JPS60252621A - Epoxy resin curable with energy radiation - Google Patents

Abstract

PURPOSE:The titled composition that is obtained by using an epoxy resin, an aluminum compound and a specific silicon compound, thus being suitable for use as an insulating material for electric appliances, because it has good storage stability, cures rapidly, and has good electric properties such as dielectric dissipation factor. CONSTITUTION:The object composition is obtained by using (A) an epoxy resin (preferably an epoxy compound or a mixture there of at least one selected from the group consisting of an acid anhydride, phenolic compound, a compound having an ethylenically unsaturated compound and imide compound, (B) an aluminum compouns and (C) a silicon compound forming silanol groups by irradiation of energy rays, preferably a compound bearing silyl ester or peroxysilyl groups, e.g., a derivative of a carbolyxic acid ester of the formula (X is direct bond, CH2, O, S) and, preferably (D) a senstitizer so that the amount of B to component A is 0.001-10pts.wt. and components C is 0.01-20.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to an energy ray-curable epoxy resin compound, and more specifically, it has improved curability and is used as an insulating material, a resist material, etc. for electrical equipment. The present invention relates to an energy beam-curable epoxy resin composition that provides a cured product having electrical properties suitable for

[Technical background of the invention and its problems]

In recent years, there has been interest in the process of curing resins with energy rays from the viewpoint of energy saving and improvement of workability. Among these, the process of curing epoxy resin with energy rays has a wide range of applications and is important. In the energy beam curing process of epoxy resins, the epoxy resin composition itself is the most important factor, as well as the curing conditions, and various formulations have been widely studied. Energy beam-curable epoxy resin compositions known to date are roughly divided into the following two types.

One of them is an epoxy resin modified with a vinyl group-containing compound such as acrylic acid and its derivatives. However, the energy beam cured product of this modified epoxy resin has a problem in that its heat resistance is considerably inferior to that of the cured product of the epoxy resin itself.

The other type is one in which an energy beam decomposition type catalyst is added to an epoxy resin, and the resin is cured by contact with the epoxy resin. The catalyst used at this time has the following formula: Yθ Ar-X('')-Ar (wherein, Ar represents a phenyl group, etc.; X represents an iodine atom, a sulfur atom, a diazo group, etc.; Y represents BF
PF, , AIIF6, SbF6, etc. ) [Macromolecules, Vol. 10, p. 1307, 1977 (Maeromo
lecules, fO+ 1307' (1977)
): Journal Fist of 2-Age Curing, Volume 5, Page 2, 1978 (Journal o
rl(adiation(:uring, dan, 2 (
1978) ; Journal Φ Op Polymer Science Φ Polymer Chemistry □Edition, Volume 17, Page 2877, 1979 CJournal o
f Polymer 5cienoe polymer
Chemistry Edition, 17.287
7 (1979): Ibid., Vol. 17, p. 1047,
1979 (1bid, 17.1047 (1979
)); Journal φ Op Polymer Science Polymer Masters Edition, Volume 17, Page 759,
1979 (Journal of polymers)
3science Polymer Lemo tars Ed
ition, 17. 759 (1979)); JP-A-55-65219; US Patent No. 4. o69.
054 specification; see British Patent No. 1516511 and British Patent No. 1518141 Tetsu et al.].

However, in the case of a composition in which an energy beam curing type catalyst is added to an epoxy resin, the resulting energy beam cured product has good mechanical strength and heat resistance, but on the other hand, the catalyst component remains in the cured product as an ionic impurity. Therefore, when this cured product is used in electrical equipment, there is a problem that electrical properties such as electrical insulation properties may deteriorate and corrosion of the electrical equipment may occur.

[Purpose of the invention]

The purpose of the present invention is to solve the above-mentioned problems, to have good storage stability at room temperature and in a cool and dark place, to be rapidly cured by energy rays, and to be able to be thermally cured at temperatures of 150°C or higher. An object of the present invention is to provide an energy beam-curable epoxy resin composition whose cured product does not contain ionic impurities, does not corrode metal materials in contact with it, and has excellent electrical properties.

[Summary of the invention]

As a result of extensive research, the present inventors found that by using an aluminum compound as a photocuring catalyst and a silicon compound that generates silanol groups when irradiated with energy rays,
The inventors have discovered that the above object can be achieved and have completed the present invention.

That is, the energy ray-curable epoxy resin composition of the present invention is characterized by comprising an epoxy resin, an aluminum compound, and a silicon compound that produces silanol groups when irradiated with energy rays.

In the following, the invention will be explained in more detail.

The epoxy resin wire used in the present invention has 1 in the molecule.
An epoxy compound having one or more epoxy groups alone or a group consisting of an epoxy compound having one or more epoxy groups in the molecule, acid anhydrides, phenolic compounds, compounds having ethylenically unsaturated groups, and imide compounds. It is one type or a mixture of two or more selected types.

The epoxy compound used in the present invention constitutes the main component of the composition of the present invention, and examples of such epoxy compounds include -functional epoxy compounds and polyfunctional epoxy compounds. -Functional epoxy compounds include, for example, tif, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, phenyl glycidyl ether, and butyl glycidyl ether.Also, polyfunctional epoxy compounds include For example, bisphenol A type epoxy resin; bisphenol F type epoxy resin; phenol novolak type epoxy resin, resin; alicyclic 1. poxy resin; heterocyclic-containing epoxy resin such as triglycidyl isocyanurate and hydantoin epoxy; hydrogenated bisphenol A
type epoxy resin; aliphatic epoxy resin such as propylene glycol diglycidyl ether, pentaerythritol polyglycidyl ether; glycidyl ester type epoxy resin obtained by reaction of aromatic, aliphatic or alicyclic carboxylic acid with epichlorohydrin ; Spiro i-containing epoxy resin; glycidyl ether type epoxy resin which is a reaction product of an O-allyl-phenol novolac compound and epichlorohydrin; a diallyl bisphenol compound having an allyl group at the 0-position of each hydroxyl group of bisphenol A and epichlorohydrin; Examples include glycidyl ether type epoxy resins which are reaction products of the above, and one or more selected from the group consisting of these resins may be used as appropriate.

Examples of the phenolic compound used in addition to the epoxy compound include bisphenol compounds such as bisphenol A, bisphenol F, and bisphenol S, and condensates of phenols such as phenol, cresol, catechol, and bisphenol A, and formaldehyde.

The ethylenic compounds used in the present invention include:
For example, styrene and styrene derivatives, unsaturated carboxylic acids, unsaturated carboxylic acid salts, esters of unsaturated carboxylic acids with aliphatic hydroxy compounds, aliphatic polyhydroxy compounds, aromatic hydroxy compounds or aromatic polyhydroxy compounds, 2 Examples include oligoesters obtained by esterification reactions with polyhydric carboxylic acids having a valence of more than 2, polyhydroxy compounds having a valence of 2 or more, and unsaturated carboxylic acids.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid.

Specific examples of aliphatic hydroxy compounds include methanol, ethanol, propatool, butanol, and the like.

Examples of aliphatic polyhydroxy compounds include ethylene glycol, triethylene glycol, tetraethylene glycol, tetramethylene glycol, neopentyl glycol, 1,10-decanediol, 1,2-butanediol, and 1,3-butanediol. , dihydric alcohols such as propylene glycol; trihydric alcohols such as trimethylolethane, trimethylolpropane, and their multimers; tetrahydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, and other multimers pentaerythritol Examples include the above-mentioned alcohols; sugars such as sorbitol and d-mannitol; and dihydroxycarboxylic acids such as dihydroxymaleic acid.

Examples of aromatic hydroxy compounds and aromatic polyhydroxy compounds include phenol, hydroquinone, catechol, resorcinol, phloroglucinol, and pyroganol.

Specific examples of esters of aliphatic hydroxy compounds and unsaturated carboxylic acids include acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid n-tetrabyl ester, acrylic acid 1so-propyl ester, and acrylic acid ethyl ester.
Acrylic acid esters such as n--j methyl ester, acrylic acid ter4-butyl ester; methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid n-propyl ester, methacrylic acid 1ao-propyl ester, methacrylic acid n-butyl ester, Methacrylic acid esters such as methacrylic i tart-butyl ester; itaconic acid methyl ester, itaconic acid ethyl ester, itaconic acid n-7'lopyl ester, itaconic acid 1so-propyl ester, itaconic acid n-butyl ester, itacon ffl terL-7 "A collection of itaconic acid esters such as thyl esters, as well as croton-removed methyl esters, crotonic acid ethyl esters, crotonic acid n
Examples include crotonic acid esters such as -furobil ester, 1so-propyl crotonic acid ester, crotonic acid...-butyl ester, and tsrt-butyl hycrotonic acid ester.

Specific examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol triacrylate, 1°3-butanediol diacrylate, tetramethylene glycol diacrylate,
diacrylic acid propylene/glycol ester, triacrylic acid trimethylolpropane ester, triacrylic acid) IJ, >1 thi0-/l/ethane ester,
Diacrylic acid tetraethylene glycol ester, diacrylic acid tetraethylene glycol ester, diacrylic acid pentaerythritol ester, triacrylic acid pentaerythritol ester, tetraacrylic acid pentaerythritol ester, diacrylic acid dipentaerythritol ester, triacrylic acid dipentaerythritol ester , dipentaerythritol tetraacrylate ester, dipentaerythritol pentaacrylate ester, dipentaerythritol hexatriacrylate ester, tripentaerythritol octaacrylate ester, sorbitol triacrylate ester, sorbitol tetraacrylate ester, sorbitol pentaacrylate ester, acrylic esters such as hexaacrylic acid sorbitol ester and polyester acrylate oligomer; dimethacrylic acid tetramethylene glycol ester, dimethacrylic acid triethylene glycol ester, trimethacrylic acid trimethylolpropane ester, trimethacrylic acid trimethylolethane ester, Pentaerythritol dimethacrylate ester, pentaerythritol trimethacrylate ester, dipentaerythritol dimethacrylate ester, pentaerythritol dimethacrylate ester, pentaerythritol trimethacrylate ester, dipentaerythritol dimethacrylate ester, dipentaerythritol tetramethacrylate ester, octamethacrylic acid tripentaerythritol ester, dimethacrylic acid ethylene glycol ester, dimethacrylic acid 1,3-
Methacrylic acid esters such as butanediol ester, tetramethylene glycol dimethacrylate ester, sorbitol tetramethacrylate ester; ethylene glycol nisdel diitaconate, diitacone dipropylene glycol ester, 1,3-bucundiol diitaconate ester, diitaconic acid 11 '4-butanediol ester, diitaconate tetramethylene glycol ester, shitaconate pentaerythritol ester,
Itaconic acid esters such as triitaconate dipentaerythritol ester, pentaitaconate cichentaerythritol ester, hexytaconate dipentaerythritol ester, tetraitaconate sorbitol ester; dicrotonic acid ethylene glycol ester, cyclotonic acid furopylene gelicol ester, dicroton Crotonic acid esters such as acid tetramethylene/glycol ester, dicrotonic acid pentaerythritol ester, tetracrotonic acid sorbitol ester; incrotonic acid esters such as diisocrotonic acid ethylene glycol ester, diisocrotonic acid pentaerythritol ester, tetraisocrotonic acid nlubitol ester, etc. maleic acid esters such as cymaleic acid ethylene glycol ester, cymaleic acid triethylene glycol ester, cymaleic acid pentaerythritol ester, and tetramaleic acid sorbitol ester; and mixtures of the above-mentioned esters.

Specific examples of oligoesters include oligoester acrylate and oligoester methacrylate (hereinafter, either one or the other will be simply referred to as oligoester (meth)acrylate).

Oligoester (meth)acrylate is acrylic acid,
It is a reaction product obtained by the esterification reaction of methacrylic acid or polycarboxylic acid with a polyol, and is a reaction product obtained by the following general formula: represents an ester group having at least one ester bond consisting of a monovalent carboxylic acid, and p is 1 to 6.
-! : is an integer. ) has the estimated structural formula.

Examples of the polyol constituting the ester group represented by Q include ethylene glycol, 1,2-propylene glycol, 1,4-buta/diol, 1,6-hexanediol, trimethylolethane, trimethylolethane, 1,2,6-hexanediol, glycerin,
Polyols such as pentaerythritol and sorbitol; and polyether type polyols such as diethylene glycol, triethylene glycol, 'tetraethylene glycol, thecaethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and polypropylene glycol, etc. Can be mentioned.

Further, examples of the polyhydric carboxylic acid constituting the ester group represented by Q include phthalic acid, isophthalic acid, terephthalic acid, tetrachloroheptatalic acid, tetrabromophthalic acid,
Aromatic polycarboxylic acids such as trimellitic acid, pyromellitic acid, pentuphenone dicarboxylic acid, and resorcinol diacetic acid; unsaturated aliphatic polycarboxylic acids such as maleic acid, fumaric acid, hemic acid, and iconic acid, and malonic acid. , saturated aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, dodecanoic acid, and tetrahydrophthalic acid.

Examples of acid anhydrides used in the present invention include:
Examples include phthalic anhydride, tetrahydrontalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, maleic anhydride, trimellitic anhydride, and hexachloroendomethylenetetrahydrophthalic anhydride. It will be done.

The imide compound used in the present invention has the general formula: (wherein, X is a divalent hydrocarbon group such as an alkylene group, a cycloalkylene group, a monocyclic or polycyclic arylene group, or
Represents a divalent hydrocarbon group bonded by a divalent group such as -CH,+, -co-, -80r, -CONT+. ) is preferable, and examples of such maleimide compounds include N,N'-phenylenebismaleimide, N,N'-hexamethylenebismale(mi)', N,N'-/ thylene-p-phenylenebismaleimide, N,N'-oxy-p-phenylenebismaleimide, N,N'-4,4'-he7sophenone-bismaleimide, N,N'-(3,3 '-dimethyl)-methylene-di-P-phenylene bismaleimide, N
, N'-(3,3'-diethyl)-methylene-p-
Examples include phenylene bismaleimide and HN,N'-metatolylene bismaleimide.

The aluminum compound used in the present invention is preferably a compound having an organic group selected from the group consisting of an alkoxy group, a phenoxy group, an acyloxy group, a β-diketonato group, a 0-carbonylphenorad group, and the like.

Among the above organic groups, examples of alkoxy groups include methoxy group, ethoxy group, impropoxy group, butoxy group, and pentoxy group; examples of phenoxy group include:
For example, phenoxy group, 〇-methylphenodoxy group, O
-Methoxyphenoxy group, P-nitronenoxy group, 2,6-dimethylphenoxy group, etc.; Examples of the acyloxy group include acetato group, propionato group, isopropionato group, butyrad group, stearado group, ethyl Examples of β-diketonato groups include acetoacetato group, probylacetoacetato group, butylacetoacetato group, diethylmalorado group, and dipivaloylmethanato group; examples of β-diketonato group include acetylacetonato group, trifluoro Examples include acetylacetonato group, hexafluoroacetylacetonato group, etc.; 0-carponylphenola) group,!
: Examples include salicylaldehydato groups.

Specific examples of the above aluminum compounds include trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, trisphenoxyaluminum, trisparamethylphenoxyaluminum,
Impropoxyjethoxyaluminum, tris-atomoxyaluminum, tris-acetoxyaluminum, tris-stearado-aluminum, tris-butyrad-aluminum, tris-propionato-aluminum, tris-isopropionato-aluminum, tris-acetylacetonado-aluminum, tris-trifluoroacetylacetonado-aluminum, tris Hexafluoroacetylacetonadoaluminum, trisethylacetoacetatoaluminum, tris(n-propylacetoacetato)aluminum, tris(igo-propylacetoacetato)aluminum, tris(1'1-butylacetoacetato)aluminum, tris Examples thereof include salicylaldehydaaluminum, trisdiethylmalonatoaluminum, trisbropylacetoacetatoaluminum, trisbutylacetoacetatoaluminum, trisdipivaloylmethanatoaluminum, diacetylacetonatodipivaloylmethanatoaluminum, and the like.

These aluminum compounds can be used alone or in combination of two or more, and the blending amount thereof is preferably 0.001 to 10% by weight based on the epoxy resin, and more preferably io, 05 to 10% by weight. 5 weight. If the blending amount is less than o or ooi weight percent, sufficient curing properties cannot be obtained, while if it exceeds 10 weight percent, it will cause increased costs and deterioration of electrical properties.

The silicon compound that produces a silanol group upon energy ray irradiation used in the present invention is a silicon compound having a silyl ester group or a peroxysilyl group, and the silicon compound having a (-) silyl ester group is represented by the following formula (1). : (In the formula, -X- is a single bond, -'cH", -Ko or -S-
represents. ) Carboxylic acid ester (if -X- is a single bond, fluorene-9-carboxylic acid ester, -X- is -C
In the case of Uma-1-Ko and -S-, 2,7-hydroxyanthracene-9-carboxylic acid ester, xanthine-9-carboxylic acid ester, and thioxanthine-9-
Cover with carboxylic acid ester. ) is preferable.

That is, the silicon compound having a silyl ester group of the present invention has the following formula: Represents a condensed ring of five alkoxy groups, or an aryl group, a nitro group, a cyano group, a carboxy group, a vinyl group, an allyl group, an acetyl group, or a benzene ring, a cyclohexane ring, etc., and ♂ is a hydrogen atom. , represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group or a vinyl group, -X- is a direct bond, -CH,
-1-〇- or -S-, and n represents an integer from 1 to 4. ).

In the above formula, the halogen atom is, for example, a chlorine atom,
Examples include bromine atom, fluorine atom, etc., having 1 to 5 carbon atoms,
Examples of the alkyl group include methyl group, ethyl group, n-
Propyl group, isopropyl group, n-butyl group, i-subbutyl group, II@6-butyl group, tert-7'thyl group,
Examples include n-pentyl group, isopentyl group, neopentyl group, etc.; examples of alkoxy groups having 1 to 5 carbon atoms include methoxy group, ethoxy group, n-propoxy group, n-
Examples of the aryl group include a butoxy group, a 5ea-butoxy group, a tert-butoxy group, and a p-pentyloxy group; examples of the aryl group include a phenyl group, a naphthyl group, an anthranyl group, and the like. Incidentally, these aryl groups may have a substituent such as a halogen atom, a nitro group, a cyan group, or a methoxy group.

Specific examples of silicon compounds having such a silyl ester group include the following formula: 'OCR.

Examples include compounds represented by: On the other hand, (b) the silicon compound having a peroxysilyl group is expressed by the following formula: , number of carbon atoms: 1
~5 alkyl group, an alkoxy group having 1 to 5 carbon atoms, or an aryl group; R2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group; n
represents an integer from 0 to 3. ) In the above formula, the alkyl group having 1 to 5 carbon atoms is
Examples include methyl group, ethyl group, n-propyl group, inpropyl group, n-butyl group, t-butyl group, 5ee-butyl group, and n-pentyl group; carbon atoms 1 to
Examples of the five alkoxy groups include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-
Examples of the aryl group include butoxy group, t-butoxy group, 5ee-butoxy group, and n-bentoky7 group;
For example, phenyl group, naphthyl group, anthranyl group, benzyl group, α, α-dimethylbenzyl group, 1.2, 3.
Examples include 4-tetrahydro-1-naphthyl group; the alkyl group and aryl group having 1 to 5 carbon atoms have a substituent such as a nitrogen atom, a nitro group, a cyano group, or a methoxy group. Good too.

Specific examples of silicon compounds having peroxysilyl groups include compounds represented by the following formula:

The blending amount of these silicon compounds is preferably in the range of 0.01 to 20% by weight based on the epoxy resin,
More preferably, it is 1 to 10% by weight. The amount added is 0.0
If it is less than 1% by weight, sufficient curing properties cannot be obtained, while if it exceeds 20% by weight, problems often arise from high costs and decomposition products of catalyst components.

In the present invention, it is possible to use a sensitizer that has the function of sensitizing the above compound to energy ray irradiation. Examples of such sensitizers include aromatic hydrocarbons, benzophenone, and derivatives thereof. , 0-benzoylbenzoic acid ester, acetophenone and its derivatives, benzoin and benzine ether and its derivatives, xanthone and its derivatives, thioxanthone and its derivatized disulfide compounds, quinone compounds, halogenated hydrocarbons and amines. .

Specific examples of aromatic hydrocarbons include benzene, JJ −
ノ 』J １ノ AL w+−＋−−１鴫 −ふ −
ノ 11 Li --- 1-Biobenzene, Chlorobenzene, Bromobenzene, Iodobenzene, Naphthalene, 1-
Methylnaphthalene, 2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 2-chloronaphthalene, l-bromonaphthalene, 2-bromonaphthalene, 1-iodonaphthalene, 2-iodonaphthalene, 1-
Naphthol, 2-naphthol, biphenyl, fluorene, p-terphenyl, acena 7f-n, p-1 aterphenyl, trinodinidine, 7-enanthrene, azulene, fluoranthene, chrysene, pyrene, 1,2-benzpyrene, anthracene, 1 , 2-benzanthracene, 9.
Examples include io-dichloroanthracene, 9,10-dibromoanthracene, 9,10-diphenylanthracene, perylene, tetracene, pentacene and benzyl.

Examples of benzophenone and its derivatives include benzophenone, 2,4-dimethylbenzophenone, and 2,4-dimethylbenzophenone.
-dichlorobenzophenone and 4,4'-bis(dimethylamino)benzophenone.

As the 0-benzoylbenzoate ester, for example, 0
Examples include -benzoylbenzoic acid methyl ester, 0-benzoylbenzoic acid ethyl ester, 0-benzoylbenzoic acid phenyl ester, and the like.

Examples of acetophenone and its derivatives include acetophenone, 4-methylacetophence, 3-methylacetophenone, and 3-methoxyacetophenone.

Examples of benzoin, benzoin ether, and derivatives thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin 1so-propyl ether, benzoin n-butyl ether, benzoin triphenylsilyl ether, and the like.

Examples of xanthone and its derivatives include xanthone, 2,4-dimethylxanthone, and 2,4-dichloroxanthone.

Examples of thioxanthone and its derivatives include thioxanthone, 2,4-dimethylthioxane) 7 and 2
Examples include 14-cyclothioxanthone.

Examples of disulfide compounds include, for example, quinone compounds such as benzoquinone, naphthoquinone, anthraquinone, 5,12-naphetacenedione, and 2,7
-Pyrenedione and the like.

Examples of the halogenated hydrocarbon include carbon tetrachloride, hexachloroethane, carbon tetrabromide, so, ct' CI(8), and the like.

Examples of amines include diphenylamine, carbazole, triphenylamine, and the like.

Others include propiophenone, anthrone, benzaldehyde, butyrophenone, 2-naphthylphenyl ketone, 2-naphthaldehyde, 2-acetonaphthone, 1-naphthylphenyl ketone, 1-acetonaphtone, 1-naphthaldehyde, fluorenone, 1- Examples include phenyl-1,2-propanedin, benzonitrile, acetone, biacetyl, acridine orange, acridine, rhodamine B1 eosin, fluorescein, and the like.

These sensitizers can be used singly or in combinations of two or more, and the amount of the sensitizers to be blended can be determined based on the epoxy resin.
, ooi to 10% by weight, more preferably 0.01 to 5% by weight.

The energy ray curable epoxy resin composition of the present invention includes:
In addition to the above components, colorants, inorganic fillers, or other additives can be added as necessary.

The energy ray-curable epoxy resin composition comprising the above-mentioned components is cured by irradiation with energy rays. As energy beam sources, electron beams and light beams can be used. Incidentally, in the case of an epoxy resin composition containing a silicon compound having a peroxysilyl group, electron beam irradiation is particularly preferred.

As an electron beam source, a device having an accelerating voltage of 150 to 3,000 KV is usually used, and the intensity of the electron beam necessary for curing the epoxy resin composition of the present invention is 104 to 1 Q'
rad, preferably 106 to 1 Qrad.

In addition, this electron beam irradiation process may be performed as a heating electron beam irradiation process, and the heating temperature during heating electron beam irradiation depends on the composition of the epoxy resin and the type of catalyst. Although it varies, it is usually 20 to 200°C, preferably 60 to 200°C.
The temperature is 120°C.

Furthermore, curing by electron beam irradiation and post-curing (after-curing) are effective for improving the curability of the resin, and this post-curing (after-curing) depends on the epoxy resin composition and catalyst. Although it varies depending on the type, it is generally preferable to carry out the treatment at 50 to 200°C, preferably 100 to 180°C, for 1 to 10 hours, preferably 2 to 5 hours.

Although the wavelength of the irradiated light varies depending on the composition of the resin composition, it is usually 180 to 700 nm, and irradiation with ultraviolet rays is particularly effective. The light irradiation time varies depending on the composition of the epoxy resin, the light source, etc., but is usually 0.1 seconds to 10 minutes, preferably 0.5 seconds to 2 minutes. Alternatively, heat rays may be irradiated, and the wavelength in that case varies depending on the resin composition, but is usually 750 to 4×10' nm. Especially 1
,000 to 1qQOOam of infrared rays is effective. The irradiation time of the heat rays varies depending on the composition of the epoxy resin, the heat source, etc., but is usually 0.1 seconds to 20 minutes, preferably 0.5 seconds to 5 minutes.

The light source may be any one that is normally used for photocuring, such as low-pressure mercury lamps, high-pressure mercury lamps, carbon arc lamps, metal halogen lamps, xenon-mercury lamps, and xenon lamps. , hydrogen discharge tube, tungsten lamp, nologen lamp, sodium discharge tube, neon discharge tube, argon discharge tube, H6-Net/-zer, Ar ion laser-1N,
Laser, CD ion laser-1'H (1-Cd laser, dye laser, etc.) may be mentioned, and one or more types selected from the group consisting of these may be used as appropriate.

Further, as a source of heat rays, any source used for ordinary drying and baking may be used, such as a near-infrared lamp, a quartz far-infrared heater, a ceramic far-infrared heater, etc.

〔Effect of the invention〕

The energy ray-curable epoxy resin composition of the present invention contains an aluminum compound as a catalyst component and a silicon compound that generates silanol groups when irradiated with energy rays. It hardens quickly by irradiation. In addition, since the obtained cured product does not contain ionic impurities, it has extremely excellent electrical properties such as dielectric loss tangent value, and when this cured product is used in electrical equipment, it There is no risk of corrosion. Therefore,
It can be applied to a wide range of applications such as coil insulation,
Its industrial value is extremely large.

[Embodiments of the invention]

Synthesis Example 1 (Synthesis of silicon compound having silyl ester group) Add 226f of xanthine-9-carboxylic acid and 294f of triphenylchlorosilane) to 3,000% of toluene (1), and gradually add 101f of triethylamine while stirring the mixture at 60°C. The resulting mixture was heated and stirred for 1 hour.The resulting salt was removed, and the toluene solution was concentrated to obtain triphenylsilylxanthine-9-carboxylic acid ester.

The chemical shift value of NMR is cDct, medium, with TMS as the internal standard δ (ppn+) = 4.93.6.80
~764.

Incidentally, triphenylsilyl ester of fluorene-9-carboxylic acid was also synthesized using a method similar to the above method.

Examples 1 and 2 As an epoxy resin, Celoxide 2021 (trade name,
Manufactured by Daicel; alicyclic, epoxy equivalent: 145), ERL
-4234 (trade name, manufactured by UCC; alicyclic, epoxy equivalent: about 140); bisphenol A was used as the phenolic compound;
Using hydroquinone, trimethylolpropane diacrylate; Using methylhexahydrophthalic anhydride as the acid anhydride; , using tris(improvil acetoacetate)aluminum; as a silicon compound, tidriphenylsilylxanthine-9-carboxylic acid ester, triphenylsilylfluorene-9-
A carboxylic acid ester was used and benzophenone was used as a sensitizer.

The epoxy resin composition obtained from these
After coating to a thickness of approximately 5 μm on a mm-thick aluminum plate, ESI's CB-150 was used as an electron beam curing device at an accelerating voltage of 166 KV.

The above-mentioned coating material was cured under the conditions of a current of 3 mA and a radiation dose of 10 Mrad.

Further, as Comparative Example 1, a product using triphenylsulfonium hexafluorophosphate as a catalyst was cured in the same manner as in Examples 2 and 3 above.

The dielectric loss tangent value (t@nδ) of the cured resin surface was measured at 150° C., and a lead hardness test, which indicates the surface hardness of the coating film, and a cross-cut test, which indicates the adhesion of the coating film, were also conducted. The obtained results are listed in Table 1 together with the resin composition (unit: f).

Example 3 ERL-4221 (trade name, manufactured by UCC Corporation, following (Rinoalicyclic epoxy resin, epoxy weight i:: 130, molecule i:
260) 10 t,) 0.3 f of lithethylacedoacetaluminum, and 0.5 t of butylperoxytriphenylsilane were mixed and uniformly dissolved. When this energy beam-curable epoxy resin composition was applied onto a glass plate and irradiated with an electron beam using an ESI (curtain type) electron beam irradiation device, the result was 20 Mrad.
It was hardened.

In addition, gelation did not occur when electron beam irradiation was not performed.

1 Example 4 Chissonox 206 (trade name, manufactured by Chisso ■, below (2)
) epoxy compound, epoxy equivalent near 0, molecular weight:
139) 13 f, Epicot 828 (trade name, manufactured by Shell Chemical Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 190-210, molecular weight: 380) 51) Lisethyl acedoacet aluminum 0.5F, di( t
-7'Tylperoxy)diphenylsilane 0.5F was mixed and uniformly dissolved.

The energy ray-curable epoxy resin composition was applied onto an aluminum plate, and then heated in the same manner as in Example 3.
When irradiated with electron beams, the reaction system had already turned into a gel.

Example 5 ERL-4221: 100 t, Epicote 154 (
Product name, manufactured by Shell Chemical Co., Ltd., phenol novolac type epoxy resin, epoxy equivalent: 172-180) 3 (1° Ebicor) 828:10f,) Mixed with 0.3 t of lissalicylaldehydatoaluminum, L-butylperoxytriphenylsilane 42 and dissolved uniformly.

When this energy ray-curable epoxy resin composition was applied onto a glass plate and irradiated with rays at an intensity of 30 Mrad, a good cured resin surface was obtained.

When the dielectric loss tangent value (tan δ) of this cured resin surface was measured, it was 3.0 at 100°C.

Next, after curing this cured resin surface at 130°C for 5 hours, Lan 6 was measured again, and it was found to be 18
It was 4.3% at 0°C.

Example 6 ERL-4221: 60 f, Epicote 152 (
Trade name, manufactured by Shell Chemical Co., Ltd., phenol novolac type epoxy resin, epoxy equivalent: 172-179) 209° Trissalicylaldehydatoaluminum 2f.

4f of t-butyltriphenylperoxysilane was mixed and uniformly dissolved.

The energy ray-curable epoxy resin composition was applied onto an aluminum plate, and electrolyzed in the same manner as in Example 5.
When irradiated with coronal beams, a good cured resin surface was obtained.

The dielectric loss tangent value (tan δ) and volume resistivity of this cured resin surface were measured.
．． It was 2 inches and 2.4×10Ωm.

Next, after curing this cured resin surface at 130°C for 5 hours, tnn 6 was measured again, and it was found to be 18
It was 42% at 0°C.

Comparative Example 2 ERL-4221: 100 f, Epicote 154:
30f1 Epicote 828:3Of and diphenyliodonium hexafluoroantimonate 03f were mixed and uniformly dissolved.

This energy beam-curable epoxy resin composition was applied onto an aluminum plate, and irradiated with electron beams in the same manner as in Example 5.

After curing the cured resin surface, Lan δ was measured and found to be unmeasurable.

Examples 7 to 21 Fifteen energy ray-curable epoxy resin compositions having the compositions (parts by weight) shown in Table 2 were prepared.

In addition, as the epoxy resin, ERA, -4221 (trade name, manufactured by UCC Co., Ltd., alicyclic epoxy resin, epoxy resin -1i)
1:145), Chissonox 206 (product name, Chisso special), Chissonox 234 (product name, Chisso special,
Alicyclic epoxy resin of the following formula (2), epoxy equivalent: approximately 140), Epicote 828 (trade name, Shell Kagaku Tokusei, bisphenol A type epoxy resin, epoxy equivalent: 1)
90-210, molecular weight: 380), same 1001 (trade name, same, epoxy weight: 450-525, molecular weight:
900) and 1004 (trade name, epoxy equivalent: 900 to 1000. Molecules: approximately 1000) were used.

Bisphenol A and catechol were used as phenolic compounds.

As the ethylenic compounds, (1) trimethylolpropane triacrylate ester and (2) pentaerythritol dimethacrylate ester were used.

(3) Epiclon B-570 (trade name,
Manufactured by Dainippon Ink & Chemicals ■; Methyl-Δ4-tetrahydrofucle M) and (4) Rikazid MH-700 (
(trade name, methylbexahydrophthalic anhydride, manufactured by Shin Nippon Rika@) was used.

(5) N,N'-phenylene bismaleimide and (6) N,N'-4,4'-benzophenone bismaleimide were used as imide compounds.

Further, as the aluminum compounds, (i) trisacetylacetonadoaluminum, (b) tris n-butylacetylacetoaluminum, and (c) trissalicylaldehydatoaluminum were used.

Furthermore, the silicon compounds include those having a peroxysilyl group, namely (a) triphenyl (t-butylperoxy) silane, ('b) triphenyl (α, α-dimethylbenzylperoxy) silane, and (C) vinyldiphenyl. (1-Butylperoxy)silane and (d)diphenyl(α,α-dimethylbenzylperoxy)silane were used.

As a sensitizer, (A) naphthacene, (B) benzophenone, (qbenzoin-1so-propyl ether and
>2°4-dimethylxanthone was used.

Each of the energy beam-curable epoxy resin compositions was applied onto an aluminum plate, and the compositions of Examples 7 to 15 were cured by electron beam irradiation under the same conditions as Example 3. .

Further, for Examples 16 to 21, in addition to the above conditions, after-curing was performed at 150° C. for 30 minutes.

Claims (1)

[Scope of Claims] 1. The compounding amount of the epoxy resin, the aluminum compound, and the silicon compound that produces silanol groups when irradiated with energy rays is as follows:
o, ooi ~ 10% by weight based on the epoxy resin, respectively
and 0.01 to 20% by weight of an energy ray-curable epoxy resin composition.・2. The epoxy resin consists of an epoxy compound or a mixture of an epoxy compound and one or more selected from the group consisting of acid anhydrides, phenolic compounds, compounds having ethylenically unsaturated groups, and imide compounds. An energy beam-curable epoxy resin composition according to claim 1. 3. The energy ray-curable epoxy resin composition according to claim 1, wherein the silicon compound that produces a silanol group upon energy ray irradiation is a silicon compound having a silyl ester group or a peroxysilyl group. 4. A silicon compound having a silyl ester group has the following formula (
■): (wherein -X- is a direct bond, -CI(t-, -total or -
Represents S-. ) The energy ray-curable epoxy resin composition according to claim 3, which is a derivative of a carboxylic acid ester represented by: 5. The energy ray-curable epoxy resin composition according to claim 1, further comprising a sensitizer.