JPS6356509A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To produce the titled composition useful as laminate material, prepreg, etc., providing a cured material having improved high-temperature strength at relatively low temperature by short time heating, having improved storage stability, containing an N-substituted unsaturated imide compound, a specific metallic salt monomer and a polymer. CONSTITUTION:The aimed composition containing (A) an N-substituted unsaturated imide compound (preferably N,N'-substituted bismaleimide compound) and a metallic salt monomer and/or polymer [preferably aluminum poly(meth) acrylate or copper poly(meth)acrylate] shown by formula I and/or formula II (X is any of substituent group; Mx is metal). EFFECT:Has improved adhesivity, can provide rapid curing property and has good balance of molding and processing properties and heat resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a heat-resistant resin composition, and particularly to a resin composition suitable for laminated materials, molding materials, and prepregs.

[Conventional technology]

Conventionally, resin compositions based on N-ff1-maleimide compounds have been considered for laminated materials, molded materials, prepregs, etc. that require heat resistance. In particular, N, N'-
Addition products of substituted bismaleimide compounds and aromatic diamines, epoxy compounds, combination systems with unsaturated polyester resins, etc. have been mainly used. However, even with this composition, there were difficulties in achieving quick curing properties, improved adhesion, and a balance between moldability and heat resistance.

[Problem that the invention seeks to solve]

In the above-mentioned conventional techniques, special consideration has been given to improving adhesion, which has conventionally been addressed by improving the wettability of the surface of the adhered object or adding a coupling agent to the resin composition. However, even with these means, it is not always possible to fully achieve the objective, and this is a major obstacle in improving the performance and reliability of applied products such as laminated materials, molding materials, and prepregs.

An object of the present invention is to provide a resin composition that has excellent adhesive properties, can be quickly cured, and has well-balanced moldability and heat resistance.

[Means for solving problems]

The above object is achieved by adopting the following configuration. Namely.

(i) One or more N-substituted unsaturated imide compounds (Q) and the general formula % Formula % [In the formula, X represents various substituents and Mx represents a metal. ] Metal salt monomer and/or polymer (b)
A heat-resistant resin composition comprising:

(ii) The heat-resistant resin or resin composition according to item (i), wherein the one or more N-substituted unsaturated imide compounds are N,N'-substituted bismaleimide compounds.

(■) The metal salt monomer and/or polymer (b) represented by the general formula (1) and/or [■] is a polyaluminum acrylate, copper polyacrylate polynata, aluminum acrylate, polycopper methacrylate. The heat-resistant resin composition according to item (i) is selected from among the above.

In the present invention, a compound having one or more unsaturated imide groups is, for example, m > 1 [wherein R2 and R3 are H, CHs, C2H1%,
-Ce Hs e-CH=CHz, C1, Br, or F, and may be the same or different. The maleimide-based compound represented by ] or) is [wherein Rz and Ra are the same as above, and R4 is -e
H2-CH2-CH2, O, +7) There is a mismatch.

m is 1 or more. ] or Diels-Alda addition reaction products of these unsaturated imide compounds.

Among these unsaturated imide compounds, in particular, [in the formula, R
represents an alkylene group, an arylene group, or a divalent organic group substituted thereof], for example,
N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-dodecamethylene bismaleimide, N,N'-m-phinidine bismaleimide, N,N'-4 , 4'-diphenyl ether bismaleimide, N, N'-4,4'-diphenylmethane bismaleimide, N, N'-4,4-dicyclohexylmethane bismaleimide, N, N'-4゜4'-
Meta-xylene bismaleimide, N,N'-4,4'
-diphenylcyclohexane bismaleimide, 2,2-
Bis(4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis[3-methyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[
3-chloro-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-promo 4-(4-
maleimidophenoxy(phenyl)propane, 2゜2-
Bis[3-ethyl-4-(4-maleimidophenoxy)
phenyl]propane, 2,2-bis[3-propyl-4
-(4-maleimidophenoxy)phenyl]propane,
2,2-bis[3-isopropyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3
-butyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis(3-3ee-butyl-4-
(4-maleimidophenoxy)phenyl]propane, 2
, 2-bis(3-methoxy-4-(4-maleimidophenoxy)phenyl)propane, 1°1-bis(4-(4
-maleimidophenoxy)phenyl]ethane, 1,1-
Bis[3-methyl-4-(4-maleimidophenoxy)
phenyl]ethane, 1,1-bis[3-chloro-4-(
4-Maleimidophenoxy)phenyl]ethane, l, l
-bis(3-promo4-(4-maleimidophenoxy)phenyl)ethane, bis(4-(4-maleimidophenoxy)phenylcomethane, bis[3-methyl-4-(
4-Maleimidophenoxy) phenylcomethane, bis[
3-Chloro-4-(4-maleimidophenoxy)phenylcomethane, bis[3-promo 4-(4-maleimidophenoxy)phenylcomethane, 1.1. l, 3, 3,
3-hexafluoro-2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 1,1°1.3
, 3.3-hexachloro-2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 3,3-bis(4-(4-maleimidophenoxy)phenyl)pentane, 1,1-bis(4 -(4-maleimidophenoxy)funinyl]propane, 1,1,1,3,3.3-hexafluoro-2,2-bis[3,5-dibromo-4(4
-maleimidophenoxy)phenyl]propane, 1.1
, 1.3.3.3-hexafluoro-2゜2-bis[3
-Methyl-4(4-maleimidophenoxy)phenyl]
Examples include propane, and one or more of these can be used. In addition, a mixture of a plurality of these types can be used. Furthermore, mixtures of mono-substituted maleimide, tri-substituted maleimide, tetra-substituted maleimide and substituted bismaleimide can be used as appropriate.

Further, in the present invention, the metal salt monomer and/or polymer (b) represented by the general formula % formula % [wherein X represents various substituents and Mx represents a metal] is, for example, calcium acrylate. .

Magnesium acrylate, zinc acrylate, aluminum acrylate, copper acrylate, beryum acrylate, tin acrylate, lead acrylate, cobalt diacrylate,
Manganese diacrylate, nickel diacrylate, ferric diacrylate, calcium methacrylate, magnesium methacrylate, zinc methacrylate, aluminum methacrylate, copper methacrylate, beryum methacrylate, tin methacrylate, lead methacrylate, cobalt dimethacrylate, manganese Dimethacrylate, nickel dimethacrylate, ferrite dimethacrylate, or monomers represented by the following, and oligomers and polymers derived from these monomers. These metal-containing salts,
The blending ratio of oligomer and polymer (b) in the resin composition is not particularly limited, but preferably,
1 to 10 parts by weight per 100 parts by weight of the unsaturated imide compound
When used in a range of 0 parts by weight, it is convenient for achieving both heat resistance and adhesiveness.

Furthermore, various modifiers and additives may be added to the resin composition of the present invention depending on the purpose and use thereof, within a range that does not impair the effects of the present invention. Such compounds include
For example, epoxy compounds.

Phenolic compounds (including phenolic resins), unsaturated polyester resins, first class amine compounds.

Butadimane compounds (including acrylic copolymers), phenoxy resins, siloxane compounds, fluorocarbon compounds, styrene, vinyltoluene, α-methylstyrene, divinylbenzene, diallylphthalate, diallylphthalate prepolymer, chlorstyrene, dichlorostyrene , bromstyrene, dibromstyrene, diallylbenzene phosphonate, diallylaryl phosphonate, diallylaryl phosphinic acid ester, acrylic acid ester, methacrylic acid ester, triallyl cyanurate, triallyl cyanurate prepolymer.

Examples include tribromophenol allyl ether and polyester resin. Also, two or more of these can be used in combination.

In addition, in the present invention, the ethylene type carbon-carbon double bond of the unsaturated imide compound and the terminal vinyl group of the compound (,), or
A catalyst is used to complete the crosslinking between the terminal allyl group and the crosslinking agent. Such catalysts include, for example, benzoyl peroxide.

Parachlorobenzoyl peroxide, 2,4-dichloropenzoyl peroxide, cabrylyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, bis(1-hydroxycyclohexyl peroxide), hydroxy Butyl peroxide, tertiary butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, di-tertiary 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 peroxyisobutyrate , di-tert-butyl-di-perphthalate and the like.

Moreover, these can also be used in combination of two or more types.

Furthermore, the composition of the present invention can be used for various purposes and purposes.
One or more of the following materials can be used in combination.

For example, in the case of application as a molding material, various inorganic fillers such as zircon, silica, fused silica glass, clay, water-containing alumina, calcium carbonate, quartz glass, glass, asbestos, Boyce strength, stone wax, magnesite, etc. ,
Mica, kaolin.

Talc, graphite, cement, carbonyl iron, barium compounds, ferrite, lead compounds, molyfden disulfide,
Zinc white, titanium white, carbon black, silica sand, wollastonite, etc. can be used, and various mold release agents 1, such as fatty acids, waxes, etc., and various coupling agents, such as epoxy silane, Vinyl silane, borane compounds.

Alkoxy titanate compounds etc. can be used,
Furthermore, known flame retardant materials such as antimony, phosphorus, etc., or flexible materials can be used as required.

In addition, in the case of use as a varnish etc., various solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-diethylformamide are used as organic polar solvents. , N-methylformamide, dimethylsulfoxide, N,N-diethylacetamide, hexamethylphosphoramide, pyridine, dimethylsulfone, tetramethylsulfone, dimethyltetramethylenesulfone, etc. can be used,
Also, phenol as a phenolic solvent.

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.

<Examples 1 to 6> As a compound having one or more N-substituted unsaturated imide groups, N-phenyl monomaleimide and N.

N'-substituted-4,4'-diphenylmethane bismaleimide can also be used as metal salt compounds such as polyaluminum acrylate, copper polyacrylate, polyaluminum methacrylate, polycopper methacrylate, and silicon methacrylate (the following formula )% Formula% (All of the above compounds are manufactured by Asada Chemical Industry Co., Ltd.).

Further, a composition containing 4,4'-diaminodiphenylmethane and dixyl oxide as a curing catalyst in the predetermined amounts shown in Table 1 was prepared.

To each of these compositions was added 70 g of 1 spherical fused silica powder.
Add weight percent at 180°C.

After pressure molding at 70 kg/ai for 3 minutes, the deformation temperature and bending strength of the cured product were further measured at 200°C for 5 hours. Results of beer strength of MCL obtained by impregnating N-methylpyrrolidone-methylethylketone with equal volume mixture varnish (solid content 43%), removing the solvent and drying, applying prepreg and pressure molding with 35μ copper foil. are shown in Table 1.

This result shows that it has an excellent balance between heat resistance and adhesiveness.

<Example 7> N-phenyl monomaleimide 3 (l amount m, N.

N'-film-4,4'-diphenylmethane bismaleimide 40 parts by weight, polyaluminum methacrylate 1
0 heavy weight, 3.3'-diallylbisphenynol F3
A composition containing 0 parts by weight and 1 part by weight of dicumyl peroxide was prepared at 150'C, 15h +23
The heat resistance and coil dust content of the cured product cured under the conditions of 0° C., 5 hours and +250° C., 15 hours were checked. 27
Weight growth rate when left at 0°C (the standing time to reach 10% is 210 hours, and there are no cracks in the cured product even after leaving it at 270°C for 200 hours. Also, dust retention in the coil is good. No peeling between coil layers was observed.

, 4 /

Claims (1)

[Claims] 1. One or more N-substituted unsaturated imide compounds (a) and general formula ▲ Numerical formula, chemical formula, table, etc. ▼...[I] and/or ▲ Numerical formula , chemical formulas, tables, etc.▼...[II] [In the formula, X represents various substituents and Mx represents a metal. ] Metal salt monomers and/or polymers (
A heat-resistant resin composition comprising b). 2. The heat-resistant resin composition according to claim 1, wherein the one or more N-substituted unsaturated imide compounds are N,N'-substituted bismaleimide compounds. 3. The metal salt monomer and/or polymer (b) represented by the general formula [I] or [II] is contained in polyaluminum acrylate, copper polyacrylate, polyaluminum methacrylate, or polycopper methacrylate. The heat-resistant resin composition according to claim 1, wherein the heat-resistant resin composition is selected from the following.