JPS6296521A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition excellent in heat resistance, moisture resistance and adhesion to copper foil, by mixing a epoxy resin with a specified dicyclopentadiene, phenolic polymer and, optionally, a cure accelerator. CONSTITUTION:The titled composition is obtained by mixing 1 equivalent of an epoxy resin (A) having at least two epoxy with 0.05-1.5 equivalent (in terms of phenolic hydroxyl groups) of a dicyclopentadiene/phenolic polymer (B) of the formula (wherein R is H or a lower alkyl and n is 0-10) as a curing agent and, optionally, 0.01-3.0wt% based on component A, cure accelerator (C) (e.g., benzyldimethylamine) and, optionally, a curing agent (cure accelerator), a curing catalyst, a diluent, a filler, a pigment, a flame retardant, etc., are added to the mixture. A laminate obtained from this composition is useful for printed wiring boards.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an epoxy resin composition with excellent heat resistance, moisture resistance, adhesiveness, etc., and a laminate that can be suitably used as a printed wiring board, etc. It is possible to provide the following.

[Conventional technology and its problems]

Epoxy resin laminates have excellent electrical properties, mechanical properties, etc., and are therefore widely used as printed wiring boards.

Dicyandiamide is the mainstream curing agent for these epoxy resins, but it is insufficient in terms of moisture resistance and has problems in heat resistance after moisture absorption.

In order to improve this moisture resistance, it is known to use a phenol novolak resin as a hardening agent, but this has the disadvantage that its use is limited due to its reduced adhesion to copper foil.

[Means for solving problems]

As a result of intensive studies to solve the above-mentioned problems, the present invention has been developed by using an epoxy resin composition that uses dicyclopentadiene phenolic polymer as a curing agent, thereby improving heat resistance, moisture resistance, and copper foil adhesion. It was discovered that a laminate with improved properties could be obtained, and the work was completed based on this knowledge.

That is, in the present invention, the following general formula (1
This is an epoxy resin composition containing 0.05 to 1.5 equivalents of a dicyclopentadiene phenolic polymer represented by the following formula as a phenolic hydroxyl group, and optionally using a curing accelerator.

General formula (1): (R in the formula is hydrogen or a lower alkyl group, n is O-
It is a positive number of 10. ) Hereinafter, the configuration of the present invention will be explained.

The epoxy resin of the present invention is not particularly limited, but specifically includes bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolak epoxy resin, halogenated bisphenol A based epoxy resin,
These include halogenated bisphenol F-based epoxy resins, halogenated phenol novolac-based epoxy resins, polyglycol-based epoxy resins, alicyclic epoxy resins, etc., and these may be used alone or in combination of two or more. Among these, bisphenol A-based epoxy resins, phenol novolak-type epoxy resins, and halogenated bisphenol A-based epoxy resins are particularly preferred.

The dicyclopentadiene phenolic polymer of the present invention is represented by the above general formula (1). The amount used is usually 0.05 to 1.5 equivalents, preferably 0.2 to 1.5 equivalents of the phenolic hydroxyl group of the dicyclopentadiene phenolic polymer, relative to the engineering equivalent of the epoxy resin.
It is in the range of 1 equivalent. If the amount is less than 0.1 equivalent, the improvement in adhesion is insufficient;

If the amount exceeds the equivalent amount, methylene chloride resistance tends to decrease, which is not preferable. As a commercially available dicyclopentadiene phenolic polymer, one in which R in formula (1) is a methyl group is manufactured by Sanyo Kokusaku Pulp ■, product name: DC400
There is.

Examples of the curing accelerator of the present invention include tertiary amines such as benzyldimethylamine and dimethylaminomethylphenol, and imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole. Examples include modified products of these imidazoles with acrylonitrile, trimellitic acid, dicyandiamide, etc., quaternary ammonium salts, quaternary phosphonium compounds, etc., which may be used alone or in combination as appropriate.
Among these, tertiary amines, imidazoles, and modified imidazoles are particularly preferred. The amount used is O0 old to 3.0% of the resin component, preferably 0.1 to 0.5%.
is within the range of

The composition of the present invention has the above-mentioned components as essential components, but may also contain other known phenol novolac resins, talesol novolac resins, bisphenol novolak resins, hisphenols, halogenated bisphenols, dicyandiamide, etc. Various additives such as curing agents, curing accelerators or curing catalysts, known diluents, fillers, pigments, flame retardants, etc. can be used in combination.

The epoxy resin composition of the present invention is prepared using the above components. The mixing method is not particularly limited and may be any known method.

In addition, when manufacturing laminates, etc., varnish is usually prepared and applied to glass cloth, glass nonwoven fabric, glass mat, etc.
Impregnated into a base material for laminates such as glass paper, and heated to temperature 1.
00 to 200°C, preferably 120 to 160°C, heat-dry it to B-stage to obtain a prepreg, use one or more sheets of the prepreg, and if desired, overlay a metal foil, especially an electrolytic copper foil on the surface, and adjust the temperature. 100~200℃,
Preferably 150-180°C, pressure 5-100 kg/
ctl+, preferably 0.2-3 at 20-70 kg/-
A laminate is formed by time lamination molding. The varnish may be prepared by any conventional method, but it may be prepared using epoxy resin or dicyclopentadiene phenolic polymer. A method of dissolving and mixing in a container and then mixing other additives and a curing accelerator is preferred.

〔Example〕

The present invention will be explained below with reference to Examples. Note that parts and percentages in Examples and the like are based on weight.

Example-1 Bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy ■, trade name: Epicoat 1001, epoxy equivalent: 4
50~soo > ioo part and dicyclopentadiene
Phenolic polymer (manufactured by Yamama Kokusaku Pulp Jun, product name;
DC400, hydroxyl equivalent 200-220'') were dissolved and mixed in acetone (epoxy group: hydroxyl M=1
:1) Then, 0.2 part of benzyldimethylamine was mixed therein as a curing accelerator to prepare a varnish.

This varnish was impregnated into a 0.18 vm thick glass woven fabric treated with epoxy silane and dried at 150°C for 6 minutes to prepare a prepreg with a resin content of 40%.
Copper foil with a thickness of 18 mm is layered on both sides, and the temperature is 170.
℃ and a pressure of 50 kg/cd for 2 hours to obtain a double-sided copper-clad laminate having a thickness of 1.6 fl.

The properties of the obtained laminate are shown in Table 1.

Comparative Example-1 In Example-1, 4 parts of dicyandiamide was substituted with N,N-
The procedure was the same except that a solution dissolved in dimethyformamide solution was used.

The properties of the obtained laminate are shown in Table 1.

Example-2 100 parts of brominated bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy ■, trade name: Epicoat 1045, epoxy M450-500), 35 parts of the same dicyclopentadiene phenolic polymer as in Example-1 were dissolved and mixed in acetone (epoxy group: hydroxyl group -1:0.7
9) After that, 0.2 part of 2-ethyl-4-methylimidazole was added and mixed as a curing accelerator to prepare a varnish.

This varnish was impregnated into the same glass woven fabric as in Example-1,
A prepreg with a resin content of 43% was prepared by drying at 140°C for 8 minutes.
layered with copper foil, temperature 160'C1 pressure 80kg/ci
Lamination molding was carried out for 3 hours to obtain a double-sided copper-clad laminate having a thickness of 1.6 mm.

The properties of the obtained laminate are shown in Table 1.

Comparative Example-2 In Example-2, 17.7 parts of a phenol novolak resin was used instead of the dicyclopentadiene phenolic polymer to prepare a varnish for a laminate (epoxy group:
Hydroxyl group = 1:0.79) The other conditions were the same.

The properties of the obtained laminate are shown in Table 1.

Example-3 90 parts of brominated bisphenol A-type epoxy resin similar to Example-2, phenol novolak-type epoxy resin (manufactured by Yuka Shell Epoxy ■, trade name: Epicote 15)
4. Epoxy equivalent 176-181) 10 parts, Example-
31 parts of dicyclopentadiene phenolic polymer similar to 1 and 20 parts of tetrabromobisphenol A
were dissolved and mixed in acetone (epoxy group: hydroxyl group = 1
:0.9) and then added 2-ethyl-4 as a curing accelerator.
-0.5 part of methylimidazole was added and mixed to prepare a varnish.

This varnish was impregnated into a 0.1-thick glass woven fabric treated with cationic silane and dried at 160''C for 5 minutes to prepare a prepreg with a resin content of 45%.

Thickness 1. Layer three sheets of this prepreg on both sides of the OR inner layer wiring board, and then layer 18-thick electrolytic copper foil.
Lamination molding was carried out under conditions of a temperature of 180° C. and a pressure of 20 kg/cni for 1 hour to obtain a multilayer printed board with a thickness of 1.6 fins.

The properties of the obtained multilayer printed board are shown in Table 1.

[Operation and effect of the invention]

As described above, the epoxy resin composition of the present invention has moisture resistance,
It has excellent heat resistance, good adhesion to copper foil, and good resistance to methylene chloride, making it possible to manufacture these excellent laminates, which are suitable for use as printed wiring boards. be.

Claims (1)

[Claims] Epoxy resin 1 having two or more epoxy groups in the molecule
An epoxy compound containing 0.05 to 1.5 equivalents of dicyclopentadiene phenolic polymer represented by the following general formula (1) as a phenolic hydroxyl group, and using a curing accelerator as necessary. Resin composition. General formula (1): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R in the formula is hydrogen or a lower alkyl group, and n is 0 to
It is a positive number of 10. )