JPH0858018A - Laminated sheet - Google Patents

Abstract

PURPOSE: To prevent the generation of static electricity in a single-side copper clad laminated sheet or copper foil free laminated sheet by adding an antistatic agent to a fiber base material and an insulating layer composed of a thermosetting resin. CONSTITUTION: An antistatic agent is added to an insulating layer by a method impregnating a base material with thermosetting resin varnish mixed with the antistatic agent or a method preliminarily applying the antistatic agent to the surface of a release material and diffusing the antistatic agent into a resin from the surface of the release material at the time of the pressing of a prepreg under heating. Further, there is a method preliminarily applying the antistatic agent to the surface of a fiber base material and diffusing the same throughout a resin during molding processing. These methods may be combined. The content of the antistatic agent is pref. 0.01-5wt.% and, in the case of below 0.01%, the effect of antistatic effect is low and, in the case of above 5%, surface resistance is markedly lowered.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate used for a printed wiring board, and more particularly to a single-sided copper clad laminate having a copper foil layer on one side of an insulating layer.

[0002]

2. Description of the Related Art A single-sided copper-clad laminate is a single-sided laminate of one or more prepregs obtained by impregnating a glass fiber base material or a cellulosic fiber base material with a thermosetting resin varnish and drying. Place the copper foil on the other side, and on the other side, place a release film such as a plastic film that does not adhere to the prepreg or a metal foil that does not adhere to the prepreg (aluminum foil, copper foil, etc.). It is manufactured by heating and pressing.

For a thin single-sided copper-clad laminate having a thickness of 0.8 mm or less, a release material is sandwiched between prepregs, copper foils are arranged on both sides, and heat and pressure are applied.
A method of manufacturing two sheets at the same time is also practiced.

[0004]

However, the one-sided copper-clad laminate obtained in this manner has a remarkable occurrence of static electricity, and in particular, the insulating layer is a one-sided copper-clad laminate made of a glass fiber base material and an epoxy resin. When handling laminated plates, the impact of static electricity is transmitted to the hands when handling laminated plates, making it difficult to work.
Further, in order to process the printed board, when one by one is put in the printing line, a plurality of sheets may be put in at the same time because of electrostatic attraction.

The generation of static electricity is most remarkable in the single-sided copper-clad laminate, and is slightly observed in the laminate without copper foil, but it is hardly seen in the double-sided copper-clad laminate. The present invention aims to prevent static electricity from being generated in a single-sided copper-clad laminate or a copper foil-free laminate.

[0006]

The present invention is characterized in that an antistatic agent is contained in an insulating layer composed of a fiber base material and a thermosetting resin.

The thermosetting resin used in the present invention includes phenol resin, epoxy resin, polyimide resin, unsaturated polyester resin, vinyl ester resin, melamine resin, etc. These may be used alone or in combination of two or more kinds. .

If necessary, these known resins include known phosphorus-based and antimony-based flame retardants, clay, talc, aluminum hydroxide, wollastonite, silica, glass powder, magnesium hydroxide, alumina, calcium aluminate, carbonic acid. An inorganic filler such as calcium is added.

The fiber base material used in the present invention is a glass woven fabric using long glass fibers such as E glass, C glass, D glass and S glass, and glass such as E glass, C glass, D glass and S glass. Examples thereof include a glass non-woven fabric in which short fibers are bonded with an organic binder, and a paper base made of cellulosic fibers or organic fibers. These fiber substrates are used alone or in combination such as glass woven fabric and glass nonwoven fabric, or glass woven fabric and paper substrate.

As the antistatic agent, nonionic, anionic, cationic or amphoteric surfactants are used. Among them, anionic alkyl phosphate ester salts, alkyl ether phosphate salts, Alkyl allyl ether phosphate is preferable because of its excellent heat resistance.

Specific compounds include monostearyl phosphate triethanolamine salt, monooleyl phosphate triethanolamine salt, monolauryl phosphate triethanolamine salt, monoacetyl alcohol ethylene oxide phosphate triethanol amine. Examples thereof include amine salts and monononylphenol ethylene oxide phosphoric acid ester triethanolamine salts, which can be used alone or in combination of two or more kinds.

As a method of incorporating an antistatic agent into the insulating layer, a method of mixing the antistatic agent with a thermosetting resin varnish to impregnate the base material, or applying an antistatic agent to the surface of the release material is used. In addition, when heating and pressing the prepreg, a method of diffusing into the resin from the surface of the release material, a method of applying it to the surface of the fiber base material and diffusing into the resin during the molding process are available. is there. You may use these methods together. The content of the antistatic agent is preferably 0.01 to 5% by weight,
If it is less than 01%, the effect of preventing static electricity is small, and if it exceeds 5%, the surface resistance is remarkably reduced, which is not preferable.

The antistatic agent need not be included in the entire insulating layer. For example, in the case of a single-sided copper-clad laminate, an antistatic agent may be included in the prepreg located on the surface without copper foil.

[0014]

Since the insulating layer contains the antistatic agent, the static electricity generated during handling is easily dissipated and the static electricity is not applied.

[0015]

【Example】

Example 1 Brominated epoxy resin (epoxy equivalent 470 g / eq)
100 parts (weight part the same below), dicyandiamide 3
Parts, 2-ethyl-4-methylimidazole 0.17 parts,
A resin varnish for impregnation was prepared by mixing 25 parts of 2-methoxyethanol, 25 parts of N, N dimethylformamide and 0.3 part of monostearyl phosphate triethanolamine salt.

A glass woven fabric (thickness: 0.2 mm, basis weight: 210 g / m ² ) was impregnated with this so that the resin content was 40% by weight, and dried to obtain a prepreg (this is referred to as prepreg A).
I got

Three prepregs A are superposed, an electrolytic copper foil having a thickness of 35 μm is arranged on one surface, and a thickness of 20 is formed on the other surface.
A release aluminum foil of μm is placed and the temperature is 170
Press-molded at ℃, pressure 4MPa for 30 minutes, thickness 0.6
A single-sided copper clad laminate having a size of mm was obtained.

When 300 sheets of the obtained single-sided copper-clad laminate were transferred one by one by an automatic transfer device, a plurality of sheets were not adsorbed at the same time during transfer, and static electricity was generated during handling. It never happened.

Example 2 Monostearyl phosphate triethanolamine 4 parts was dissolved in 100 parts of methyl ethyl ketone, and a glass woven cloth (thickness 0.2 mm, basis weight 210 g / m ² ) was prepared. The ethanolamine salt was applied and dried so that the amount attached was 0.2% by weight.

Brominated epoxy resin (epoxy equivalent 47
0 g / eq) 100 parts (parts by weight, the same applies hereinafter), 3 parts of dicyandiamide, 0.17 parts of 2-ethyl-4-methylimidazole, 25 parts of 2-methoxyethanol, 25 parts of N, N dimethylformamide are mixed and impregnated. Resin varnish was prepared and impregnated on a glass woven cloth coated with monostearyl phosphate ester triethanolamine salt so that the resin content was 40% by weight and dried to obtain a prepreg (this is referred to as prepreg B). It was

20 μm thick release aluminum foil,
One piece of prepreg A, two pieces of prepreg B, and electrolytic copper foil having a thickness of 35 μm were laminated in this order, and a single-sided copper-clad laminate having a thickness of 0.6 mm was obtained in the same manner as in Example 1.

When 300 sheets of the obtained single-sided copper-clad laminate were transferred one by one by an automatic transfer device, a plurality of sheets were not adsorbed at the same time during transfer and static electricity was generated during handling. It never happened.

Example 3 4 parts of monostearyl phosphate triethanolamine salt was dissolved in 100 parts of methyl ethyl ketone to give a thickness of 20.
An aluminum foil for release having a thickness of μm was coated and dried so that the amount of the monostearyl phosphate ester triethanolamine salt attached was 0.2% by weight.

With the coating surface of the monostearyl phosphate triethanolamine salt facing the prepreg side, a release aluminum foil, prepreg B, thickness 35
The electrolytic copper foils having a thickness of μm were stacked in this order, and a single-sided copper-clad laminate having a thickness of 0.6 mm was obtained in the same manner as in Example 1.

When 300 sheets of the obtained single-sided copper-clad laminate were transferred one by one by an automatic transfer device, a plurality of sheets were not adsorbed at the same time during transfer, and static electricity was generated during handling. It never happened.

Comparative Example Three prepregs B were superposed, an electrolytic copper foil having a thickness of 35 μm was arranged on one surface, and a release aluminum foil having a thickness of 20 μm was arranged on the other surface at a temperature of 170 ° C. Pressure 4MP
It was press molded with a for 30 minutes to obtain a single-sided copper-clad laminate having a thickness of 0.6 mm.

When 300 sheets of the obtained single-sided copper-clad laminate were transferred one by one by an automatic transfer device, a plurality of sheets were simultaneously adsorbed 10 times during the transfer.

[0028]

As the antistatic agent is contained in the insulating layer made of the fiber base material and the thermosetting resin, the static electricity generated during the handling is dissipated without giving an unpleasant impact to the operator. Also, two or more sheets no longer stick to each other due to static electricity.

Claims (2)

[Claims] 1. A laminate comprising an insulating layer made of a fiber base material and a thermosetting resin containing an antistatic agent. 2. A single-sided copper-clad laminate having a copper foil layer on one surface of the insulating layer according to claim 1.