JPS6052948B2 - Epoxy resin copper clad laminate - 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. The object of the present invention is to obtain a copper-clad laminate with excellent adhesive properties.

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, which reduces adhesion to copper foil. Although the interlayer adhesion is good, the glass transition temperature is low at 130-160°C, so the epoxy resin softens due to the heat generated during drilling during the production of multilayer printed circuit boards and adheres to the inner layer copper foil in the drill hole, resulting in smear failure. Furthermore, when connecting an LSI to a substrate by bonding, the substrate 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 with copper foil and interlayer adhesion are low.
The present invention improves the above-mentioned drawbacks, and uses 3 methyl 5 succinyl anhydride 3 cyclohexene 1.
By adding and using a reaction product of dicarboxylic acid anhydride and aromatic diamine, it is possible to obtain an epoxy resin copper-clad laminate with excellent heat resistance, high adhesion to copper foil, and high adhesion between layers. It was made.

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, mat, 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. There are general base materials for laminates, such as combination base materials. The copper foil is not particularly limited, and copper foils used for copper-clad laminates are generally used. As a resin for laminates, the epoxy equivalent is 250~
A reaction product of 3 methyl 5 succinyl anhydride 3 cyclohexene 1.2 dicarboxylic acid anhydride (hereinafter simply referred to as MCTC) shown by the following structural formula and an aromatic diamine shown by the following general formula for 1000 epoxy resin was prepared. It is used by adding it. Structural formula (MCTC) General formula (aliphatic diamine) NH2-R-NH2 However, R is represented by a group such as 1-('''' ゛)1.

The reason why an epoxy resin having an epoxy equivalent of 250 to 1000 is used in the present invention is extremely important in order to obtain high adhesion to copper foil and interlayer adhesion. If the epoxy resin has an epoxy equivalent of less than 250, the adhesion to copper foil and interlayer adhesion will decrease, and if the epoxy equivalent exceeds 1000, the melt viscosity of the resin will be extremely high, making it difficult to use the resin for laminates as a substrate for laminates. When a prepreg is created by impregnating the material and drying it, the volatilization of the solvent is inhibited, causing a foaming phenomenon in the prepreg, which causes lipoid defects in which air bubbles are difficult to escape from the laminate during lamination molding. Epoxy resins include glycidyl ether of bisphenol A, glycidyl ether of halogenated bisphenol A, reaction product of glycidyl ether of bisphenol A and bisphenol S (4,4 dihydroxydiphenyl sulfone), glycidyl amine type, etc. Either a glycidyl-based epoxy resin or a non-glycidyl-based epoxy resin such as a cyclohexene derivative type alicyclic resin can be used. MCTC used in the present invention has excellent heat resistance and a high melting point of 168 to 16 CfC, so it does not volatilize when drying the prepreg, has high solubility in the diluent acetone, and has relatively slow reactivity, so it can be used for storage of epoxy resin varnish. Although it has good stability, it has poor adhesion to copper foil and interlayer adhesion, so MCTC and aromatic diamine are reacted to form an acid anhydride with a large molecular weight, and then added to the epoxy resin. It has improved heat resistance, adhesion to copper foil, and interlayer adhesion. Although the ratio of MCTC and aromatic diamidan is not particularly limited, it is preferable that the amount of aromatic diamine is 0.025 to 0.5 mol per mol of MCTCl. That is, the amount of aromatic diamine is 0.
This is because if the amount is less than 0.025 mol, it is difficult to improve the adhesion with the copper foil and the interlayer adhesion, and if it exceeds 0.5 mol, the heat resistance tends to decrease. The reaction between MCTC and aromatic diamine is preferably carried out in a solvent such as acetone.
This is because if the reaction is carried out without a solvent, partial gelation tends to occur and it tends to be difficult to form a transparent epoxy resin varnish. A method for adding the reaction product of MCTC and aromatic diamine to the epoxy resin may be to add an epoxy resin pre-diluted with a solvent to the reaction product of MCTC and aromatic diamine containing a solvent. The reaction product containing the above-mentioned solvent may be added to the epoxy resin diluted with a solvent. This epoxy resin varnish has good storage stability, and after impregnating the base material for a laminate and laminating dry prepreg, copper foil with adhesive 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. Further, by removing the adhesive-coated copper foil from the surface of the laminate, a laminate can be obtained by heat lamination molding. Furthermore, 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. Incidentally, the epoxy resin varnish of the present invention can also be used in paints and adhesives. Next, the present invention will be explained based on examples. Example 1 Put 160y of acetone, 14.4" diamino 3.3" and 7.9y of dimethyldiphenylmethane into a Mitsuro flask and heat at 600C for 15 minutes.
Heated for 1 minute to obtain a clear solution, then MCTC56. ly
was added and heated again at 60°C to obtain a clear solution.

A liquid epoxy resin 297' in which 80q of bisphenol A type epoxy resin having an epoxy equivalent of 300 was previously dissolved in 20y of methyl ethyl ketone was added to this reaction product, and the mixture was further heated at 55 to 70°C for 6 minutes to form a transparent epoxy resin varnish. Obtained. The above epoxy resin varnish was impregnated into a plain woven glass cloth with a thickness of 0.1 wm so that the resin content was 45%.
Dry to obtain a prepreg, laminate four sheets of this prepreg, and place one sheet each of adhesive-coated copper foil with a thickness of 0.03577171 on the top and bottom surfaces.The laminate is sandwiched between metal plates for a mold and molded. A double-sided copper-clad epoxy resin laminate was obtained by laminating 18 powder at a pressure of 20k9/Cltll90°C. Example 2 A double-sided copper-clad epoxy resin laminate was obtained in the same manner as in Example 1, except that 16.95 y of 4.4"diamino-3.3" dimethyldiphenylmethane was used.

Example 3 Acetone 150y 14.4" Diamino 3.3" Dichlorodiphenylmethane 9.8y A double-sided copper-clad epoxy resin was prepared in the same manner as in Example 1 except that a bisphenol A type epoxy resin with an epoxy equivalent of 950 was used. A laminate was obtained.

Comparative Example 1 4.4″ Diamino 3.3″ Dichlorodiphenylmethane 2
Dissolve 9.4 g in 230 g of methyl ethyl ketone, and add bisphenol A with an epoxy equivalent of 475 to the solution.
Preliminary mold epoxy resin 80y with methyl ethyl ketone 20y
A double-sided copper-clad epoxy resin laminate was obtained in the same manner as in Example 1, except that an epoxy resin varnish containing liquid epoxy resin 2979 dissolved in g was used.

Comparative Example 2 5 liters of MCTCl was placed in a Mitsuro flask. 6y and epoxy
Add bisphenol A type epoxy resin with an amount of 185
Heat 3 powders at 70-180℃, cool and add 400y of acetone
A double-sided copper-clad epoxy resin laminate was obtained in the same manner as in Example 1, except that an epoxy resin varnish was obtained by dissolving the epoxy resin.

The performance of the double-sided copper-clad epoxy resin laminates of Examples 1 to 3 and Comparative Examples 1 and 2 is shown in Table 1. The laminates of the present invention have good heat resistance, good adhesion to copper foil, and interlayer adhesion. It was confirmed that the epoxy resin copper-clad laminate of the present invention is superior.

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, the epoxy equivalent of the laminate resin is 250. ~1000
An epoxy resin copper-clad laminate, characterized in that a reaction product of 3 methyl 5 succinyl anhydride 3 cyclohexene 1.2 dicarboxylic anhydride and an aromatic diamine is added to the epoxy resin. 2 3 methyl 5 succinyl anhydride 3 cyclohexene 1.2
The epoxy resin copper-clad laminate according to claim 1, wherein the amount of aromatic diamine is 0.025 to 0.5 mol per mol of dicarboxylic acid anhydride.