JPS6357627A - Production of flame-retarding resin composition for laminate - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent flame retardancy, varnish storage stability and laminate purchability at low temp. by mixing brominated bisphenol A/alkylene oxide adduct diglycidyl ether with tetrabromobisphenol A and reacting the mixture by using a tert. amine as a catalyst. CONSTITUTION:100pts.wt. brominated bisphenol A/alkylene oxide adduct digylicdyl ether of formula I (wherein R1-2 are each CH2, C2H4 or a group of formula II and m and n are 1-6) is mixed with 40pts.wt. or below tetrabromobisphenol A, and the obtained mixture is reacted at, e.g., about 90 deg.C for 4hr in the presence of a tert. amine (e.g., benzyldimethylamine) as a catalyst.

Description

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

BACKGROUND OF THE INVENTION In recent years, in view of the safety of household electrical appliances, there has been an increasing demand for flame retardant printed circuit boards used therein.

At the same time, due to a wide range of requirements, especially the dimension f: precision requirements, low-temperature punching performance or non-heating punching performance, as well as price requirements, are becoming stricter year by year. Therefore, there is a need for flame-retardant resins and flame retardants for laminates that are low in price and have excellent low-temperature punching properties or non-heat punching properties with little deterioration in properties. It was difficult to satisfy the objectives of

That is, the interlaminar tightness of the produced laminate is significantly reduced due to the reduction in reaction characteristics and crosslink density with conventional flame retardant resins and low molecular weight additive flame release agents that do not have reactivity as dynamic flame agents. In particular, the punching property (two problems include delamination, powder falling during punching, and clogging of the die).If a reactive flame retardant is used, the above-mentioned drawbacks are small.

Is the softening point of the laminated plate due to the increase in the crosslinking density of the resin when it is made into a laminated plate? :? It shifts to the #J temperature side, making it unsuitable for low-temperature or non-heating punching, and due to its reactivity, the storage stability of compounded resins and coated substrates 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 (from two different requirements for characteristics, each has its own merits).

Although they are used together while taking their shortcomings into consideration, there are many problems.

Problems to be Solved by the Invention Conventional flame-retardant resins and performance/flame agents have various limitations in terms of properties as described above, so it is necessary to change the blending ratio of Br, P, and H to achieve the optimal flame-retardant effect. The degrees of freedom to obtain are very C-narrow;
As a result, the amount used to ensure flame retardancy has increased, resulting in a decrease in punching workability and other properties, and there have been problems with high costs.

The present invention solves the above-mentioned problems of conventional flame retardant resins and flame retardants, and exhibits flame retardant effects even when used in small amounts.
The object of the present invention 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 The present invention is intended to achieve the above objects.

Brominated bisphenol A alkyl oxide adduct diglycidyl ether C nitetrapromobisphenol A represented by general formula (1) % formula %? : A flame-retardant resin composition for laminates obtained by blending and reacting with tertiary agonist as a catalyst.

Brominated bispheno-k A represented by the general formula [I]
By using fluoro-cytoadduct diglycidyl ether and tetrabromo-bisphenol A in combination, the alkyl oxide structure of the former (2, therefore, the conventional brominated bisphenol A diglycidyl ether 1) exhibits insufficient flexibility. .For the general formula [I], the Br content is higher than C2 by reacting brominated pinol A.

Flame retardant effect: Increased amount of injected resin can be reduced, making it cheaper. In addition, by leaving an epoxy group as a reactive group at the bottom end of one reactive molecule, it is a reactive flame retardant resin with excellent flexibility. : You can get what you want. The alkyl oxide group with OT flexibility suppresses crystallization of the resin and improves storage stability.

Examples The blending ratio of general formula [I] and tetrabromobisphenol A is not particularly limited, but general formula [1]
40 parts by weight or less of tetrabromobisphenol A per 3100 parts by weight. When the compounding ratio of tetrabromobisphenol A increases, the amount of unreacted substances increases, leading to a decrease in heat resistance, chemical resistance, and electrical properties, as well as a strong tendency for powder to fall during punching, hole clogging, and a decrease in interlayer adhesion. I don't like it.

In general formula (1), @ R 凰 and R ro have 4 or more carbon atoms C
If the temperature exceeds 2, the heat resistance will be slightly lowered, and the compatibility with methanol-rich phenolic resins will also be lowered.

Convenient catalysts include tertiary amines such as benzyldimethylamine, trimethylamine, triethylamine, and triethanolamine.

The flame retardant resin obtained by the present invention can be used alone or with a relatively small amount of a cooling type flame retardant such as triphenyl phosphate or frominated diphenyl ether, but in either case. Compared to the conventional method, the amount of filtration required for the total casing of flame retardant resin and flame retardant can be reduced.

60% toluene bath of diglycidyl ether shown as rLt4otn and tetrabromobisphenol A210
F and 2.19 g of benzyldimethylamine were charged into a Mitsuro flask and reacted at 90° C. for 4 hours (reactant A).

In order to confirm the effect of reactant A, fL? : A tung oil-modified phenol resin was separately obtained as a resin for the spray plate to be blended in the following manner. In a Mitsuro flask, 720 tons of tung oil, 580 F of m-cresol, para-toluenesulfone ff1Q,
After adding 74941 and reacting at -80℃ for 1 hour, phenol 5 (10?, 86 minutes) was dehydrated and condensed to 7!A.
Added methanol and added J@ fat content 50% (adjusted (reactant B).

The solid content ratio of the reactant A and reactant B is A/B=20/8.
Dissolve in a mixed bath at a ratio of 0%, add 7N parts of triphenyl phosphate, and use it as a varnish. One sheet of copper foil with adhesive and eight sheets of the above-mentioned coating base material were combined, heated and pressurized to form a piece with a thickness of 1.6 mm.
A fi-tacked and refurbished knoll resin @ laminate was obtained.

60 ratio of toluene + liquid 140 of diglycidyl ether shown by 10+CHs 0F)-CFin
0 “t and tetrabromobisphenol A210f
and 2.1f" of triethylamine were charged into a Mitsuro flask and reacted at 90°C for 4 hours (Reactant C).

Similar to Example 1, 1 reactant C and reaction 'jIAB were mixed and dissolved at a solid content ratio of c/B: 2o/80, and a 1.6W thick one-sided steel-clad phenol resin was prepared in the same manner as in Example. I got pickled ribs.

140Of a 60-ratio toluene solution of ether, 360F of tetrabromobisphenol A, and 5.6F75F of triethanolamine were charged into a three-tube flask, and reacted at 90°C for 4 hours (Reactant D).

Same as Example 1, 1 reaction product and reaction material B were mixed at solid content ratio D/
B: Mixed at a ratio of 20/8U, carried out in the same manner as in ml 1, a piece of IfI steel-clad phenolic resin with a thickness of 1.6+III! I got the 11th board.

f) 57" lomobisphenol 560f and benzyldimethylamine 5.6f'it: The mixture was charged into a three-necked flask and reacted at 90°C for 4 hours (reactant E).

As in Example 1, 1 reactant E and reactant B were mixed at a solid content ratio of E/
3 = 20/80 and mixed and dissolved in the same manner as in Example 1 to obtain a single-sided copper-clad coffin board with a thickness of 1.6 cm.

Comparative Example 1 The π-tung oil-modified phenol resin used in Example 1 (reactant B
) and a 60% solution (F) of brominated bisphenol A diglycidyl ether were dissolved in a mixed bath at a solid content ratio of B/F: 80/20, and further 7 parts of triphenyl phosphate was added to form a varnish, Thereafter, in the same manner as in Example 1, a single-sided copper-clad phenol open FTT laminate with a thickness of 1.6 m was obtained.

Comparative Example 2 Tung oil-modified phenol resin (reactant B) used in [Example]
) and 6(]% solution of brominated bisphenol A diglycidyl ether M (F) and triphenylphosphate) (
G) Fl' solid content ratio B/F/G = 60730/1
A copper-clad laminate with a thickness of 1.6 mm was obtained in the same manner as in Example 1. The test results of the laminates obtained in Examples and Comparative Examples are shown in 1st! ! Shown below.

Table 1 Effects of the Invention As is clear from the above test results (2. The amount of flame retardant used can be reduced compared to Invention C2, and the low-temperature punchability of the laminate is improved. Further C: Flame-retardant resin The storage stability of the solution and coated paper is improved and has great industrial value.

Claims (1)

[Claims] General formula [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼…………[ I ] [R_1, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ mn = Integer from 1 to 6] A method for producing a flame-retardant fat composition for a laminate, which comprises blending tetrabromobisphenol A with the brominated bisphenol A alkyl oxide adduct diglycidyl ether shown above and reacting the mixture with a tertiary amine as a catalyst.