JPS63291919A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent shelf stability in a varnish state, providing a cured material having excellent heat resistance and flexibility, comprising a bis-o-allylphenol compound, a specific ether imide compound of addition type and an epoxy compound. CONSTITUTION:(A) A bis-o-allylphenol compound shown by formula I (X is nothing, -CH2 or group shown by formula II) is blended with (B) ether imide compound of addition type shown by formula III (R1-R4 are H or lower alkyl; R5 and R6 are H or methyl; D1 and D2 are 2-24C bifunctional organic group) and (C) an epoxy compound to give the aimed composition. For example, o- diallylbisphenol A is used as the component A. For example, 2,2-bis[4-(4- maleimido-phenoxy)phenyl]propane is used as the component B. Further diglycidyl diether of bisphenol A is preferably used as the component C.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a thermosetting resin composition, and in particular, it has excellent moldability such as storage stability, and the cured product has good heat resistance and flexibility. The present invention relates to a resin composition for insulating electrical equipment that can exhibit excellent properties.

[Conventional technology]

BACKGROUND ART Conventionally, it has not been easy to obtain materials with excellent heat resistance and thermal shock resistance for molding resins for large electrical equipment, such as large-capacity rotating electric machine coils and transformer coils. Generally, cured resin products with excellent heat resistance are hard and have poor thermal shock resistance.For molded large parts where thermal shock resistance is important, heat resistance must be sacrificed, and the heat resistance classification is The reality is that there are very few F-type products (155°C or higher).

Regarding thermosetting resin compositions for the above-mentioned uses, Japanese Patent Publication No. 58-17532 (Japanese Unexamined Patent Application Publication No. 55-92714 issue)
There are several proposals regarding this. This composition satisfies the heat resistance and flexibility to a certain degree among the compositions that have been studied in the past, and the use of this composition is being developed.

[Problem that the invention seeks to solve]

However, the prior art has a problem with compatibility in a varnish state. In other words, festival compositions made of bis-orthoallylphenol compounds, conventional bismaleimides, and polyfunctional epoxy compounds have poor storage stability, become cloudy and become heterogeneous during storage, and therefore have various effects on the life of festivals. Improvements have been made, but at present there is no definitive method.

The purpose of the present invention is to provide a festival composition with extremely excellent storage stability, as well as impart heat resistance and flexibility to the cured product.
An object of the present invention is to provide a thermosetting resin composition having excellent cold and heat cycle resistance.

This composition can be applied to prepregs, plywood boards, adhesives, paints, molding materials, etc., in addition to being used as solvent-free panels for electrical insulation of class H grade or higher with excellent heat resistance. Therefore, it can be used not only for electrical insulation purposes, but also as coating materials for electronic components, sealing materials for adhesives (including silver paste, etc.), and/or structural materials for automobiles, communication applications, and aerospace applications. be.

[Means for solving problems]

The present invention has been completed by discovering that the above object can be achieved by taking the following steps. The summary is as follows.

(1) At least a bis-orthoallylphenol compound represented by the following general formula (1) % formula % and general formula (n) [wherein Rs to R4 are hydrogen, lower alkyl group, lower alkoxy group, chlorine] or bromine, which may be the same or different from each other, R5 and R,8 are hydrogen, methyl group, ethyl group, trifluoromethyl group, trichloromethyl group, and may be the same or different from each other. May also be DA.

D2 is a divalent organic group having 2 to 24 carbon atoms. ] A thermosetting resin composition comprising an addition type etherimide compound represented by the following formula and a polyfunctional epoxy compound.

(2) General formula (1) is A thermosetting resin composition characterized by:

(3) General formula (U) is A thermosetting resin composition characterized by:

(4) The polyfunctional epoxy compound is and/or υ A thermosetting resin composition characterized by:

(5) A polyfunctional epoxy compound, [wherein m is 2 to 30]. ] A thermosetting resin composition.

(6) A thermosetting resin composition characterized in that the polyfunctional epoxy compound is a novolac type phenolic epoxy resin.

(7) A thermosetting resin composition characterized in that the epoxy compound is a cyclohexene epoxycarboxylate compound.

(8) At least any of the following general formula CI) CHs CF3 Ce H5 ■ -C-9-C-1-8O2- Ca
HI5 Ru. ] A bis-orthoallylphenol compound represented by the general formula (II) [In the formula, R1 to R4 represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and are mutually the same or different. R6 and Ra may be hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different.

Also, Dl.

D2 is a divalent organic group having 2 to 24 carbon atoms. ] A thermosetting resin composition comprising an addition type etherimide compound represented by the following formula, an epoxy compound, and a phenol compound.

(9) The phenolic compound has the following general formula, (wherein R
7 is hydrogen, a methyl group, or an alkyl group.) A thermosetting resin composition characterized in that it is a novolac type phenol resin represented by the following formula.

(lO) The phenolic compound is H and/or H (wherein R8 is H, -CHa, -OH, -NHzt-3
It is either OzNHz or -S OaH. n
is 2-300. ) A thermosetting resin composition.

[Effect]

Storage stability of the varnish composition, which is a feature of the present invention.

The effect of improving heat resistance, flexibility, and cold/heat cycle resistance is due to the general formula (n
) is derived from a combination of addition-type etherimide compounds represented by In other words, compared to conventionally used bismaleimide compounds, the addition type etherimide compound of the present application exhibits unique behavior in terms of compatibility, and also has a good balance between flexibility and heat resistance of the cured product. This is an epoch-making composition that makes it possible to

In the present invention, the bis-orthoallylphenol compound represented by the general formula (1) is, for example, (I-a) CHa (1-c) Fa (1-d) (1-a) ( 1-f) (1-g) ci-h), and more than one type can be used in combination.

Moreover, in the present invention, general formula (U) [Wherein R1-R4, and RIS-Rs and Di.

D2 is as described above. For example, the addition type etherimide compound represented by:

etc., and more than one type can be used in combination.

Copolymers of the above compounds with addition reactants such as amine compounds, phenolic compounds, and/or thiocol compounds, and compounds with polymerizable functional groups are also useful. . Further, the following formula, [wherein R1-R4, Ra, R6, and Dl are the same as above. ] An ether compound having one additional imide group and - amino groups at the terminal may be used in combination with the compound of general formula (II).

Further, in the present invention, an addition reaction product of an addition type etherimide compound of general formula (n) and an amine compound can also be used. Examples of such amine compounds include primary diamines such as m-phenylenediamine, p-phenylenediamine, benzidine, and 3,3'-dimethyl-4
, 4-diaminbiphenyl, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, 4,4'-diaminodiphenylmethane, 1,1-bis(4-aminophenyl)ethane, 2,2-bis(4 -aminophenyl)
Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)-1,3-dichloro-1,1,3,3-tetrafluoropropane, 4° 4'-diaminodiphenyl ether,
4.4'-diaminodiphenyl sulfide, 3,3
'-Diamino diphenyl sulfide, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,3'-diaminodibenzophenone, 4,4
-diaminobenzophenone, 3,4'-diaminobenzophenone, N,N-bis(4-aminophenyl)aniline, N,N-bis(4-aminophenyl)methylamine,
N,N-bis(4-aminophenyl)-n-butylamine, N,N-bis(4-aminophenyl)amine, m
-aminobenzoyl-p-aminoanilide, 4-aminophenyl-3-aminobenzoate, 4°4'-diaminoazobenzene, 3,3'-diaminoazobenzene, bis(3-aminophenyl)diethylsilane, bis(4-
aminophenyl) phenylphosphine oxide, bis(4-aminophenyl)ethylphosphine oxide,
1,5-diaminonaphthalene, 2,6-diamitubiridine, 2,5-diamino-1,3,4-oxadiazole, m-xylylenediamine, p-xylylenediamine,
2*4 (p-β-amino-tertiary butylphenyl) ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl) ) Benzene, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 2.11-diaminododecane, 1.12-diaminooctadecane, 2
, 2-dimethylpropylenediamine, 2゜5-dimethylhexamethylenediamine, 3-methylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 4
, 4-dimethylhebutamethylenediamine, 5-methynonamethylenediamine, 1,4-diaminocyclohexane,
Bis(p-aminocyclohexyl)methane, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy)ethane, bis(3-7minopropyl)sulfide, N,N-bis(3-aminopropyl)methyl Examples include amines.

Further, an example of N-7 aryl substituted aromatic triamine is 2.4
-diaminodiphenylamine, 2,4-diamino-5-
Methyl-diphenylamine, 2,4-diamino-4'-
Examples include methyl-diphenylamine, 1-anilino-2,4-diaminonaphthalene, and 3°3'-diamino-4-anilinobenzophenone.

In addition, the general formula [■] (wherein R1'' R4 represents hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. R6 and R6 are hydrogen, methyl 2,2'-bis(4- (4-aminophenoxy)phenyl]propane, 2,2'-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane,
2,2'-bis[3-chloro-4-(4-aminophenoxy)phenyl]propane, 2゜2'-bis[3-promo 4-(4-aminophenoxy)phenyl]propane, 2,2'- Bis[3-ethyl-4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[3-propyl-4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[3- Isopropyl-4-(4-
aminophenoxy)phenyl]propane, 2,2-bis[3-butyl-4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[3-sac-butyl-4
-(4-aminophenoxy)phenyl]propane, 2,
2'-bis[3-medoxy4-(4-aminophenoxy)phenyl]propane, 1,1-bis(4-(4-aminophenoxy)phenyl)ethane, 1,1-bis[3
-Methyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis(3-chloro-4-(4-aminophenoxy)phenyl)ethane, 1,1-bis[3-promo 4-(4 -aminophenoxy)phenyl]ethane,
Bis(4-(4-aminophenoxy)phenylcomethane, bis[3-methyl-4-(4-aminophenoxy)phenylcomethane, bis[3-chloro-4-(4-7minophenoxy)phenylcomethane, Bis [3-promo 4
-(4-aminophenoxy)phenylcomethane, 1,1
,1,3,3.3-hexafluoro-2,2-bis(4
-(4-aminophenoxy)phenyl]propane, 1,
1,1,3,3,3-hexachloro-2,2-bis-(
4-(4-aminophenoxy)phenyl]propane, 3
,3-bis(4-(4-aminophenoxy)phenyl)
Pentane, 1,1-bis(4-(4-aminophenoxy)phenyl)propane, 1,1,1,3,3゜3-hexafluoro-2,2-bis[3,5-dimethyl-4-(
4-aminophenoxy)phenyl]propane, 1,1,
1,3,3.3-hexafluoro-2,2-bis[3,
5-dibromo-4(4-aminophenoxy)phenyl]
Propane, 1゜1.1,3,3.3-hexafluoro-
Examples include 2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane.

Also usable are polyamines represented by the general formula (wherein R is an alkylidene group containing a methylene group, and n is a number on average of 0.1 or more).

Note that these amine compounds may be used in combination (v may also be used).

The polymerization mechanism of each component in the present invention is complicated, but the functional groups in each component react with each other to cause polymerization, condensation, and addition polymerization. It is thought that addition polymerization reactions between an amino group and a maleimide group and (3) an addition polymerization reaction between a maleimide group and an allyl group occur.

In addition, in the present invention, the epoxy compound refers to the above-mentioned
This function is essential for improving the molding workability and adhesion of compositions made of compounds represented by general formula [I] and general formula [■], and also suppresses the decrease in heat resistance of cured products as much as possible. It is desirable to have Such epoxy compounds include, for example, diglycidyl ether of bisphenol A, butadiene jepoxide, 3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexane carboxylate, vinylcyclohexane dioxide, 4, 4'-di(1,2-epoxyethyl)
Diphenyl ether, 4,4'-(1,2-epoxyethyl)biphenyl, 2゜2-bis(3,4-epoxycyclohexyl)propane, glycidyl ether of resorcinol, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin Ether, bis-(2゜3'-epoxycyclopentyl)ether, 2-(3,
4-epoxy)cyclohexane-5,5-spiro(3,
4-epoxy)-cyclohexane-m-dioxane, bis-(3,4-epoxy-6-methylcyclohexyl)
Adipate, N,N'-m-phenylenebis(4,5-
Functional epoxy compounds such as epoxy-1゜2-cyclohexane)dicarboximide, triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1,3.5-tri(1,2-epoxyethyl)benzene, 2.2 Tri- or higher-functional epoxy compounds such as ',4,4'-tetraglycidoxybenzophenone, polyglycidyl ether of phenolformaldehyde novolac, triglycidyl ether of glycerin, and triglycidyl ether of trimethylolpropane are used.

Among these, the following compounds are particularly effective in achieving the effects of the present invention.

That is, l8 (R is an alkyl group such as Hy CHa or CzHs,
[In the formula, m and n are 1 to 50, and 50 > m + n
>1. ] Also, in the present invention, cyclohexene dioxide, dicyclopentadiene dioxide, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexane carbonate, cyclohexene epoxy carboxy A rate compound is useful 0, for example, CHZ O ＼ / Carboxylate CHCH CH CH CH CHS C) -ICHS CH C00C: Hzchchz HA H [○ HA ■ H Hz, etc. Rate -based compounds, etc. There are two types, and more than one type can be used together. Among these compounds, endomethylene cyclohexene carboxylates are particularly useful.

In addition, reaction derivatives of cyclohexene epoxycarboxylate compounds with ethylenically unsaturated double bonds and/or compounds having bonding units reactive with epoxy groups, such as addition polymers, copolymers, etc. ) can also be used.

One or more of these compounds can be used in combination depending on the use and purpose. It is effective to use an epoxy resin curing agent in combination with the resin composition of the present invention. They are: Hiroshi Kakiuchi: Epoxy Resin (published September 1970), pages 109-149, L 66, and Epoxy R, by Neville.
e5ins (Me Grav-Hill Book
Con+panyInc: New York, 1
957) pages 63-141, P, E,
Written by Brunis: εpony Re5ins Tec
h-nology (Interscience P
publishers, New York.

(published in 1968), pages 45 to 111, such as aliphatic polyamines, aromatic polyamines, amines including secondary and tertiary amines, carboxylic acids, carboxylic acid anhydrides, aliphatic and aromatic Group polyamide oligomers and polymers, trifluoroboric acid-amine complexes.

There are synthetic resin initial condensates such as phenol resin, melamine resin, urea resin, and urethane resin, as well as dicyandiamide, carboxylic acid hydrazide, and the like. Among these, carboxylic acid anhydrides and phenolic resins are particularly useful.

As the carboxylic acid anhydride, in particular, methyl nadic anhydride (MNA), (MHAC-P)hexahytomethyl phthalic anhydride (Hitachi Chemical Co., Ltd. HN-5500), and tetrahydromethyl phthalic anhydride (Hitachi Chemical Co., Ltd. HN-2200) are used. Useful. In addition, aliphatic tetracarboxylic dianhydrides, such as m-phenylene bis (succinic anhydride) p-phenylene bis (succinic acid anhydride) m-phenylene bis (glutaric acid anhydride) p-phenylene bis (glutaric acid anhydride) acid anhydrides) etc. are useful. A method for synthesizing the compound is described in Kobunshi, March 35, issue, page 263 (1986).

In addition, conventionally known carboxylic acid anhydrides can also be used in combination. For example, 3.3', 4.4'-beresophenonetetracarboxylic dianhydride, pyromellitic dianhydride, 2,3,6.7-naphthalenetetracarboxylic dianhydride, 3.3', 4゜4'-diphenyltetracarboxylic dianhydride, 1゜2.5.6-naphthalenetetracarboxylic dianhydride, 2.2', 3.3'-diphenyltetracarboxylic dianhydride, 2,2 -bis(3,4-dicarboxyphenyl)propane dianhydride, 3,4,9゜1
0-perylenetetracarboxylic dianhydride, bis(3,4
-dicarboxyphenyl)ether dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride,
Decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6
, 7-hexahydronaphrene-1,2,5,'6-tetracarboxylic dianhydride, 2,6-cyclonaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2. 7-
Cyclonaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5.8-tetracarboxylic dianhydride, phenanthrene-1,8 , 9゜10-tetracarboxylic dianhydride, cycloventary 1.2,3.4-tetracarboxylic dianhydride, pyrrolysile 2.3,4.5-tetracarboxylic dianhydride, piraciso-2, 3,5,6-tetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-
dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride,
Bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride and thiophene-2,3 , 4,5-tetracarboxylic dianhydride, and others. Among these, preferred dianhydrides include 3,3',4'4'-benzophenonetetracarboxylic dianhydride, pyromellitic anhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride. 3.3'.

4.4'-biphenyltetraboreic acid dianhydride, 3.
3',4,4'-diphenyl ether tetracarboxylic dianhydride.

These catalysts include, for example, tertiary amines such as triethanolamine, tetramethylbutanediamine, tetramethylpentanediamine, tetramethylhexanediamine, triethylenediamine, dimethylaniline, oxyalkyl amines such as dimethylaminoethanol, dimethylaminopetanol, etc. Amine or Tris (dimethylaminomethyl)
There are amines such as phenol, N-methylmorpholine, and N-ethylmorpholine.

Also, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium iodide, trimethyldodecylammonium chloride, benzyldimethyltetradecylammonium chloride, benzylmethylpalmitylammonium chloride, allyldodecyltrimethylammonium bromide, benzyldimethylstearylammonium bromide, stearyl There are quaternary ammonium salts such as trimethylammonium chloride and benzyldimethyltetradecylammonium acetate.

Also, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-methyl-
4-ethylimidazole, 1-butylimidazole, 1
-Propyl-2-methylimidazole, 1-benzyl-
2-Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-azine-2-methylimidazole, 1-azine-2-undecyl Imidazole such as imidazole, triphenylphosphine tetraphenylborate, tetraphenylphosphonium tetraphenylborate, triethylamine tetraphenylborate, N-methylmorpholinetetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, 2-ethyl- Examples include tetraphenylboron salts such as 1,4-dimethylimidazole tetraphenylborate. Further, a metal chelate compound consisting of at least one metal selected from aluminum, titanium, tin, zinc, lead, and zirconium and a ligand selected from β-diketones and β-keto acid esters is used. For example, tris(2,4-pentanedionato)aluminum, (2,4-pentanedionato)bis(ethylacetoacetate)aluminum, tris(ethylacetoacetate)aluminum, bis(ethylacetoacetate) titanium), tetrakis(2,4-pentanedionato) titanium, dibutylbis(2,4-pentanedionato)tin, dimethylbis(ethylacetoacetate)tin, bis(2,4-pentanedionato)4KK lead , bis(ethylacetoacetate) lead, and tetrakis(ethylacetoacetate) zirconium.

The film-forming material also contains an alcohol-1 compound of at least one metal selected from aluminum, titanium, tin, zinc, lead, and zirconium. Such alcoholate compounds include, for example, aluminum methylate, aluminum methylate, aluminum propylate, aluminum n-butyrate, mono-3ec-butoxyaluminum, dii-propylate, ethylaluminum, diethylate, ethylaluminum. , Jimmy propylate, titanium, tetra-1-propylate, tin, tetra-1-
propylate, zinc, dime propylate, lead, di-
There are mepropylene, zirconium, tetra-1-propylate, etc., and one or more of them can be used, and some or all of them can be used as a prepolymer by polycondensation. It's okay.

Furthermore, the resin composition of the present invention can also be used in combination with bismaleimide compounds that have already been put into practical use, depending on the use and purpose thereof. For example, a compound represented by the linear formula [wherein R8 represents an alkylene group, an arylene group, or a divalent organic group substituted thereof], such as N,N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N
' -dodecamethylene bismaleimide, N, N' -m
-Phenylene bismaleimide, N,N'-4,4'-
Diphenyl ether bismaleimide, N, N'-4,4
' -diphenylmethane bismaleimide, N, N'-4
, 4'-dicyclohexylmethane bismaleimide, N
.

N'-4,4'-methaxylene bismaleimide, N,
Examples include N'-4,4'-diphenylcyclohexane bismaleimide, and two or more of these may also be used in combination.

Furthermore, mixtures of mono-substituted maleimide, tri-substituted maleimide, tetra-substituted maleimide and substituted bismaleimide can also be used as appropriate.

Depending on the use and purpose, the resin composition of the present invention may also contain compounds having polymerization reactivity with unsaturated bisimide, such as styrene, vinyl I-luene, α-methylstyrene, divinylbenzene, diallylphthalate, Diallyl phthalate prepolymer, chlorstyrene, dichlorostyrene, bromstyrene, dibromstyrene, diallylbenzene phosphonate, diallyl arylphosphylate, acrylate, methacrylate,
Triallyl cyanurate, triallyl cyanurate prepolymer, tribromophenol allyl ether, and the like are used. In addition, the crosslinking agent is not limited to one type, but two or more types can be used in combination, and various modifications and modifiers can be added. Furthermore, the unsaturated polyester resin is not limited to one type. It is also possible to mix two or more of them.

The blending ratio of the etherimide compound represented by the general formula (II) of the present invention and the unsaturated polyester resin is not particularly limited, but in order to impart heat resistance.

It is appropriate for the former to be in the range of 10 to 100 parts by weight to the latter 10 to 100 parts by weight.

It is desirable to add a polymerization initiator to the resin composition of the present invention in order to complete its curing by heating for a short time. Such polymerization initiators include benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-diglolobenzoyl peroxide, cabrylyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, Bis(1-hydroxycyclohexyl peroxide, ), hydroxyhebutyl peroxide, tertiary butyl hydroperoxide, p-menthane hydroperoxide, tertiary butyl perbenzoate, tertiary butyl peracetate, tertiary butyl Organic peroxides such as peroctoate, tertiary butyl peroxyisobutyrate, and di-tertiary phthyl perphthalate-1 are useful, and one or more of them can be used.

Moreover, a system in which the above-mentioned epoxy compound is used in combination with a catalyst is particularly useful. Examples of such a combination system include a combination system of an imidazole catalyst and dixyl oxide, and/or a combination system of a metal chelate type compound and peroxide.

In the present invention, known promoters such as mercaptans, sulfides, β-diketones, metal chelates, and metal soaps can also be used in combination with the above-mentioned polymerization catalyst.

In order to improve the storage stability of the resin composition at room temperature, for example, quinones such as p-benzoquinone, naphthoquinone, and phenanthraquinone, hydroquinone, p-
Known polymerization inhibitors such as phenols and nitro compounds and metal salts such as tertiary-butylcatechol and 2,5-di-tertiary-butylhydroquinone can be used if desired.

Furthermore, various materials may be blended into the resin composition of the present invention depending on its use. That is, for example, for use as a molding material, zircon oxide, silica, alumina, aluminum hydroxide, titania, subsalt flower, calcium carbonate,
Magnesite, clay.

Inorganic fillers such as kaolin, talc, silica sand, glass, fused silica glass, asbestos, mica, various whiskers, carbon black, graphite and molybdenum disulfide, etc.
Mold release agents such as higher fatty acids and waxes, epoxy silanes, vinyl silanes.

Coupling agents such as borane and alkoxytitanate compounds are included. Further, flame retardant agents such as halogen-containing compounds, antimony oxide, and phosphorus compounds can be used as necessary.

In addition, various polymers such as polystyrene, polyethylene, polybutadiene, polymethyl methacrylate, polyacrylic ester, acrylic ester-methacrylic ester copolymer, phenolic resin, epoxy resin,
Known resin modifiers such as melamine resin or urea resin can be used.

It can also be used as a solution, such as in festivals. The solvents used in this case are N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-
Methylformamide, dimethylsulfoxide, N, N
-diethylacetamide, N,N-dimethylmethoxyacetamide, hexamethylphosphoramide, pyridine, dimethylsulfone, tetramethylsulfone, dimethyltetramethylenesulfone, etc., and the phenolic solvent group includes phenol, cresol, xylenol, etc. There is.

The above substances may be used alone or in combination of two or more.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these in any way.

〔Example〕

<Example 1> As a polyfunctional epoxy compound, polyglycidyl ether EOCN-102S (
Manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 211, softening point: 66.4°C
), polyglycidyl ether of resorcin-modified novolac type phenol resin (manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 182, softening point 60°C), YL-931 represented by the following formula (manufactured by Yuka Shell Epoxy Co., Ltd.,
epoxy equivalent: 196, softening point: 88°C), RE-2 represented by the following formula (manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 195, softening point: 81°C), and dicyclopentadiene, a polyglycidyl ether of phenolic polymer DCE -400 (manufactured by Dezumi Kokusaku Pulp Co., Ltd.)
YL-933 (manufactured by Yuka Shell Epoxy Co., Ltd.) represented by epoxy equivalent of 310, softening point of 55-80°C, number average molecular weight of 800-1500; alicyclic vinyl epoxy ether oligomer represented by EHPE-3156 (manufactured by Daicel Corporation); , epoxy equivalent: 225) As a cyclohexene epoxy carboxylate compound, predetermined parts by weight of endomethylene (1-methyl) cyclohexene epoxy carboxylate represented by H were separately collected.To these, as an orthoallylphenol compound, ortho diallyl bisphenol F(DABF
), and 2,2-bis(4-(4-maleimidophenoxy)) as an addition type etherimide compound.
phenyl]propane, (abbreviated as DAPP-bismaleimide) to 2,2-(4-(4-maleimidophenoxy)
phenyl)-('1-(4-aminophenoxy)phenyl]propane, (abbreviated as DAPP-monomaleimide). Also, as a curing agent, methylnadic anhydride (MHAC-
P) as a curing accelerator, imidazole-based 2-ethyl-4-methylimidazole (2E4MZ; manufactured by Shikoku Kasei Co., Ltd.) and aluminum trimachilate <ALCH-TR;
(manufactured by Yoken Fine Chemical Co., Ltd.) were blended in the predetermined amounts shown in Tables 1 and 2 to create 16 types of blended compositions.

Al3F DAPP-bismaleimide ER332 Ha DAPP-Monomaleimide ○H Number average molecular weight = 475 Novolac type phenolic resin HPGO7N.

(Hitachi Chemical Co., Ltd.) This compound was poured into molds for various characteristic specimens at 120°C, heating time +160°C, working time +230°C.
Heat curing was performed at ℃ for 15 hours.

Measurement of heating loss is 15nuaX 25m@X 2t
The weight loss rate was expressed after the sample was left at 270°C for four days.

<Examples 17 to 22 Comparative Examples> As epoxy compounds, EOCN-102S and E
HPE-3150 (manufactured by Daicel Chemical Co., Ltd.; epoxy equivalent: 1
79, melting point 76°C) As a curing agent, novolac type phenol HP607N and M resin oligoarylphenol compound as DABF bismaleimide compound, DAPP-bismaleimide,
The predetermined amounts of DDM-bismaleimide shown in Table 3 were blended, and 2 parts by weight of triphenylphosphine p-1oo and 0.5 parts by weight of dixyl oxide (DCPO) were separately added as curing accelerators. Department (D
(CPO was melted in DABF in advance) As a coupling agent, 1.5 parts by weight of epoxysilane KBM303 (Shin-Etsu Chemical Co., Ltd., $1), as a mold release agent, 2.0 parts by weight of Hoechst Wax E (manufactured by Hoechst Japan Co., Ltd.) Parts by weight, as a coloring agent: carbon black (Cabot ml) 2.
0 parts by weight, and a predetermined amount of quartz glass powder was added as a filler to prepare mixed carved products of different types (including comparative examples).

Next, these were made from 70~ using two 8'φ diameter sails.
After heating and kneading for 8 minutes at 85° C., the mixture was cooled to obtain a molding material for semiconductor encapsulation.

Using this molding material, 4M-bit D-RAM memory LSIs (chips, 50 each) were encapsulated using a transfer molding machine at 175°C, 70hgf/ad, and for 2 minutes. A resin-sealed semiconductor device was obtained.

Pressure and Hookah test of this semiconductor device (LSI sealed product): Defective rate after PCT (121°C, 2 atm supersaturated steam test), defective rate when left in PCT after immersion in solder bath, and after cooling/heating cycle Table 3 shows the occurrence of cracks in the sealed products. Conventional N, N'
- Compared to the case of using DDM bismaleimide, which is bismaleimide, when DAPP-bismaleimide is used, the moisture resistance reliability and heat resistance reliability are significantly improved.

<Example 23> As an epoxy compound, bisphenol A type epoxy resin DER332160 parts by weight As a bismaleimide compound, 2.2-bis(4-(4-maleimidophenoxy)phenyl)hexafluoropropane,
150 parts by weight and DA of DAPP-bismaleimide
PP adduct (1;4 adduct) Diallylbisphenol F 100 parts by weight MHAC
-P 150 parts by weight was added and dissolved in methyl ethyl ketone, 900 parts by weight, and DCP
12 parts by weight of O and 3,9-bis(2-(3,5-diamino-2,4,6-driazaphenyl)ethyl)2,4,
8.10-tetraoxaspiro(5,5)undecane (
CTU-Guanamine Ajinomoto Co. II) 2 parts by weight were added.

Claims (1)

[Claims] 1. At least the following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, there is no X, -CH_2-, ▲There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
-O-, ▲Mathematical formulas, chemical formulas, tables, etc.▼, -SO_
It is either one of 2-. ] and the general formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [In the formula, R_1 to R_4 are hydrogen, lower alkyl group, lower alkoxy group, chlorine or bromine, which may be the same or different. R_5 and R_6 are hydrogen,
These are a methyl group, an ethyl group, a trifluoromethyl group, and a trichloromethyl group, and they may be the same or different. Further, D_1 and D_2 are divalent organic groups having 2 to 24 carbon atoms. ] A thermosetting resin composition comprising an addition type etherimide compound represented by the following formula and an epoxy compound. 2. The thermosetting resin composition according to claim 1, wherein the general formula [I] is ▲a mathematical formula, a chemical formula, a table, etc.▼. 3. The thermosetting resin composition according to claim 1, wherein the general formula [II] is ▲a mathematical formula, a chemical formula, a table, etc.▼. 4. Thermosetting according to claim 1, wherein the epoxy compound is: ▲ has a mathematical formula, chemical formula, table, etc. ▼ and/or ▲ has a mathematical formula, chemical formula, table, etc. ▼ Resin composition. 5. Epoxy compounds have ▲mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, m is 2 to 30. ] The thermosetting resin composition according to claim 1. 6. The thermosetting resin composition according to claim 1, wherein the epoxy compound is a novolac type phenolic epoxy resin. 7. Claim 1, wherein the epoxy compound is a cyclohexene carboxylate compound
The thermosetting resin composition described in . 8.At least the following general formulas [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, there is no There are tables, etc.▼,
-O-, ▲Mathematical formulas, chemical formulas, tables, etc.▼, -SO_
2-. ] and the general formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [In the formula, R_1 to R_4 are hydrogen, lower alkyl group, lower alkoxy group, chlorine or bromine, which may be the same or different. R_5 and R_6 are hydrogen,
These are a methyl group, an ethyl group, a trifluoromethyl group, and a trichloromethyl group, and they may be the same or different. Further, D_1 and D_2 are divalent organic groups having 2 to 24 carbon atoms. ] A thermosetting resin composition comprising an addition type etherimide compound represented by the following formula, an epoxy compound, and a phenol compound. 9. Phenol compounds have the following general formula, ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein R_7 is hydrogen, methyl group, alkyl group, alkoxy group, -OH, ▲ mathematical formula, chemical formula, table, etc.) There is▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
9. The thermosetting resin composition according to claim 8, wherein the thermosetting resin composition is a novolak type phenolic resin represented by any one of , Cl, and Br. 10. Phenolic compounds ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and/or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_8 is H, -CH_3, -OH, -NH_2
, -SO_2NH_2, -SO_3H. n is 2-300. ) The thermosetting resin composition according to claim 8.