JPS6246574B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to epoxy resin compositions for laminates.

Conventionally, various curing agents and accelerators have been known for use in epoxy resin compositions for laminates.
Each has its advantages and disadvantages.

For example, dicyandiamide, although the most widely used, is not sufficient for applications where the produced laminates require a high degree of heat, moisture, and solvent resistance. When acid anhydrides are used, the coated paper fabric in particular tends to absorb moisture, impairing moldability during lamination molding and deteriorating the performance of the laminated product. When aromatic polyamines are used, originally excellent performance can be obtained, but it is difficult to obtain resin compositions and coated paper fabrics that have an appropriate reaction rate and a reasonably long pot life in the manufacturing process of laminate products. Furthermore, even when an aromatic polyamine is used as a curing agent, the curing reaction can be accelerated by using a Lewis acid such as a boron trifluoride-amine complex or an imidazole as an accelerator. It has the disadvantage of becoming yellowish brown and having poor solvent resistance.

The present invention eliminates the above-mentioned drawbacks, has excellent heat resistance,
A low-molecular-weight phenol resin condensate is added and blended into an epoxy resin composition for laminates that uses an aromatic polyamine as a curing agent, with the aim of providing a laminate product that has moisture resistance and solvent resistance. It is.

In the present invention, the low-molecular phenol resin condensate promotes the reaction between the epoxy resin and the aromatic polyamine, so aromatic polyamines, which conventionally could not be used due to slow curing and difficulty in coating and molding, can be used in appropriate amounts. By adding the low molecular weight phenol resin condensate, the reaction rate can be adjusted to an appropriate level, and the excellent electrical insulation, heat resistance, and moisture resistance inherent to the aromatic polyamine-cured epoxy resin composition can be ensured.

In addition, since the low-molecular-weight phenol resin condensate does not promote the reaction between the epoxy resin and the aromatic polyamine at room temperature, there is no risk of shortening the pot life of the compounded varnish and coated paper fabric.

In addition, conventional epoxy resin laminates inherently have poor solvent resistance, which often causes deterioration of the board in the printed wiring board manufacturing process that uses organic solvents, particularly methylene chloride. Laminated products using epoxy resin compositions are
Since it contains a phenolic resin with excellent solvent resistance, the above-mentioned problems are solved.

The aromatic polyamine used in the present invention is
These include diaminodiphenylmethane, tetrachlorodiaminodiphenylmethane, diethyldiaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl ether, and phenylenediamine.

Next, the present invention will be explained by examples.

Add 2 moles of 37% formalin and 1 mole of barium hydroxide to 1 mole of phenol, react at 80°C for 3 hours, neutralize the reaction product with 20% dilute sulfuric acid, remove the neutralized salt, and dilute with methanol to a concentration of 50%. % to prepare a low molecular weight phenol resin condensate.

Next, after dissolving 75 parts of epoxy resin Epicoat #1001 (manufactured by Ciel Chemical Co., Ltd.) in 75 parts of methyl ethyl ketone, 16 parts of the above-mentioned low-molecular-weight phenol resin condensate varnish and 12 parts of tetrachlorodiaminodiphenylmethane were added to the solution. A coating varnish (hereinafter referred to as the varnish of the present invention) was prepared by mixing.

The gelation time of the varnish of the present invention is 3 minutes at 160℃50
It was hot in seconds.

For comparison, a varnish was prepared in which only Epicote #1001, methyl ethyl ketone, and tetrachlorodiaminodiphenylmethane were mixed at the above blending ratio without adding any low-molecular-weight phenol resin condensate.
The gelation time measured at 160℃ was 18 minutes.
It was hot in 30 seconds. In addition, the varnish of the present invention was heated at 25°C.
When the gelation time and viscosity were measured after being left for 100 hours, almost no change was observed compared to immediately after blending.

A non-alkali plain woven glass cloth having a thickness of 0.18 mm was impregnated with the varnish of the present invention and dried at 130° C. for 10 minutes to obtain a coated cloth having a resin content of 35% by weight. Nine plies of this coated fabric and an electrodeposited copper box with a thickness of 35 microns were stacked and heated and pressed for 60 minutes at a temperature of 170°C and a pressure of 60 kg/cm ² to produce a 1.6 m/m thick copper-clad laminate (hereinafter referred to as "bond"). An invention laminate) was obtained. The obtained laminate of the present invention
It was immersed in methylene chloride kept at 40°C for 5 minutes and its appearance was examined, but no abnormalities were observed. Note that when a laminate to which no low-molecular-weight phenol resin condensate was added was immersed in methylene chloride under the same conditions as above, significant surface roughness occurred.

As described above, the epoxy resin composition for laminates of the present invention can eliminate the conventional drawbacks and provide laminates with excellent characteristics, and its industrial value is extremely large.

Claims (1)

[Claims] 1. An epoxy resin composition for laminated products, which is obtained by blending a low-molecular-weight phenol resin condensate into an epoxy resin composition containing an aromatic polyamine as a curing agent.