JPS6356517A - Production of flame-retardant resin composition for laminated sheet - Google Patents

Abstract

PURPOSE:To obtain the titled composition, useful for electrical machinery and apparatus, etc., exhibiting flame retardant effect in a small amount and having excellent flexibility as well as storage stability adding tetrabisphenol A and then an aromatic amine to a specific diglycidyl ether and reacting the reactants one after another. CONSTITUTION:Diglycidyl ether of brominated bisphenol A.alkylene oxide adduct expressed by formula I (R1 and R2 are -CH2-, -C2H4- or formula II; m and n are 1-6) is blended and reacted with tetrabromobisphenol A, using a tert. amine as a catalyst and an aromatic amine is added to the resultant product in an equimolar number to residual epoxy and reacted with the product to provide the aimed composition.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a sparsely soluble resin composition for laminates that has excellent flame retardancy, varnish storage stability, and low-temperature punching processability of laminates.

BACKGROUND OF THE INVENTION In recent years, there has been an increasing demand for flame-retardant printed circuit boards used in home-use machinery for safety reasons.

At the same time, there are a wide variety of requirements, especially dimensional accuracy, low-temperature punching performance or no-heat punching performance, and price requirements that are becoming stricter year by year. Flame retardant resins and flame retardants for laminates with excellent punching properties and non-heating punching are required, but it has been difficult to satisfy the above objectives with conventional flame retardant resins and flame retardants. .

That is, as conventional flame retardant resins and flame retardants, reactive flame retardants that have one reactivity with low molecular weight additive flame retardants that have no reactivity are known. When a separable flame retardant is used, the heat resistance, chemical resistance, electrical properties, and crosslinking density of the resin are reduced, resulting in a significant decrease in the interlaminar tightness of the produced laminate. In particular, punching properties (one of the two is peeling between layers, powder falling during punching,
The die hole may become clogged. - If reactive flame retardants are conveniently used, although the above-mentioned disadvantages are small, the increase in resin crosslink density when made into a laminate shifts the softening point of the laminate to a higher temperature side, resulting in low-temperature or unheated punching. In addition, due to its reactivity, the storage stability of the compounded resin and coating substrate deteriorates.

As representative examples of the former, brominated bisphenol A, brominated diphenyl ether, triphenyl phosphate, and their alkyl derivatives have been put into practical use. A typical example of the latter is brominated epoxy resin. in fact,
Wide variety.

Problems to be Solved by the Invention Conventional flame retardant resins and flame retardants have various limitations in customization as described above, so it is necessary to change the blending ratio of Br, P, and H to obtain the optimal flame retardant effect. The degree of freedom for
(2) This resulted in a decrease in punching workability and a decrease in other properties, and furthermore, there was a problem of high cost.

The present invention solves the above-mentioned problems of conventional flame retardant resins and flame retardants, and exhibits flame retardant effects with a small amount of use.
The purpose is to provide a flame-retardant resin composition for laminates that has excellent flexibility and storage stability without degrading other properties.

Means for Solving the Problems This invention has been made to achieve the above objects.

Tetrabromobisphenol Ai is added to the brominated bisphenol A alkyl oxide adduct diglycidyl ether represented by the general formula [I] and reacted with tertiary amine as a catalyst. This is a flame-retardant resin composition for a spray plate that is obtained by adding and reacting the following.

Action By using T in combination with the brominated bisphenol A alkyl oxide adduct diglycidyl ether represented by general formula [I] and tetrabromobisphenol A', the alkyl oxide structure of the former transforms it into the conventional brominated bisphenol A diglycidyl ether. Demonstrates flexibility that was not sufficient in the past. or. , general formula [I] has a slightly lower Br content than brominated bisphenol A diglycidyl ether, so it is tetrabromobisphenol A? : By reacting and further (by reacting diaromatic amine, B
In addition to increasing the r content, the reactivity with resol type phenol tlW is increased to 1 by the remaining work on the 1NH- group, which is a reactive group at the end of the reactive molecule, and is an inexpensive reactive type combustion release with excellent flexibility. Resin can be obtained.

Although there is no particular limitation on the blending ratio of general formula [I] and tetrabromobisphenol A, general formula CI
) It is preferable that the amount of tetrabromobisphenol A4011 is less than 1 part per 100 Nljt parts.

Furthermore, if the amount of aromatic amine added is greater than the number of moles of the remaining epoxy, the storage stability of the blended solution and the storage stability of the coated paper base material will deteriorate due to the action of the remaining -NH- groups.

In general formula [I], when the number of carbon atoms in Ra and Rs is 4 or more: 2, heat resistance decreases and compatibility with a methanol-rich phenol resin decreases.

Example Next (2) Detailed explanation of the present invention.

-OHmO(3Hx-cHCHm) 60% toluene mK1400f, tetrabromobisphenol 2109 and benzyldimethylamine 2.1f' of diglycidyl ether represented by 3Hx-cHCHm were added to a Mitsuro flask, and 90%
The mixture was allowed to stand at ℃ for 4 hours. After the reaction was completed, the epoxy equivalent was measured by the tetramethylammonium bromide-perchloric acid method and found to be 1300 for the entire solution. continue,
53 f of an aromatic amine represented by the formula Ha N-Q-CHs O-MHz was added and reacted at 80° C. for an additional 4=1 hour (2 (reactant)).

In order to confirm the effect of Reactant 1, a tung oil-modified phenol resin was separately obtained as a resin for a laminate to which ink was mixed in the following manner. Mitsuro flask (; tung oil 720f, m-
Cresol 580 f.

Paratoluenesulfone alO, 74f? : Throw in...
After heating at 80℃ for 1 hour, phenol 5oOf, 86%
The resin content was adjusted to 50 ml by sacrificing 4 sets of paraform and 35 ml of 2 sz aqueous ammonia, and then adding methanol.

The solid content ratio of this tung oil f-7 enol resin and the reactant 1 is 80/2.
A varnish was obtained by mixing and dissolving at a ratio of 0. This was coated on 11 mils kraft paper so that the amount of ζ2 resin was 50% and dried to obtain coated paper. One sheet of 35μ thick copper foil with adhesion agent and eight sheets of the above-mentioned coated paper were combined and heated and pressed to a thickness of 1.6III+
A phenol W fat laminate was obtained.

-faH-cHa -O+CHs -C3H-CB.

60% toluene'fl of diglycidyl ether represented by 6'0'
jW14oot and tetrabromobisphenol A210
f and triethylamine 2.1f7ja: Pour two into a Mitsulo flask and react at 90°C for 4 hours. Then, after measuring and confirming the epoxy equivalent in the same manner as in Example 1 - Formula H,
Add 611 of the aromatic amine indicated by N-○-8-Q-N&"?l' and further heat at 80°C;
The reaction was allowed to proceed for 1 hour (reactant 2). Using the tung oil-modified phenolic resin of Example 1 and reactant 2, the following procedure was carried out in the same manner as in Example 1 (
A single-sided steel clad layer with a thickness of 1.6 cm was obtained.

1400f of a 60% toluene solution of diglycidyl ether shown in implementation fIJ3 and tetrabromobisphenol A210? and 2.11 parts of triethanolamine were charged into Mitsuro flask C2, and reacted at 90°C for 4 hours. Next, in the same manner as in Example 1, the aromatic amine 154r represented by EvoNHn was prepared.
I put it in.

The reaction was further carried out at 80° C. for 1 hour (reactant 3).

Using the tung oil modified phenolic resin of Example 1 and reactant 2,
Thereafter, the same procedure as in Example 1 was carried out to obtain a single Ifi copper-clad laminate having a thickness of 1.6 mm.

Comparative Example 1 The tung oil-modified phenol resin and brominated bisphenol A diglycidyl ether used in [Example] were mixed in a solid ratio to tung oil-modified phenol/brominated bisphenol A.
Diglycidyl ether: Mix and dissolve in a ratio of 80/20 to obtain a varnish, and use the same method as in Example below to obtain a thickness of 1.
A copper-clad laminate of No. 6 was obtained.

Comparative Example 2 The tung oil-modified phenol resin used in Example 1, brominated bisphenol A diglycidyl ether, and triphenyl phosphate were mixed in a solid content ratio of tung oil-modified phenol mJjW/brominated bisphenol A diglycidyl ether/triphenyl phosphate= 60/3 (1/
Mix and dissolve at a ratio of 1 ('l) to make a varnish, and the following is the fruit!
If! Example 1] and IWl were fitted to obtain a copper-clad laminate board with a thickness of 1.6 m.

Table 1 shows the property test results of the laminates obtained in Examples and Comparative Examples.

As is clear from the above test results in the IJsI table, the amount of flame retardant used can be reduced and the low-temperature punching properties of Dan@root can be improved. This improves performance and has great industrial value.

Claims (1)

[Claims] General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
...[I] [R_1, R_2=-CH_2-, -C_2H_4, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ m, n = integers of 1 to 6] Tetrabromobisphenol A is blended with the brominated bisphenol A alkyl oxide adduct diglycidyl ether shown by and reacted with a tertiary amine as a catalyst. A method for producing a flame-retardant resin composition for a laminate, which further comprises adding an aromatic amine to the same number of moles as the remaining epoxy and reacting the same.