JPH0158207B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a thermosetting resin composition that is converted into a resin with excellent heat resistance. In recent years, as electric and electronic devices have become larger in capacity, smaller and lighter, and more reliable, insulating materials with excellent heat resistance have been required. As such heat-resistant resins, heterocyclic polymers such as polyimide are excellent in that they maintain high stability and strength at high temperatures. However, they are generally polycondensation type, and their application as molding materials, laminated materials, or powder materials for coating film formation is limited because they emit volatile substances during curing and are difficult to melt and mold. has been done. In order to improve these drawbacks, proposals have been made to use addition-polymerizable imide compounds such as bismaleimide in combination with epoxy compounds, unsaturated polyesters, and the like. However, even with these, there are problems with fast curing, solubility in various solvents, material cost, etc., and molding materials, prepreg materials, etc.
This has hindered the commercialization of applications such as powder materials for coating film formation and adhesives. In view of the above-mentioned circumstances, the present invention aims to provide a heat-generating product that has good solubility in solvents and can be converted into a cured product with excellent high-temperature strength by heating to a temperature range of about 150 to 200°C for a short time. The purpose is to provide a curable resin composition. Its characteristics are: (a) General formula (In the formula, R ¹ represents hydrogen or a methyl group,
^R2 represents a divalent organic group); (b) an N-vinyl-pyrrolidone compound; and (c) polyparahydroxystyrene. In the present invention, (a) general formula (In the formula, R ¹ represents hydrogen or a methyl group, and R ² represents a divalent organic group.) Examples of the bismaleimide include N,N'-ethylene dimaleimide, N,N'-ethylenebis [ 2-methylmaleimide], N,N'-trimethylene dimaleimide,
N,N'-tetramethylene dimaleimide, N,
N'-hexamethylene dimaleimide, N,N'-hexamethylenebis[2-methylmaleimide], N,
N′-dodecamethylene dimaleimide, N,N′-m
-Phenylene dimaleimide, N,N'-p-phenylene dimaleimide, N,N'-(oxy-p-
phenylene) dimaleimide, N,N'-(methylene-di-p-phenylene) dimaleimide, N,
N'-(methylene-di-p-phenylene)bis[2-methylmaleimide], N,N'-2,4-tolylene dimaleimide, N,N'-2,6-tolylene dimaleimide, N,N' -m-xylylene dimaleimide, N,N'-p-xylylene dimaleimide, N,N'-oxypropylene dimaleimide,
There are N,N'-substituted bismaleimides such as N,N'-ethylenebis(oxypropylenemaleimide) and N,N'-oxydiethylene dimaleimide.
Used alone or in combination of two or more. In the present invention, the N-vinyl-pyrrolidone compound (b) includes, for example, N-vinyl-2
-pyrrolidone, N-vinyl-2-piperidone, N
-Vinyl-ε-caprodactum, N-vinyl-5
-Methyl-2-pyrrolidone, N-vinyl-3,
3,5-trimethyl-2-pyrrolidone, 3-methyl-2-pyrrolidone, or N-vinyl-2
- Dimer of pyrrolidone, also N-vinyl-pyrrolidone, acrylonitrile, allyl alcohol,
Allyl acetate, ethylene, maleic anhydride,
Copolymers such as methyl methacrylate, styrene, vinyl acetate, vinyl chloride, vinylene carbonate, vinyl cyclohexyl ether, vinyl phenyl ether, and polyvinylpyrrolidone are available, and one or more of these may be used in combination. can. In the present invention, the bismaleimide (a) and N
- Vinyl-pyrrolidone compound (b) has a weight ratio of 1
It can be used in the range of 9 to 1 to 9 to 1. When the amount of bismaleimide (a) increases, the fluidity of the composition decreases and moldability deteriorates, and when it decreases, the heat resistance decreases. A more preferred weight ratio is 1:4 to 4:1. In addition, polyparahydroxystyrene compounds
(c) is the general formula It is a compound having an average molecular weight of 500 to 10,000 and is commercially available from Maruzen Sekiyu Co., Ltd. N resin or a copolymer of M resin and a diene compound is used. The blending ratio of the polyparahydroxystyrene compound is 10 to 1000 parts by weight based on 100 parts by weight of the sum of the bismaleimide (a) and the N-vinylpyrrolidone compound (b). In this case, it is possible to obtain a cured product which is the object of the present invention. Furthermore, an unsaturated polyester resin may be added to the resin composition of the present invention. The unsaturated polyester resin is made of unsaturated dibasic acids, saturated dibasic acids and their anhydrides, or lower alkyl ester derivatives thereof, diols, alkylene monooxides, and derivatives thereof, etc., in the presence or absence of a catalyst. A polyester resin matrix containing an unsaturated group synthesized by condensation or addition polymerization using reactions such as esterification and transesterification, and an ethylene-based (e.g., vinyl group, allyl group, etc.) polymerizable compound , and a mixture with a peroxide catalyst. In addition, vinyl ester resins obtained by reacting epoxy compounds such as bisphenol A type and novolac type with methacrylic acid or acrylic acid are also useful. Here, typical unsaturated dibasic acids and saturated dibasic acids include maleic acid, maleic anhydride, fumaric acid, chloromaleic acid,
Dichloromaleic acid, citraconic acid, citraconic anhydride, mesaconic acid, methaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, methylglutaric anhydride, pimelic acid, Hexahydrophthalic acid and anhydride, tetrahydrophthalic acid, carpicic anhydride, Hett's acid and its anhydride, tetrachlorophthalic acid and its anhydride, tetrabromophthalic acid and its anhydride, lower alkyl esters thereof, etc. are used. , ethylene glycol as a diol component,
Diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, 2,2-diethylpropanediol 1,3, neopentyl glycol, diglomneopentyl glycol, pisphenol Dioxyethyl ether, hydrogenated bisphenol A,
2,2-di(4-hydroxypropoxyphenyl)propane, ethylene oxide, propylene oxide, 3,3,3-trichloropropylene oxide, 2-methyl-3,3,3-trichloropropylene oxide, phenyl glycidyl ether , allyl glycyl ether, etc. are used. Further, if necessary, a trifunctional or higher functional polybasic acid and/or a polyhydric alcohol may be used in combination within a range that does not impair the object of the present invention. Examples of crosslinking agents include styrene, vinyltoluene, α-methylstyrene, divinylbenzene, diallyl phthalate, diallyl phthalate prepolymer, chlorstyrene, dichlorostyrene, bromustyrene, dibromostyrene, diallylbenzenephosphonate, and diallyl phosphonate. , acrylic ester, methacrylic ester, triallyl cyanurate, tribromophenol allyl ether, etc. are used. In the present invention, the acid component, alcohol component, and crosslinking agent are not limited to one type, and two or more types can be used in combination. It is also possible to add various modifications and modifiers. Further, the unsaturated polyester resin is not limited to one type, but a mixture of two or more types is also possible. Moreover, a polymerization initiator can be added to the resin composition of the present invention. For example, benzoyl peroxide, parachlorobenzoyl peroxide,
2,4-dichlorobenzoyl peroxide, cabrylyl peroxide, lauroyl peroxide,
Acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, bis(1-hydroxycyclohexyl peroxide),
Hydroxyhebutyl peroxide, t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, 2,5
-dimethylhexyl-2,5-dihydroperoxide, ditertiary-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5 di(t-butylperoxy)hexane, 2,5-dimethylhexyl-2 , 5-di(paoxybenzoate), t-butyl perbenzoate, t-butyl peracetate, t-butyl peroctoate, t-butyl peroxyybutyrate, di-
One type or a combination of two or more types of organic peroxides such as t-butyl di-perphthalate can be used. Further, in the present invention, it is also possible to use the above-mentioned catalyst together with the following known promoters. Namely, lauryl mericcaptan, N-butyl sulfite,
Diphenyl sulfite, p-toluenesulfonic acid, quaternary ammonium salt, β-diketones, peracetic acid type epoxy compound, sulfonium salts, sulfur dioxide gas, hydrogen sulfide, manganese naphthenate, vanadyl octoate, copper naphthenate, naphthene These include calcium acid, other metal salts of naphthenic acid, metal chelate compounds, amines, phosphorus-containing compounds, and sulfur-containing compounds. Moreover, the following polymerization inhibitors can also be used. For example, p-benzoquinone, naphthoquinone, phenanthraquinone, paraxyloquinone, 2,5-diphenyl-p-benzoquinone,
Quinones such as 2,5-diacetoxy-p-benzoquinone, hydroquinones such as hydroquinone, pt-butylcatechol, 2,5-di-t-butylhydroquinone, mono-t-butylhydroquinone, di-t-butyl , paracresol, hydroquinone monomethyl ether, phenols such as alphanaphthol, organic and inorganic copper salts such as copper naphthenate, amidines such as acetamidine acetate, acetamidine sulfate, phenylhydrazine hydrochloride, hydrazine hydrochloride, etc. hydrazine salts, other secondary ammonium salts, amines, nitro compounds, oximes, sulfur, polyhydric phenols, and amine hydrochlorides can be used. Furthermore, the resin composition of the present invention may contain known resin modifiers such as polyethylene, polystyrene, phenolic resin, epoxy resin, melamine resin, urea resin, and fluorine resin, stearic acid, Mold release agents such as zinc stearate, calcium stearate, Hoechstwax, and carnauba wax; coupling agents such as vinylsilane, epoxysilane, and aminosilane that have a coupling effect between resin and filler; titanic acid, chromium oxide, ultramarine blue, and valves. Coloring agents such as handles and carbon black, thickeners such as magnesium oxide, and thixotropic agents such as silicic anhydride having a silanol group and a size of 10 to 20 mμ can also be added. Next, the present invention will be specifically explained by showing examples. In each of the following examples, parts in φ mean parts by weight. Examples 1 to 5 N,N'-(methylene-di-p-phenylene)
dimaleimide, N-vinyl-2-pyrrolidone, and polyparahydroxylstyrene (Maruzen Sekiyu Co., Ltd.)
PHP-113 (average molecular weight: 1700) was used to prepare blends in the predetermined amounts shown in Table 1. Add 3 parts by weight of dicumyl peroxide (DCPO) to this,
After stirring in a heating state at 50 to 80°C, the above mixture was poured into a bending test mold, and heated at 200°C for 30 minutes.
Time cured. The bending strength of the specimen was measured at 150°C. The retention rate of bending strength after being left at 240°C for 30 days was also shown.

[Table] Examples 6 to 9 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, N-vinyl-2-pyrrolidone, and polyparahydroxystyrene with different average molecular weights (Maruzen Oil Co., Ltd.) A composition was prepared in which PHP-031 average molecular weight 2200, PHP-040 average molecular weight 8300) and triallyl isocyanurate (TAIC) were blended in the predetermined proportions shown in Table 2. Each of these includes DCPO, a coupling agent
KBM-503 (manufactured by Shin-Etsu Chemical), wollastonite (CaSiO ₃ ) as a filler, and fused silica glass powder were blended in the proportions shown in Table 2. This composition was kneaded with two rolls at 60 to 80°C for 10 minutes to obtain the desired composition. These compositions were transfer-molded into bending test pieces under the conditions of 170° C., 70 kg/cm ² , and 1.5 minutes.

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Claims (1)

[Claims] 1 (a) General formula (In the formula, R ¹ represents hydrogen or a methyl group,
R ² represents a divalent organic group); (b) an N-vinyl-pyrrolidone compound; and (c) polyparahydroxystyrene. 2. The heat-resistant resin composition according to claim 1, wherein the weight ratio of bismaleimide to N-vinyl-pyrrolidone compound is from 1:4 to 9:1.