JPS6298793A - Epoxy resin compound for printed circuit substrate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an epoxy resin composition for printed wiring boards that has excellent heat resistance, heat discoloration resistance, adhesiveness, etc., and is suitable for use as printed wiring boards, etc. The present invention provides a laminate plate that can be suitably used.

[Conventional technology and its problems]

The goals of electronic equipment design are to achieve miniaturization, high reliability, and low cost through high-density wiring, and printed wiring boards have also been improved and developed to meet these demands.

When laminates are manufactured using epoxy resin and phenol novolac resin, which is inexpensively manufactured, as a curing agent to reduce costs, the electrical performance is very good, but there are problems with heat resistance, heat discoloration resistance, and copper foil adhesion. It had the disadvantage of being inferior in quality.

[Means for solving problems]

The present invention was developed as a result of various intensive studies on the drawbacks that occur when laminates are manufactured using the above-mentioned phenolic novolac resin as a curing agent for epoxy resin, and in particular on improving copper foil adhesion. Heat resistance when used in combination with a hardening agent.
It was discovered that copper foil adhesion could be improved without impairing moisture resistance, etc., and the product was completed based on this knowledge.

That is, the present invention provides a synchropentadiene phenolic polymer represented by the following general formula (1) of 0.1 to 0.8 epoxy, novolak, per equivalent of an epoxy resin having two or more epoxy groups in the molecule. This is an epoxy resin composition for printed wiring boards, which contains 0.1 to 1.1 equivalents of resin and a curing accelerator.

General formula (1): (R in the formula is hydrogen or a lower alkyl group, n is 0-
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, halogenated bisphenol A-based epoxy resins, and halogenated phenol novolac-type epoxy resins are particularly preferred.

The synchropentadiene phenolic polymer of the present invention is represented by the above general formula (1), and is used in the following amount per equivalent of the epoxy resin.

The phenolic hydroxyl group of the synchropentadiene phenolic polymer is usually 0.1 to 0.8 equivalent, preferably 0.
．． It is in the range of 2 to 0.5 equivalents. If the amount is less than 0.1 equivalent, the improvement in adhesion is insufficient, and if it exceeds 0.8 equivalent, the resistance to methylene chloride tends to decrease, which is not preferable. Further, as a commercially available synchropentadiene phenolic polymer, one in which R in formula (1) is a methyl group is manufactured by Yamaba Kokusaku Pulp 0 Kiku, product name: DC400.

Examples of the novolak resin of the present invention include phenol novolak resin, talesol novolak resin, and bisphenol novolak resin, which may be used alone or as a mixture. Among these, phenol novolac resins and bisphenol novolak resins are particularly preferred.

The amount of phenolic hydroxyl group in the novolak resin used is usually 0.1 to 1.1 equivalents, preferably 0.3 to 0.8 equivalents, per equivalent of epoxy resin. 0.1
If the amount is less than the equivalent, methylene chloride resistance tends to decrease.
If the amount exceeds 1.1 equivalent, adhesiveness tends to decrease, which is not preferable.

In addition, the total amount used for the epoxy resin such as synchropentadiene phenolic polymer and novolak resin explained above is 0.5 to 1 equivalent of epoxy group.
It is preferably in the range of 1.5 equivalents, particularly 0.7 to 1.1 equivalents.

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 trimellitic acid, dicyandiamide, etc., quaternary ammonium salts, quaternary phosphonium compounds, etc., which may be used alone or in combination as appropriate, but among these, tertiary amines Particularly preferred are imidazoles, imidazoles, and modified imidazoles. The amount used is 0.01 to 3.0 of the resin component.
%, preferably in the range of 0.1-0.5%.

The composition of the present invention has the above-mentioned components as essential components, but if desired, it may further contain various additives such as other curing accelerators or curing catalysts, known diluents, fillers, pigments, and flame retardants. Can be used together.

A normal fest is prepared using the above ingredients, and this is impregnated into a base material for a laminate such as glass cloth, glass nonwoven fabric, glass mat, glass paper, etc. at a temperature of 100 to 200°C.
B-sta is preferably heated and dried at 120 to 1 dO°C.
ge to produce a prepreg, use one or more sheets of the prepreg, layer a metal foil, especially an electrolytic copper foil on the surface if desired, and heat at a temperature of 100 to 200°C, preferably 150°C.
~180℃, pressure 5~100kg/c+yf,
A laminate is preferably formed by lamination molding at 20 to 70 kg/clTl for 0.2 to 3 hours.

Although the varnish may be prepared by any conventional method, it is particularly preferable to dissolve and mix an epoxy resin, a synchropentadiene phenolic polymer, a novolak resin, etc. in a solvent, and then mix a curing accelerator.

〔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 (Yuka Shell Epoxy Japan Co., Ltd., trade name: Epicote 1001, epoxy equivalent: 45
0-500) 100 parts, dicyclopentadiene phenolic polymer (Yamaba Kokusaku Pulp Wa Seibu, product name, DC
400, hydroxyl equivalent: 200-220) and 22 parts of phenol novolac resin (manufactured by Meisho Kasei, product name: ++-i,
After dissolving and mixing 11 parts of hydroxyl group equivalent (104 to 108) in acetone (epoxy group: hydroxyl group = Co, 99), 0.0% of benzyldimethylamine was added as a curing accelerator.
Two parts were added and mixed to form a varnish.

This varnish was impregnated into a 0.18 mm 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%. Layer the foil and heat to 170℃
, pressure 50kg/cn? Lamination molding was carried out for 2 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-1 In Example-1, the dicyclopentadiene phenolic polymer was not used, and 22 parts of phenol novolak resin was used instead (epoxy group: hydroxyl group = i:o,
99) The rest was exactly the same.

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

Example-2 Brominated bisphenol A-type epoxy resin (oiled shell epoxy G1), trade name: Epicoat 1045, epoxy equivalent 450-500) 100 parts, synchropentadiene phenolic polymer similar to Example-1
14 parts and 13 parts of the same phenol novolak resin as in Example-1 were dissolved and mixed in acetone (epoxy group: hydroxyl group = 1:0.9), and then 2-ethyl-4-methylimidazole 0 was added as a curing accelerator. .2 parts were added and mixed to make a varnish.

This varnish was impregnated into a glass woven fabric similar to Example 1 (!) and dried at 140°C for 8 minutes to prepare a prepreg with a resin content of 43%.
Layer 8ρ copper foil, temperature 160℃, pressure 80kg/c
n? Laminated molding was carried out under the conditions of 3 hours, and the plate thickness was 1. A double-sided copper-clad laminate of Omm was obtained.

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

Ratio 1 Example-2 In Example-2, the phenol novolac resin was not used to prepare the varnish for the laminate, but 40 parts of dicyclopentadiene phenolic polymer was used (epoxy group: hydroxyl group = 1:0.9). The same was true.

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 epoxy resin (
Made by Yuka Shell Epoxy Gl, trade name: Epicoat 15
4. Epoxy equivalent 176-181) 10 parts, Example-
Dicyclopentadiene phenolic polymer similar to 1
10 parts, bisphenol A novolak resin (manufactured by Ciba Geigy, product name: XD4049, hydroxyl equivalent: 120
~130) 14 parts and tetrabromobisphenol A
After dissolving and mixing 20 parts in acetone (epoxy group: hydroxyl group = 1 + 0.95), 2-
A varnish was prepared by adding and mixing 0.5 part of ethyl-4-methylimidazole.

This varnish was treated with cationic silane to a thickness of 0.1 m.
A prepreg with a resin content of 45% was prepared by impregnating a glass woven fabric with the resin and drying it at 160° C. for 5 minutes.

Three sheets of this prepreg were stacked on each side of a 1.0 mm thick inner layer wiring board, and then an 18 uw thick electrolytic copper foil was layered, and lamination molding was performed at a temperature of 180°C and a pressure of 20 kg/c+rf for 1 hour. A multilayer printed board with a thickness of 1.6 mm was obtained.

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 for printed wiring boards of the present invention has excellent moisture resistance and heat resistance, and has excellent adhesive strength with copper foil.
The methylene chloride resistance is also good, and these excellent laminates can be manufactured, and the laminates are suitably used as printed wiring boards.

Patent applicant: Mitsubishi Gas Chemical Co., Ltd.

Claims (1)

[Claims] For 1 equivalent of epoxy resin having two or more epoxy groups in the molecule, 0.1 to 0.8 equivalents of synchropentadiene phenolic polymer represented by the following general formula (1), 0.1 to 1 equivalent of novolak resin An epoxy resin composition for printed wiring boards, which contains .1 equivalent and a curing accelerator.