JPH01118520A - Method for producing flame-retardant resin composition for laminates - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention can provide a laminate with excellent flame retardancy, heat resistance, flexibility, and low-temperature punching processability, and has excellent storage stability. Method for producing flammable resin composition.

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 (comprised of laminated boards) used therein. At the same time, among the wide variety of required characteristic items, demands for low-temperature punching workability or non-heating punching workability and heat resistance are becoming stricter year by year due to demands for dimensional accuracy.

In contrast, it has been difficult to completely satisfy these requirements with conventional flame retardant resins or flame retardants.

That is, as conventional flame retardants, there are known low molecular weight additive flame retardants that do not have reactivity and reactive flame retardants that have reactivity. If a flame retardant is added, the heat resistance, chemical resistance, and electrical properties of the resin blended with it will decrease, and
As the crosslinking density decreases, the glabella adhesion of the obtained laminate significantly decreases. In particular, with regard to punching workability, defects such as flaking between the eyebrows, falling powder during punching, and clogging of the die are likely to occur.

When used in combination with reactive flame retardants, the above disadvantages are small, but due to the increase in the crosslinking density of the resin when made into a laminate, the softening temperature of the laminate moves to a higher temperature side, and it can be used at low temperatures or without heating. Also, due to its reactivity, the storage stability of the compounded resin and coated substrate becomes poor.

A typical example of the former is brominated bisphenol A1
Examples include brominated diphenyl a) liphenyl phosphate and its alkyl derivatives, and 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, especially the combination of nitrogen (Br is often used in practice) and phosphorus, has advantages from other aspects as well.

In other words, elements that have flame retardant effects () chlorogen, phosphorus, nitrogen,
Boron, etc.) is more effective when used in combination than when used alone due to their synergistic effect.
As a result, the total amount of flame retardant used can be reduced of
In addition, since the additive flame retardant has an excellent molding 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, even if it were possible to find a blending ratio that exhibits the optimal flame retardant effect in a composite system of Br and P, it would not be possible to easily increase the amount used due to the drawbacks of the additive type flame retardant mentioned above.
It was not possible to increase the amount of stone chips that would provide sufficient flexibility.

Problems to be Solved by the Invention From the above, flame retardant resins and flame retardants that conventionally use P-based compounds have various restrictions on the properties of laminates, so there is a lack of freedom in the blending ratio to obtain the optimal flame retardant effect. The degree of flame retardancy is very narrow, and it cannot be said that the blending system with the highest flame retardant effect is necessarily selected. It is an object of the present invention to provide a flame-retardant resin composition for a laminate, which can provide a laminate with excellent flexibility and low-temperature punching processability, and also has excellent storage stability.

Means for Solving the Problems The present invention has been made to achieve the above objects.
Brominated bisphenol A diglycidyl ether and brominated bisphenol A alkyl oxide adduct diglycidyl ether represented by general formula (1) are reacted using a tertiary amine as a catalyst, and then triphenyl hepta-osphite is reacted, and formaldehyde is further reacted. This is a method for producing a flame-retardant resin composition for a laminate, which is characterized by reacting the following.

Effect By using brominated bisphenol A diglycidyl ether and brominated bisphenol A alkyl oxide adduct diglycidyl ether represented by general formula (1), the presence of the alkyl oxide group in the latter gives flexibility, This reaction type exhibits flexibility that was not sufficient in the conventional brominated bisphenol A diglycidyl ether, and still has a reactive group, the epoxy group, at the end of the reaction molecule, resulting in a highly flexible reaction type. Flame retardant resin can be obtained.

At the same time, incorporating an alkyl oxide group into the molecular skeleton
By widening the spacing of the bromine-substituted bisphenol A structure by a flexible alkyl oxide group,
Storage stability is improved because crystallization is suppressed.

In general formula (1), when R,,R, has a carbon number of 4 or more, the heat resistance slightly decreases, and when the resulting composition is used by blending it with a methanol-rich phenol resin, the compatibility decreases. .

Triphenylphosphite causes an ester reaction with the hydroxyl group of the reactant of the compound represented by the general formula (1) and the furomated hisphenol A diglycidyl ether, and chemically bonds to the reactant molecules while releasing phenol. (see equation (2)).

OH+Q-0-fsoO-Q Because triphenylphosphite is trifunctional, it can itself become the center of crosslink formation. As a result of this reaction, triphenylphosphite participates in the crosslinking of the reactant and is incorporated into its skeleton, thereby exposing the various drawbacks of phosphate esters, which are conventional additive flame retardants. It is possible to have a higher phosphorus content than in the past without reducing the flame retardance, 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. By reacting with the epoxy group, the generated phenol slightly lowers the crosslink density and further improves flexibility.

However, it is inevitable that unreacted phenol remains until this point i. Therefore, the present invention provides a reaction product of brominated bisphenol A diglycidyl ether and diglycidyl nitrate triphenyl phosphite represented by the general formula (1), and further methylolates the produced phenol to impart reactivity. Characterized by the addition of formaldehyde.

As described above, the flame retardant resin according to the present invention has phosphorus atoms,
By incorporating brominated bisphenol A diglycidyl ether and the compound represented by the general formula (1) into the crosslinked structure of the reactant, the syrin content can be increased compared to conventional methods without deteriorating the properties, and the unit usage amount can be increased. In addition to increasing the equivalent flame retardant effect, a portion of the produced phenol reacts with epoxy groups, thereby improving flexibility. Furthermore, by converting free phenol into methylol, all the components in the system can participate in the reaction with the phenolic resin containing this as a flame release agent.

EXAMPLE There is no particular restriction on the mixing ratio of pro-prophylated bisphenol A diglycidyl nityl and brominated bisphenol A alkyl oxide adduct diglycidyl ether represented by the general formula (1) in an amount equivalent to carrying out the present invention. However, in order to exhibit effects on flexibility and storage stability, it is desirable that the latter be at least 5 parts by weight per 100 parts by weight of the former. As the amount of the latter increases,
Since flexibility and storage stability are improved, it may be used alone. However, when compared to the case where the former is blended in a large amount, B
Since the r content decreases, 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. As a catalyst that can be used for the reaction between the two, tertiary amines such as trimethylamine, triethylamine, triethanolamine, and benzyldimethylamine are used. If a primary or secondary amine is used, a three-dimensional crosslinked structure will not be formed, and the flame retardant resin obtained according to the present invention will lose its compatibility with the phenolic resin used in the blend.

Force a The amount of catalyst that can be added is preferably in the range of O,OS to 5% based on the solid weight of the prophylated bisphenol A diglycidyl ether and the compound represented by the general formula (1).

Regarding the usage ratio of pro-brominated bisphenol A diglycidyl ether, the compound represented by the 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)]≧[molecular weight of triphenylphosphite X 1/3].

The amount of formaldehyde to be used is preferably within the range of [mole aX3 of triphenylphosphite]≧[number of moles of formaldehyde]≧[number of moles of triphenylphosphite]. If used in excess, formaldehyde will remain; if used in small quantities, phenol will remain.

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, but in either case,
The total amount of flame retardant resin and flame retardant used can be reduced.Next, an embodiment of the present invention will be described.

Example 1 Bromine content 48 t, epoxy equivalent 400, hydroxyl equivalent f
i 2200 brominated bisphenol A diglycidyl ether (60%) toluene solution 920g, 60g of diglycidyl ether of formula 1a): r-7 dissolved t1.613f/t% dimethylbenzylamine 2.7
6p was put into a Mitsuro flask and reacted at 90°C for 3 hours.

Next, add triphenylphosphite 20Ii,
After reacting at 80°C for 4 hours, 869b paraformaldehyde 12J[-, V] was added, and the reaction was further continued at 80°C for 2 hours (Reactant 1).

Additionally, a tung oil-modified phenol resin was separately obtained in the following manner.

720p of tung oil, m-cresol sso,y, and 0.749p of paratoluenesulfonic acid were put into a Mitsuro flask, and after reacting at 80°C for 1 hour, phenol soo,y was added.

86% paraformaldehyde 450II and 35 g of 25% aqueous ammonia were added, the reaction was carried out at 80°C, and when the reaction product hardened on a 160°C heating plate for 6 minutes, it was dehydrated and concentrated, and then methanol was added. In addition, the resin content was adjusted to v4 to 50q6.

The solid content ratio of the tung oil-modified phenolic resin and the reactant 1 is [tung oil-modified phenolic resin]/[reactant 1].
The mixture was mixed and dissolved in a ratio of 80/20, and coated and dried on a kraft paper base of 11 mils to a resin adhesion amount of 509b.

A 35μ thick copper foil coated with an adhesive and eight sheets of the above-mentioned coated paper base material were combined and laminated, and heated and pressed to obtain a single-sided copper-clad laminate having a thickness of 1.6 mm.

Example 2 1380 g of a toluene solution of brominated bisphenol A diglycidyl ether having a bromine content of 448%, an epoxy equivalent i of 400, and a hydroxyl equivalent of 2200, and 153 g of a 60% toluene solution of the diglycidyl ether represented by formula (b).
and 2.09 g of triethylamine were charged into a Mitsuro flask and reacted at 90° C. for 3 hours.

Next, add triphenyl phosphite 309 and
After reacting for 4 hours at 0°C, 86% paraformaldehyde 15
g was added thereto, and the reaction was further continued at 80° C. for 2 hours (Reactant 2).

Using Reactant 2 and using the same blending amount and method as in Example 1, a single-sided copper-clad laminate with a thickness of 1.6 mm was obtained.

Comparative Example 1 The tung oil-modified phenolic resin used in Example 1 and a 60% toluene solution of brominated bisphenol A diglycidyl ether with a bromine content of 48 T and an epoxy equivalent of 400 were mixed in terms of solid content ratio, [tung oil-modified phenolic resin]/ (Bromated bisphenol A diglycidyl ether) = 80/20
The mixture was mixed and dissolved at a ratio of 1.5 mils, coated on 11 mils kraft paper and dried.
A 6M single-sided copper-clad) laminate was obtained.

Comparative Example 2 Tung oil modified phenolic resin used in Example 1 Comparative Example 1
The solid content of brominated bisphenol A diglycidyl ether and triphenyl phosphate was [
Tung oil modified phenolumite fat)/(brominated bisphenol A diglycidyl ether)/() liphenyl phosphate) were mixed and dissolved in a ratio of 60/30/10, and this was coated on 11 mils kraft paper and dried. Then, a single-sided steel-clad laminate having a thickness of 1.6M was obtained in the same manner as in Example 1.

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

, 10 Hook Table 1 Effects of the Invention As is clear from the above test results, the present invention has improved flame retardant effect, and provides flame retardant properties for laminates with excellent flexibility and heat resistance. A resin composition can be produced, and the storage stability of the resin solution and coating substrate can also be improved.

Further, by the method of the present invention, since the system contains almost no unreacted components exhibiting a mercury-like action, in addition to the above-mentioned effects, the chemical resistance of the laminate is also significantly improved.

Claims (1)

[Claims] Brominated bisphenol A diglycidyl ether and brominated bisphene represented by the general formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (1) Integer Nord A where m and n = 1 to 6 Production of a flame-retardant resin composition for a laminate, which comprises reacting an alkyl oxide adduct diglycidyl ether using a tertiary amine as a catalyst, then reacting triphenylphosphite, and then reacting formaldehyde. Law.