JPS636015A - Production of flame-retarding resin composition for laminate - Google Patents

Abstract

PURPOSE:To obtain a resin composition for laminates, excellent in flame retardancy, flexibility, etc., by reacting a brominated bisphenol A diglycidyl ether successively with its alkylene oxide adduct and a phosphoric ester. CONSTITUTION:Brominated bisphenol A diglycidyl ether (A) is reacted with an alkylene oxide adduct (B) of component (A) of formula I (wherein R1 and R2 are each -CH2-, -C2H4 or the like and m and n are each 1-6) in the presence of a tert. amine as a catalyst. The product is mixed with a phosphoric ester of formula II (wherein l is 1 or 2, R2 is a 1-6C alkyl, phenyl, formula III or the like, p is 1-3 and R4 is a 1-3C alkyl), e.g., formula IV, in such an amount that the number of moles of the hydroxyl groups contained in this phosphoric ester is smaller than that of the epoxy groups left in components A and B after the reaction and reacted to obtain the purpose flame-retarding resin composition for laminates.

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, flexibility, low-temperature punchability, and 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 used therein.

At the same time, there are a wide variety of required characteristics, especially dimensional accuracy requirements, low-temperature punchability or no-heat punchability, and price requirements are becoming stricter year by year. Therefore, there is a need for a flame-retardant resin for laminates that is low in price, has little property deterioration, and has excellent low-temperature punching or no-heat punching properties. It was difficult to satisfy the objectives of

That is, as conventional flame retardant resins and flame retardants, low molecular weight additive flame retardants that do not have °C1 reactivity and reactive flame retardants that have reactivity are known. When an additive flame retardant is used, the heat resistance, chemical resistance, and electrical properties of the laminate deteriorate, and furthermore, the crosslinking density of the resin decreases, resulting in a significant decrease in interlayer adhesion. In particular, regarding punchability, delamination between layers, powder falling, and clogging of the die hole occur during punching. - On the other hand, when reactive flame retardants are used, although the above-mentioned disadvantages are small, the increase in crosslinking density when made into a laminate moves the softening point of the laminate to a higher temperature side, making it easier to punch at low temperatures or without heating. Moreover, because of its natural 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 °C brominated epoxy resin.

In reality, this is due to a wide variety of characteristic requirements.

Both are used together, taking into account their respective strengths and weaknesses. In addition, the combination of both, especially halogen (Br is often used in practice) and P, has advantages from other aspects as well. In other words, the flame retardant effect increases when multiple elements that have a flame retardant effect (halogen, P, N, B, etc.) are used in combination than when used alone due to their mutual effect. This results in a reduction in the total amount of flame retardant resin and flame retardant used. Furthermore, since additive flame retardants have excellent plasticizing effects, their combined use can improve flexibility and punchability.

However, to give an example of the most frequently used composite system of Br and P, conventional Br-based flame retardants have been put into practical use as both additive and reactive flame retardants as mentioned above, but P-based Regarding C, only the additive type has been put into practical use. Therefore, even if a combination of I3r and P that exhibits the optimum flame retardant effect is found, the amount of C used cannot be easily increased due to the disadvantages of additive flame retardants.

Problems to be solved by the invention Conventional flame retardant resins and flame retardants have various limitations in terms of properties, so it is difficult to freely change the ratio of halogen, P, N, etc. to obtain the optimal flame retardant effect. The degree of flame retardancy was very narrow, and it could not necessarily be said that the blending system with the highest flame retardant effect was selected. In addition, in terms of flexibility and low-temperature punchability, the amount of additive flame retardants used is limited, and conventional flame retardant resins have a high content of reactive flame retardants, which reduces flexibility. It was not suitable for low-temperature punching.

As a result, the amount used to ensure flame retardancy increases, resulting in problems such as deterioration of low-temperature punchability and other properties, and increase in cost.

The present invention solves the above-mentioned problems of conventional flame retardant resins and flame retardants, exhibits flame retardant effects even when used in small amounts, has excellent flame retardancy, and has other properties. It is an object of the present invention to provide a flame-retardant resin composition for a laminate that has excellent flexibility, low-temperature or non-heat punching properties, and storage stability without deterioration.

Means for Solving the Problems The present invention has been made to achieve the above object, and includes brominated bisphenol A diglycidyl ether,
-Formula (I) (R,,R, is -0E(,-1-C,H,-1-0H
-CH, -0H.

After reacting a brominated bisphenol A alkyl oxide adduct diglycidyl ether selected from (m, n = an integer of 1 to 6) using a tertiary amine as a catalyst,
- a phosphoric ester represented by the formula (n) (selected from p + r≦5), in which the number of moles of hydroxyl groups contained in the phosphoric ester is greater than the number of moles of epoxy groups remaining after the reaction of the former two; This is a flame-retardant resin composition for laminates obtained by adding and reacting so as to reduce the amount.

Effect By using brominated bisphenol A diglycidyl ether and brominated bisphenol A alkyl oxide adduct diglycidyl ether represented by the general formula CI), flexibility is imparted by the alkyl oxide structure of the latter, and conventional brominated bisphenol A By exhibiting flexibility that was not sufficient with diglycidyl ether, and by leaving an epoxy group, which is 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, incorporating an alkyl oxide group into the molecular skeleton widens the spacing between the brominated bisphenol-containing structures by the flexible alkyl oxide group, thereby suppressing crystallization and improving storage stability.

The mixing ratio of brominated bisphenol A diglycidyl ether and brominated bisphenol A alkyl oxide adduct diglycidyl ether represented by the general formula CI) is not particularly limited; In order to exhibit the effect, 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 improve, so it may be used alone. However, since the Br content is slightly lower than the former, it is better to adjust the mixing ratio of the three depending on the application system in order to obtain the desired flame retardant effect (1° - formula (I)). [, 几1, 几, when the number of carbon atoms is 4 or more, the heat resistance is slightly decreased, and the compatibility with methanol-rich phenolic resin is also decreased.

As a reaction catalyst, tertiary amines such as trimethylamine, triethylamine, triethanolamine, and benzyldimethylamine are used.

When primary or secondary amines are used, a three-dimensional crosslinked structure is likely to be formed, resulting in loss of compatibility with the phenolic resin. The amount of the catalyst added is preferably in the range of 0.05 to 5.05 times the solid weight of the brominated bisphenol A diglycidyl ether and the compound represented by the general formula [■].

-The hydroxyl group of the phosphoric acid ester represented by the formula □(n) is
Extremely high reactivity with epoxy groups, even without catalyst
If heated to 50'C or higher, the reaction will occur in a short time. Due to this reactivity, the phosphoric acid ester binds to the brominated epoxy resin that has been polymerized to some extent and goes to C, so it can be relatively freely phosphoroused without exposing the drawbacks of the additive-type phosphoric esters mentioned above. It is possible to increase the amount of acid ester used. In this way, the mutual effect of Br and :P increases to the point where it can be effectively exerted.

Regarding the usage amount of the phosphoric acid ester represented by the general formula (n), the amount of epoxy remaining after the reaction of the brominated bisphenol A diglycidyl ether and the brominated bisphenol A alkyl oxide adduct diglycidyl ether represented by the general formula [I] It is necessary to make the number of moles of the hydroxyl group of the phosphate ester smaller than the number of moles of the group.

That is, when the number of hydroxyl groups in the latter is greater than the number of epoxy groups in the former, the pH of the phenolic resin solution blended for the laminate becomes acidic, promoting the condensation reaction of the phenolic resin, and causing problems during the production of the laminate. This speeds up the curing reaction and makes it difficult to control.

The amount of phosphoric acid ester to be used is not particularly limited within the above range, but the amount of phosphoric acid ester used is not particularly limited.
On the other hand, when the P contained in the phosphoric acid ester becomes less than 2 scratches, the effect on flame retardancy decreases. Within the above range, as the amount of phosphoric acid ester used increases, the number of terminals where the reaction ends between the epoxy group and the phosphoric acid ester increases, and the flexibility effect of the phosphoric acid ester is also added, making it more flexible. Improves sex.

From the above, the amount of phosphoric acid ester to be used can be appropriately selected depending on the desired flame retardant effect and flexibility effect of the applied system.

The number of hydroxyl groups (A=1 or 2) in the phosphoric acid ester represented by the general formula (n) is not particularly limited, and a single structure of it or 2 or a mixture thereof can be used. - In the formula [■], mg=
When the amount of the phosphoric acid ester shown by 1 increases, the average molecular weight of the reaction system increases and the flexibility slightly decreases, but the interlayer adhesion improves.

Further, the phosphoric ester that can be used is an alkyl phosphoric ester in which R is an alkyl group having 1 to 6 carbon atoms;
There are also phosphoric acid esters which are RIs, a caffeinyl group, a 1- to 3-substituted alkyl (carbon number 1-3) phenyl group, and a 1- to 3-substituted bromo or chlorophenyl group. Those too,
A single structure, a composite of the above structures, or a mixture thereof can be used. It is unsuitable as a flame retardant resin for laminates because its solubility in phenolic resin solutions containing a large amount of alkyl phosphoric acid or methanol is reduced. In the phenyl phosphate ester, the number of carbon atoms in the alkyl group substituted by the phenyl group is preferably 3 or less for the same reason as described above. Furthermore, when the phenyl group is substituted with Br or 02, C exhibits a more remarkable effect on flame retardancy.

From the above characteristic trends, for brominated bisphenol A diglycidyl ether, - brominated bisphenol A alkyl oxide adduct diglycidyl ether represented by the formula [E] and - phosphate ester represented by the formula (n) By selecting the total amount used and the structure, number, and mixing ratio of substituents, a flame-retardant resin with predetermined characteristics can be obtained.

The flame retardant resin of the present invention can be used alone or in combination with a relatively small amount of an additive flame retardant such as triphenyl phosphate or brominated diphenyl ether. The total amount of plastic resin and flame retardant used can be reduced.

Example Next, the present invention will be explained in detail.

Example 1 A solution of brominated bisphenol A diglycidyl ether with a bromine content of 48 mm and an epoxy weight of 1400 mm in toluene at 60 mm.

613P of a toluene solution of diglycidyl ether represented by 613P and 2.769P of dimethylbenzylamine were placed in a Mitsuro flask and reacted at 90°C for 3 hours. More OH.

Oh.

Phosphate ester represented by (weight ratio b / c = 1
/L) 7354 and reacted at 80°C for 2 hours (reactant (1)).

Additionally, a tung oil-modified phenol resin was separately obtained in the following manner. Tung oil 720 in a Mitsuro flask? , m-cresol 58
0y-, para-toluenesulfonic acid 0.7454 was added, and after reacting with go'c for 1 hour, phenol 500y-186
Yu paraform 450? , 351 of 25% aqueous ammonia was added, the reaction was proceeded at 80°C, and when the curing time reached 6 minutes on a 160"C heating plate, it was dehydrated and concentrated. Later, methanol was added to reduce the resin content to 50'l. Adjusted to.

This tung oil-modified phenolic resin and the reactant (1) were mixed at a solid content ratio of tung oil-modified phenolic resin/reactant (11=8
The varnish was mixed and dissolved in a ratio of 0/20, and the varnish was coated on 11 Mils kraft paper to a resin adhesion of 50% and dried.

One sheet of 35μ thick copper foil with adhesive and eight sheets of the coated and dried base material were combined and heated and pressed to obtain a single-sided copper-clad paper base phenolic resin laminate with a thickness of 1.6 mm.

Example 2 13805 L of brominated bisphenol diglycidyl ether toluene solution as in Example 1 and OH.

60 liters of diglycidyl ether shown in toluene solution 1
53P and triethylamine 1.84? was charged into a Mitsuro flask, and 975- of the phosphoric acid ester (weight ratio e/f = L/1) shown in the reaction at 90"C for 3 hours was charged and reacted at 80"C for 2 hours (reactant (2) )).

The tung oil-modified phenolic resin of Example 1 and the reactant (2) were used in the same proportions as in Example 1, and the thickness was 1.5 mm in the same manner as in Example 1.
A 6Wa single-sided copper-clad paper-based phenolic resin laminate was obtained.

Example 3 Diglycidyl ether 920? shown as a 60W toluene solution of brominated bisphenol A diglycidyl ether as in Example t? and triethanolamine 4.605
+- was put into a Mitsuro flask and reacted at 90°C for 3 hours. Furthermore, a phosphoric ester represented by (weight ratio h
/ i = 1/1) and reacted for 2 hours at so''c (reactant (3)).

Using the tung oil-modified phenolic resin and reactant (3) in the same proportions as in Example 1, and in the same manner as in Example 1, a single-sided copper-clad paper-based phenolic resin laminate with a thickness of 1.6 tms was prepared. Obtained.

Example 4 A 60 liter toluene solution of brominated bisphenol A diglycidyl ether as in Example 153? 604) A 1379% toluene solution of diglycidyl ether represented by 604 and dimethylbenzylamine 9,2051' were charged into a Mitsuro flask and reacted at 90°C for 3 hours. Furthermore, a phosphoric acid ester represented by (weight ratio/L=1/1) 5
3aP was added and reacted at 80°C for 2 hours (reactant (4)).

A single-sided copper-clad paper-based phenolic resin laminate with a thickness of 1.6 mm was obtained.

Comparative Example 1 Tung oil-modified phenolic resin used in Example 1 and 60% toluene solution of brominated bisphenol A diglycidyl ether with 400 fiL of epoxy and tung oil-modified phenol resin/brominated bisphenol were mixed at solid content ratio. Diglycidyl ether A was mixed and dissolved in a ratio of 80/20, and using this varnish, a phenolic resin laminate with a one-sided copper-clad paper base having a thickness of 1.6 B 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 was tung oil modified fluor resin/brominated bisphenol A diglycidyl ether/triphenyl phosphate = 60/30.
Using this varnish, a phenolic resin laminate with a one-sided copper-clad paper base having a thickness of 1.6 cm was obtained in the same manner as in Example 1 using this varnish.

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

Table 1 Effects of the Invention From the above test results, the present invention can reduce the amount of flame retardant used and improve the low-temperature degreasability of the laminate. Furthermore, the storage stability of the base material is improved, and the industrial value is extremely high.

Claims (1)

[Claims] Brominated bisphenol A diglycidyl ether and general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
[I] (R_1, R_2 are -CH_2-, C_2H_4-,
▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Selected from m, n
= an integer of 1 to 6) brominated bisphenol A
After reacting the alkyl oxide adduct diglycidyl ether with a tertiary amine as a catalyst, the general formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (l = 1 or 2
)...[II] (R_3 is an alkyl group with 1 to 6 carbon atoms, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (p = an integer of 1 to 3, R_4 is an alkyl group with 1 to 3 carbon atoms), ▲Mathematical formulas, chemical formulas, tables, etc.▼(r=1
~3 (an integer of 3, A method for producing a flame-retardant resin composition for a laminate, which comprises adding and reacting the former two so that the number of moles of the epoxy group is smaller than the number of moles remaining after the reaction.