JPS61151221A - Production of flame-retarding phenolic resin - Google Patents

Abstract

PURPOSE:To obtain a flame-retarding phenolic resin which can give a resin laminate of excellent low-temperature punchability without detriment to electrical properties, etc., by adding a specified compound to the reaction system of a phenolic resin and reacting the mixture. CONSTITUTION:A flame-retarding phenolic resin is produced by adding a compound of formula I to the reaction system for producing a resol phenolic resin. In formula I, R1 and R2 are each a 2-10C monovalent aliphatic or aromatic residue and R3 is a 2C or higher monovalent aliphatic or aromatic residue. An example of the compound of formula I includes a compound of formula II. The most excellent effect can be obtained by adding the compound of formula I when a phenol is reacted with an aldehyde in the presence of a basic catalyst. The amount of the compound of formula I used is 2-30wt% based on the phenol feed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing flame-retardant phenolic resins used in the production of phenolic resin laminates, etc.

[Prior art]

Recently, there has been a demand for insulating materials (2) for laminated plates used in telecommunication equipment and electronic equipment that have excellent punching properties at room temperature or relatively low temperatures around room temperature, from the viewpoint of automation of processing equipment and energy conservation. Therefore, as a resin for laminated boards, a phenol resin is usually used in which various mono-alkyl phenols are used in combination with phenol and modified with a drying oil or the like.

On the other hand, insulating materials (= laminates used (versus two).

The demand for flame retardancy is increasing due to the trend of placing emphasis on safety.

Conventional flame retardant C for laminates can be achieved by using an additive flame retardant in which a halogen or phosphorus compound is added to the resin, or by using a reactive flame retardant that is chemically bonded to the resin. Each of them has advantages and disadvantages. Examples of the former include tetrabromobisphenol A and triphenyl phosphate, but since the flame retardant remains unreacted with C1 in the product, properties such as heat resistance and solvent resistance deteriorate.As for the latter, Conventionally, Epoquine compounds with halogen substituents have been widely used, and they have excellent heat resistance and melt resistance C2, but when used in heavy lightning, flexibility decreases and punchability at low temperatures decreases. It has the disadvantage of causing a decrease in

[Purpose of the invention]

In the present invention, a specific compound is added to the reaction system of phenolic resin for the purpose of improving the flammability of phenolic resin, and the main purpose is to deteriorate the electrical properties and other properties. To provide a flame-retardant phenolic resin which provides a phenolic resin laminate with extremely excellent punching workability at low temperatures without causing any damage.

However, even if the main purpose of the present invention is as described above, the use of the flame-retardant phenolic resin obtained by the present invention is not limited to the phenolic resin laminate C2. As long as there is a strong demand for flame retardancy, this flame-retardant phenolic resin will naturally be used for purposes other than laminates (= effective (
It can be used on two sides.

[Structure of the invention]

The present invention uses a reaction system for producing a resol type phenolic resin with the general formula % formula % ((in the formula, ``ma'' is a monovalent aliphatic or aromatic compound having 2 to 10 carbon atoms with or without a substituent). A flame retardant product characterized by adding a compound (1) which is a monovalent aliphatic or aromatic residue having 2 or more carbon atoms with or without a substituent. This is a method for producing phenolic resin.

° This invention (resol type phenol iHll)
i Magota is manufactured using the usual method (:). However, it is somewhat simple (: to explain, raw materials
=, and examples of phenols include C, -C!, such as phenol, cresol, propylphenol, furfural, nonylphenol, and canny dimer. .

Alkylphenols and the like are used. In addition, products obtained by reacting oils and fats such as tung oil, linseed oil, dehydrated castor oil, and cashew nut oil with phenols under acidic catalysts are also used as phenols. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and furfural. etc. As the basic catalyst, hydroxides such as sodium hydroxide, aqueous ammonia, amines, etc. are used, and a resol type phenol resin is thereby obtained.

Usage mode of compound CI do it.

However, the best effect is obtained when the following usage mode (=) is used. Namely, when phenols and aldehydes are reacted under a basic catalyst (: this is the mode of addition).

The amount C of compound [■] to be used is preferably set within the following range. That is, it is 2 to 30% by weight based on the amount of phenols charged. This amount is 2
If it is less than (9)% by weight, the flame retardancy tends to be insufficient, and if it exceeds (9)% by weight, the crosslinking density tends to increase and the punching workability of the laminate tends to deteriorate.

〔Effect of the invention〕

The flame-retardant phenolic resin obtained by method C of the present invention has excellent electrical properties, solvent resistance, etc., and can be imparted with flame retardancy without reducing flexibility.
It can be used for molded products, laminates, etc. Special C: It is extremely suitable as a resin for laminates used as printed circuit boards whose required properties are improving year by year.

〔Example〕

The present invention will be explained below with reference to Examples.

Synthesis Example 1 850.9 g of tung oil, 1150 g of metacresol, and 2 g of para-toluenesulfonic acid were mixed and reacted at 100° C. for 1 hour. Next, paraternary butylphenol 50J
, 25% ammonia water 12JF, and compound 100.9 having the following structural formula as compound (I) were placed in a reaction vessel and reacted at 90° C. for 2 hours. Water was then removed under reduced pressure and a solvent was added to produce a resin varnish.

Synthesis Example 2 Synthesis Example 1 except that the compound (III) is not used.
A resin varnish was produced in exactly the same manner.

Example 1 Commercially available flame retardant tetrabromobisphenol A diglyndyl ether was added to 10% of the resin solid content C of the varnish of Synthesis Example 1 to 2%.
% by weight was added. Cotton linter paper C2, which had been previously undercoated with a water-soluble phenol formaldehyde resin varnish, was impregnated with the above varnish and dried to produce a resin-impregnated base material with a resin adhesion content of 50% by weight.

Layer 8 sheets of this base material, 160-165℃, 80K
Heat and press for 60 minutes under lamination conditions of 1.6 m thick.
m phenolic resin laminates were produced.

Example 2 Resin solid content of Synthesis Example 1 (compared to 2, commercially available flame retardant Tetoh 77
'Lomobisphenol A diglycidyl ether 10w@
% and 5% by weight of triphenyl phosphate were added.

Hereinafter, a tubonol resin laminate was manufactured in exactly the same manner as in Example 1.

Comparative Example 1 A phenolic resin laminate was produced in exactly the same manner as in Example 1, except that the varnish of Synthesis Example 2 was used.

Comparative Example 2 A phenolic lubrication laminate was produced in exactly the same manner as in Example 2, except that the varnish of Synthesis Example 2 was used.

Comparative Example 3 A phenolic resin laminate was produced in exactly the same manner as in Example 2, except that the varnish of Synthesis Example 2 was used and the amount of triphenyl phosphate added was changed to 10% by weight C2.

Table 1 shows the properties of the phenolic resin laminates obtained in the above Examples and Comparative Examples.

Table-1 Characteristic values of laminates <Test method> Solvent resistance was measured according to JIS 06481.

Punching workability is based on A8TMD-6171=.

As is clear from the above examples, the flame-retardant phenolic resin obtained by the method of the present invention has excellent flame retardancy, solvent resistance, etc. Excellent punchability. As described above, the twist-resistant phenolic resin according to C2 of the present invention has significantly superior properties compared to conventional phenolic resins.

Claims (1)

[Claims] 1. The reaction system for producing resol type phenolic resin has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ [I] (In the formula, R_1 and R_2 are carbon atoms with or without substituents Represents a number of 2 to 10 monovalent aliphatic or aromatic residues, and R_3 has 2 carbon atoms with or without a substituent.
Indicates the above monovalent aliphatic or aromatic residue. ) A method for producing a flame-retardant phenolic resin, which comprises adding a compound [I] represented by: 2. The compound [I] has the following structural formula [
II], ▲ Numerical formulas, chemical formulas, tables, etc. , R_3 represents a divalent aliphatic residue having 2 to 6 carbon atoms,
n is 1, 2 or 3. ) The method for producing a flame-retardant phenolic resin according to claim 1.