JPS5958020A - Preparation of oil-modified phenolic resin for lamination - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

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

Conventionally, it is known that novola-type phenolic resins have superior dimensional stability of molded products compared to resol-type phenolic resins. To obtain laminated products using novolac type phenolic resin, it is common to use a varnish made by dissolving the novolac type phenolic resin in an organic solvent and adding and mixing hexamine or resol type phenolic resin. When added, it is difficult to completely dissolve the hexamine, and especially in dry oil-modified varnishes, hexamine may settle over time. Furthermore, when hexamine-added varnish is heated, the resin reacts and the viscosity suddenly increases by +4, impairing the ability to impregnate the base material.

On the other hand, the phenolic resin commonly used in the production of laminate products is a resol type phenol 4AI resin mainly composed of mononuclear methylolphenols, but this resol type phenol resin produces condensed water and unreacted substances during the curing process. Because a large amount of volatile matter is generated, 1U laminate products undergo large shrinkage and expansion due to heating and moisture absorption, which causes warping and twisting. Further, when oil modification is carried out, there are further problems such as compatibility with varnish and 11 molecules of the drying oil-phenol adduct.

The present invention aims to eliminate the above-mentioned conventional drawbacks and to provide an oil-modified phenolic resin for laminates suitable for obtaining laminates with good dimensional stability and punching workability.

In the present invention, a drying oil-phenol adduct obtained by reacting orthocresol and phenols with a drying oil under an acidic catalyst or a mixture of the drying oil-phenol adduct and phenols is mixed with formaldehyde and first under an acidic catalyst. It is characterized by reacting under a basic catalyst to form a novolac, and then reacting under a basic catalyst to form a resol.

In the present invention, orthocresol is used because it has relatively high reactivity with drying oils, and polymerization of drying oil-phenol adducts does not occur during resolization.
This is because the effect as an internal plasticizer is also great.

The drying oil used in the present invention includes tung oil, dehydrated castor oil,
These include linseed oil and tall oil. Examples of phenols include phenol, m-cresol, p-cresol, xylenol, butylphenol, octylphenol, nonylphenol, cashew nut oil, and urushiol. The reaction between phenols and drying oil involves hydrochloric acid,
The process is carried out using an acidic catalyst such as an inorganic acid such as sulfuric acid or phosphoric acid, toluene sulfone or a Lewis acid.

As the acidic catalyst used to react the drying oil-phenol compound or a mixture of this and phenol with formaldehyde, the inorganic acid or organic acid used in the reaction of the phenol with the drying agent may be used. . The formaldehyde used in the reaction under the acidic catalyst has a heptal ratio of 02 to 04 (preferably ζ) relative to the phenol.

After formaldehyde conversion with a drying oil-phenol adduct, it is further reacted with formaldehyde under a basic catalyst to form a resol. Is the molar ratio of aldehydes added above? 1 to 15 of the total formaldehyde relative to the phenol is suitable. As the basic catalyst, amine catalysts such as ammonia, ethylenediamine, and trimethylamine, or metal hydroxides are used. After formaldehyde is reacted to a predetermined degree of reactivity under a basic catalyst, if necessary, a two-solvent for dehydration under reduced pressure is added to prepare a coating varnish.

The oil-modified phenolic resin according to the present invention can be made into a laminate by impregnating it into a base material such as cotton linda 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. Moreover, the oil-modified phenolic resin according to the present invention was added to 11
4. When impregnating the wood, it is also possible to mix a water-soluble phenol resin initial condensate or to use a batter pre-impregnated with the initial condensate.

Next, the present invention will be explained in detail.

Example orthocresol soy, phenol 450 9 paulownia/[
13,250 g of p-toluenesulfonic acid and 04 g of para-toluenesulfonic acid were mixed and reacted at 80 to 85°C for 120 minutes to obtain a tubonol-tung oil adduct. Subsequently, 188 g of 85-chiparaformaldehyde was processed and reacted at 80-85°C for 150 minutes. The temperature was lowered to 60°C, and 15 g of 25% ammonia water and 263g of 85% paraformaldehyde were added and reacted at 70 to 75°C for 240 minutes. A phenol resin varnish was obtained.

A coated paper with a resin content of 46 Jyusha was obtained by impregnating and drying kraft paper, which had been previously undercoated with a water-soluble phenol (sub) fat initial condensate, with the itb modified phenol resin varnish described in -. 9 sheets of coated paper and copper foil with adhesive on one side,
60 at temperature 1600C, pressure 100Kp/cyl
A copper-clad laminate having a thickness of 16 mm was obtained by heating the plate for 1 minute.

Comparative Example Phenol 500g, tung oil 250g, para-toluenesulfonic acid 0. 4 17 mixed, 8 0-850
The reaction was carried out at C for 120 minutes. Next, Section 25 Ammonia 7k 1 5 9, 85 Hiroparaformaldehyde 230
g was added and reacted at 80 to 85°C for 240 minutes. Next, after dehydration under reduced pressure, 'Ib was diluted with acetone to obtain an oil-modified phenol resin varnish with a resin concentration of 50%.

A trowel 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 laminate of the following example and comparative example.

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 nopora, a laminated product with little dimensional change due to heating can be obtained. In addition, since orthocresol is efficiently added to the drying oil, the phenol-drying oil adduct is difficult to polymerize in the resolization reaction, and has a strong effect as an internal plasticizer (laminated products with good punching workability can be obtained). The industrial value of the present invention is great.

1 person with patent

Claims (1)

[Claims] 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 a laminated Ichikawa oil-modified phenolic resin characterized by reacting it under a basic catalyst.