JPH02158338A - Heat resistant copper-plated laminated plate - Google Patents

Abstract

PURPOSE:To obtain a heat resistant copper-plated laminated plate having excellent heat resistance, moisture resistance and moldability by laminating, molding and integrating prepreg formed by impregnating a glass base material with heat resistant resin containing epoxy resin, bis-phenol A novolac resin and dicyandiamide as indispensable components and drying it, and a copper foil. CONSTITUTION:As epoxy resin of component of a heat resistant resin, bis-phenol A novolac epoxy resin is used most desirably. As the bis-phenol A novolac epoxy resin of the other component, the resin obtained by condensing bis-phenol A and aldehyde in the presence of acid catalyst is used to improve safety, drill workability, close contact with a base material, moisture resistance. As dicyandiamide of the component, that normally available in the market is used to improve storage stability of the resin. The components are mixed, an sufficiently mixed to prepare heat resistance resin, which is dissolved in solvent as resin solution. A glass base material is impregnated with the resin solution, and dried to form prepreg. The thus obtained prepreg, and a copper foil are laminated, molded and integrated to manufacture a copper-plated laminated plate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Objective of the Invention (Industrial Application Field) The present invention relates to a heat-resistant copper-clad laminate having excellent heat resistance, moisture resistance, and formability.

(Conventional technology) In the field of printed wiring, as the density of wiring increases, multilayering and
As through holes become smaller in diameter, there is a demand for copper-clad laminates that do not generate smear during drilling and have good drillability. In addition, as industrial equipment such as computers and industrial measuring instruments tend to become smaller and lighter, their wiring boards are becoming smaller than conventional G-10 or F
R-4) Demand for wiring substrates with better heat resistance (higher glass transition temperature) and moisture resistance is increasing.

By the way, the cause of smear is that the resin used in the substrate matrix softens due to the frictional heat during drilling.In order to improve drillability, the glass transition point of the resin must be raised. It is necessary to improve heat resistance. As such copper-clad laminates having good heat resistance, laminates are manufactured using polyimide resin, modified polyimide resin, or the like as a matrix resin.

However, they have the disadvantages of high price and excessive quality, and G-1L, which has good cost performance.
Heat-resistant substrates such as <or FR-5) are increasingly being used.

(Problems to be Solved by the Invention) However, in conventional G-11 (FR-5) etc., aromatic amines and the like are used as curing agents for epoxy resins in order to balance their high heat resistance. This has the disadvantage that it is generally highly toxic and the storage stability of the prepreg is poor.

The present invention was made in view of the above circumstances, and has heat resistance,
The objective is to provide a heat-resistant copper-clad laminate with excellent moisture resistance and moldability (prepreg storage stability).

[Structure of the Invention] (Means for Solving the Problems) As a result of intensive research by the present inventors to achieve the above object, the above object is achieved by using a heat-resistant resin having the composition described below. Having observed this, we have completed the present invention.

That is, the heat-resistant copper-clad laminate of the present invention is a prepreg obtained by impregnating and drying a glass base material with a heat-resistant resin containing (A) an epoxy resin, (B) a bisphenol A novolac resin, and (C) a dicyandiamide as essential components. and silver foil are integrated by lamination molding.

The heat-resistant resin used in the present invention includes (A) epoxy resin, (
B) Bisphenol A novolak resin and (C) dicyandiamide are essential components.

As the heat-resistant resin component (A) epoxy resin,
It has two or more epoxy groups in one molecule, and includes those normally used for laminated boards, but is not particularly limited.

Among these, bisphenol A novolak epoxy resin is most preferably used in terms of the balance of properties. Examples of other epoxy resins include bisphenol A epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, glycidylamine type epoxy resins, heterocyclic epoxy resins, halogenated epoxy resins, etc. Mixing or pre-reaction transfer can be used.

Bisphenol A novolac resin (B), which is another component of the heat-resistant resin, is a resin made by condensing bisphenol A and aldehyde under an acid catalyst, and has a distribution of bisphenol A from monomers to multimers. things are used.
The molecular weight of the bisphenol A novolac resin is preferably about 2 to 5 mer, and if the average molecular weight is too large or too small, the viscosity will be inappropriate and moldability will deteriorate. The blending ratio of the bisphenol A novolak resin is such that the hydroxyl group equivalent is 0.6 to 0.6 to the epoxy group of the above-mentioned epoxy resin.
1.4 is desirable. When the hydroxyl equivalent is less than 0.6 or more than 1.4, heat resistance decreases, which is not preferable.

Dicyandiamide (C), which is a component of the heat-resistant resin, is not particularly limited and may be any commercially available dicyandiamide. Note that dihydrazides also have substantially the same effect as dicyandiamide. The blending ratio of dicyandiamide is preferably 0.001 to 0.2 equivalents to the epoxy resin. If the blending ratio is less than 0.001 equivalent, it will not have any effect on curability, and if it exceeds 0.2 equivalent, the storage stability will be poor, which is undesirable.6 or more components are blended and mixed thoroughly to easily form a heat-resistant resin. You can make it. This heat-resistant resin can be dissolved in an appropriate solvent to form a resin solution, which is then impregnated into a glass substrate and dried to produce a prepreg.

Examples of the glass substrate used in the present invention include glass cloth, glass nonwoven fabric, glass paper, etc., and these can be used alone or in combination of two or more.

The copper foil used in the present invention may be either rolled copper foil or electrolytic copper foil, and is not particularly limited as long as it is commonly used for laminated boards.

A copper-clad laminate can be manufactured by integrally laminating and molding the thus obtained prepreg and silver foil.

(Function) Since the heat-resistant copper-clad laminate of the present invention uses bisphenol A novolac resin as a curing agent for epoxy resin, it is non-toxic and safe, and its transition point increases due to reaction with epoxy resin. As a result, drilling processability is improved and the adhesion between resin and base materials such as glass fibers is improved.
Improves moisture resistance. Furthermore, by using dicyandiamide as a curing agent, the storage stability of the resin is improved.

(Example) Next, the present invention will be specifically explained using examples.

Example 1 Bisphenol A 10 kg, 37% Polmarin 10
kg is reacted under an acidic catalyst and then dehydrated to obtain bisphenol A novolak resin [A].

Bisphenol A novolac type epoxy resin (Epicron N865, trade name manufactured by Dainippon Ink Chemical Co., Ltd.) 70 k
g, brominated bisphenol A type epoxy resin (Evototo YDB400, trade name manufactured by Tobu Kasei Co., Ltd.) 50 k
q, the above bisphenol A novolac resin [A] 35k
g, 0.3 kg of dicyandiamide, 20 kg of methyl cellosolve, and 103 days of methyl ethyl ketone were added to prepare a heat-resistant resin solution (varnish) with a resin content of 60%. Next, 100 parts by weight of this varnish was added with 2-ethyl-
After adding 0.06 part of 4-methylimidazole and applying this varnish to a 0.18 part m thick lath cloth surface-treated with a silane coupling agent, the varnish was dried at a temperature of 160°C until the resin content was 43. % prepreg was made. 8 sheets of this prepreg and 18μ■ silver foil were laminated, and the temperature was 170℃.
C. and a pressure of 40 kg/cm2 for 90 minutes to produce a copper-clad laminate having a thickness of 1.6 mm. This @ tension laminate was tested for silver foil peeling strength, soldering heat resistance at 300° C., measling resistance, water absorption, and prepreg storage stability, and the results are shown in Table 1.

In both cases, the effects of the present invention were confirmed.

The peel strength and soldering heat resistance for silver foil are J r 5C-
6481, Miesling resistance is 121'C, 2a
tllll, 5 hour pressure kicker test (P
CT), floated in a solder bath at 260°C for 30 seconds and examined.
The water absorption rate was determined by measuring the amount of water absorbed after the PCT, and the storage stability of the prepreg was examined by moldability using a prepreg stored at 25° C. for 130 days.

Example 2 Bisphenol A novolac type epoxy resin 8 in the reaction pot
0kg, tetrabromobisphenol A60kg, tetraethylammonium chloride O, OO15tag,
Add 15 kg of toluene and react at 130°C for 5 hours.
Obtain a modified novolac type epoxy resin [B] having an epoxy equivalent of 300 and a bromine content of 20%. This modified novolac type epoxy resin [13] 120k (1, the same bisphenol A novolac resin [A] as in Example 1) 3
5 kq, dicyandiamide 0.3 bg, methyl cellosolve 20 kg, and methyl ethyl ketone 103
kg to prepare a heat-resistant resin solution (varnish) with a resin content of 60%. Thereafter, prepregs and copper-clad laminates were manufactured in the same manner as in Example 1, and their properties were tested in the same manner as in Example 1. The results are shown in Table 1.

The effects of the present invention were clearly demonstrated.

Examples 3 to 4 Prepregs and copper-clad laminates were manufactured in the same manner as in Example 1 with the compositions shown in Table 1, and various properties were tested in the same manner.The results are shown in Table 1.

The effects of the present invention were confirmed.

Comparative Examples 1 to 3 Prepregs and copper-clad laminates were manufactured in the same manner as in Example 1 using the compositions shown in Table 1, and their properties were tested in the same manner. The results are shown in Table 1.

[Effects of the Invention] As is clear from the above explanation and Table 1, the heat-resistant copper-clad laminate of the present invention has excellent heat resistance, moisture resistance, and formability.
It has a good balance of these properties, does not use toxic amines, is safe, has good workability, and is suitable as a highly reliable printed wiring board.

Claims (1)

[Claims] 1. A prepreg obtained by impregnating and drying a glass base material with a heat-resistant resin containing (A) an epoxy resin, (B) a bisphenol A novolac resin, and (C) a dicyandiamide as essential components, and a copper foil. , a heat-resistant copper-clad laminate characterized by integrated lamination molding.