertiary amine such as (dimethylaminomethyl)phenol and a salt thereof; an imidazole such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole or 2-heptadecylimidazole Organophosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine; tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methyl Imidazolium tetraphenylborate, N-methyl Tetraphenylborate such as tetraphenylborate. The amount of the curing accelerator is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the total amount of the component (A), the component (B), and the other epoxy compound in the composition of the present invention.

The sensitizer is a compound which expands the wavelength range in which the energy ray is applicable when hardened by the energy ray. Examples of the sensitizer include benzophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 4,4-dihydroxybenzophenone, and 2-methylbenzophenone. 3-methylbenzophenone, 4-methylbenzophenone, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone, 4-methoxybiphenyl Benzophenones such as ketone, 4,4-dimethoxybenzophenone, 3,3-dimethyl-4-methoxybenzophenone, 4-phenylbenzophenone; Ketone, 4-methoxyacetophenone, 2,4-dimethoxyacetophenone, 2,5-dimethoxyacetophenone, 2,6-dimethoxyacetophenone, 4,4 -dimethoxyacetophenone, 4-ethoxyacetophenone, diethoxyacetophenone, 2,2-diethoxyacetophenone, 2-ethoxy-2-phenylbenzene Acetones such as ketones and 4-phenylacetophenones; hydrazine, hydroxy hydrazine, 1-nitroguanidine, aminoguanidine, 2-chloroindole, 2-methylindole, 2-B Anthraquinones such as hydrazine, hydrazine sulfonic acid, 1,2-benzopyrene, 1,4-hydroxyindole (indene); anthracene, 1,2-benzopyrene, 9-cyanoguanidine, 9,10-Dicyanoguanidine, 2-ethyl-9,10-dimethoxyanthracene, 9,10-bis(phenylethyl)anthracene and the like; 2,3-dichloro-6-di Cyanide P-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, methoxybenzoquinone, 2,5-dichloro-p-benzoquinone, 2,6-dimethyl-1 , 4-benzoquinone, 9,10-phenanthrenequinone, camphorquinone, 2,3-dichloro-1,4-naphthoquinone, Ketones and other anthracenes; 9-oxosulfur 2-methyl-9-oxosulfur 2,4-dimethyl-9-oxosulfur Isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-isopropyl-9-oxosulfur Oxygen sulfur a class of cyclobenzoheptanes such as dibenzosuberone, dibenzosuberene, dibenzosuberenol, dibenzosuberane; Oxynaphthalene, benzoin isopropyl ether, 4-benzylidenebiphenyl, o-benzhydrylbenzoic acid, methyl o- benzhydrylbenzoate, 4-benzylidene-4-methyl-diphenyl An aromatic compound such as thioether, benzoin, and benzoin methyl ether; and coumarin, thiophene as a dye-sensitizing substance Department, 吖 Department, acridine system, A compound or the like. The amount of the sensitizer added is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 2 parts by mass, per 100 parts by mass of the total of the components (A) and (B).

Examples of the metal oxide fine powder include inorganic materials such as minerals. Specific examples thereof include colloidal cerium oxide, cerium oxide filler, cerium oxide such as cerium oxide, metal oxides such as alumina, zinc oxide, and titanium oxide, mica, montmorillonite, vermiculite, and diatomaceous earth. Sericite, kaolinite, vermiculite, feldspar powder, vermiculite, erbium, talc, iron talc, leaf wax Minerals such as stone, etc., may be modified by organic modification or the like. Among these, cerium oxide is preferred.

The particle diameter of the metal oxide fine particles described above is preferably 100 μm or less, and more preferably 50 μm or less in terms of heat resistance. The amount of the metal oxide fine particles to be added is preferably from 0.1 to 80% by mass, more preferably from 0.5 to 70% by mass, based on the cerium-containing curable resin composition of the present invention.

As the weather resistance imparting agent, a well-known and common user such as a light stabilizer, an ultraviolet absorber, a phenol antioxidant, a sulfur-based antioxidant, or a phosphorus-based antioxidant can be used. For example, examples of the light stabilizer include hindered amines; and examples of the ultraviolet absorber include 2-hydroxybenzophenones, 2-(2-hydroxyphenyl)benzotriazoles, and 2-(2-hydroxyl groups). Phenyl)-4,6-diaryl-1,3,5-three Classes, benzoates, cyanoacrylates; as phenolic antioxidants, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propane Acid ester], dibutylhydroxytoluene (BHT), 2,6-di-t-butyl-p-cresol (DBPC), etc.; as the sulfur-based antioxidant, dialkyl thiodipropionate, The β-mercaptopropionic acid alkyl esters; and the phosphorus-based antioxidants include organic phosphites.

When the weather resistance imparting agent is used, the content thereof is preferably a cerium-containing curable resin of the present invention in terms of heat resistance, electrical properties, hardenability, mechanical properties, storage stability, and handleability. The composition is 0.0001 to 50% by mass, more preferably 0.001 to 10% by mass.

The cerium-containing curable resin composition of the present invention has good fluidity at room temperature (25 ° C) and is excellent in handleability. With regard to fluidity, it is preferred to use an E-type viscometer at room temperature (25 ° C) in a state in which no fine metal oxide powder is contained. The viscosity measured was 50 Pa. Below s, more preferably 10 Pa. s below.

The cured product obtained from the cerium-containing curable resin composition of the present invention has transparency, crack resistance, heat resistance, solvent resistance, alkali resistance, weather resistance, stain resistance, flame retardancy, moisture resistance, It is excellent in mechanical properties such as gas barrier properties, flexibility, elongation or strength, electrical insulating properties, and low dielectric constant, optical properties, electrical properties, and the like, and particularly has low surface tackiness and excellent heat resistance. Therefore, the cerium-containing curable resin composition of the present invention can be applied to a sealing material for display materials, optical materials, recording materials, semiconductors, etc. in the field of electrical/electronic materials, high-voltage insulating materials, to be insulated, vibration-proof, waterproof, and preventive. Potting/sealing agent for wet purpose, prototype mastering method for plastic parts, coating material, interlayer insulating film, insulating package, optical waveguide, optical fiber protective material, optical lens, adhesive for optical machine, high heat resistance adhesive A highly heat-dissipating material, a high heat-resistant sealing material, a member for a solar cell/fuel cell, an insulating coating material, a photosensitive drum for a photocopier, and the like can be suitably used as a coating material.

Example

Hereinafter, the present invention will be further illustrated by the examples, but the present invention is not limited by the examples.

In addition, unless otherwise indicated, the "part" or "%" in the embodiment is based on the quality standard. In addition, the mass average molecular weight is a mass average molecular weight in terms of polystyrene in the case of GPC (Gel Permeation Chromatography) analysis using tetrahydrofuran as a solvent. Further, the epoxy equivalent is measured in accordance with JIS K-7236 (Method for Epoxy Resin).

[Manufacturing Example 1: Chain-like siloxane compound a-1]

130 g of ion-exchanged water, 550 g of a 48% aqueous sodium hydroxide solution, and 100 g of toluene as a solvent were placed in a glass reaction vessel containing a thermometer and a stirring device, and stirred at a temperature of 30 ° C or lower for 1 hour while stirring. 129 g (1 mol) of dimethyldichloromethane was added dropwise, and after completion of the dropwise addition, stirring was further continued at 105 ° C for 5 hours. After the obtained sodium chloride solution was washed with 500 g of ion-exchanged water to remove the purified sodium chloride, the solvent was distilled off under reduced pressure at 60 °C. To the reaction was added 12.1 g (0.1 mol) of dimethylvinylchloromethane to which 63 g (0.8 mol) of pyridine was added and dissolved, and the mixture was stirred at 70 ° C for 30 minutes. Thereafter, the mixture was washed with water (100 g of ion-exchanged water), and then the solvent was distilled off under reduced pressure at 100 ° C to obtain a chain-like siloxane compound a-1 having a vinyl group at both ends. In the formula (1a), R ¹ to R ⁴ are a methyl group, and the mass average molecular weight obtained by GPC is 40,000 (a corresponds to 538).

[Manufacturing Example 2: Chain-like siloxane compound a-2]

A mixture of 116 g (0.9 mol) of dimethyldichloromethane and 25.3 g (0.1 mol) of diphenyldichloromethane was used instead of 129 g (1 mol) of dimethyldichloromethane in Production Example 1, except The same operation as in Production Example 1 was carried out to obtain a chain-like siloxane compound a-2 having a vinyl group at both ends. Chain-like oxane compound a-2 In the formula (1a), R ¹ to R ² are a methyl group, and R ³ to R ⁴ are a mixed group of a methyl group and a phenyl group (methyl group: phenyl = 9:1) The mass average molecular weight obtained by GPC is 20,000 (a corresponds to 230).

[Manufacturing Example 3: Chain-like siloxane compound a-3]

A mixture of 90.3 g (0.7 mol) of dimethyldichloromethane and 75.9 g (0.3 mol) of diphenyldichloromethane was used instead of 129 g (1 mol) of dimethyldichloromethane in Production Example 1, except The same operation as in Production Example 1 was carried out to obtain a chain-like siloxane compound a-3 having a vinyl group at both ends. Chain-like siloxane compound a-3 In the formula (1a), R ¹ to R ² are a methyl group, and R ³ to R ⁴ are a mixed group of a methyl group and a phenyl group (methyl group: phenyl = 7:3) The mass average molecular weight obtained by GPC is 10,000 (a is equivalent to 88).

[Manufacturing Example 4: High molecular weight epoxy siloxane compound A-1]

In a glass reaction vessel containing a thermometer and a stirring device, a chain siloxane compound a-1 40 g (1 mmol), 2,4,6,8-tetramethylcyclotetraoxane 1.44 g (6) was charged. Methyl), platinum-divinyltetramethyldioxane complex (Karstedt catalyst) 10 mg, and 50 g of toluene as a solvent were reacted at 105 ° C for 2 hours while stirring. After removing unreacted 2,4,6,8-tetramethylcyclotetraoxane and a solvent under reduced pressure at 80 ° C, 0.92 g (8 mmol) of allyl glycidyl ether and toluene 50 as a solvent were charged. g, the mixture was reacted at 105 ° C for 3 hours while stirring. After completion of the reaction, the unreacted allyl glycidyl ether and the solvent were distilled off under reduced pressure at 80 ° C to obtain a high molecular weight epoxy siloxane compound A-1. The high molecular weight epoxy siloxane compound A-1 is an epoxy oxirane compound in which the groups represented by the formula (2) are bonded to each other by a group represented by the formula (1), and is a compound of the formula (1). In the formula (2), R ¹ to R ⁴ are a methyl group, and in the formula (2), R ⁵ is a methyl group, E ¹ is a 3-glycidoxypropyl group, and b is a compound of 3. Further, the epoxy equivalent of the high molecular weight epoxy siloxane compound A-1 was 6,700.

[Manufacturing Example 5: High molecular weight epoxy siloxane compound A-2]

The same operation as in Production Example 4 was carried out, except that the chain siloxane compound a-2 20 g (1 mmol) was used instead of the chain oxy siloxane compound a-1 40 g (1 mmol) in Production Example 4. The high molecular weight epoxy siloxane compound A-2 was obtained. The high molecular weight epoxy oxirane compound A-2 is an epoxy oxirane compound in which the groups represented by the formula (2) are bonded to each other by a group represented by the formula (1), and is a compound of the formula (1). In the formula (2), R ¹ to R ² are a methyl group, R ³ to R ⁴ are a mixed group of a methyl group and a phenyl group (methyl group: phenyl = 9:1), and a is 230. R ⁵ is a methyl group, E ¹ is a 3-glycidoxypropyl group, and b is a compound of 3. Further, the epoxy equivalent of the high molecular weight epoxy siloxane compound A-2 was 3,400.

[Manufacturing Example 6: High molecular weight epoxy siloxane compound A-3]

The same operation as in Production Example 4 was carried out, except that the chain siloxane compound a-3 10 g (1 mmol) was used instead of the chain siloxane compound a-1 40 g (1 mmol) in Production Example 4. The high molecular weight epoxy siloxane compound A-3 was obtained. The high molecular weight epoxy siloxane compound A-3 is an epoxy oxirane compound in which the groups represented by the formula (2) are bonded to each other by a group represented by the formula (1), and is a compound of the formula (1). In the formula (2), R ¹ to R ² are a methyl group, R ³ to R ⁴ are a mixed group of a methyl group and a phenyl group (methyl group: phenyl = 7:3), and a is 88. R ⁵ is a methyl group, E ¹ is a 3-glycidoxypropyl group, and b is a compound of 3. Further, the high molecular weight epoxy siloxane compound A-3 has an epoxy equivalent of 1600.

[Manufacturing Example 7: High molecular weight epoxy siloxane compound A-4]

The production example 4 was carried out except that 1,2-epoxy-4-vinylcyclohexane 0.99 g (8 mmol) was used instead of 0.92 g (8 mmol) of the allyl glycidyl ether in Production Example 4. The same operation was carried out to obtain a high molecular weight epoxy siloxane compound A-4. The high molecular weight epoxy siloxane compound A-4 is an epoxy oxirane compound in which the groups represented by the formula (2) are bonded to each other by a group represented by the formula (1), and is a compound of the formula (1). Wherein R ¹ to R ⁴ are a methyl group and a is 538. In the formula (2), R ⁵ is a methyl group, E ¹ is a 2-(3,4-epoxycyclohexyl)ethyl group, and b is 3 compounds. Further, the epoxy equivalent of the high molecular weight epoxy siloxane compound A-4 was 6,700.

[Manufacturing Example 8: High molecular weight epoxy siloxane compound A-5]

The chain siloxane compound a-2 20 g (1 mmol) was used instead of the chain fluorinated compound a-1 40 g (1 mmol) in Production Example 4, and 1,2-epoxy-4- The same procedure as in Production Example 4 was carried out except that 0.99 g (8 mmol) of vinylcyclohexane was used instead of 0.92 g (8 mmol) of the allyl glycidyl ether in Production Example 4 to obtain a high molecular weight epoxy oxirane. Alkane compound A-5. The high molecular weight epoxy siloxane compound A-5 is an epoxy oxirane compound in which the groups represented by the formula (2) are bonded to each other by a group represented by the formula (1), and is a compound of the formula (1). In the formula (2), R ¹ to R ² are a methyl group, R ³ to R ⁴ are a mixed group of a methyl group and a phenyl group (methyl group: phenyl = 9:1), and a is 230. R ⁵ is a methyl group, E ¹ is a 2-(3,4-epoxycyclohexyl)ethyl group, and b is a compound of 3. Further, the epoxy equivalent of the high molecular weight epoxy siloxane compound A-5 was 3,400.

[Production Example 9: High molecular weight epoxy siloxane compound A-6]

In a glass reaction vessel containing a thermometer and a stirring device, a chain siloxane compound a-2 16 g (0.8 mmol) and 2,4,6,8-tetramethylcyclotetraoxane 0.144 g (0.6) were charged. Methyl), platinum-divinyltetramethyldioxane complex (Karstedt catalyst) 10 mg, and 50 g of toluene as a solvent, reacted at 105 ° C for 2 hours while stirring, and added allylic acid The glycidyl ether was 0.92 g (8 mmol), and further reacted at 105 ° C for 3 hours. After completion of the reaction, the unreacted allyl glycidyl ether and the solvent were distilled off under reduced pressure at 80 ° C to obtain a high molecular weight epoxy siloxane compound A-6. The high molecular weight epoxy oxirane compound A-6 is an epoxy oxirane compound in which the group represented by the formula (2) is bonded by a group represented by the formula (1), and is represented by the formula (2). a mixture of an epoxy oxirane compound obtained by linking a group represented by the following formula (3) to a group represented by the formula (1), and is in the formula (1), R ¹ ~ R ² is a methyl group, and R ³ to R ⁴ are a mixed group of a methyl group and a phenyl group (methyl group: phenyl = 9:1), and a is 230. In the formula (2) and the formula (3), R ⁵ is a methyl group, E ¹ is a 3-glycidoxypropyl group, and b is a compound of 3. Further, the epoxy equivalent of the high molecular weight epoxy siloxane compound A-6 was 5,100.

[Production Example 10: Low molecular weight epoxy siloxane compound B-1]

2,4,6,8-tetramethylcyclotetraoxane 48 g (0.2 mol) and allyl glycidyl ether 114 g (1 mol) were placed in a glass reaction vessel containing a thermometer and a stirring device. 10 mg of platinum-divinyltetramethyldioxane complex (Karstedt catalyst) and 200 g of toluene as a solvent were reacted at 105 ° C for 3 hours while stirring. Thereafter, the unreacted allyl glycidyl ether and the solvent were distilled off under reduced pressure at 100 ° C to obtain a low molecular weight epoxy siloxane compound B-1. The low molecular weight epoxy oxirane compound B-1 is a compound of the formula (4), R ⁶ is a methyl group, E ² is a 3-glycidoxypropyl group, and d is 4, and the epoxy equivalent is 174. .

[Production Example 11: Low molecular weight epoxy siloxane compound B-2]

The production example 10 was carried out except that 124 g (1 mol) of 1,2-epoxy-4-vinylcyclohexane was used instead of the allyl glycidyl ether 114 g (1 mol) in Production Example 10. The same operation was carried out to obtain a low molecular weight epoxy siloxane compound. The low molecular weight epoxy oxirane compound B-2 is a compound of the formula (4), R ⁶ is a methyl group, E ² is a 2-(3,4-epoxycyclohexyl)ethyl group, and d is 4, And the epoxy equivalent is 184.

[Manufacturing Example 12: Low molecular weight epoxy siloxane compound B-3]

65.6 g (0.2 mol) of tetrakis(dimethyloxoxyalkyl)decane was used instead of 2,4,6,8-tetramethylcyclotetraoxane 48 g (0.2 mol) in Production Example 10, The same operation as in Production Example 10 was carried out to obtain a low molecular weight epoxy siloxane compound B-3. The low molecular weight epoxy siloxane compound B-3 is in the formula (25), R ⁸ to R ⁹ are a methyl group, E ² is a 3-glycidoxypropyl group, and e is 3, f and g are 1 The compound has an epoxy equivalent of 226.

[Production Example 13: Comparative epoxy oxymethane composition D-1]

According to Example 1 of International Publication No. 2008/133108, 2,4,6,8-tetramethylcyclotetraoxane 80 g, 1,3- was charged into a glass reaction vessel containing a thermometer and a stirring device. 37.2 g of divinyltetramethyldioxane, 122.6 g of 2-epoxy-4-vinylcyclohexane, and 1,4-two as a solvent 925 g of alkane was stirred under heating, and 10 mg of platinum-divinyltetramethyldioxane complex (Karstedt catalyst) was added at 70 ° C, and then reacted at 65 to 100 ° C for 8 hours. After cooling to 30 ° C, 925 g of acetonitrile was added, and the mixture was stirred at 30 ° C for 2 hours, and further 800 g of activated carbon was added thereto, and the mixture was stirred at 30 ° C for 48 hours. After the activated carbon is removed by filtration, the filtered activated carbon is washed with acetonitrile, and the washing liquid is recovered and mixed with the filtrate obtained above. Distillation of 1,4-two from the recovered mixture under reduced pressure and at a heating temperature of 40 ° C using an evaporator The alkane and acetonitrile were combined to obtain a comparative epoxy oxane composition D-1. The epoxy equivalent of the epoxy oxirane composition D-1 was 251.

[Manufacturing Example 14: Comparative Composition D-2]

According to Example 14 of International Publication No. 2008/133108, 55.0 g of 2,4,6,8-tetramethylcyclotetraoxane was introduced into a glass reaction vessel containing a thermometer and a stirring device, and the following formula ( 29) 63.0 g of a polyoxyalkylene compound, 110 g of 2-epoxy-4-vinylcyclohexane, and 1,4-two as a solvent 1000 g of alkane was stirred under heating, and 10 mg of platinum-divinyltetramethyldioxane complex (Karstedt catalyst) was added at 70 ° C, and then reacted at 65 to 100 ° C for 8 hours. Then, the same operation as in Production Example 11 was carried out to obtain a comparative epoxy siloxane composition D-2. The epoxy equivalent of the epoxy oxirane composition D-2 was compared to 272.

[Examples 1 to 23, Comparative Examples 1 to 28]

The high molecular weight epoxy siloxane compound A-1 to 5 is used as the component (A), and the low molecular weight epoxy siloxane compound B-1 to 3 is used as the component (B), and the following compounds C-1 to 3 are used for comparison. The compositions D-1 to 2 and the following compound D-3 were mixed as the component (C) and the following compound E-1 as a curing accelerator, and the compositions shown in the following Tables 1 and 2 were mixed to prepare an example. The cerium-containing curable resin composition of 1 to 23 and Comparative Examples 1 to 28. Using the obtained cerium-containing curable resin composition, a test piece was prepared according to the following <Preparation of a test piece>.

(C) component

C-1: 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate as epoxy hardening catalyst (photocuring catalyst) salt

C-2: 1-(phenylallyl) four as an epoxy hardening catalyst (thermosetting catalyst) Hydrothiophene hexafluoroantimonate

C-3: methylhexahydrophthalic anhydride as epoxy hardener

Comparison of low molecular weight epoxy compounds

D-3: phenol novolac type epoxy resin (degree of condensation 8), epoxy equivalent of 177

Hardening accelerator

E-1: Diazabicycloundecene octoate

<Preparation of test piece>

The cerium-containing curable resin compositions of Examples 1 to 23 and Comparative Examples 1 to 28 were applied to a square glass substrate having a length of 50 mm, a width of 50 mm, and a thickness of 1 mm so as to have a film thickness of 20 μm. The test pieces of Examples 1 to 23 and Comparative Examples 1 to 28 were obtained by photohardening or heat curing under the following conditions.

(photohardening condition)

The glass substrate to which the cerium-containing curable resin composition of Examples 1 to 14 or Comparative Examples 1 to 15 was applied was irradiated with ultraviolet rays at a rate of 10 mJ/cm ² (wavelength at 365 nm) using a high pressure mercury lamp, followed by 120 ° C. The inside of the thermostat was post-baked for 10 minutes to harden it.

(thermosetting conditions)

The glass substrate coated with the cerium-containing curable resin composition of Examples 15 to 23 or Comparative Examples 16 to 28 was heated in a thermostat at 120 ° C for 1 hour, and then heated at 150 ° C for 2 hours. It hardens.

Using the obtained test piece, the following dust adhesion test and heat-resistant adhesion test were performed.

(dust adhesion test)

The test piece was placed in a container containing powdered silicone (manufactured by Wako Pure Chemical Industries, Ltd., trade name: Wakogel C-100) until the whole was buried. After the test piece was pulled out from the container, it was dropped three times on the glass plate from the height of 10 cm so that the hardened surface was perpendicular. after that. The transmittance of light at 800 nm of the test piece was measured. The results are shown in Tables 1 and 2. The lower the transmittance, the more viscous the surface. Furthermore, the transmittance of the 800 nm light of the test piece before the adhesion of the silicone rubber was 99% or more.

(heat resistance adhesion test)

The test piece was placed in a thermostatic chamber at 200 ° C, and the test piece was subjected to microscopic observation every 30 days until 120 days, and peeling or cracking of the cured product was examined. The number of days when peeling and cracking were first discovered is shown in Tables 1 and 2. In addition, those who have not seen any peeling or cracking after 120 days are recorded as 120 days or more.

Claims (4)

An antimony-containing resin composition containing at least two epoxy group-containing groups and an epoxy group having a group represented by the following formula (1) as a component (A) An oxyalkylene compound having, as a component (B), an epoxy oxirane compound having 1 to 10 germanium atoms and at least two epoxy group-containing groups in one molecule; and an epoxy hardening compound as the component (C) , (wherein R ¹ to R ⁴ represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, and a represents a number of 20 to 10,000). The cerium-containing curable resin composition of claim 1, wherein the component (A) is a group represented by the following formula (2) or a group represented by the following formula (2) and a formula (hereinafter) 3) an epoxy oxirane compound in which the group represented by the above formula (1) is bonded, (wherein R ⁵ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, and E ¹ represents an epoxy group-containing group, and b represents a number of 2 to 5) (wherein c represents a number of 2 to 6 such that b-c+1 is 0 to 4, and R ⁵ , E ¹ and b are synonymous with the general formula (2)). The cerium-containing curable resin composition according to claim 1 or 2, wherein the component (B) is an epoxy compound represented by the following formula (4): (wherein R ⁶ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, E ² represents an epoxy group-containing group, and d represents a number of 3 to 6). The cerium-containing curable resin composition of claim 1 or 2, wherein the content of the component (B) is from 3 to 50 parts by mass based on 100 parts by mass of the total of the components (A) and (B).