JPH0678472B2 - Laminated phenol resin composition - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a phenol resin composition for laminates, which is excellent in low-temperature punching processability, and has good heat resistance and moisture resistance.

[Technical Background of the Invention and Problems Thereof] Recent developments in electronic devices are remarkable and diversified, and as a result, various strict conditions are imposed on component materials. Currently, the properties required for paper base material-phenolic resin copper-clad laminates are mainly low-temperature punching workability, dimensional stability (including warpage, etc.) against heat during processing or moisture absorption during storage, heating and This is because there is little change in electrical characteristics due to moisture absorption. In order to satisfy these requirements, various modifications have been made to phenolic resins, and one of them is epoxy modification to improve heat resistance and moisture resistance.
In consideration of flame resistance, epoxy modification is mainly brominated epoxy resin modification.

However, although the epoxy-modified phenolic resin has an effect on heat resistance and moisture resistance, it has an adverse effect on another required property, that is, low-temperature punching workability,
There was a drawback that the punching temperature did not drop.

[Object of the Invention] The present invention has been made in view of the above-mentioned drawbacks, and an object thereof is a laminate having excellent low-temperature punching processability and having excellent heat resistance, moisture resistance and other various properties of an epoxy-modified phenol. It is intended to provide a phenolic resin composition for a board.

[Summary of the Invention] As a result of intensive studies to achieve the above-mentioned object, the present inventor conducted plasticization of an epoxy-modified phenol resin by using an epoxy ester compound of a brominated bisphenol A type epoxy resin and a fatty acid. As a result, the inventors have found a resin composition which is excellent in low-temperature punching workability and has good characteristics such as heat resistance and moisture resistance, and has completed the present invention.

That is, in the present invention, the brominated bisphenol A type epoxy resin (a) and the fatty acid (b) are added to (a) epoxy group /
(B) A phenol resin composition for laminates, which comprises an epoxy ester compound obtained by reaction in an equivalent ratio of carboxylic acid groups of 1 to 5.

Examples of the brominated bisphenol A type epoxy resin (a) used in the present invention include YDB400T-60 (manufactured by Tohto Kasei Co., Ltd.,
Trade name), Epicron 153 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) and the like. These may be used alone or in admixture of two or more.

Examples of the fatty acid (b) used in the present invention include coconut oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, dehydrated castor oil fatty acid, dimer acid thereof, and the like. These may be used alone or in combination of two or more. To use.

The above-mentioned brominated bisphenol A type epoxy resin (a)
The fatty acid (b) is reacted with the epoxy ester compound to obtain an epoxy ester compound, and the reaction is carried out in an equivalent ratio [(a) epoxy group / (b carboxylic acid group)] of 1 to 5. When the equivalence ratio is less than 1.0, that is, when unreacted fatty acid is present, heat resistance and moisture resistance are poor, and when the equivalence ratio exceeds 5, the glass transition temperature Tg of the resin is low.
And the low temperature punching workability is inferior. It is preferably in the range of 1-2. The reaction between brominated bisphenol A type epoxy resin and fatty acid is 200
It is carried out at a temperature of up to 240 ° C., and an epoxy ester compound can be obtained with an acid value of 5 or less as the end point.

The epoxy ester compound used in the present invention is used as a part of a flame retardant for a phenol resin composition. Further, as the phenol resin component of the phenol resin composition, an oil-modified phenol resin, a melamine-modified phenol resin, or the like used in a paper-phenol laminate is used.

The phenolic resin composition for a laminated plate of the present invention contains a phenolic resin, an epoxy ester compound, a flame retardant, etc., but other additives can be added if necessary and within the range not impairing the effects of the present invention. .

[Examples of the Invention] Next, the present invention will be specifically described with reference to Examples.

Example [Resin Production Example 1] Benzoguanamine 187 was placed in a four-necked flask equipped with a condenser.
g, phenol 113 g, and 37% formalin 349 g were charged, and after monoethylamine was added to adjust the pH to 6, the mixture was heated to 90 ° C. with stirring and reacted for 4 hours. Then dehydrated under reduced pressure and diluted with methanol to give a resin solid content of 55% by weight and a viscosity of 1.
A uniform melamine-modified phenol resin solution (A) having 5 poise (25 ° C.) and gelation time of 2 minutes and 40 seconds (150 ° C.) was produced.

[Resin Production Example 2] A four-necked flask with a condenser was charged with 250 g of phenol, 340 g of cresol, 300 g of nonylphenol, 350 g of tung oil, 720 g of 37% formalin, and monomethylamine was added to adjust the pH.
After adjusting to = 6, the mixture was reacted at 100 ° C for 3 hours. Then, it was dehydrated under reduced pressure and dissolved in a mixed solvent of toluene / methanol = 7/3, and the resin solid content was 55% by weight and the viscosity was 2.3 poise (25
C.) and a gelation time of 2 minutes and 10 seconds (150.degree. C.) to prepare an oil-modified phenolic resin solution (B).

[Resin Production Example 3] 250 g of phenol, 340 g of cresol, 300 g of nonylphenol, and 72% formalin 72 in a four-necked flask with a condenser.
After charging 0 g and adjusting the pH to 6 by adding monomethylamine, the mixture was reacted at 100 ° C. for 3 hours. Then, it was dehydrated under reduced pressure and dissolved in a toluene / methanol = 7/3 mixed solvent to give a modified phenol resin solution (C having a resin solid content of 55% by weight, a viscosity of 1.9 poise (25 ° C) and a gelation time of 2 minutes (150 ° C). ) Was manufactured.

[Manufacture of Epoxy Ester Compound] In a four-necked flask with a condenser, brominated bisphenol A type epoxy resin YDB400 T60 (manufactured by Toto Kasei Co., trade name epoxy equivalent 400) 666 g, and coconut oil fatty acid (molecular weight 2
17) 195 g was charged and reacted at 220 ° C. under reflux of xylene until the acid value became 0 to produce an epoxy ester compound (I).

A phenol resin composition solution for a laminated board was produced according to the composition shown in Table 1.

Comparative Example A phenolic resin composition solution for laminated plate was produced according to the composition shown in Table 1.

The resin solutions obtained in the examples and comparative examples were impregnated and applied to 10 mils kraft paper to prepare a processed paper having a resin impregnation amount of 50% by weight and a resin flow of 8%. Next, 8 sheets of this processed paper and 35 μm copper foil with adhesive were overlapped and heat-pressed at 170 ° C. and 100 kg / cm ² for 75 minutes to produce a copper-clad laminate having a thickness of 1.6 mm.
The copper clad laminate was tested for water absorption, insulation resistance, flame retardancy, and punching workability. The results are shown in Table 1, and the present invention is excellent in low-temperature punching workability, has the same water absorption rate, insulation resistance, and flame retardancy as conventional ones, and the effect of the present invention was confirmed.

[Effects of the Invention] In the present invention, an epoxy ester compound obtained by reacting a brominated bisphenol A type epoxy resin with a fatty acid is blended in a phenol resin composition and the resin is plasticized. It is a phenol resin composition for laminates which is excellent in heat resistance and moisture resistance. By using the copper clad laminate of the composition of the present invention, it is possible to obtain a highly reliable electronic device or the like that sufficiently satisfies strict requirements.

Claims (1)

[Claims] 1. A brominated bisphenol A type epoxy resin (a) and a fatty acid (b), (a) epoxy group / (b)
A phenolic resin composition for a laminated board, which comprises an epoxy ester compound obtained by reaction in an equivalent ratio of carboxylic acid groups of 1 to 5.