JPS60260642A - Preparation of phenolic resin laminate - Google Patents

Abstract

PURPOSE:To obtain a laminate having excellent punchability, heat resistance, etc., by impregnating a base material with a phenol-formaldehyde resin modified with a drying oil, and a phenol-formaldehyde-polyamine reaction product incorporated therein, followed by lamination thereof. CONSTITUTION:A phenol (e.g. phenol or bisphenol A) is allowed to react with formaldehyde at about 60-120 deg.C in the presence of a polyamine containing two or more amino groups (e.g. ethylenediamine or diethylenetriamine). 1-20pts.wt. phenol-formaldehyde-polyamine reaction product obtained is incorporated into 100pts.wt. phenol-formaldehyde resin modified with a drying oil. The obtained resin component is dissolved in an organic solvent to prepare a varnish, and a base material for a laminate such as a sheet of paper, a glass cloth, etc. is impregnated with this varnish, dried and laminated to give an aimed phenolic resin laminate.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of industrial application) The present invention relates to phenolic resin and
Concerning a method for manufacturing a laminate.

(Background of the Invention) Recently, insulating materials, especially those used in consumer electronic equipment, have been made of laminates and copper-clad! The R-layer plate is required to have excellent punching workability with relatively low teeth in the vicinity of the strength or strength, from the viewpoint of zero punching of power loe equipment, labor saving, etc.

For this reason, phenol formaldehyde resin modified with tung oil is used as the drying oil.

However, due to the modification caused by tung oil, etc., the curing speed is slow and the cross-linking strength is also reduced, so the resin in the mold plate tends to be insufficiently cured, resulting in a decrease in properties such as heat resistance and aggressiveness. do. Furthermore, during punching, interlayer flaking is likely to occur due to the low crosslinking density.

In other words, the conventional reaction product of tung oil and phenols has a low number of moles of phenol added to tung oil, and because a polymer of tung oil is generated, the reaction with formaldehyde, i.e.,
The resin formation reaction and mill hardening reaction slow down the reaction rate and mill hardening speed, causing a decline in the properties of the steel.

In addition, as a countermeasure to this problem, a reaction product in which 6 moles of metacresol were added to 1 mole of tung oil has been proposed, but this was not sufficient in terms of mass production and economical considerations.

(Object of the Invention) An object of the present invention is to provide a method for manufacturing a phenolic resin laminate having excellent punching workability.

(Structure of the Invention) The present invention provides a reaction product obtained by reacting phenols and formaldehyde in the presence of a polyvalent amine having a valence of two or more, a resin component attached to a drying oil-modified phenol formaldehyde resin, and a laminated layer. Is it impregnated into the board base material, dried, and laminated? ! This is a method for manufacturing a phenolic resin laminate having one characteristic.

As the phenol, phenol, alkylphenol (for example, cresol xylenol, ethylphenol, butylphenol), phenylphenol, bisphenol A solsolyl, etc. are used.

The polyvalent amine having a valence of 2 or more has an aliphatic hydrocarbon skeleton with 2 to 6 carbon atoms, and has an amino radical sound of 1゜ and 2 to 4 carbon atoms in the molecule.
Preferably those with 0 such polyvalent amines include
Diamines (eg, ethylenediamine, triethylenediamine, putrescine, gadaverine, hexamethylenediamine), triamines (eg, diethylenetriamine), tetramines (eg, triethylenetetramine), and the like are used.

Phenols, formaldehyde, and polyvalent amines are 1 mole of phenols, 175 to 1 mole of polyvalent amine, and 172 to 1 mole of formaldehyde.
It is preferable to react for 0 minutes to 5 hours.

This phenol-formaldehyde polyamine reaction product is preferably one that crosslinks with the drying oil-modified phenol resin, and is preferably a relatively low-molecular one of about 2- to 5-nuclear bodies. The reaction product of the amine is added in an amount of 1 to 20 parts by weight per 100 parts by weight of the dry oil-modified phenol formaldehyde resin.

Dry oil denatured fu'-1 HO 1J-ade 8° Compensation 1 ・
(() is produced by reacting a drying oil such as tung oil with phenols, and converting it into a resol with formaldehyde. The resin component of n0 or more is dissolved in an organic swamp agent to make a varnish, and is then used to produce paper, glass cloth, glass non-woven fabric. A prepreg is obtained by impregnating and drying the base material, and the required number of prepregs are heat-pressed and laminated to form a phenol resin laminated 1ii according to a conventional method.

Example: 87.5 g of tung oil, 141 g of phenol, and 0.08 g of toluenesulfonic acid were mixed and reacted at 110°C for 1 hour.
g Paraformaldehyde 60 Reacted 0 Next, the reaction solution was dehydrated to remove water under reduced pressure.As dehydration progresses, the liquid level gradually rises and when the temperature reaches 70°C, the reaction product becomes transparent. Subsequently, dehydration was performed, and when the gel time reached 3 minutes and 30 seconds, the dehydration was stopped and the resin was rapidly cooled.
Fug? 11" forceps and reacts at 80℃ for 2 hours. Next, reaction 5- Remove water from the liquid under reduced pressure, dehydrate with hot water until the temperature reaches 80℃, pour into a vat and quench to obtain a resin. 5 parts by weight of the resin (2) was mixed with 100 parts by weight of the resin (2), and the mixture was soaked in a 1:1 mixed bath agent of methanol and acetone to produce a 50% by weight resin varnish.

Craft paper that had been precoated with an ice-water bathable phenol formaldehyde varnish for lower mO was impregnated with the above varnish, and then dried to obtain a prepreg with an N resin content of 50% by weight. A predetermined number of sheets of this were stacked together. , 160-1
A laminated plate having a thickness of 1.6 ml was obtained by heating and pressing at 65° C. and 80 kg/(60 minutes and 711 hours under the lamination conditions of I).The various properties of this laminated plate are shown in the attached table.

Comparative Example To the resin obtained in Example, methanol and acetone were added in a ratio of 1:1.
A laminate was obtained by bathing it in a mixed solvent of 50% by weight and using the same method as in the examples.The properties of this laminate are shown in the attached table.

6- (Effects of the invention) The KLn of the present invention can produce a laminate with excellent heat resistance, bath agent resistance, punching force and loe resistance.〇7-

Claims (1)

[Claims] 1.7 The reaction product obtained by reacting enols with formaldehyde in the presence of a polyvalent amine having a valence of 2 or more, impregnated with a resin component mixed with a drying oil-modified phenol formaldehyde resin, impregnated into a base material for a laminate, and dried. A method for manufacturing a phenolic resin laminate, characterized by lamination molding.