JPS6026490B2 - Production method of oil-modified phenolic resin for laminated products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an oil-modified phenolic resin for laminates.

It has been known that novolak type phenolic resins have better dimensional stability than resol type phenolic resins.

To obtain a laminated product using a nopolak type phenolic resin,
Generally, a varnish is used in which hexamine or resol type phenolic resin is mixed with a solution of novolak type phenolic resin dissolved in an organic solvent. However, since it is difficult to completely dissolve hexamine in the above-mentioned varnish, the hexamine tends to settle over time, and this tendency is particularly noticeable in drying oil-modified varnishes. In addition, when hexamine-mixed varnish is heated, the reaction progresses and clay rapidly rises, impairing its ability to impregnate the base material. Furthermore, when a resol type phenol resin is mixed with a novolac type phenol resin, there is a drawback that the advantages of the novolac type phenol resin are lost. On the other hand, a method is known in which formaldehyde is added to a novolac type phenol resin and the mixture is reacted under a hexamine or aqueous ammonia catalyst to form a resol.

However, in this case, the methylenation reaction tends to occur, the clay in the reaction system rises, and there is a drawback that it becomes difficult to continue the reaction before the methylolation reaction progresses sufficiently. Since high viscosity resin has poor flow, the flow of the resin attached to the coated substrate is lost before the solvent and condensed water cannot be sufficiently removed during the coating process on the substrate. In addition, alkali metals such as caustic soda, caustic potash, barium hydroxide,
When an alkali metal compound is used, metal ions remain in the laminate, increasing the hygroscopicity of the laminate and reducing its electrical insulation. The present invention eliminates the above-mentioned conventional drawbacks and provides an oil-modified phenolic resin for laminates with good dimensional stability.

The present invention relates to a drying oil obtained by reacting phenols and a drying oil under an acidic catalyst.
It is characterized by reacting a mixture of a phenol adduct and phenols with formaldehyde under an acidic catalyst to form a novolac, and then reacting this with formaldehyde under a tertiary amine catalyst to form a resol. It is something to do.

Examples of the phenols used in the present invention include phenol, cresol, xylenol, butylphenol, octylphenol, nonylphenol, cashew nut oil, and urushiol. For the reaction between phenols and drying oil, an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid, an organic acid such as toluenesulfonic acid or xylene sulfonic acid, or an acidic catalyst such as a Lewis acid is used. As the acidic catalyst used in the reaction between the drying oil-phenol adduct and formaldehyde, the inorganic acid or organic acid used in the reaction between the phenol and the baggage oil may be used.

The molar ratio of formaldehydes reacted under an acidic catalyst to phenols is preferably 0.1 to 0.3. In addition, it is also possible to add each of the above-mentioned phenols during the reaction of the drying oil-phenol adduct and formaldehyde under an acidic catalyst. After the drying oil-phenol adduct is converted into a novolac, it is reacted with formaldehyde under a tertiary amine catalyst to form a resol.
The molar ratio of formaldehydes added is 1 to 1.0 molar ratio of total formaldehydes, including formaldehydes used for novolacization under acidic catalyst, to phenols.
5 mol is suitable.

Examples of tertiary amines include trimethylamine, triethylamine, penzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl,
-Methylimidazole, 2-heptadecylimidazole, etc. are suitable. After formaldehyde is reacted to a predetermined degree of reactivity using a tertiary amine catalyst, a solvent is added over vacuum dehydration as necessary to prepare a coating varnish. The oil-modified phenolic resin according to the present invention is impregnated into a base material such as cotton linter paper or kraft paper, then the number of elements of the base material is overlapped, and if necessary, copper foil is further overlaid on one or both sides and heated. Press to obtain a laminate or copper-clad laminate.

Furthermore, when a base material is impregnated with the oil-modified phenolic resin according to the present invention, it is also possible to mix a water-soluble phenolic resin initial condensate or to use a base material in which the initial condensate has been previously impregnated. As mentioned above, since the oil-modified phenolic resin varnish according to the present invention converts the phenol-drying oil adduct into borac, it can be used to produce laminated products with little dimensional change due to heating.

Further, since a tertiary amine catalyst is used in the resolization reaction, the methylenation reaction can be suppressed and the methylolization reaction can be effectively promoted. Next, examples of the present invention will be described.

Example Synthesis Cresol (65% meta-cresol, 35% para-cresol) was added to 450 tung oil and 0.5 mol of sulfuric acid and reacted for 1200 minutes at 80 to 85 q0 to form a cresol-tung oil adduct. I got it.

Subsequently, 85% paraformaldehyde was added for 94 hours to
The reaction was carried out at ~85'0 for 150 minutes. Then increase the temperature to 6
Lowered to 0qo, 30% trimethylamine 15 minutes, 85%
Paraformaldehyde was added for 132 hours and reacted for 4 hours at 80 to 8,500 hours, followed by dehydration under reduced pressure and diluted with methanol to obtain an oil-modified phenol resin varnish with a resin concentration of 50%. Kraft paper that had been undercoated with a water-soluble phenol resin initial condensate was impregnated with the oil-modified varnish and dried to obtain coated paper with a resin adhesion content of 46%.

Layer adhesive-plated copper foil on one side of this nine-ply coated paper,
A copper-clad laminate having a thickness of 1.6 skin/skin was obtained by heating and pressing at a temperature of 160 oo and a pressure of 100 k9/skin for 60 minutes. (Implemented product)
.

Comparative Example 1 The reaction was carried out under the same conditions as in the Example, except that 25% aqueous ammonia was added in place of the 30% trimethylamine in the above Example.

28 minutes after the aqueous ammonia was added and the reaction mixture reached 80 qo, the viscosity of the reaction system suddenly increased, so the reaction was stopped. The obtained reaction product was a gelled product that did not dissolve in acetone or toluene. Comparative Example 2 Synthetic cresol 480 yen, nonylphenol 200 yen,
To the mixture were added 450 tung oil and 0.5 mol of baltoluene sulfonic acid, and the mixture was reacted at 80 to 85°C for 120 minutes.

Next, 20 minutes of 25% ammonia water and 220 hours of 85% paraformaldehyde were added and reacted for 290 minutes at 80 to 85 degrees centigrade, dehydrated under reduced pressure and diluted with acetone to obtain an oil-modified phenol resin varnish with a resin concentration of 50%. Using this oil-denatured varnish, a copper-clad laminate was obtained under the same conditions as in the Example (Comparative Example 2). The performance of the above implemented product and comparative product 2 is the first
Shown in the table.

Claims (1)

[Claims] 1 Drying oil obtained by reacting phenols and drying oil in the presence of an acidic catalyst - phenol adduct or the above-mentioned drying oil -
A mixture of a phenol adduct and a phenol is reacted with formaldehyde under an acidic catalyst, and then this is reacted with a third
1. A method for producing an oil-modified phenolic resin for laminated products, which comprises reacting with formaldehyde under a grade amine catalyst.