JPS6253323A - Production of epoxy resin laminated board - Google Patents

Abstract

PURPOSE:To obtain a laminated board, having improved heat resistance and suitable for copper-clad laminated boards, multilayered printed circuit boards, etc., by adding and reacting a specific organic compound with a specific polyfunctional epoxy resin, reacting the resultant reaction product with an epoxy resin, impregnating a base material with the resultant reaction product and hot-pressing the formed laminate. CONSTITUTION:(A) An organic compound having >=2 functional groups reactive with epoxy groups, e.g. dihydroxyphenyl compound, in excess is added and reacted with (A) a polyfunctional epoxy resin having >=3 epoxy groups in one molecule as a nucleus, e.g. o-cresol novolak type epoxy resin, and (C) an epoxy resin having >=2 epoxy groups, e.g. diglycidyl ether bisphenol A type epoxy resin, is then reacted with the resultant reaction product to give a resin. a curing agent is then incorporated with a curing agent to afford a varnish and a base material is impregnated with the varnish, laminated and hot-pressed to afford the aimed laminated board. 5-30pts.wt. component (A) is preferably used for 100pts.wt. epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing epoxy resin laminates used in electrical P2JR material laminates, copper attack laminates, and multiplex printed wiring boards.

(Prior Art) Epoxy anti-grease laminates are widely used in the fields of electricity and electronics, and these laminates cause problems such as blistering and peeling during the heating and cooling process that occurs during the processing process.

In order to solve these problems such as peeling and peeling, diglycidyl ether and sphenol A type epoxy resins are modified using polyfunctional epoxy resins such as novolac type epoxy resins.

(The problem that the invention seeks to solve) However, although this can improve the problem to some extent, the effect is not sufficient.

The present invention provides a method for manufacturing an epoxy resin laminate having excellent heat resistance.

(Means for solving all problems) The present invention uses a polyfunctional epoxy resin having six or more epoxy groups in one molecule as a core, and an organic compound having two functional groups that react with the epoxy groups is added in excess. After reacting in the presence of a catalyst to produce a radial copolymer, the chain length is extended using an epoxy resin having at least two epoxy groups, and the copolymer is reacted with the unreacted organic compound to have an epoxy group at the end. This method of producing an epoxy resin laminate is characterized by impregnating a base material with a varnish obtained by producing a resin and blending a curing side with an FC resin, and then heating and pressing the required number of sheets.

As the polyfunctional epoxy resin, epoxy resins such as orthocresol novolak epoxy and phenol novolac epoxy are preferred. In addition, tetrahydroxyphenylethane tetracrysyl ether, trihydroxyphenylmethane triglydyl ether, resorcinol novolac type epoxy 84nt, glycerin triglycidyl ether, tetraglycidyldiacinodiphenylmethane, triglycidyl isocyanurate, and the like may also be used.

The epoxy equivalent of the polyfunctional epoxy resin is preferably 150 to 500, preferably 180 to 250;
Heat resistance can be improved by using 5 to 60 parts per 0 parts (the same applies below 1 part).

The organic compound used to obtain the radial copolymer has two groups at both ends that react with epoxy groups, such as OH groups, NH groups, and COOH groups, and is used in excess.

For example, bisphenol A, bisphenol F1 tetrabromobisphenol A russorcin, maleic acid and its anhydride, phthalic acid and its anhydride, etc. are used. Dihydroxydiphenyl compounds are preferred. The organic compound is added in an amount of 2 to 5 equivalents, preferably 3 equivalents, to 1 equivalent of the polyfunctional epoxy resin.

As the reaction catalyst for obtaining the copolymer, 2ethyl 4
Imidazoles such as methylimidazole and 2-phenylimidazole, benzyldimethylamine, and 6th class amines such as 2.4.6 tris(dimethylaminomethyl)phenol are used, and 0.1- to 100 parts of epoxy resin is used.
1 boiling reaction is carried out. The reaction is carried out at 50 to 200°C for 60 minutes to 5 hours. The reaction may be carried out in a solution.

The epoxy resin used for chain length extension and reaction of unreacted organic compounds is preferably a diglycidyl ether and suphenol A type epoxy resin with an epoxy equivalent of 17.
A value of 0 to 1000, preferably 180 to 200 is good.

The reaction is carried out at a temperature of 50 to 200°C for 60 minutes to 5 hours.

As the curing agent, an amine type curing agent such as dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, or 0-phenylenediamine is used, and the amount thereof used is preferably 0.5 to 1.0 equivalent to the epoxy resin.

As the organic solvent, acetone, methyl ethyl ketone, toluene, xylene, dimethyl formamide, methyl cellosolve, etc. are used, and the concentration of the epoxy resin is preferably 40 to 80%.

Paper, glass cloth or glass paper serving as a base material is impregnated with the varnish for epoxy resin laminates according to the present invention, and
Dry for α5 to 30 minutes in a drying device at a temperature of 200°C,
A semi-cured epoxy resin prepreg is manufactured.

Pressure 10-100kg / using manufactured prepreg
arp, heat and press at a temperature of 150 to 180°C for 60 to 180 minutes to produce a laminate.

(Function) After studying the heat resistance of epoxy resin laminates, we found that the reason why the heat resistance of conventional epoxy resin laminates is not that of light is due to the curing speed of the polyfunctional epoxy resin and diglycidyl ether bisphenol A type epoxy resin used for modification. It is thought that this is because a non-uniform cured product is formed due to the difference in the temperature. In the present invention, in order to obtain a uniformly cured product, a multifunctional epoxy resin with a fast curing speed is incorporated into the molecular chain in advance.
It is believed that the heat resistance of the laminate can be improved by making the surface roughness 6 uniform during the curing process.

Example Multifunctional epoxy resin was prepared by dissolving 100 parts of ESCN220F (Sumiman Kagaku (Ceramics product name: Epoxy "Ht218)" in 25M of methyl ethyl ketone to create Fireguard #20.
Add 300 parts of Tetrabromobisphenol A (trade name manufactured by Teijin Kasei), add 1 or 2 parts of 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Toki), and heat the mixture at 60℃ for 2 hours.
After reacting for a period of time, R-140P (trade name of bisphenol A type epoxy resin manufactured by Mitsui Petrochemical Co., Ltd.)'fr: 600 parts As a yaturing agent, 50 parts of dicyandiamide was dissolved and added to 600 parts of dimethylformamide to prepare a varnish. This varnish was impregnated into a base glass cloth (manufactured by Nitto Boseki Co., Ltd., product name 18W, treated with epoxy silane), and a prepreg with a resin content of 38 to 42% was dried at 150°C for 3 minutes. Pressure 40kg/al11 heating temperature 16
A copper-clad laminate having a thickness of 1.6 nm was produced at 5° C. and for a heating time of 120 minutes.

This copper clad lamination/all etching removed from 11 plates of steel 50X
A 50mm test piece was prepared and pressure cutter treated (
(in water vapor at 121°C) and then soldering heat resistance test (in water vapor at 260°C).
0 second immersion).

Further, the test pieces of 50×100 mra were subjected to boiling treatment (immersion at 260° C. for 20 seconds) at intervals of 6 spaces in the width direction of the test pieces from which the copper foil had been completely etched, and the occurrence of searing was observed. The results are shown in the attached table.

Comparative Example As an epoxy resin, 90 parts of Araldite 8011 (product name manufactured by Nippon Ciba Geigy) and 10 parts of ESCN220F (orthocresol novolac epoxy resin, product name manufactured by Sumitomo Chemical ■) were dissolved in 25 parts of methyl ethyl ketone, and 3 parts of dicyandiamide was added. dimethylformamide 6
Add 2 ether/4 methylimidazole (
A varnish was prepared by adding 2 parts of α2 parts of Shikoku Kasei@). Copper-clad FFI laminates were manufactured in the same manner as in the examples using the varnish prepared by Tokumaki, and their properties are shown in the attached table.

Note) Heat resistance evaluation ○ No abnormality × Measling or fukn occurrence Measling occurrence status ○ No abnormality △ Some measling × Significant measling (Effect of the invention) Epoxy with excellent heat resistance according to the present invention Resin laminates can be manufactured.

Claims (1)

[Claims] 1. An organic compound having two functional groups that react with epoxy groups is added in excess to a polyfunctional epoxy resin having three or more epoxy groups in one molecule, and then two or more functional groups are reacted. A method for producing an epoxy resin laminate, which comprises impregnating a base material with an epoxy resin obtained by adding and reacting an epoxy resin having an epoxy group, and then stacking the required number of sheets and heating and pressurizing them. 2. The method for producing an epoxy resin laminate according to claim 1, wherein the polyfunctional epoxy resin is an orthocresol novolak epoxy resin. 3. The method for producing an epoxy resin laminate according to claim 1, wherein the organic compound reacted with the polyfunctional epoxy resin is a dihydroxydiphenyl compound.