JPS61246050A - Manufacture of laminated sheet - Google Patents

Abstract

PURPOSE:To enable to fully display both the characteristics of 1,2-polybutadiene and of epoxy resin by a method wherein specified glass non-woven fabric, which is impregnated with 1,2-polybutadiene and dried and cured to the C-stage and, after that, further impregnated with epoxy resin and dried and cured to the B-stage, is partially or wholly molded laminated to each other. CONSTITUTION:Firstly, glass non-woven fabric is impregnated with 1,2- polybutadiene and dried and cured to the C-stage and, after that, further impreg nated with epoxy resin and dried and cured to the B-stage so as to obtain glass non-woven fabric prepreg, the weight ratio of 1,2-polybutadiene to epoxy resin is 10/90-95/5. The resultant prepregs are partially or wholly molded laminated in order to obtain the titled laminated sheet. Normally used epoxy resin is employed as said epoxy resin. Modified 1,2-polybutadiene, the end group of which is modified to hydroxyl group, epoxy group, carboxyl group or the like, is preferable. Radical polymerization agent is used for curing 1,2- polybutadiene. Normally used amine compound, acid compound, phenol resin or the like is used for curing epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing a laminate having excellent high frequency characteristics and good adhesive strength.

Conventional technology In order to reduce the size and weight of electronic equipment and increase the frequency of electronic devices such as those exemplified by IJN, the laminates used for -11JN wiring boards have high heat resistance, interlayer adhesion strength, and copper foil peeling strength. There is a demand for a material with improved hardness and a low dielectric constant. In order to satisfy the high frequency characteristics, 1.2 polybutadiene is used, but the interlayer adhesion and copper foil adhesion strength are weak and it is not practical. On the other hand, commonly used epoxy resins have excellent heat resistance, interlayer adhesion strength, and copper foil adhesion strength, but have a high rate of rust, making them unsuitable for high-frequency printed wiring boards.

Problems that the invention seeks to solve Conventionally, it has been difficult to simultaneously satisfy heat resistance, interlayer adhesion strength, copper foil adhesion strength, and high frequency characteristics. Means for Solving the Problems In order to achieve the above objects, the present invention impregnates a glass nonwoven fabric base material with 1,2-polybutadiene, and after drying, hardens it in a C stage. Thereafter, an epoxy resin is impregnated and dried and cured to the B stage, and a glass nonwoven fabric prepreg with a weight ratio of 1.2 polybutadiene/epoxy resin of 10/90 to 9515 is laminated and molded as part or all of it. Function In the present invention, by using 1.2 polybutadiene and epoxy resin in combination, the characteristics of both can be exhibited to obtain a laminate with excellent high frequency characteristics, heat resistance, and adhesive strength. However, what is important here is to advance the curing of the 1,2-polybutadiene that has been impregnated into the glass nonwoven fabric substrate and dried to the C stage. This prevents 1,2-polybutadiene from seeping into the epoxy resin as it melts and hardens when the glass nonwoven fabric prepreg is partially or completely laminated. It can be demonstrated to the fullest. If the glass nonwoven fabric I is impregnated with dried 1,2-polybutadiene and cured only to the B stage, the 1,2-polybutadiene will seep into the epoxy resin during lamination molding, and the heat resistance of the molded laminate will deteriorate. and adhesive strength decreases.

It is also possible to impregnate and dry a glass nonwoven fabric base material with a varnish made of a mixture of 1,2-polybutadiene and epoxy resin to produce a glass nonwoven fabric prepreg, but the compatibility of both resins is poor when made into a varnish. The cured product is also too soft to be used practically. Regarding the resin in the glass nonwoven fabric prepreg, if the weight ratio of 1,2-polybutadiene is less than 10% by weight, the dielectric constant of the WtW4 plate becomes high, and the present invention cannot achieve its purpose. On the other hand, when 1,2-polybutadiene exceeds 95% by weight, the dielectric constant becomes low, but the adhesive strength decreases, and the copper foil peel strength and interlayer adhesive strength become weak.

EXAMPLE The epoxy resin used in the present invention is a commonly used one, and the 1,2-polybutadiene may have its terminal group modified to a hydroxyl group, epoxy group, carboxyl group, etc. However, if a large amount of modified material is included, the dielectric constant becomes high, which is not desirable. 1.2-
To cure polybutadiene, radical polymerizing agents (e.g., dicrugol oxide, benzoyl peroxide, etc.) are used, and for curing of epoxy resins, commonly used avanized adducts, oxidized adducts, and phenols are used. Use resin etc.

The Geras nonwoven fabric base material used in the present invention is preferably one using a thermosetting or thermoplastic resin binder or a cellulose fiber binder, but is not particularly limited.

Next, the present invention will be explained in detail.

Examples 1 to 3 100 parts by weight (hereinafter simply referred to as "parts") of 1.2-polybutadiene (product name B-1000, manufactured by Japan W) and 3.5 parts of diqueous rubber oxide were dissolved in toluene to determine the solid content. A varnish containing 40% heavy feed was prepared (varnishe).

A varnish was prepared by dissolving 100 parts of an epoxy resin (Epoxy #500, trade name Epicote 1001, manufactured by Shell Chemical) in dimethyl ethyl ketone (Varnish ■).

Glass non-woven fabric (75t/W?) was impregnated with varnish I, dried and cured to C stage, and then varnish ■ was impregnated and dried and cured to B stage, resulting in a total resin amount of 891% by weight.
A glass nonwoven fabric prepreg was obtained. Stack 4 sheets of prepreg and cover both sides with 35μ thick copper foil! Pressure 3
1. Heat and pressurize at 5 Kq/d and 170°C for 60 minutes.
2? III! A double-sided copper-clad laminate of 1 thickness was obtained.

The weight ratio of 1,2-polybutadiene in the resin in the glass nonwoven prepreg is 80% by weight in Example 1, 50% by weight in Example 2, and 20% by weight in Example 3. Table 1 shows the properties of the laminates of each example.

Comparative Example 1 A double-sided steel-clad laminate with a thickness of 1.2 was obtained in the same manner as in the above Example except that the weight ratio of the epoxy resin was 0. Its characteristics are shown in Table 1.

Comparative Example 2 A double-sided copper-clad laminate with a thickness of 1,2 mm was obtained by changing the amount of 1,2-polybutadiene to O in the same manner as in the above example, and keeping the other conditions the same. Its characteristics are shown in Table 1.

Example 4 Glass cloth was impregnated with varnish (2) to a resin content of 40% by weight on both sides of the glass nonwoven fabric Presoreg in Example 2, and one glass cloth Presoreg was placed on each side. Place a 35μ thick copper foil and apply pressure 35)Cw/i
The product was heated and pressed at a temperature of 170° C. for 60 minutes to obtain a double-sided copper-clad laminate with a thickness of 1°6. Its properties are shown in Table 2.

Comparative Example 3 A double-sided copper-clad laminate with a thickness of 146 mm was obtained in the same manner as in Example 4 using four sheets of glass non-woven fabric prepregs in Comparative Example. Shown in the table.

Comparative Example 4 '4M A 35μ thick copper foil was placed on both sides of the 8 sheets of glass cloth prepreg used in Example 4, and heated and pressed at a pressure of 35 Kq/crA and a temperature of 170°C for 60 minutes to form 1.6M thick both sides. Copper-clad 1) A laminate was obtained. Its properties are shown in Table 2.

Between the glass cloth! 〇 Comparative Example 5 Indicates adhesive strength 〇Comparative Example 5 In a glass nonwoven fabric prepreg having the same weight ratio of 1.2-polybutadiene as in Example 2, the degree of curing of 1,2-polybutadiene impregnated into a lath nonwoven fabric and dried was set as the B stage. value 15%) Others are the same as in Example 2 (strain 1
．． Double-sided steel-clad laminate with a thickness of 2 mm? Obtained. Its characteristics are shown in Table 1.

Effects of the Invention As described above, the present invention is a method of laminating partially or entirely glass nonwoven fabrics obtained by impregnating and drying 1,2-polybutadiene and curing it to the C stage, then impregnating it with epoxy resin, drying it, and curing it to the B stage. By compacting 1), 1.
The characteristics of both 2-polybutadiene and epoxy resin can be fully exhibited. This makes it possible to obtain a laminate with excellent high frequency properties, heat resistance, and adhesive strength, and its industrial value is extremely great.

Claims (1)

[Claims] 1. A glass nonwoven fabric base material is impregnated with 1,2-polybutadiene, dried and cured to the C stage, and then impregnated with an epoxy resin, dried and cured to the B stage, to form a 1,2-polybutadiene/epoxy resin. The weight ratio of 10/90 to 95
1. A method for manufacturing a laminate, characterized in that part or all of glass nonwoven fabric prepreg having a particle size of 1.5 or 1.5 is laminated and molded. 2. The method for manufacturing a laminate according to claim 1, characterized in that laminated molding is carried out using a glass nonwoven fabric prepreg as a core layer and epoxy resin-impregnated glass fabric prepregs arranged on both surfaces.