JPH0611778B2 - Method for producing resol type phenolic resin composition for laminated plate - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing a resol-type phenolic resin composition for a laminate, which has flame resistance, excellent processability, and electrical characteristics.

[Technical Background of the Invention and Problems Thereof] In recent years, due to the remarkable development of the electronic industry, the usage conditions of printed wiring boards have become severe, and the characteristics required for substrates have become more and more severe. In particular, it has become an indispensable condition to have excellent electrical properties, physical properties, workability due to chipping of parts, automatic insertion, high density patterning, etc., and flame retardance from the viewpoint of safety. ing.

Conventionally, various methods have been studied to combine punching workability and flame retardancy in a laminated plate, and from the viewpoint of flame retardancy, modifiers such as drying oil used for improving punching workability are: Flame retardation is difficult and complicated.

There are advantages and disadvantages in flame retarding, that is, using an addition type flame retardant in which a halogen or phosphorus compound is added to the resin and using a reaction type flame retardant that is chemically bonded to the resin.

The former has the drawbacks that the flame retardant remains unreacted in the product, resulting in deterioration of properties such as heat resistance and solvent resistance, and more powder generated during punching.

Therefore, a reactive flame retardant is preferable in order not to cause deterioration of properties, but there is a drawback that the punching workability at the low temperature side is slightly inferior.

[Object of the Invention] The present invention is intended to solve the above problems, and to provide a reactive flame retardant which is excellent in punching workability and flame retardancy and which does not cause deterioration of the properties of a laminate. It is an object of the present invention to provide a method for producing the used resol-type phenolic resin composition for laminated plates.

[Summary of the Invention] That is, the method for producing a resol-type phenolic resin composition for laminated plates of the present invention comprises a reaction type flame retardant synthesized by a reaction between a fatty acid or a fatty acid ester of a drying oil or a semi-drying oil and a halogenated compound. It is characterized by reacting with phenols in the presence of an acidic catalyst and then with formaldehyde in the presence of a basic catalyst.

The drying oil used in the present invention includes tung oil, linseed oil, soybean oil and the like, and the semi-drying oil includes rapeseed oil, sesame oil and the like. Examples of the halogenated compound include 2,2,2-tribromoethanol, para-bromophenethyl alcohol, dibromobenzyl alcohol and the like.

The blending ratio of the fatty acid and the halogenated compound in the synthesis of the reactive flame retardant according to the present invention can be arbitrarily selected, but it is suitable to select so that the product has the halogen content described below. That is, the halogenated ester compound to be produced preferably has a halogen content of 10 to 50% and an average molecular weight of 300 to 1000, more preferably a halogen content of 15 to 30% and an average molecular weight of 400 to 60.
A value of 0 is suitable. As the halogenated ester compound, a brominated ester compound or a chlorinated ester compound is preferable. Among such brominated ester compounds, commercially available compounds include, for example, GX-60 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
25 (bromination rate 27%) and GX-6026 (bromination rate 16%) (both are trade names).

The phenols used in the present invention include phenol,
Alkylphenols such as cresol and xylenol, arylphenols such as phenylphenol and cumylphenol, and polyhydric phenols such as halogenated phenols and bisphenol A can also be used.

Examples of the acidic catalyst used in the present invention include organic sulfonic acids such as benzenesulfonic acid and toluenesulfonic acid, organic sulfonic acid salts such as toluenesulfonic acid chloride, metal salts such as tin chloride and zinc chloride, and phosphorus. acid,
It includes inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as formic acid and oxalic acid.

As the basic catalyst used in the present invention, ammonia, hexamethylenetetramine, triethanolamine, monomethylamine, amines such as ethylenediamine, sodium hydroxide, potassium hydroxide, calcium hydroxide,
Examples thereof include hydroxides of alkali metals and alkaline earth metals such as magnesium hydroxide, and inorganic salts such as sodium carbonate.

Examples of formaldehyde used in the present invention include formalin solution and paraformaldehyde.

In the present invention, first, an acidic catalyst is added to a halogenated ester compound of a drying oil or a semi-drying oil fatty acid and a phenol, and the mixture is subjected to 0.5 at a temperature of 80 to 150 ° C. under strong acidity.
Allow to react for ~ 3 hours. A basic catalyst is added to the resulting reaction product to neutralize it, and the reaction product is reacted with formaldehyde in a pH range of about 5 to 9 for 1 to 6 hours to form a resol. Here, the usage ratio of the halogenated ester compound and the phenol is 80 to 200 parts by weight of the halogenated ester compound to 100 parts by weight of the phenol, and the usage ratio of these reaction products and formaldehyde is 1 mol of the reaction product. , Formaldehyde 1.1 to 1.9 mol.

Next, the reaction solution is dehydrated under reduced pressure to obtain the resol-type phenol resin composition for laminated plates according to the present invention.

In addition, in the present invention, a compatible flame retardant may be appropriately added to the resol-type phenol resin composition for laminated plates.

The thus-obtained resol-type phenolic resin composition for laminated plate is dissolved and diluted in an organic solvent and impregnated in a paper base material such as kraft paper, and a plurality of the laminated substrates are heat-pressed. As a result, the desired laminate is obtained.

Examples of the Invention Next, examples of the present invention will be described.

Example 1 In a four-necked flask with a condenser, tung oil brominated ester (GX-6025 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 100 g, phenol 100 g, and paratoluenesulfonic acid 0.2 g.
Was charged, reacted at 100 ° C. for 2 hours, adjusted to pH 6 with 140% of 37% formalin and monomethylamine, and then reacted at 100 ° C. for 2 hours. After the reaction, dehydration under reduced pressure,
Diluted with toluene: methanol = 1: 2 solution, resin solid content 55%, viscosity 1.5 poise (25 ° C.), gelation time 3
A varnish having a time of 10 seconds (150 ° C.) was prepared.

Example 2 Tung oil brominated ester (G
X-6026 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 200 g, 100 g of phenol and 0.2 g of paratoluenesulfonic acid were charged, reacted for 2 hours at 100 ° C., 140 g of 37% formalin was added, and the pH was adjusted to 6 with monomethylamine. The reaction was carried out at 100 ° C for 2 hours. After the reaction, dehydration under reduced pressure,
Diluted with toluene: methanol = 1: 2 solution, resin solid content 56%, viscosity 1.7 poise (25 ° C.), gelation time 4
A varnish of minutes (150 ° C.) was prepared.

Example 3 Cresyl diphenyl phosphate was added to the resin composition obtained in Example 1 to give a bromination rate of 12% and a phosphation rate of 1
% To prepare a varnish having a gelation time of 4 minutes (150 ° C.).

Example 4 Cresyl diphenyl phosphate was added to the resin composition obtained in Example 2 and mixed so that the bromination rate was 8.5% and the phosphation rate was 1.8%, and the gelation time was 5 minutes 10 Seconds (1
A varnish of 50 ° C.) was prepared.

Comparative Example 1 A four-necked flask with a condenser was charged with 110 g of phenol, 90 g of tung oil, and 0.2 g of paratoluenesulfonic acid,
After that, the reaction is carried out in the same manner as in Example 1 to give a resin solid content of 55.
%, Viscosity 2.0 poise (25 ° C.), gelation time 3 minutes (1
A varnish of 50 ° C.) was prepared.

Comparative Example 2 Tetrabromodiphenyl ether and cresyl diphenyl phosphate were mixed with the resin composition obtained in Comparative Example 1 so that the bromination rate was 12% and the phosphation rate was 1%, and the gelling time was 5 minutes 30 seconds (150 ℃) was prepared.

Comparative Example 3 YDB-400T60 was added to the resin composition obtained in Comparative Example 1.
(Toto Kasei Co., Ltd.) and cresyl diphenyl phosphate were mixed so that the bromination rate was 12% and the phosphation rate was 1%, and a varnish with a gelation time of 2 minutes and 30 seconds (150 ° C.) was prepared.

The resin compositions obtained in the above Examples and Comparative Examples were impregnated and applied to 10 mils kraft paper to obtain a resin impregnation amount of 50% by weight,
A processed paper having a resin flow of 8% was obtained. Eight sheets of this processed paper and one sheet of copper foil with adhesive were superposed on each other and molded under heat and pressure conditions of 170 ° C. and 100 kg / cm ² for 75 minutes to obtain a copper clad laminate having a thickness of 1.6 mm. The test results for the properties of the obtained copper clad laminate are shown in the table.

[Effects of the Invention] As is clear from the above examples, the resol-type phenolic resin composition for laminates according to the present invention is superior in flame retardancy to conventional ones, and at the same time has excellent electrical characteristics and physical properties. It also has characteristics.

Claims (4)

[Claims] 1. A reaction-type flame retardant synthesized by the reaction of a fatty acid or a fatty acid ester of a drying oil or a semi-drying oil with a halogenated compound is reacted with a phenol in the presence of an acidic catalyst, and then a basic catalyst is added. A method for producing a resol-type phenol resin composition for flame-retardant laminates, which comprises reacting with formaldehyde in the presence of the same. 2. The halogen content of the reactive flame retardant is 10-5.
It is 0%, The manufacturing method of the resol type phenolic resin composition for laminated boards of Claim 1. 3. The method for producing a resol-type phenolic resin composition for laminated plates according to claim 1, wherein the halogenated compound is a brominated compound. 4. A method for producing a resol-type phenolic resin composition for a laminated plate according to claim 1, wherein a compatible flame retardant is added to the resin composition.