JPS60166340A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:A composition having extremely raised heat resistance of cured material, obtained by adding a polyglycidyl compound to a glycidyl group-containing epoxy compound. CONSTITUTION:(A) 5-95wt% polyglycidyl compound shown by the formula (R is H, 1-10C alkyl, or aryl; n is 0-1,000; benzene nucleus may contain 0-4 halogens selected from chlorine and bromine) is blended with (B) 95-5wt% epoxy resin containing two or more glycidyl groups in the molecule. An epoxy resin comprising a polyglycidyl ether of polyhydric phenol, or bisphenol A and epichlorohydrin is used as the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy resin composition with excellent heat resistance.

Epoxy resins have excellent mechanical and electrical properties, and have recently been widely used in the fields of electricity, adhesives, civil engineering, and painting. Especially recently, when used in fields such as electronic materials and aircraft, epoxy resins with high heat resistance have become necessary.

As a general-purpose epoxy resin, an epi-bis type epoxy resin obtained from bisphenol A and epichlorohydrin is known, but its cured product does not have sufficient heat resistance. In order to improve heat resistance, phenol novolac and cresol novolac are glycidylated with epichlorohydrin, and phenol novolac epoxy resins and cresol novolak-type exoxy resins are used), but there are limits to the heat resistance. there were.

The present inventors expressed the following general formula (4)% formula% (wherein, 1t is a hydrogen atom, 1t is an alkyl group having 1 to 10 carbon atoms, and 1t is an allyl group. 00
is an integer of 0, and the benzene nucleus may have 0 to 4 10 groups selected from chloro and bromine. The inventors have discovered that the heat resistance of a cured product can be significantly improved by adding a polyglycidyl compound represented by the following formula to an epoxy resin having two or more glycidyl groups in the molecule, and have thus arrived at the present invention.

Regarding the method for producing the polyglycidyl compound represented by the general formula (4), the present inventors previously discovered a patent application filed in 1983.
As shown in No. 50960, it can be easily produced by reacting polyp-hydroxystyrenes and epihalohydrin in the presence of a phase transfer catalyst, followed by dehydrohalogenation reaction with caustic alkali.

Epoxy resins that can be mixed with the polyglycidyl compound represented by general formula (4) are not particularly limited as long as they have two or more glycidyl groups in the molecule, but
Examples include polyphenolic epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, and cresol novolak epoxy resin, 4,4.4', 4'-
Tetraglycidyldiaminodiphenylmethane, N, N,
Aromatic amine epoxy resins such as O-4 liglycidyl-m-amine phenol, glycidyl ester type epoxy resins such as terephthalic acid diglycidyl ester, tetrahydroterephthalic acid diglycidyl ester, etc. can be used.

The amount of the polyglycidyl compound represented by general formula (A) to be added can be arbitrarily selected within the range of 5 to 95% by weight based on the total amount of the epoxy resin. If it is less than 5%, the effect of addition is small, and if it exceeds 95%, it is difficult to mix with the curing agent.

The curing agent applicable to the composition of the present invention can be arbitrarily selected from those known as curing agents for general epoxy resins. For example, acid anhydrides, aromatic diamines, BF, -amine complexes, etc. can be used.

The composition of the present invention is particularly useful when it is desired to increase the heat resistance of epoxy resins that have insufficient heat resistance. When applied to a general-purpose bisphenol A type epoxy resin, a remarkable increase in heat distortion temperature is observed, and an improvement in heat resistance is achieved.

The present invention will be explained below using specific examples, but the present invention is not limited only to these examples.

Example 1 Using poly-p-hydroxystyrene with a molecular weight of 3,000 to 12,000 as a starting material, it was glycidylated with epichlorohydrin according to the method of Example 1 of Japanese Patent Application No. 58-50960 to obtain a polyglycidyl compound (Polyglycidyl Compound A).
. The epoxy equivalent weight of this product was 208.

50 parts (parts by weight, same hereinafter) of the above polyglycidyl compound A, Epicoat 828 (manufactured by Shell Petroleum ■, bisphenol A type epoxy resin, epoxy equivalent 184-194)
) 50 parts, methylhimic anhydride (manufactured by Hitachi Chemical) 8
0 parts and 2 parts of benzyldimethylamine were mixed, and 100 parts
C. for 3 hours, then cured at 150.degree. C. for 15 hours. Heat distortion temperature of this cured product (As TMD-648)
is 162°C.

Comparative Example 1 For comparison, a mixture of 100 parts of Epikote 828, 82 parts of methylhimic acid anhydride, and 222 parts of penzyldimethyla was cured under the same conditions, and the heat distortion temperature of the cured product was measured to be 145°C.

Examples 2 to 4 Polyglycidyl Compound A and Epicote 828 used in Example I are shown in Table 1 10/90.80/705015
o and 100° using 4,4'-diaminodiphenylmethane (abbreviated as DDM) as a curing agent.
C. for 1 hour and then at 200.degree. C. for 1 hour. Table 1 shows the results of measuring the heat distortion temperature of the cured product.

Comparative Example 2 Polyglycidyl compound A using only Ebicor 1-828
A similar experiment was conducted without using , and the results are shown in Table 1.

Claims (3)

[Claims] (1) An epoxy resin composition comprising 5 to 95% by weight of a polyglycidyl compound represented by the following general formula (A) and 95 to 5% by weight of an epoxy resin having two or more glycidyl groups in the molecule. (In the formula, R represents either a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an allyl group. n is an integer of 0 to 1000, and the benzene nucleus is chloro,
It may have 0 to 4 10 groups (selected from bromine). ) (2) The epoxy resin composition according to claim 1, wherein the epoxy resin having two or more glycidyl groups in the molecule is a polyglycidyl ether of polyhydric phenol. (3) The epoxy resin composition according to claim 1, wherein the epoxy resin having two or more glycidyl groups in the molecule is an epoxy resin obtained from bisphenol A and epichlorohydrin.