JPS63312832A - Copper-clad epoxy resin laminate - Google Patents

Abstract

PURPOSE:To obtain copper-clad epoxy resin laminate having excellent moisture resistance, solder heat resistance, warpage characteristic and punching workability by employing bisphenols and tertiary amine is bisphenol epoxy resin. CONSTITUTION:A paper cloth base material is coated and impregnated with a resin composition which contains an indispensable ingredients bisphenol epoxy resin, bisphenols represented by a formula, tertiary amine to form a prepreg. The material is coated and impregnated with the composition, and dried. Then, prepregs made of glass base materials are superposed on front and rear faces of the prepreg using a plurality of the paper base materials, heated, press- laminated and integrated. Thus, a copper-clad epoxy resin laminate having good moisture resistance, solder heat resistance, warpage characteristic and punching workability can be obtained.

Description

[Detailed description of the invention] [Object of the invention] (Industrial application field) The present invention provides an epoxy resin with excellent moisture resistance and punching workability.
! Regarding Hiroshi laminates.

(Conventional technology) With the development of various industries in recent years, excellent performance has been required for electronic and electrical component materials, structural materials, and mechanical component materials. Superior performance is now required. That is,
There is a desire for a material that has excellent electrical insulation, mechanical strength, moisture resistance, water resistance, heat resistance, etc., and is inexpensive.

One such synthetic resin laminate is paper epoxy copper clad laminate (NEMA), which is a paper base material impregnated with epoxy resin and molded.
There are standard PR-3), paper/glass composite base epoxy copper clad laminates (NEMA standard CEM-1), etc., but these copper clad laminates have punched holes in order to reduce product cost. This is often done using a press, so excellent punching workability is required. Conventionally, in order to improve punching workability, it has been achieved by adding a small amount of flexibility imparting agent to the epoxy resin composition to plasticize it and reduce the shear path force.

However, most of the flexibility-imparting agents are aliphatic, such as polyglycol-type glycidyl ether, epoxidized vegetable oil, and polyolefin-type epoxy resin, so the moisture resistance of the cured product is poor, and the base material is Coupled with the fact that the paper easily absorbs moisture, @ tension laminates had problems such as blistering caused by soldering when absorbing moisture and poor warping characteristics when absorbing moisture.

(Problems to be Solved by the Invention) The present invention has been made to solve the above-mentioned problems. The purpose of the present invention is to provide an epoxy resin-based 'vA laminate.

[Structure of the Invention] (Means for Solving the Problems) In order to achieve the above object, the present inventor has conducted intensive research and found that an aromatic bifunctional hardener is added to bisphenol-type epoxy resin. The present invention has been completed based on the discovery that the above object can be achieved by using bisphenols, which are chemical compounds, in combination with tertiary amines, which are curing accelerators. That is, the present invention uses a prepreg obtained by impregnating and drying a paper fabric base material with a resin composition containing (A) a bisphenol-type epoxy resin, (B) a specific bisphenol, and (C) a tertiary amine as essential components. This is an epoxy resin copper-clad laminate that is characterized by the fact that:

The (A,) bisphenol type epoxy resin used in the present invention is preferably an epoxy resin using bisphenol as a starting material and having an epoxy equivalent of 1000 or less.
If the epoxy equivalent exceeds 1000, the viscosity of the face increases, impregnating the paper fabric substrate becomes poor, and the moisture resistance of the copper-clad laminate decreases, which is not preferable. As a specific epoxy resin, for example, Epicoat 1001. Epicote 82
Bisphenol A-type epoxy resins such as 8 (manufactured by Yuka Shell Co., Ltd., trade name), YD-7011 (manufactured by Tobu Kasei Co., Ltd., trade name), bisphenol F-type epoxy resins such as Ebicuron 830 (manufactured by Dainippon Ink & Chemicals, trade name), etc. Epoxy resin, YDB-
400 (manufactured by Tobu Kasei Co., Ltd., trade name), Araldite 801
Examples include brominated bisphenol A type epoxy resins such as No. 1 (trade name, manufactured by Ciba Geigy), which may be used alone or as a mixture of 2'8 or more.

The bisphenols represented by the general formula (B) used in the present invention (wherein X represents a hydrogen atom, a bromine atom, or a chlorine atom, and R represents a carbon atom, a sulfur atom, a group, an ethyl group, or an oxygen atom) include: Examples include bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A, which may be used alone or as a mixture of two or more. It is desirable to use a novolac type phenol resin in combination with bisphenols.The mixing ratio of the novolac type phenol resin is within the range of 5 to 5 hydroxyl groups of the bisphenols: hydroxyl group equivalent of the novolak type phenol resin = 90:10 to 30 nia0. If the equivalent ratio of the novolac type phenolic resin exceeds 70%, it will be less effective in improving the punching workability of the copper-clad laminate by reducing the shear path force, which is the objective of the present invention, and if the equivalent ratio is less than 10%. This is undesirable because it tends to impair other properties such as a decrease in mechanical properties and electrical properties.Also, the ratio of the hydroxyl groups of the novolac type phenol resin and bisphenols to the epoxy equivalent is 0.4 to 1.
．． 6. Examples of the tertiary amine (C) used in the present invention include benzyldimethylamine, triethanolamine, tridimethylaminomethylphenol, and various imidazoles. Use alone or as a mixture of two or more. The blending ratio of the tertiary amine is preferably 0.03 to 0.5 parts by weight per 100 parts by weight of the bisphenol-type epoxy resin, bisphenols, and other components. If it is less than 0.03 parts by weight, the reaction will take a long time and the soldering heat resistance will be poor, and if it exceeds 0.5 parts by weight, the pot life of the resin composition 'f/lJ (varnish) will be short and the workability will be affected. Less desirable.

The resin composition used in the present invention contains a bisphenol-type epoxy resin, bisphenols, and tertiary amine as essential components, but other components may be added as necessary, as long as it does not contradict the purpose of the present invention.

The above-mentioned components are dissolved in an organic solvent such as acetone to form a varnish. This varnish is applied and impregnated onto a paper fabric base material by an appropriate method such as a dipping method, a dipping squeeze method, a squeezing method, a contact method, etc. to prepare a prepreg. The amount of resin attached to the prepreg is preferably 30 to 70% by weight. Paper fabric base materials used for the prepreg include linter paper, kraft paper, mixed paper thereof, glass cloth, glass paper, glass nonwoven fabric, etc. It can be selected and used as appropriate. A resin composition is coated and impregnated onto a paper fabric base material, and then dried. The f&fl is cut to the appropriate size, and in the case of NEMA standard PR-3, prepare prepreg made of multiple sheets of paper base material only, and in case of OEM-1, glass is used on the front and back of prepreg that uses multiple sheets of paper base material. A copper-clad laminate can be manufactured by stacking prepregs made of base materials and integrating them by heating and pressurizing lamination molding.

The epoxy resin copper-clad laminate manufactured in this way is
It can be widely used in electrical equipment, etc.

(Function) In the present invention, by using a bisphenol type epoxy resin and bisphenols, the bisphenol epoxy resin and bisphenols react in a linear manner, which imparts flexibility to the resin composition. Furthermore, since the bisphenol type epoxy resin and bisphenols are aromatic compounds, the cured product has good water resistance and moisture resistance. Furthermore, when bisphenols are dissolved in a solvent, it becomes a solution with an extremely low viscosity of several seven micropores, so it is estimated that it contributes to the viscosity of the entire varnish, improves impregnation into the base material, and contributes to improved hygroscopicity. be done.

(Examples) Next, the present invention will be specifically explained by examples, but the present invention is not limited to these examples.
In the following examples and comparative examples, "parts" means "parts by weight."

Example I YDB-400 (manufactured by Tobu Kasei Co., Ltd., epoxy resin brand name)
400 parts (1 equivalent), 100 parts of bisphenol A<0.
88 equivalents) and 20 parts of MP-120 (manufactured by Gunei Kagaku Co., Ltd., novolak type phenolic resin trade name) (0.1 g equivalent)
and 0.3 part of benzyldimethylamine and acetone were added thereto to prepare an epoxy resin varnish.
Using this varnish, impregnate linter paper with a weight of 130 g/12 pre-impregnated with 5% by weight of water-soluble phenolic resin.
Dry at 50°C to prepare prepreg (A) with a resin content of 60% by weight.
), 8 sheets of this prepreg (A) were stacked on one side with a 35 μm thick copper foil, heated at 170°C.
After heating and pressing at 70K (1/C12) for 70 minutes and cooling, an epoxy resin copper-clad laminate with a thickness of 1.6U was manufactured.

This copper-clad laminate was tested for punching workability, water absorption, soldering heat resistance, and warping, and the results are shown in Table 1.
The remarkable effects of the present invention were confirmed.

Example 2 Epicote 1001 (manufactured by Yuka Shell Co., Ltd., epoxy resin trade name) 500 parts (1 equivalent Jl), tetrabromobisphenol A 200 parts (0.74 per unit) and MP-120 (
20 parts (0.1 g equivalent) of 2-
An epoxy resin varnish was prepared by adding 0.35 parts of ethyl-4-methylimidazole and acetone. Using this varnish, a prepreg and an epoxy resin copper-clad laminate were manufactured in the same manner as in Example 1. In addition, similar tests were conducted on the properties of the fibers, and the results are shown in Table 1. The remarkable effects of the present invention were confirmed.

Example 3 Using the epoxy resin varnish prepared in Example 1, a 0.181 m thick crow cloth was coated and impregnated and dried at 150°C to produce a prepreg (B) with a resin content of 50% by weight. A) 6 sheets are stacked, prepreg (B) is stacked on the front and back sides, and a thickness of 35 μm is added on one side.
170℃, 70kQ/CIm
A composite-type copper-clad laminate was manufactured by heating and press-forming for 70 minutes.

This copper-clad laminate was subjected to the same tests as in Example 1, and the results are shown in Table 1. The remarkable effects of the present invention were confirmed.

Comparative Example 1 An epoxy resin varnish was prepared by dissolving Epicote 1001 (100 parts above) and 30 parts of het acid anhydride in acetone. Using this varnish, a prepreg was made in the same manner as in Example 1, and then an epoxy resin copper-clad laminate was manufactured. This copper-clad laminate was subjected to the same tests as in Example 1, and the results are shown in Table 1.

Comparative Example 2 65 parts of YDB-400 (mentioned above), polyglycol type glycidyl ether (170Cl/OQ per epoxy)
) and 80 parts of methylnadic acid were dissolved in acetone to prepare an epoxy resin varnish. Using this varnish, prepregs and epoxy resin copper-clad laminates were manufactured in the same manner as in Example 1, and the same tests as in Example 1 were conducted, and the results are shown in Table 1.

Comparative Example 3 Using the varnish prepared in Comparative Example 2, prepreg and composite type copper-clad laminates were manufactured in the same manner as in Example 3. This copper i5! The same tests as in Example 1 were conducted on the laminate, and the results are shown in Table 1.

[Effects of the Invention] As is clear from the above explanation and Table 1, the epoxy resin copper-clad laminate of the present invention has excellent moisture resistance, so there is less sagging or warping after soldering when moisture is absorbed. Moreover, it has good punching workability and is useful in practice.

Claims (1)

[Claims] 1 (A) Bisphenol type epoxy resin (B) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X is a hydrogen atom, bromine atom or chlorine atom, R is a carbon atom, a sulfur atom or ▲Mathematical formulas, chemical formulas, tables, etc.▼, R^1 represents a hydrogen atom, methyl group, ethyl group, or oxygen atom) Resin composition containing bisphenols and (c) tertiary amine as essential components An epoxy resin copper-clad laminate characterized by having an insulating part formed from a prepreg obtained by impregnating and drying a paper fabric base material. 2. The prepreg is composed of a plurality of sheets of prepreg prepared by impregnating a paper base material with a resin composition and drying it, and a prepreg prepared by impregnating a glass base material with a resin composition and drying it on the front and back sides thereof.Claim 1 Epoxy resin copper-clad laminate described in Section 1.