JPS6220913B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy resin copper-clad laminate for industrial equipment, electronic parts, and electrical equipment, and its objects are heat resistance, high adhesion to copper foil,
The object of the present invention is to obtain a copper-clad laminate with excellent adhesion between high-rise layers. Conventionally, epoxy resin copper-clad laminates for industrial equipment, electronic parts, and electrical equipment are used by adding amine curing agents such as dicyandiamide and diaminodichlorodiphenylmethane to the epoxy resin.
Adhesion with copper foil and interlayer adhesion are good, but the glass transition temperature is low at 130 to 160°C, so the heat generated during drilling during multilayer printed circuit board manufacturing softens the epoxy resin, causing the inner layer copper foil inside the drill hole to soften. When bonding an LSI to a board, the board softens due to heat and pressure, making it impossible to obtain a highly reliable connection. Furthermore, when a tetrabasic acid anhydride curing agent is added to the epoxy resin, the glass transition temperature is as high as 190° C. or higher, but the adhesiveness to copper foil and interlayer adhesion are low. The present invention aims to improve the above drawbacks, and uses a reaction product of bisphenol F diglycidyl ether and 4,4' dihydroxydiphenyl sulfone (hereinafter simply referred to as bisphenol S) as a resin for laminates. (2.5 dioxotetrahydrofuryl)
By adding and using 3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride (hereinafter simply referred to as MCTC), an epoxy resin copper-clad laminate with excellent heat resistance, high adhesion to copper foil, and high interlayer adhesion is obtained. I was able to do that. Next, the present invention will be explained in detail. The base material for the laminate used in the present invention is woven fabric, nonwoven fabric, matte, paper, etc. made of inorganic fibers such as glass and asbestos, organic synthetic fibers such as polyester, polyamide, polyvinyl alcohol, and acrylic, and natural fibers such as cotton. General base materials for laminates, such as combination base materials.
The copper foil is not particularly limited, and copper foils used for copper foil laminates are generally used. As a resin for laminates, we use a reaction product of bisphenol F diglycidyl ether and bisphenol S.
It is used with the addition of MCTC. Bisphenol F diglycidyl ether has a low glass transition temperature but high adhesiveness, Bisphenol S has low adhesiveness but good heat resistance, and MCTC takes advantage of the properties of a high thermal decomposition initiation temperature to combine the above three components. This makes it possible to obtain an epoxy resin varnish having excellent properties such as high glass transition temperature, high adhesiveness, and high thermal decomposition onset temperature. Bisphenol F diglycidyl ether and bisphenol S
The ratio between bisphenol F diglycidyl ether and bisphenol S is not particularly limited, and the reaction product (hereinafter simply referred to as reaction product)
The ratio of MCTC to 1 epoxy equivalent of the reaction product is preferably 0.3 to 1.1, although the ratio is not particularly limited. Further, in order to adjust the curing speed, curing accelerators such as imidazoles, tertiary amines, 1.8 diazabicyclo(5.4.0) undecene, etc. can be added to the epoxy resin varnish of the present invention. The above epoxy resin varnish has good storage stability, and after impregnating the base material for a laminate and laminating dry prepreg, adhesive-coated copper foil is placed on one side or the top and bottom of the laminate, and then heated and laminated. In this way, an epoxy resin copper-clad laminate having a high glass transition temperature, high adhesion to copper foil, and excellent interlayer adhesion is obtained. Alternatively, a laminate can be obtained by removing the adhesive-coated copper foil from the surface of the laminate and performing heating lamination molding. Next, the present invention will be explained based on examples. Example Add 180 g of bisphenol F diglydyl ether with an epoxy equivalent of 178 and 60 g of bisphenol S to a three-necked flask, heat at 170-180°C for 5 hours to obtain a transparent solution, then add 400 g of acetone and MCTC60.
g was added and heated at 65 to 70°C for 50 minutes to obtain a transparent epoxy resin varnish. A plain weave glass cloth with a thickness of 0.1 mm is impregnated with the above epoxy resin varnish to a resin content of 45%, dried to obtain a prepreg, four sheets of this prepreg are laminated, and a thickness is further applied to the top and bottom surfaces of the epoxy resin varnish.
A laminate with one 0.035mm adhesive-coated copper foil placed on each was sandwiched between metal mold plates and molded under a molding pressure of 20Kg/
cm ² and laminate molded at 190° C. for 180 minutes to obtain a double-sided copper-clad epoxy resin laminate. Comparative Example 1 250 g of bisphenol A type epoxy resin with an epoxy equivalent of 185 and 150 g of MCTC in a three-necked flask.
was added and heated at 170 to 175° C. for 30 minutes, cooled, and then 400 g of acetone was added to obtain an epoxy resin varnish. The same procedure as in Example was repeated to obtain a double-sided copper-clad epoxy resin laminate. Comparative Example 2 5.4 g of dicyandiamide and 2 ethyl 4
A double-sided copper-clad epoxy resin laminate was obtained in the same manner as in the example except that 0.54 g of methylimidazole was added to obtain an epoxy resin varnish. The performance of the double-sided copper-clad epoxy resin laminates of Examples and Comparative Examples 1 and 2 is shown in Table 1. The laminates of the present invention have better heat resistance, better adhesion to copper foil, and better interlayer adhesion than those of the present invention. The superiority of epoxy resin copper-clad laminates was confirmed. 【table】

Claims (1)

[Claims] 1. In a copper-clad laminate made by impregnating a laminate base material with a laminate resin and heating and laminating dry prepreg and copper foil, bisphenol F diglycidyl ether and 4,4 are used as the laminate resin. ’5 for reaction products with dihydroxydiphenyl sulfone.
(2.5 dioxotetrahydrofuryl) 3 methyl 3 cyclohexene 1.2 An epoxy resin copper-clad laminate characterized in that it is used with the addition of dicarboxylic acid anhydride.