JPH01118521A - Preparation of flame-retardant resin composition for laminate - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. having excellent heat resistance and can stability, by reacting two specified kinds of glycidyl ether in the presence of a tert. amine and reacting the product with triphenyl phosphite. CONSTITUTION:The aimed resin compsn. is obtd. by reacting a brominated bisphenol A diglycidyl ether and a brominated bisphenol A alkyl oxide adduct diglycidyl ether of formula I in the presence of a tert. amine as a catalyst and reacting the product with triphenyl phosphite. In the formula, R1 and R2 are each -CH2-, -C2H4- or formula II; m and n are each 1-6. As the triphenyl phosphite is trifunctional, it is possible for the compd. itself to act as a center of crosslink formation. A high phosphorus content can be therefore achieved and the amt. of P can be increased to a point where the synergistic effect of Br and P to flame retardancy becomes the most effective.

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 a laminate, which can provide a laminate with excellent flame retardancy and heat resistance, and has excellent storage stability.

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 (composed of laminated boards) used therein.

At the same time, among the wide variety of required property items, demands for low-temperature punching properties, or non-heating punching properties, and heat resistance are becoming stricter year by year due to demands for dimensional accuracy.

On the other hand, it has been difficult to completely satisfy these requirements using conventional flame retardant resins or flame retardants.

That is, as conventional flame retardants, there are known low molecular weight additive flame retardants that are not reactive and reactive flame retardants that are reactive.

When an additive flame retardant is used, the heat resistance, chemical resistance, and electrical properties of the resin blended with the flame retardant are reduced, and furthermore, the interlayer adhesion is significantly reduced due to a reduction in crosslinking density. In particular, regarding punching processability, interlayer peeling, powder falling during punching,
Defects such as die hole clogging are more likely to appear.

When used in combination with a reactive flame retardant, although the above-mentioned disadvantages are small, the increase in the crosslinking density of the resin when it is made into a laminate moves the softening temperature of the laminate to a higher temperature side, allowing it to be heated to a lower temperature or lower temperature. Because of their reactivity, they are unsuitable for punching, and due to their reactivity, there are nyleals, triphenyl phosphate, and their alkyl derivatives, and representative examples of the latter include brominated epoxy resins.

In reality, due to a wide variety of property requirements, additive type flame retardants and reactive type flame retardants are used in combination, taking into account their respective advantages and disadvantages.

In addition, the combination of both, particularly halogen (Br is often used in practice) and phosphorus, has advantages from other aspects as well.

In other words, rather than using elements that have flame retardant effects (halogen, phosphorus, nitrogen, boron, etc.) alone, when multiple of them are used together, the flame retardant effect increases due to the synergistic effect, and as a result, the flame retardant effect increases. The total amount of fuel used can be reduced. Further, since the additive flame retardant has an excellent plasticizing effect, the flexibility and punching workability of the laminate can be improved by using it in combination.

However, to give an example of the most frequently used composite system of Br and P, both the additive type and the reactive type are in practical use for the Br type, but only the additive type is in practical use for the P type. has not been standardized.

Therefore, in a composite system of Br and p, even if it is possible to find a blending ratio that exhibits the optimum flame retardant effect, the above-mentioned additions are necessary.

Due to the disadvantages of type flame retardants, it has not been possible to easily increase their usage.

Problems to be Solved by the Invention From the above, flame retardant resins and flame retardants that conventionally use P-based compounds have been found to have a flexible blending ratio in order to obtain the optimal flame retardant effect due to various constraints on the properties of laminates. The degree of flame retardancy was very narrow, and it could not be said that the blending system with the highest flame retardant effect was necessarily selected.

In view of the above points, the present invention provides a flame retardant resin composition for laminates that can be blended and used to obtain laminates with excellent flame retardancy and heat resistance, and also has excellent storage stability. The purpose is to

Means for Solving the Problems The present invention has been made to achieve the above objects.
After reacting brominated bisphenol A diglycidyl ether with brominated bisphenol A alkyl oxide adduct diglycidyl ether represented by the general formula (1) using a tertiary amine as a catalyst, triphenylphosphite ((C,H
, O), and P) for producing a flame-retardant resin composition for a laminate.

Effect By using together brominated bisphenol A diglycidyl ether and brominated bisphenol A alkyl oxide adduct diglycidyl ether represented by the general formula (1), flexibility is imparted to the alkyl oxide structure of the latter. Demonstrates flexibility that was insufficient in bisphenol A diglycidyl ether, and
By leaving an epoxy group as a reactive group at the end of the reactive molecule, a reactive flame-retardant resin with excellent flexibility can be obtained. At the same time, it is possible to introduce an alkyl oxide group into the molecular skeleton through a reaction! The spacing between the rom-substituted bisphenol A structures is widened by the flexible alkyl oxide group, which suppresses crystallization and improves storage stability. The reason why a tertiary amine is used as a catalyst for the above reaction is that primary and secondary amines tend to form a three-dimensional cross-bridge structure in the reaction product, making it difficult to use the produced flame retardant resin composition. When used in combination with phenolic resin, compatibility is lost. In addition, when R,,R, in general formula (1) has a carbon number of 4 or more, the heat resistance slightly decreases, and the produced flame-retardant resin composition is mixed with methanol-rich phenolic resin and used. When the compatibility decreases.

Triphenyl-7-osphite causes an ester reaction with the hydroxyl group of the reaction product of the furomated hisphenol A diglycidyl ether and the compound represented by the general formula (1), and chemically reacts with the reaction product while releasing phenol. Binding (Formula 1 Formula %) Triphenyl 7-osphite can itself be the center of crosslink formation due to its trifunctionality. Through this reaction, triphenyl-7-osphite participates in the crosslinking of the reaction product and is incorporated into its skeleton. It is possible to increase the phosphorus content, and the amount used can be increased to the point where the synergistic effect of Br and P on flame retardancy is most effective. As shown in formula (2), when triphenylphosphite undergoes an ester reaction with 1 mole of hydroxyl group, 1 mole of phenol is produced. The generated phenol slightly lowers the crosslinking density by reacting with the epoxy group, thereby improving flexibility.

In carrying out the present invention, there are no particular restrictions on the mixing ratio of the brominated bisphenol A diglycidyl ether and the brominated bisphenol A alkyl oxide adduct diglycidyl ether represented by the general formula (1). However, in order to have an effect on flexibility and storage stability, it is desirable that the latter be 5 parts by weight or more per 100 parts by weight of the former. As the latter increases, flexibility and storage stability deteriorate, so it may be used alone. However, since the Br content is slightly lower than when the former is blended in large amounts, it is better to adjust the mixing ratio of the two depending on the application system in order to obtain a predetermined flame retardant effect. The tertiary amine used as a catalyst for both reactions is trimethylamine, triethylamine, triethanolamine, benzyldimethylamine, etc. As a catalyst additive, brominated bisphenol A diglycidyl ether and the general formula (1) are used as tertiary amines. It is preferably in the range of 0.05 to 5% based on the solid weight of the compound to be added.

Regarding the usage ratio of brominated bisphenol A diglycidyl ether, the compound represented by general formula (1), and triphenylphosphite, in order to avoid unreacted triphenylphosphite remaining, [brominated bisphenol A diglycidyl ether] It is preferable that the hydroxyl group equivalent of the reaction product of the ether and the compound represented by the general formula (1)]≧[triphenylphosphite molecule ff1X'A).

When the flame retardant resin of the present invention is blended and used, it can be used alone or in combination with a relatively small amount of additive flame retardant such as triphenyl phosphate or brominated diphenyl ether. However, in either case, the total amount of flame retardant resin and flame retardant used can be reduced.

An embodiment of the present invention will be described.

Example 1 780 g of a 60% toluene solution of prophylated bisphenol A diglycidyl ether with a bromine content of 48%, an epoxy weight of 1400, and a hydroxyl group of 12,500 g. Formula (a) -O-CH, -CH, -0-CH, -CH-CH, (a
520 f of a 60% toluene solution of diglycidyl ether represented by ) and 2.7 l of dimethylbenzylamine were charged into a Mitsuro flask and reacted at 90°C for 3 hours. Furthermore, 18f of triphenylphosphite was added, and 80
The reaction was carried out at ℃ for 2 hours (reactant 1).

Separately, a tung oil modified phenolic resin was obtained as follows.

Tung oil 720f, m-cresol 580 in Mitsuro flask
Phenol 50 (1° 86% paraformaldehyde 450 F, 25% aqueous ammonia 35 F) was added, and the reaction was carried out at 80°C. When the reaction product had been hardened for 6 minutes on a 160° C. hot plate, it was dehydrated and concentrated, and methanol was subsequently added to adjust the resin content to 5,096.

The solid content ratio of this tung oil modified phenolic resin and the reactant 1 is [tung oil modified phenolic resin]/[reactant 1] = 80
The mixture was mixed and dissolved at a ratio of /20, coated on an 11 mils kraft paper base material and dried to give a resin adhesion of ff15096.

One 35μ thick copper foil coated with adhesive and eight of the above-mentioned coated base materials were combined and laminated, and heated and pressed to obtain a single-sided copper-clad laminate with a thickness of 1.6 m.

Example 2 1,253 y of the same brominated bisphenol A diglycidyl ether toluene solution as in Example 1, 135 y of a 60% toluamine solution of diglycidyl ether represented by the formula, and 1.6 f of triethyl ether were charged into a Mitsuro flask. , and reacted at 90°C for 3 hours. Next, triphenylphosphite 299 was added and reacted at 80° C. for 4 hours (Reactant 2).

Using reactant 2, a thickness of 1.6. A single-sided copper-clad laminate was obtained.

Comparative Example 1 The tung oil modified phenolic resin used in Example 1 and the 6096 toluene solution of brominated bisphenol A diglycidyl ether with an epoxy equivalent of 400 were combined with the bromine content of 4896 and the solid content ratio [tung oil modified phenolic resin] / (
Brominated bisphenol A diglycidyl ether) =
The mixture was mixed and dissolved in a ratio of 80/20, coated on 11 mils kraft paper, and dried. A single-sided copper-clad laminate having a thickness of 1.6 mm was obtained in the same manner as in Example 1.

Comparative Example 2 Tung oil modified phenolic resin used in Example 1 and Comparative Example 1
The solid content ratio of the brominated bisphenol A diglycidyl ether and triphenyl phosphate used in [tung oil modified phenol resin]/[brominated bisphenol A]
Diglycidyl ether)/()riphenyl phos7ate] was mixed and dissolved in a ratio of 60/30/10, coated on 11 mils kraft paper and dried, and the following Example 1 was prepared.
A single-sided copper-clad laminate having a thickness of 46 ffil was obtained in the same manner as above.

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

Table 1 Effects of the Invention As is clear from the above test results, the present invention improves the flame retardant effect and makes it possible to produce a flame retardant resin composition for a laminate with excellent flexibility and heat resistance. The storage stability of the resin solution and coating substrate is also improved.

Claims (1)

[Claims] Brominated bisphenol A diglycyl ether and general formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) Brominated bisphenol A alkyl oxide represented by m and n = integers from 1 to 6 1. A method for producing a flame-retardant resin composition for a laminate, which comprises reacting an adduct diglycidyl ether with a tertiary amine as a catalyst and then reacting it with triphenyl phosphite.