JPH03281521A - Liquid curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition suitable as an electrical insulating material for impregnation, etc., providing a cured material having excellent heat resistance, comprising a polymaleimide compound, liquid alkenylphenol compound, polyepoxy compound and a specific liquid polymerizable saturated compound. CONSTITUTION:The objective compound comprising (A) 100 pts.wt. polymaleimide compound (e.g. N,N'-ethylenebismaleimide) containing at least two maleimide groups in one molecule, (B) preferably 30-180 pts.wt. alkenyl group-containing alkenylphenol compound which is liquid at 20 deg.C, (C) preferably 10-200 pts.wt. polyepoxy compound (e.g. diglycidyl ether of bisphenol A) containing at least two epoxy groups in one molecule and having <=1,000 average molecular weight and (D) preferably 40-400 pts.wt. polymerizable saturated compound liquid at 20 deg.C, containing allyl ester, (meth)acryl and/or vinyl bonded to aromatic ring in one molecule.

Description

Detailed Description of the Invention (Field of Application of Ryuto) The present invention relates to a liquid curable resin composition containing a maleimide compound that provides a cured product with excellent heat resistance, and particularly for use as an electrical insulating material for impregnation. This is something you will encounter when doing something.

(Prior art) With the demand for smaller size, higher performance, and higher reliability of electrical equipment,
Insulating materials for electrical equipment are also required to have chemical stability and physical reliability at high temperatures. In particular, importance has been placed on solvent-free heat-resistant resins that can sufficiently perform the required insulation function even under severe thermal conditions as wire-cutting materials for military vehicles and motors.

Epoxy resin, which has traditionally been widely used as impregnated insulation resin for electrical equipment, has low viscosity, good workability, and excellent compatibility with insulating materials such as glass cloth and mica, but has poor heat resistance. Lowest type 2 (maximum operating temperature if /33C
) is a limitation.

Various types of polyimide-based impregnating resins have been proposed, but the ones proposed so far have had advantages and disadvantages.

For example, Tokuko Sho 32-3! ! ! The polyimide-based impregnated resin described in the publication tends to increase in viscosity during storage and has poor compatibility with the main raw material bismaleimide resin, resulting in problems in workability, such as precipitation during delivery. Also, Tokukai Shoujμ
Although the polyimide-based impregnated resin described in the -100≠Za No. 2 publication can prevent the crystallization of bismaleimide to some extent, it has the drawback of poor long-term thermal stability because it uses monomaleimide.

Additionally, a composition of epoxy resin and polyimide has been proposed (Japanese Unexamined Patent Publication No. 6-7-2/Otsu), but this resin composition has a higher heat resistance than epoxy resin 1] 1 alone. There is some improvement, but the degree of improvement is not sufficient.

(Problem to be solved by the invention) The present invention aims to provide a liquid curable resin composition that does not cause thickening or crystallization during storage and can provide a cured product with excellent heat resistance. .

(Solutions for Problem 11) The liquid curable resin composition of the present invention has excellent heat resistance and contains the following components (A), (B), (C) and (D). This is a resin composition that provides a cured product.

Component (A): /Polymaleimide compound having at least 2 maleimide groups in the molecule Component (B): /Having 7 or more alkenyl groups in the molecule. 20T: liquid alkenylphenol compound (C) component = 7 polyepoxy compounds having at least two epoxy groups in the molecule and an average molecular weight of 1000 or less (D) component: / allyl ester group, acrylic in the molecule A 20C liquid penetrating unsaturated compound having at least one group selected from vinyl groups, methacrylic groups, and aromatic rings. ) to (ij+).

(1) Bismaleimide compounds: Specific examples thereof include N,N'-ethylene bismaleimide, N,N'-, sameethylene bismaleimide, N
, N'-m-phenylene bismaleimide, N, N'
-p-phenylene bismaleimide, N, N'-(
1AII'-diphenylmethane) bismaleimide, N,
N'-(44,4<'-diphenyl ether)bismaleimide, N,N'-methylenebis(3-chloro-p-)
Unishin) bismaleimide, N, N'-(lIL, lI
L'-diphenylsulfone) bismaleimide, N'
-(41,4t'-dicyclohexylmethane)bismaleimide, N,N'-(α,α'-Yoshihiro'-dimethylenecycloheJP?n)bismaleimide, N,N'fli-medium silylene bismaleimide N , N'-(tA, 4"
-Sifninylcyclohexane) bismalei? )',
N, N'-(g≠'-diphenyl-/, /-propane)bismale(mi)", N+N'-(Il,, san'-
trifiniru(4/,/-ethane) bismaleimide, N
, N'-(%!'-tri;7-=/Izmethane)bismaleimide, N,N'-(J,j-triazole)-X
To ZU-bismaleimide.

N'-(3,!'-dimethyl-≠≠'-diphenylmethane) bismaleimide, N, N'-(3,3'-diethyl-yo!'-dimedel-4t,4t'-diphenylmethane) bismaleimide, etc. can give.

(N-phenylmethylene)maleimide shown in the following - ship stock: In the formula, n is a number from 0 to 3.

(iii) A polymaleimide compound represented by the following general formula (see Japanese Patent Application Laid-Open No. 2003-110003).

+1 In the formula, X represents a hydrogen atom, an I.rogen atom, an alkyl group having a carbon number of /~≠, or an alkoxy group having a carbon number of 7 to 0.

In the present invention, the 20C liquid alkenylphenol compound of component (B) is a phenolic compound having at least/one phenolic hydroxyl group and an alkenylphenol compound having at least/one phenolic hydroxyl group.
An alkenylphenol ether is produced by a method known per se in which alkenylphenol ether is reacted with an alkali metal hydroxide and a reaction solvent in the presence of an alkali metal hydroxide and a reaction solvent, and the resulting alkenylphenol ether is reacted with 7!
; It can be produced by a known method of causing Claisen transition by heat treatment at a high temperature of 0-230C. Examples of compounds having at least one phenolic hydroxyl group used in the production reaction include phenol, cresol, tert-methylphenol, xylenol, 2-phthyl≠-methylphenol, p-phenylphenol, bisphenol A, bisphenol F, and hydroquinone. , resorcinol, catechol, phenol novolac mm, yvsol novolac resin, /, /
, /-tris(hydroyacyphenyl)methane, Otsu/, 3
- Examples include tris(hydroyacyphenyl) bread.

Examples of the polyepoxy compound as component (C) in the present invention include bisphenol diglycidyl ether (commercially available products thereof include, for example, Epicoat T Core, Epikot! 2!, and Piza 3μ, manufactured by Yuka Shell Epoxy Co., Ltd.)
,same! , 31. There is. ), diglycidyl ether of bisphenol F, diglycidyl ether of brominated bisphenol A, glycidyl ester compounds obtained from epoxidized phenol novolac phthalic acid or hexahydrophthalic acid, etc. and epichlorohydrin, aromatic amines such as aminophenol and diaminodiphenylmethane. and epichlorohydrin, cycloaliphatic epoxy resins obtained from dicyclopentadiene and peracetic acid, tllt-butanediol diglycidyl ether, 46-hexanesiol diglycidyl ether, and the like.

Examples of the 20C liquid polymerizable unsaturated compound of component CD) in the present invention include the following compounds (1) to (fil).

(1) Allyl esters: Specific examples include diallyl phthalate, triallyl trimellitate, diallyl hexahydrophthalate, and the like.

(li) (meth)acrylate compounds: Specific examples include methyl (meth)acrylate,
Tetrahydrofurfuryl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, 4-darbutanediol di(meth)acrylate, neobentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, (meth)acryloxyethyl Succinate, trimethylolpropane tri(meth)acrylate, 2-hydroxy-3-tripropyl(meth)acrylate, λ-hydroxy-3-phenoxyprobyl(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa (meth)acrylate, bisdiethylene glycol phthalate (meth)acrylate, di(meth)acrylate of bisphenol F dioxydiethylene glycol,
Bisphenol F dioxypropylene glycol di(
meth)acrylate, bisphenol A dioxydiethylene glycol di(meth)acrylate, bisphenol F type epoxy di(meth)acrylate, bisphenol A type epoxy di(meth)acrylate, cohydroxyethyl acryloyl phosphate, bis(cohydrosethylacryloyl) Polyester (meth) obtained by reacting phosphate, 2-hydroxyethyl acryloyl ethyl phosphate, dibasic acid or its acid anhydride, diol, and acrylic acid or methacrylic acid.
Examples include acrylate, urethane (meth)acrylate obtained by reacting diisocyanates, diols, and acrylic acid or methacrylic acid. Note that "(meth)acrylate" described in this specification is a general term for acrylate and methacrylate.

(ji+) Aromatic vinyl compounds: Specific examples thereof include styrene, α-methylstyrene, divinylbenzene, and vinyltoluene.

In the curable resin composition of the present invention, the physical properties of the resin can be adjusted in various ways by changing the blending ratio of component (A), component (B), component (C), and component (D). For example, in order to obtain a cured product that particularly requires heat resistance, the proportion of the acid component [A] is increased and the proportion of the component (D) is decreased. Also, if you want to lower the resin viscosity, (
D) Increase component L and decrease component (A). In addition, when trying to obtain a cured product that requires adhesiveness, (C
) Increase the proportion of component (A) and decrease the proportion of component (D). Furthermore, component (B) acts as a curing agent for both component (A) and component (C), but in general, if the proportion of component (B) is too high, the heat resistance of the cured product will be affected. On the other hand, if it is too small, the cured product becomes brittle.

In general, the blending ratio of each component (A) to (D) is:
30 to 30 parts of component (B) to 100 parts by weight of component (A)
/gO parts by weight, component (C) is 10-200 parts by weight, (D
) is preferably within the range of ≠o-tAoo parts by weight.

A radical initiator can be added to the resin composition of the present invention for the purpose of promoting polymerization, if necessary. Examples of the initiator include benzoyl peroxide, diisobrobyl peroxycarbonate, lauroyl peroxide,
Peroxides such as dicumyl peroxide and t-butyl peroxybivalate, azoinobutyronitrile, 22'
Examples include azo compounds such as -azobis(2-methylbutyronitrile).

Furthermore, the resin composition of the present invention may contain (A
) e, min and a catalyst that accelerates the reaction between component (B) and component (C) as a curing agent thereof can be added. Examples of catalysts include tertiary amines such as trilobylamine and tris(dimethylaminomethyl)phenol, salts of these tertiary amines, imidazoles such as 2-methylimidazole and λ-ethyl≠-methylimidazole, phenylphosphine, trin
Examples include phosphine derivatives such as -butylphosphine.

The resin composition of the present invention is prepared by a method in which components (A), (B), (C), and (D) are heated and melted and mixed to form a uniform composition. It will be done.

The resin composition of the present invention has a suitable @modification, for example, 100-
2! It is easily cured by heating at OC temperature for 7 to 20 hours, yielding a cured product with excellent heat resistance.

(Examples, etc.) The following is a more detailed explanation of Examples and Comparative Examples.

Example 1 N,N'-(4',μ'-diphenylmethane)bismaleimidota O, 0 parts by weight of o,o'-diallylbisphenol A, diglycidyl ether of bisphenol A (Yuka Shell Epoxy Co., Ltd.) Product Name: Epicoat Za, 2j) In the heavy part, place dimethacrylate of dioxydiethylene glycol ether of bisphenol A/20, and add 0.3 parts by weight of triphenylphosphine at temperature/θOC for 30 minutes and mix uniformly. It was made into a solution.

Next, the temperature was lowered to roc, 0.21 g of dicumyl peroxide was added and stirred, then poured into a metal mold, heated at 1 soc for 3 hours, then heated to 200C! Cured by heating for a period of time, length ia 7 mm, width/near mm, thickness O, pm
A cured product of m was obtained.

The physical properties of this cured product are shown in Table/.

Examples 2 to g Comparative Examples/ Each curable resin composition was prepared in the same manner as in Example/, using each of the polymaleimide compounds, alkenylphenol compounds, polyepoxy compounds, and polymerizable unsaturated compounds shown in Table/, respectively. were prepared and each composition was cured in the same manner.

The physical properties of each cured product are shown in Table/.

Notes for the following margin table/: Umbrella/...N, N'-(IA≠'-diphenylmethane bismaleimide-2...N, N'-(3,3'-diethyl-yo!'-
Dimethyl-each q'-diphenylmethane bismaleimide skewer 3-・-o, o'-Schiff'J rubisphenol A$≠
-@@Q, Q'-Diallylbisphenol F prison!
...YSE company trade name, diglycidyl ether-6 of bisphenol A...YSB company trade name, bisphenol F diglycidyl ether umbrella 7...YSE company trading company name Product name Functional glycidylamine type engineered poxy compound ml.・・YaE Trading Company Name Product Name Lycidyl Ester Type Epoxy Compound ・・Contest Bisphenol Dioxydiethylene Glycol Dimethacrylate *10 ・・・Bisphenol A Dioxydiethylene Glycol Diacrylate ・/・・Trial Remeritate△ Shin72m#-Bisphenol F dioxydiethylene glycol diacrylate-73...Dicumyl peroxide umbrella/1It-/triphenylphosphine skewer/j...NOF Co., Ltd. product name, 1-Buderbao Medium dibenzoate umbrella/z...Brand name of Shikoku Kasei Co., Ltd., 2-undecyl-imidazole umbrella 17...E-type viscometer*/za...ASTM D-Otsu≠fK 1/ri...
- Temperature raised at 7 OC/min in air using a thermobalance (effect of the invention) The liquid curable resin composition of the present invention is liquid and has excellent workability and storage stability, as well as a cured product with excellent heat resistance. give.

Claims (2)

[Claims] (1) A liquid curable resin composition that provides a heat-resistant cured product containing the following components (A), (B), (C) and (D). (A) Component: A polymaleimide compound having at least two maleimide groups in one molecule (B) Component: An alkenylphenol compound that is liquid at 20°C and having one or more alkenyl groups in one molecule (C) Component: Polyepoxy compound (D) component having at least two epoxy groups in one molecule and having an average molecular weight of 1000 or less: Allyl ester group, acrylic group, methacrylic group, and vinyl group bonded to an aromatic ring in one molecule Polymerizable unsaturated compound that is liquid at 20°C and has one or more selected groups (2) (A) component, (B) component, (C) component and (D)
The blending ratio of the components is (B) per 100 parts by weight of component (A).
) component is 30 to 180 parts by weight, component (C) is 10 to 20 parts by weight
The liquid curable resin composition according to claim 1, wherein the component (D) is 40 to 400 parts by weight.