JPH0967420A - Production of resole-type phenolic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production process of a resole-type phenolic resin composition which is excellent in impregnation into the substrate and gives electric laminated boards with a high insulation resistance. SOLUTION: A phenol compound is allowed to react with formaldehyde using a tertiary amine. In this case, the amount of the tertiary amine is set to less than 0.03 mole per mole of the phenol compound. Subsequently, ammonia is added to the product to continue the reaction. In this case, the amount of the ammonia is adjusted to less than 0.09 mole per mole of the phenol compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a resol type phenolic resin composition which is useful, for example, for electrical laminates.

[0002]

Resol-type phenolic resins are used in electrical laminates. That is, a resol-type phenolic resin composition (varnish) containing a resol-type phenolic resin is once impregnated into a base material such as kraft paper and then dried to form a prepreg, and the prepreg is thermocompressed to form an electrical laminate. Manufactured.

The drying time required for the production of this prepreg depends on the reaction rate of formation of the resol type phenol resin. Therefore, in order to accelerate the reaction rate, it is effective to increase the amount of the catalyst, but the molecular weight of the resin in the B stage in the resol-type phenol resin composition increases, and as a result, impregnation of the base material becomes difficult, From the viewpoint of performance as an electrical laminate, it has a bad influence on heat resistance and insulation resistance.

[0004]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, an object of the present invention is to provide a resol type phenolic resin composition which has good impregnating ability for a base material and gives an electric laminate having high insulation resistance. It provides a manufacturing method.

[0005]

The method for producing a resol-type phenolic resin composition according to claim 1 of the present invention is the method for producing a resol-type phenolic resin composition in which phenols and formaldehyde are reacted in the presence of a catalyst. As the above catalyst, a tertiary amine is used in an amount of 0.0 to 1 mol of phenol.
It is characterized by reacting phenols with formaldehyde in an amount of 3 mol or less, and then reacting ammonia in an amount of 0.09 mol or less with respect to 1 mol of phenol, in the presence of a tertiary amine. Of the two-step reaction including the reaction in the presence of ammonia after this reaction, 0.
The reaction with a tertiary amine in an amount of 03 mol or less suppresses the polymerizing reaction of the resol-type phenol resin and improves the impregnating property of the base material, and as a result, an electrical laminate having high insulation resistance can be provided. It is possible.

[0006]

Embodiments of the present invention will be specifically described below.

The method for producing the resol type phenolic resin composition of the present invention comprises reacting phenols with formaldehyde in the presence of a catalyst. Phenols, cresols, derivatives thereof, and more specifically A phenol modified with tung oil can be used for the material, and a known raw material composition for producing a resol-type phenol resin can be applied.

The present invention is characterized in that a resol-type phenol resin composition is produced by a two-step reaction. In the first reaction, phenols and formaldehyde are reacted with a tertiary amine as a catalyst, and the reaction product On the other hand, in the next reaction, ammonia is added as a catalyst to promote the reaction. That is, the first reaction is accelerated in the presence of 0.03 mol or less of the tertiary amine with respect to 1 mol of the phenol. In this reaction, mainly methylation proceeds,
When the tertiary amine is reacted in excess of 0.03 mol, methylolation proceeds excessively, and unreacted phenol contributing to the crosslinking reaction becomes insufficient. As the tertiary amine, trimethylamine, triethylamine, benzyl-cured methylamine and the like are used.

The reaction in the presence of ammonia after the reaction in the presence of a tertiary amine is carried out with 0.09 mol or less of ammonia per mol of phenol. That is, when the amount of ammonia exceeds 0.09 mol, a high-molecular-weight resol-type phenol resin is generated, and the impregnability into the base material required as a varnish is not improved, resulting in the insulation resistance of the electrical laminate. Because it does not increase.

The method for producing the resol-type phenolic resin composition according to the examples and the characteristics of the electrical laminate using the resol-type phenol will be described below.

[0011]

【Example】

Example 1 100 parts by weight of phenol (hereinafter simply referred to as “part”) and 70 parts of formalin (37% by weight of formaldehyde (hereinafter simply referred to as “%”)) were reacted to obtain a resol-type phenol reaction product A. Also, melamine 100
And 100 parts of formalin (37% formaldehyde) were reacted to obtain a melamine reaction product. A mixture of 50 parts of these resol-type phenol reaction products A and 50 parts of melamine reaction products B and an aqueous methanol solution 100
Parts were mixed to form a primary varnish. 126 this primary varnish
Primary prepreg A was obtained by first impregnating g / m ² of kraft paper and then drying in a dryer at 135 ° C. for 30 seconds.

Next, 60 parts of phenol and 40 parts of tung oil were subjected to an addition reaction in the presence of 0.5 part of paratoluenesulfonic acid to obtain a tung oil-phenol reaction product. After neutralizing the tung oil-phenol reaction product with triethanolamine, 32 parts of formalin (formaldehyde 37%) was added, and further 0.9 parts of triethylamine as a reaction catalyst of phenol and formaldehyde (0. 014 mol) was added, and the mixture was reacted at a reaction temperature of 80 ° C. for 60 minutes. Ammonia water (ammonia 2
5%) 1.8 parts (0.04 per mol of phenol)
(2 mol) was added, and the mixture was reacted at 80 ° C. for 30 minutes, and then dehydrated under reduced pressure, and the obtained product was diluted with methanol to obtain a secondary varnish consisting of the resole-type phenol resin composition of the present invention.

After impregnating the primary prepreg A with this secondary varnish, it was dried in a dryer at 155 ° C. for 120 seconds to obtain a secondary prepreg B.

Next, eight sheets of this secondary prepreg B were stacked, and a copper foil having a thickness of 0.35 mm was placed on the uppermost layer through an adhesive to give a pressure of 1.
Thermocompression molding at 00 kg / cm ^{2 at} a temperature of 160 ° C. for 60 minutes,
An electrical laminate was obtained. Insulation resistance (JI
S1302) and bending strength were measured.

(Example 2) In place of the secondary varnish in Example 1, 1.8 parts of triethylamine (0.02 mol per mol of phenol) and 3.6 parts of aqueous ammonia (based on 1 mol of phenol) were used. 0.08 mol) at 70 ° C
Except that a secondary varnish obtained by reacting for 30 minutes with the secondary varnish was used, and that the secondary varnish was impregnated with the primary prepreg A and then dried for 70 seconds in a dryer at 155 ° C. to obtain a secondary prepreg B. It carried out on the same conditions as Example 1.

(Example 3) In place of the secondary varnish in Example 1, 1.8 parts of triethylamine (0.02 mol per mol of phenol) was added, and the reaction temperature was 80 ° C.
After reacting for 0 minutes, 1.8 parts of ammonia water (0.042 mol per 1 mol of phenol) was added and the mixture was stirred at 80 ° C. for 3 minutes.
Except that a secondary varnish obtained by reacting for 0 minutes was used, and that the secondary varnish was impregnated into the primary prepreg A and then dried for 100 seconds in a dryer at 155 ° C. to obtain a secondary prepreg B. It carried out on the same conditions as 1.

COMPARATIVE EXAMPLE 1 In place of the secondary varnish of Example 1, 2.7 parts of triethylamine (0.04 mol per mol of phenol) was added, and the reaction temperature was 80 ° C.
After reacting for 0 minutes, 5.4 parts of ammonia water (0.12 mol per mol of phenol) was added and the mixture was heated at 80 ° C. for 30 minutes.
Except that the secondary varnish obtained by the partial reaction was used and that the secondary varnish was impregnated with the primary prepreg A and then dried for 60 seconds in a dryer at 155 ° C. to obtain a secondary prepreg. It is the same.

(Comparative Example 2) In place of the secondary varnish in Example 1, 0.9 parts of triethylamine (0.014 mol per 1 mol of phenol) was added and reacted at a reaction temperature of 80 ° C. for 60 minutes. Add 4.8 parts of ammonia water (0.11 mol to 1 mol of phenol), and add 3 at 80 ° C.
Example 1 except that a secondary varnish obtained by reacting for 0 minutes was used, and that the secondary varnish was impregnated with the primary prepreg A and then dried for 60 seconds in a dryer at 155 ° C. to obtain a secondary prepreg. The same conditions were used.

(Comparative Example 3) In place of the secondary varnish in Example 1, 0.9 parts of triethylamine (0.014 mol per 1 mol of phenol) and 1.8 parts of ammonia water (based on 1 mol of phenol) were used. 0.042 mol) was added at the same time and reacted at 80 ° C. for 60 minutes, using a varnish, and after the primary prepreg A was impregnated with this varnish, it was dried for 120 seconds in a dryer at 155 ° C. The conditions were the same as in Example 1 except that the next prepreg was used.

In the above Examples and Comparative Examples, the viscosity of the resol type phenolic resin composition (varnish) impregnated into the primary prepreg A and the impregnation of the resol type phenolic resin composition into the primary prepreg A were required only for drying. Table 1 shows the measured values of the creeping insulation resistance and bending strength of the electrical laminate produced using the drying time and the secondary prepreg.

[0021]

[Table 1]

As shown in (Table 1), when the examples and the comparative examples are compared, in the examples of the present invention, since the viscosity of the varnish is small, no high-molecular phenol resin is produced,
Therefore, the substrate has good impregnation property and the drying time is only 6
Although it takes about 0 seconds, it is clear that the insulation resistance of the electrical laminate is significantly improved.

[0023]

According to the resol type phenolic resin composition obtained by the production method of the present invention, it is possible to provide a laminate for electrical use which has a good impregnation property into a substrate and a high insulation resistance.

Claims (1)

[Claims] 1. A method for producing a resol-type phenolic resin composition, which comprises reacting phenols with formaldehyde in the presence of a catalyst, wherein a tertiary amine is used as the catalyst in an amount of 0.03 mol or less relative to 1 mol of phenol. And a formaldehyde are reacted with each other, and then ammonia is used in an amount of 0.09 mol or less with respect to 1 mol of phenol to react, and a method for producing a resol-type phenol resin composition is characterized.