JPS6213966B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a heat-resistant resin composition, and more specifically,
The present invention relates to a heat-resistant resin composition that can provide a cured product with excellent electrical insulation properties in a high temperature range (150 to 200°C). In recent years, the capacity of electrical or electronic equipment has increased,
Insulating materials with excellent heat resistance are required as size and weight are reduced, reliability increases, and productivity increases. Conventionally, as heat-resistant resins, heterocyclic polymers typified by polyimide, silicone resins, and the like are known. However, most of the heterocyclic polymers are condensation type, and they produce volatile components during curing, have poor moldability, take a long time to cure, and can only be used in certain polar solvents for applications such as varnishes. There are various difficulties, particularly in the fields of molding materials, laminated materials, and powder materials. On the other hand, silicone resins have low mechanical strength at high temperatures, poor adhesion, and high moisture repellency, so that their applications are also limited. Addition type imides (bismaleimide etc.) and epoxy compounds,
It is known to use unsaturated polyester and the like in combination. However, even in this case, there are problems in providing fast curing properties, solubility in various solvents, material costs, etc., and this is a major obstacle to commercialization for applications such as molding materials, prepregs, powder coatings, and adhesives. Ta. The present invention was made in view of the above-mentioned current situation, and its purpose is to produce a cured product with excellent high-temperature strength by heating at a relatively low temperature (150 to 200°C) for a short time (1 to 30 minutes). It converts to high temperature range (150~200
An object of the present invention is to provide a heat-resistant resin composition capable of providing a cured product having excellent electrical insulation properties at temperatures (°C). The present invention has the following configuration to achieve the above object. That is, the heat-resistant resin composition of the present invention has the following general formula [1] Contains a 1,3-diallylhydantoin compound represented by the formula (in which R ₁ and R ₂ independently represent a hydrogen atom or CH ₃ ), an N,N'-substituted bismaleimide derivative, and an amino compound. This is a heat-resistant resin composition characterized by the following. In the present invention, the N,N'-substituted bismaleimide derivative has the general formula [] A compound represented by [wherein R ₃ represents an alkylene group, an arylene group, or a divalent organic group substituted thereof], such as N,N'-ethylene bismaleimide, N,N'-hexamethylene bis maleimide, N,N'-dodecamethylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide,
N,N'-4,4'-diphenyl ether bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide, N,N'-4,4'-dicyclohexylmethane bismaleimide, N,N Examples include '-4,4'-methaxylene bismaleimide and N,N'-4,4'-diphenylcyclohexane bismaleimide, and two or more of these can also be used in combination. Furthermore, mixtures of mono-substituted maleimide, tri-substituted maleimide, tetra-substituted maleimide and the above-mentioned substituted bismaleimide can also be used as appropriate. Examples of the amine compounds used in the present invention include primary diamines such as m-phenylene diamine, p-phenylene diamine, benzidine, 3,
3'-dimethyl-4,4-diaminobiphenyl,
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'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfoxide, 4 , 4′-diaminodiphenyl sulfone,
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
-diaminopyridine, 2,5-diamino-1,
3,4-oxadiazole, m-xylylenediamine, p-xylylenediamine, 2,4(p-β
-amino-tert-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-methylheptamethylenediamine, 2,5-dimethylheptamethylenediamine,
4,4-dimethylheptamethylenediamine, 5-
Methynonamethylenediamine, 1,4-diaminocyclohexane, bis(p-aminocyclohexyl)methane, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl)sulfide,
Examples include N,N-bis(3-aminopropyl)methylamine. Further, examples of N-aryl substituted aromatic triamines include 2,4-diaminodiphenylamine,
2,4-diamino-5-methyl-diphenylamine, 2,4-diamino-4'-methyl-diphenylamine, 1-anilino-2,4-diaminonaphthalene, 3,3'-diamino-4-anilinobenzophenone and so on. Furthermore, the general formula (In the formula, R is an alkylidene group containing a methylene group, and n is a number on average of 0.1 or more.) Polyamines etc. can also be used. Note that these amine compounds may be used in combination. The composition of the present invention can be produced by simply melt-kneading the three components described above in a reaction vessel containing a reaction device such as a heating roll or a heating kneader. It can also be produced by heating and mixing an aminobismaleimide compound obtained by reacting a compound with 1,3-diallylhydantoin. The blending ratio of these three components varies depending on the properties required for the intended molded and cured product.
The percentage of (b)/(a)+(c) should be in the range of 100 to 500% in terms of heat resistance and storage stability, and in the range of 20 to 200% in terms of rapid curing. Appropriate. 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. (1) Polymerization by allyl group or vinyl group, (2) Condensation with epoxy and amino groups,
It is thought that the following reactions occur: (3) addition polymerization between amino groups and maleimide groups, and (4) addition polymerization reactions between maleimide groups and vinyl groups. The composition of the present invention thus prepared is heated, kneaded,
A molded product having excellent electrical properties can be obtained by molding for a short time such as cm ² and 3 to 5 minutes. Next, in the present invention, for example, a crosslinking agent may be added to the composition of the present invention to an extent that does not impair the effects of the present invention.
It is also possible to add an ethylenic polymerizable compound in an amount of 1 to 50 parts by weight per 100 parts by weight of (a)+(b). Examples of such compounds include styrene, vinyltoluene, alpha-methylstyrene, divinylbenzene, diallyl phthalate, diallyl phthalate prepolymer, chlorostyrene, dichlorostyrene, promstyrene, dipromstyrene, diallylbenzenephosphonate, diallyl aryl. Examples include phosphonates, diallylaryl phosphinates, acrylic esters, methacrylic esters, triallyl cyanurate, tripromophenol allyl ether, and unsaturated polyester tellenedi. Also, two or more of these can be used in combination. In addition, in the present invention, in order to complete the crosslinking between the ethylene type carbon-carbon double bond of the N,N'-substituted bismaleimide compound, the terminal vinyl group or terminal allyl group of compound (a), and the crosslinking agent, Use a catalyst. Examples of such catalysts include benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, caprylyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, bis (1-hydroxycyclohexyl peroxide), hydroxyheptyl peroxide, tertiary butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, 2, 5-dimethyl-2,5-di(tertiary butyl peroxide) hexane, 2,5-dimethylhexyl-2,5-di(peroxybenzoate), tertiary butyl perbenzoate, tertiary butyl peracetate , tertiary butyl peroctoate, tertiary butyl peroxyisoptylate,
Organic peroxides such as di-tert-butyl-di-perphthalate may be mentioned. Also these are 2
It is also possible to use more than one species in combination. Furthermore, an epoxy compound can be added to the composition of the present invention for the purpose of improving moldability. Examples of polyfunctional epoxy compounds include diglycidyl ether of bisphenol A, butadiene diepoxide, 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, 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-epoxy-1,2-cyclohexane)dicarboximide Bifunctional epoxy compounds such as para-aminophenol triglycidyl ether, polyallyl glycidyl ether,
1,3,5-tri(1,2-epoxyethyl)benzene, 2,2',4,4'-tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane, polyglycidyl of phenol formaldehyde novolac Tri- or higher functional epoxy compounds such as ether, triglycidyl ether of glycerin, and triglycidyl ether of trimethylolpropane are used. Furthermore, the composition of the present invention also has various uses,
Depending on the purpose, one or more of the following various materials can be used in combination. For example, when used as a molding material, various inorganic fillers such as zircon, silica, fused silica glass, clay, alumina alumina, calcium carbonate, quartz glass, glass, asbestos, whiskers, gypsum, and magnesite can be used. , mica,
Kaolin, talc, graphite, cement, carbonyl iron, barium compounds, ferrite, lead compounds, molybdenum disulfide, zinc white, titanium white, carbon black, silica sand, wollastonite, etc. can be used, and various mold release agents can be used. For example, fatty acids,
Waxes, etc. and various cutlet pudding agents, for example,
Epoxy silane, vinyl silane, borane compounds, alkoxy titanate compounds, etc. can be used, and if necessary, known flame retardants or flexible materials made of antimony, phosphorus, etc. can be used. In addition, when used as a varnish, etc., various solvents such as N-methyl-2 as an organic polar solvent can be used.
-pyrrolidone, N,N-dimethylacetamide,
N,N-dimethylformamide, N,N-diethylformamide, N-methylformamide, dimethylsulfoxide, N,N-diethylacetamide, hexamethylphosphoramide, pyridine, dimethylsulfone, tetramethylsulfone, dimethyltetramethylenesulfone, etc. Also, as a phenolic solvent, phenol,
One or more types of cresol, xylenol, etc. can be used alone or in combination. Further, if the amount used is a small amount, a non-solvent such as toluene, xylene, petroleum naphtha, etc. can be used in combination. The composition of the present invention is converted into a cured product with excellent high-temperature strength by heating at a relatively low temperature for a short time, has excellent storage stability at temperatures around room temperature, and can be molded at low pressure, so it can be used as a semiconductor encapsulant, It is extremely useful in its application fields such as laminated materials. Next, the present invention will be explained with reference to examples, but the present invention is not limited to these in any way. Parts in the text indicate parts by weight. Examples 1 to 3 50 parts, 100 parts, and 150 parts of 4,4'-diaminodiphenyl metal were separately blended into 100 parts of N,N'-(methylenedi-p-phenylene) bismaleimide, and three types of A formulation was created. After adding 50 parts of 1,3-diallyl-5,5'-dimethylhydantoin to each of these, as a filler,
70% by weight of quartz glass powder, 2 parts of stearic acid as a mold release agent, and epoxy silane as a coupling agent.
One part of KBM403 (manufactured by Shin-Etsu Chemical) and one part of carbon black as a coloring agent were added. These three types of blended compositions were ground and mixed in a Henschel mixer to 150 mesh or less, and then
Transfer molding was carried out at 185° C., 300 kg/cm ² for 5 minutes to prepare bending specimens and specimens for measuring electrical properties. Table 1 shows the results of the bending strength, heat deterioration properties, and electrical properties of the three types of cured products.

[Table] Examples 4 to 6 100 parts of N,N'-(methylenedi-p-phenylene)bismaleimide, 50 parts of 4,4'-diaminodiphenylmethane, 1,3-diallyl-5,5-
Three types of formulations were prepared by separately blending 10, 20, and 100 parts of dimethylhydantoin. This mixture was kneaded and molded in the same manner as in Example 1, and characteristic specimens were prepared to measure the characteristics. The measurement results are shown in Table 2.

【table】

[Table] Examples 7 to 11 Three components: 100 parts of N,N'-(methylenedi-p-phenylene) bismaleimide, 50 parts of 4,4'-diaminodiphenyl ether, and 50 parts of 1,3-diallyldimethylhydantoin In the system, epoxy compound,
A system was prepared by adding 100 parts each of ECNI273 (manufactured by Ciba Corporation; epoxy equivalent: 225), unsaturated polyester resin PS-518 (manufactured by Hitachi Chemical), triallyl isocyanurate, and diallyl phthalate, and using a kneader, Example 1 and Similar additives were added and kneaded. Table 3 shows the measurement results of the characteristics.

【table】

【table】

Claims (1)

[Claims] 1. The following general formula [] A 1,3-diallylhydantoin compound represented by the formula (in which R ₁ and R ₂ independently represent a hydrogen atom or CH ₃ ), an N,N'-substituted bismaleimide derivative, and a polyfunctional amine compound. A heat-resistant resin composition comprising: 2 N,N'-substituted bismaleimide derivative is
The composition according to claim 1, which is N,N'-(methylenedi-p-phenylene) bismaleimide.