JPS6033128B2 - 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 novolac type phenolic resins have better dimensional stability of molded products than resol type phenolic resins.

To obtain laminated products using novolac type phenolic resin,
It is common to use a varnish prepared by dissolving a novolac type phenolic resin in an organic solvent and adding and mixing hexamine or resol type phenolic resin thereto. However, when hexamine is added, it is difficult to completely dissolve it;
In particular, dry and oil-denatured varnishes have the disadvantage that hexamine settles over time. Furthermore, when hexamine-added varnish is heated, the resin reacts and the viscosity rapidly increases, impairing the ability to impregnate the base material. On the other hand, the phenolic resins commonly used in the production of laminates are resol-type phenolic resins that are mainly composed of mononuclear methylol phenols. Due to the large amount of volatile matter generated, the resulting laminate products undergo significant shrinkage and expansion due to heating and moisture absorption, causing warping and twisting.

In addition, in the case of oil modification, varnish compatibility and drying oil-
There are problems such as high molecular weight of phenolic adducts. The present invention eliminates the above-mentioned conventional drawbacks and improves dimensional stability,
An object of the present invention is to provide an oil-modified phenolic resin for laminated products suitable for obtaining laminated products with good punching processability.

The present invention deals with the use of a hostile oil-phenol adduct obtained by reacting orthocresol and phenols with bag oil under an acidic catalyst, or a mixture of the bag oil-phenol adduct and phenols, with formaldehyde. It is characterized by first reacting under an acidic catalyst to form a novolak, and then reacting under a basic catalyst to form a resol.

In the present invention, oxocresol is used because it has relatively high reactivity with drying oils, and it is difficult for the drying oil-phenol adduct to polymerize during resolization, making it suitable as an internal plasticizer. This is because the effects are great. Drying oils used in the present invention include tung oil, dehydrated castor oil, linseed oil, and tall oil.

Phenols include phenol, m-cresol, P
-Cresol, xylenol, butylphenol, octylphenol, nonylphenol, cashew nut oil, urushiol, etc. The reaction between phenols and hostile oils is carried out under the presence of 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. As the acidic catalyst used to react the drying oil-phenol adduct or the mixture of this and phenol with formaldehyde, the inorganic acid or organic acid used in the reaction between the phenol and the drying oil may be used.

The molar ratio of formaldehyde to phenol used in this reaction under an acidic catalyst is preferably 0.2 to 0.4. The drying oil-phenol adduct and formaldehyde are reacted under the acidic catalyst to form a nopolak, and then further reacted with formaldehyde under a basic catalyst to form a resol.The molar ratio of formaldehyde added is as follows. It is appropriate that the total formaldehyde, including the formaldehyde used for novolacification under acidic catalyst, is 1 to 1.5 relative to the phenol.

Basic catalysts include ammonia, ethylenediamine,
An amine catalyst such as trimethylamine or a metal hydroxide is used. After formaldehyde is reacted to a predetermined degree of reactivity under a basic catalyst, it is dehydrated under reduced pressure if necessary, and a solvent is added to prepare a coating varnish. The oil-modified phenolic resin of the present invention can be made into a laminate by impregnating it into a base material such as cotton linter paper or kraft paper, stacking the required number of sheets, then layering metal foil on one or both sides as necessary and applying heat and pressure. A metal foil-clad laminate is obtained. Further, when impregnating a base material with the oil-modified phenolic resin according to the present invention, it is also possible to mix a water-bathable phenolic resin initial condensate or to use a base material pre-impregnated with the initial condensate. Next, examples of the present invention will be described.

Example: Orthocresol 50%, Phenol 450, Taran oil 25%
Mix 0.0 ml of baratoluene sulfonic acid with 0.4 ml of baratoluene sulfonic acid,
The reaction was carried out at 0 to 85°C for 12 hours to obtain a phenol-tung oil adduct.

Subsequently, 188% of 85% paraformaldehyde was added,
Reaction was carried out for 150 minutes at 0 to 8520°C, and the temperature was increased to 600°C.
After lowering the temperature to 0 and adding 25% ammonia water for 5 hours and 85% paraformaldehyde for 263 hours, it was heated to 70 to 760℃ for 24 hours.
The reaction was allowed to proceed for 0 minutes. After dehydration under reduced pressure, the mixture was diluted with methanol to obtain an oil-modified phenolic resin varnish with a resin concentration of 50%. A coated paper having a resin adhesion content of 4% by weight was obtained by impregnating kraft paper, which had been previously undercoated with a water-based phenolic resin initial condensate, with the oil-modified phenolic resin varnish.

Nine sheets of the coated paper were stacked with adhesive-coated copper foil on one side, and heat-processed for 60 minutes using a Sakaki trowel at a temperature of 16,000 and a pressure of 100 k9/c to obtain a copper-clad laminate with a thickness of 1.6 sails. Comparative Example 500 parts of phenol, 250 parts of tung oil, and 0.49 parts of valatoluensulfonic acid were mixed and reacted at 80 to 85 qo for 120 minutes.

Next, 15 minutes of 25% ammonia water and 230 hours of 85% paraformaldehyde were added, and the mixture was reacted at 80 to 85 qC for 240 minutes. Next, the mixture was dehydrated under reduced pressure and diluted with acetone to obtain an oil-modified phenol resin varnish with a resin concentration of 50%.
A copper-clad laminate was obtained using the above varnish under the same conditions as in the example.

Table 1 shows the performance of the copper-clad laminates of the above Examples and Comparative Examples.

Table 1 As mentioned above, the oil-modified phenolic resin according to the present invention is:
Since the phenol-drying oil adduct is converted into novolak, a laminated product with little dimensional change due to heating can be obtained.

Claims (1)

[Claims] 1 A drying oil-phenol adduct obtained by reacting orthocresol and phenols with a drying oil in the presence of an acidic catalyst or a mixture of the drying oil-phenol adduct and phenols is reacted with formaldehyde in the presence of an acidic catalyst. A method for producing an oil-modified phenolic resin for laminated products, which comprises: