JPH07110901B2 - Phenolic resin composition for laminated board - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention is capable of reducing the coefficient of thermal expansion in the plate thickness direction and is highly reliable for through-holes. Regarding

(Prior Art) Conventionally, as a material of a wiring board in consumer equipment, paper-
Phenolic copper clad laminates are widely used. This copper-clad laminate has a large coefficient of thermal expansion of 3.5 to 4.5% in the plate thickness direction,
Expansion during soldering causes cracks at the hole corners of through-hole plating, resulting in low connection reliability.
Not used for double-sided through holes. Therefore, for the through-hole processing of the double-sided plate, a glass-epoxy copper clad laminate having a small coefficient of thermal expansion of 1.0 to 2.0% is used, which results in high cost of the double-sided plate.

(Problems to be Solved by the Invention) The present invention has been made in view of the above circumstances, has a small coefficient of thermal expansion in the plate thickness direction, has no cracks at the corners of through holes, and has high through hole reliability. It is intended to provide a phenolic resin composition for a laminated board.

[Structure of the Invention] (Means for Solving the Problems) The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, the composition described below has a small coefficient of thermal expansion and cracks at the corners of through holes. The present invention has been completed by finding that a copper clad laminate having no through holes and high reliability of through holes can be obtained.

That is, the present invention is (However, m and n represent 0 or an integer of 1 to 3, and m + n
= 3), a (B) phenols, (C) melamines, and (D) formaldehydes as essential components. And it is a phenol resin composition for laminated boards which contains phosphoric acid ester in a ratio of 20 to 40% by weight with respect to the entire resin composition.

The (A) phosphate ester used in the present invention may be any one having the following general formula.

However, m and n are 0 or an integer of 1 to 3, and m + n = 3.

As a specific compound And the like. These may be used alone or in admixture of two or more.

It is desirable that the phosphoric acid ester is contained in an amount of 20 to 40% by weight based on the total resin composition. This percentage
If it is less than 20% by weight, sufficient heat resistance cannot be obtained, and if it exceeds 40% by weight, electrical characteristics and through hole reliability are deteriorated, which is not preferable. This phosphoric acid ester has the characteristics that it has a small coefficient of thermal expansion and has good compatibility with the phenol resin.

Examples of the (B) phenols used in the present invention include phenol, cresol, xylenol, butylphenol, nonylphenol and the like, and all phenols usually used for laminates are included. These phenols are used alone or in combination of two or more.

Examples of (C) melamines used in the present invention include melamine,
Examples thereof include benzoguanamine, acetoguanamine, formguanamine, and the like, and all of those usually used for laminates are included. These melamines may be used alone or in admixture of two or more.

Examples of (D) formaldehyde used in the present invention include formalin and paraformaldehyde, which may be used alone or in admixture of two or more.

The phenolic resin composition for a laminated plate of the present invention is obtained by reacting essential components such as phosphoric acid ester, phenols, melamines and formaldehydes, but the reaction order of each component is not particularly limited. Usually, it is desirable to make a phenol resin composition for laminated boards by reacting phenols, melamines, and formaldehydes and then adding phosphoric acid ester. The resin composition thus obtained is dissolved and diluted in an organic solvent to form a varnish, and the varnish is impregnated into a paper base material such as kraft paper and dried to form a prepreg. Then, a laminated board can be manufactured.

(Function) By using a liquid phosphoric acid ester, which is the constituent component of the laminated plate and which is most involved in the coefficient of thermal expansion, with a small coefficient of thermal expansion and a good compatibility with the phenol resin, the compatibility with the resin is good, It was possible to obtain a resin composition having a small coefficient of thermal expansion.

(Examples) Next, examples of the present invention will be specifically described, but the present invention is not limited to these examples.

Example 1 To a four-necked flask equipped with a condenser, 126 g of melamine, 188 g of phenol, 551 g of 37% formalin and 6 g of dimethylamine were added, and the mixture was reacted for 2 hours under reflux reaction, dehydrated under reduced pressure, and added with 220 g of diphenylnonylphenyl phosphate to prepare a laminated plate. A phenol resin composition for use was manufactured. This composition was diluted with a mixed solvent of methyl etorketone: methanol = 1: 1 to give a varnish (A) having a resin solid content of 55% by weight, a viscosity of 1.5 poise (25 ° C) and a gelation time of 3 minutes 30 seconds (150 ° C). ) Was prepared.

Example 2 To a four-necked flask equipped with a condenser, 126 g of melamine, 188 g of phenol, 551 g of 37% formalin and 6 g of dimethylamine were added, and the mixture was reacted under reflux for 2 hours and dehydrated under reduced pressure. The added phenolic resin composition for laminated board was manufactured. This composition was diluted with a mixed solvent of methyl ethyl ketone: methanol = 1: 1 to obtain a resin solid content of 5: 1.
A varnish (B) having 6% by weight, a viscosity of 1.4 poise (25 ° C.) and a gelation time of 3 minutes and 30 seconds (150 ° C.) was prepared.

Comparative Example 1 Phenol 200 g, tung oil 10 in a four-necked flask with a condenser
Charge 0 g and p-toluenesulfonic acid 0.3 g, 100 ℃
After reacting for 1 hour at 40 ° C., it was neutralized with 40% aqueous ammonia.
Next, 250 g of benzoguanamine, 120 g of phenol, 460 g of 37% formalin and 5 g of dimethylamine were added, and the mixture was refluxed for 2
After reacting for a period of time and dehydration under reduced pressure, dilute with a mixed solvent of toluene: methanol = 1: 1, add 341 g of triphenyl phosphate to this and add 55% by weight of resin solid content, viscosity 1.8 poise (25 ° C), gelation time A varnish (C) of 6 minutes and 20 seconds (150 ° C.) was prepared.

Comparative Example 2 In a four-necked flask with a condenser, Nikanol H (Mitsubishi Gas Chemical Co., Ltd., trade name) 75 g, phenol 125 g, tung oil 100
g and p-toluenesulfonic acid 0.27 g were charged, and the temperature was 110 ° C.
After reacting for 1 hour at 40 ° C., it was neutralized with 40% aqueous ammonia.
Next, 200 g of benzoguanamine, 120 g of phenol, 350 g of 37% formalin and 4 g of dimethylamine were added, and the mixture was reacted under reflux for 2 hours, dehydrated under reduced pressure, diluted with a mixed solvent of toluene: methanol = 1: 1, and added with 341 g of triphenyl phosphate. Was added to prepare a varnish (D) having a resin solid content of 55% by weight, a viscosity of 1.5 poise (25 ° C.) and a gelation time of 5 minutes and 30 seconds (150 ° C.).

Ten varnishes prepared in Examples 1-2 and Comparative Examples 1-2 were prepared.
A prepreg with a resin content of 50% by weight and a resin flow of 8% was prepared by impregnating and coating it on MILLS kraft paper. 8 pieces of this prepreg and 2 pieces of copper foil with adhesive are laminated on both sides 17
A copper-clad laminate having a thickness of 1.6 mm was manufactured by integrally molding under heat and pressure for 75 minutes under conditions of 0 ° C. and 100 kg / cm ² . Various tests were conducted on this copper-clad laminate, and the results are shown in Table 1. The copper-clad laminate using the resin composition of the present invention has a small expansion coefficient in the plate thickness direction, and its effect was confirmed.

Among the various tests, the thermal cycle test, the hot oil test, and the expansion coefficient test in the plate thickness direction were performed as follows. The thermal cycle test was measured by MIL-STD-202E-102A-C. 10 hot oil tests with 260 ° C silicone oil
For 15 seconds with running water at 25 ° C, and then with triethane at 25 ° C for 20 seconds.
The measurement was performed with one second as one cycle. Both the thermal cycle test and the hot oil test were repeated until the rate of change in conductor resistance exceeded 10%. The expansion coefficient in the plate thickness direction is
The measurement was performed under the conditions of a maximum temperature of 150 ° C. and a heating rate of 3 ° C./min, and the expansion coefficient was calculated by the following formula.

[Effects of the Invention] As is clear from the above description and Table 1, the phenol resin composition for laminated plates of the present invention has a small expansion coefficient in the plate thickness direction, excellent electrical characteristics, and does not cause cracks in through holes. Through-holes are excellent in reliability, and it is possible to obtain through-hole wiring boards similar to glass epoxy boards.

Claims (2)

[Claims] 1. (A) General formula (However, m and n are 0 or an integer of 1 to 3, and m + n =
A phenolic resin composition for laminates, which comprises a phosphoric acid ester represented by 3), (B) phenols, (C) melamines, and (D) formaldehydes as essential components. 2. A phosphor according to claim 1, wherein the phosphoric acid ester is contained in a proportion of 20 to 40% by weight based on the whole resin composition.
A phenolic resin composition for laminates according to the item.