JPH01144414A - Production of flame-retardant resin composition for laminated board - Google Patents

Abstract

PURPOSE:To obtain the title composition having improved flame retarding effect and excellent flexibility and heat-resistance and useful for the production of a laminated board, by using a reaction product produced by reacting a plurality of specific glycidyl ethers and reacting the product with triphenyl phosphite. CONSTITUTION:(A) A reaction product produced by reacting (i) a brominated bisphenol A diglycidyl ether with (ii) an adduct of brominated bisphenol A alkyl oxide and diglycidyl ether of formula I (R1 and R2 are -CH2-, -C2H4- or group of formula II; m and n are 1-6) in the presence of (iii) a tertiary amine as a catalyst and reacting the reaction product with (iv) triphenyl phosphite is made to react with (B) formaldehyde and then with (C) an aromatic amine of formula III (R3 is H or CnH2n+1; n is 1-3) to obtain the objective composition. The component C is preferably the aromatic amine of formula IV or formula V.

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 a flame retardant laminate with excellent storage stability. The present invention relates to a method for producing a synthetic 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 (composed of laminated boards) used therein. At the same time, among the wide variety of required property items, demands for low-temperature punching or no-heat punching processability and heat resistance are becoming increasingly strict 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. When additive flame retardants are used, the heat resistance, heavy-duty resistance, and electrical properties of the resin blended with them decrease, and furthermore,
Due to the reduction in crosslink density, the obtained f! The adhesion of the lamina between the eyebrows is significantly reduced. In particular, with regard to punching workability, defects such as flaking between the eyebrows, powder falling during punching, and die clogging are likely to occur.

When used in combination with reactive flame retardants, although the above-mentioned disadvantages are small, the increased crosslinking density of the resin when used as a laminate moves the softening temperature of the laminate to a higher temperature side, making it easier to use at low temperatures or without heating. It becomes unsuitable for punching, and due to its reactivity, the storage stability of the compounded resin and coated substrate deteriorates.

A typical example of the former is brominated bisphenol A1
There are brominated diphenyl ales, triphenyl phosphate, and alkyl derivatives thereof, and a representative example of the latter is brominated epoxy resin.

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, 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, due to the disadvantages of additive flame retardants mentioned above, it is not possible to easily increase the amount used, and it is not sufficient to It was not possible to increase the amount to the point where it exhibited sufficient flexibility.

Problems to be Solved by the Invention From the above, flame retardant resins and flame retardants that conventionally use phosphorus 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 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-mentioned points, the present invention provides a laminated board that is excellent in flame retardancy, heat resistance, flexibility, and low-temperature punching processability by blending and using the same, and also has excellent storage stability. The object of the present invention is to provide a resin composition for flame-retardant laminates.

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 general formula (1) using a tertiary amine as a catalyst, triphenylphosphite ((C6HsO)sP) is produced. This is a method for producing a flame-retardant resin composite for a laminate, which involves reacting formaldehyde, followed by reacting an aromatic amine represented by general formula (2).

\/ (Here, R, -H or Cn H! n * 11,
n = 1 to 3) In contrast to the above-mentioned specific invention, the second invention is a case in which an aromatic amine represented by formula (3) is used in place of the aromatic amine represented by -maximum (1), The third invention is a case where an aromatic amine represented by formula (4) is used in place of the aromatic amine represented by -maximum (2).

Effect In the present invention, by reacting brominated bisphenol A diglycidyl ether with brominated bisphenol A alkyl oxide adduct diglycidyl ether represented by the general formula (1), flexibility is imparted by the alkyl oxide structure of the latter. , a reactive flame retardant with excellent flexibility by exhibiting flexibility that was not sufficient in conventional brominated bisphenol A diglycidyl ether, and by leaving an epoxy group, which is a reactive group, at the end of the reactive molecule. It is possible to obtain a synthetic resin.

At the same time, incorporating an alkyl oxide group into the molecular skeleton expands the bisphenol A structure with one bromine loss, which suppresses lees crystallization and improves storage stability.

- When R, SR, and the number of carbon atoms in maximum (1) are 4 or more, the heat resistance decreases slightly, and when the resulting composition is used by blending it with a methanol-rich phenol resin, the compatibility decreases.

Catalysts that are not used in the above reaction steps include tertiary amines such as trimethylamine, triethylamine, triethanolamine, and benzyldimethylamine. When a primary or secondary amine is used, a three-dimensional bridge #j structure is likely to be formed, and the resulting composition loses compatibility with the phenol resin blended therein.

In the step of reacting triphenylphosphite, triphenylphosphite is converted into brominated bisphenol A.
An ester reaction occurs with the hydroxyl group of the diglycidyl ether and the compound represented by the general formula (1), and the compound chemically bonds to the reactant molecules while releasing phenol (see formula (5)).

-OH+C>o-p-+o-Q)g H Since triphenylphosphite is trifunctional, it can itself become the center of crosslink formation. Through this reaction, triphenylphosphite participates in the crosslinking of the reactant and is incorporated into its skeleton. It is possible to have a phosphorus content, Br, P
The amount used can be increased to the point where the synergistic effect on flame retardancy is most effective. As shown in formula (5), 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, if this continues, it is inevitable that unreacted phenol will remain.Therefore, in the next step, in order to methylolize the produced phenol and make it reactive, formaldehyde is added and reacted. .

Furthermore, in the next step, −maximum (2) or equations (3) and (4)
An aromatic amine represented by is added and reacted, and the amine is added to the epoxy group remaining in the system so as to have an equivalent amine equivalent, thereby bonding with the remaining epoxy group. The aromatic amine has the ability to be methylolated by formaldehyde at the position ortho to the -NH group, and when the composition obtained according to the present invention is blended with a phenol resin and used, the curing reaction is suppressed. During the process, bonding with phenolic resin can be easily promoted.

In this way, by combining the entire reactive composition with the phenolic resin with which it is blended, the disadvantages similar to additives, flame retardant resins and flame retardants can be completely overcome.

EXAMPLE In carrying out the present invention, brominated bisphenol A
The mixing ratio of diglycidyl ether and the brominated bisphenol A alkyl oxide additive diglycidyl ether represented by the general formula (1) is not particularly limited; In order to achieve the desired effect, it is desirable that the latter weighs 5 or more.

As the latter increases, flexibility and storage safety improve, so it may be used alone when compounding as a flame retardant. However, since the Br content is small compared to the former, In order to obtain a flame retardant effect, it is better to adjust the mixing ratio of the three components depending on the application system.As for the amount of tertiary amine catalyst added, the amount of brominated bisphenol A diglycidyl ether and the general formula (1) shown in Solid state and general formula (
The ratio of triphenylphosphite to the reactant of the compound shown in 1) is 1. In order to avoid unreacted triphenylphosphite remaining,
It is preferable that the reaction product satisfies the following relationship: hydroxyl group equivalent of the reactant]≧[molecular weight of triphenylphosphite Xi/3].

The amount of formaldehyde used is preferably in the range of 1, [number of moles of triphenylphosphite x 3]≧[number of moles of formaldehyde]≧[number of moles of triphenylphosphite].

If used in excess, formaldehyde will remain after the reaction, and if used in excess, phenol will remain.

Furthermore, when the amount of aromatic amine added represented by -a formula (2) or formulas (3) and (4) is such that the number of moles of NH groups is greater than the number of moles of epoxy groups remaining after the first stage reaction. Due to the action of the remaining NH groups, the storage stability of the blended solution with the phenol resin becomes poor (in extreme cases, it may become cloudy immediately after blending). If the number of moles is small compared to the number of moles of the group, the storage stability of the mixed solution with the phenol resin and the coated substrate impregnated with this solution will deteriorate due to the action of the remaining epoxy groups.

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 triethylamine, pro-phenyl ether, etc. It is also possible to reduce the total amount of flame retardant resin and flame retardant used.

Embodiments of the present invention will be described in detail.

Example 1 613 g of a 60% toluene solution of brominated bisphenol A diglycidyl ether with a bromine content of 48%, an epoxy equivalent of 400, and a hydroxyl equivalent of 2.200 and 2.76 g of dimethylbenzylamine were charged into a Mitsuro flask and heated at 90°C.
The mixture was allowed to react for 3 hours.

Next, add 20g of triphenylphosphite and add 80g of triphenylphosphite.
After reacting for 4 hours at °C, 12 g of 86% paraformaldehyde
was added, and the mixture was further reacted at 80°C for 2 hours.

Subsequently, 57 g of diaminodiphenylmethane was added, and the reaction was further continued at 80° C. for 1 hour (Reactant 1).

Separately, a tung oil-modified phenol resin containing the reactant 1 obtained according to the present invention was obtained in the following manner.

Tung oil 720g in a Mitsuro flask 5rn-cresol 58
0 g and 0.74 g of p-toluenesulfonic acid were added, and after reacting at 80°C for 1 hour, 500 g of phenol was added.

Add 450 g of 86% paraformaldehyde and 35 g of 25% ammonia water, proceed with the reaction at 80''C, and when the curing time of the reactive composition on a 160°C hot plate reaches 6 minutes, dehydrate and concentrate. Afterwards, methanol is added to reduce the resin content to 50%.
NIILI N Sita.

The solid content ratio of the tung oil-modified phenolic resin and the reactant 1 is [tung oil-modified phenolic resin]/(reactant 1) -8
The mixtures were mixed and dissolved in a ratio of 0/20, and this solution was applied to 11 mils kraft paper in an amount of 50 resins, and heated and pressurized to obtain a single-sided copper-clad laminate with a thickness of 1.6 m+a.

Example 2 A 60% toluene solution of brominated bisphenol A diglycidyl ether with a bromine content of 48%, an epoxy equivalent of I of 400, and a hydroxyl equivalent of 2.200 (1,380 g) and a 60% toluene solution of a diglycidyl ether represented by formula (b) 1
53 g and 1.84 g of triethylamine were charged into a Mitsuro flask and reacted at 90° C. for 3 hours.

CH.

Next, add 30g of triphenylphosphite and
After reacting for 4 hours at o''C, 86% paraformaldehyde 1
5 g was added, and the reaction was further carried out for 2 hours at ao''c.

Subsequently, 240 g of diaminone diphenyl sulfone was added, and the reaction was further continued for 1 hour at 80"C (Reactant 2)
.

Using Reactant 2 and the tung oil-modified phenolic resin in Example 1, a single-sided copper-clad laminate with a thickness of 1.6 cm was obtained using the same blending amounts and method as in Example 1.

Example 3 Brominated bisphenol A diglycidyl ether having a bromine content of 48%, an epoxy equivalent of 400, and a hydroxyl equivalent of 2,200, 183 g of a 60% toluene solution of the diglycidyl ether represented by formula (C), and 220 g of triethanol were placed in a Mitsuro flask. and reacted at 90°C for 3 hours.

CH,+ Next, 32g of triphenylphosphite was added, and 8
After reacting at 0°C for 4 hours, 16g of 86% paraformaldehyde was added, and the reaction was further carried out at 80°C for 2 hours.

Subsequently, 180 g of diaminodiphenyl ether was added,
The reaction was further continued at 80° C. for 1 hour (reactant 3).

Using Reactant 3 and the tung oil-modified phenol resin in Example 1, a single-sided copper-clad laminate having a thickness of 1.6 aua was obtained using the same blending amount and method as in Example 1.

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% and an epoxy weight of 1400 were mixed at a solid content ratio [tung oil modified phenolic resin 1M]/ (Brominated bisphenol A diglycidyl ether) -80/
They were mixed and dissolved at a ratio of 20%. This solution was coated and dried on the same kraft paper as in Example 1 to obtain a coated dry paper, and then in the same manner as in Example 1, a single-sided copper-clad laminate with a thickness of 1.6 mm was obtained.

Comparative Example 2 Tung oil modified phenolic resin used in Example 1 and Comparative Example 1
Brominated bisphenol A diglycidyl ether and triphenyl phosphate used in solid content ratio [tung oil modified phenol resin]/[brominated bisphenol A]
diglycidyl ether]/(triphenyl phosphate) - mixed and dissolved in a ratio of 60/30/10.

This solution was coated on the same kraft paper as in Example 1 and dried to obtain a coated dry paper.
．． A single-sided copper-clad laminate of 6 pores was obtained.

Table 1 shows the test results for the laminates obtained in Examples and Comparative Examples. The storage stability of the flame retardant resin solution and the coated dry paper are also shown.

From the test results that exceed the effects of the invention, the present invention improves the flame retardant effect, contributes to the production of A-layer plates with excellent flexibility and heat resistance, and improves the storage stability of resin solutions and coated dry paper. improves. Also,
By the method of the present invention, the system can contain almost no unreacted components that act as plasticizers, so in addition to the above-mentioned effects, the chemical resistance of the product M@ is also significantly improved.

Claims (1)

[Claims] 1. Brominated bisphenol A diglycidyl ether and general formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (1) [R_1, R_2=-CH_2-, C_2-H_4-▲
There are mathematical formulas, chemical formulas, tables, etc. Selected from ▼. m, n = integer of 1 to 6] A reaction product obtained by reacting a brominated bisphenol A alkyl oxide adduct diglycidyl ether shown using a tertiary amine as a catalyst, and then reacting it with triphenylphosphite. , react with formaldehyde,
Furthermore, general formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) (Here, R_3=H or C_nH_2_n_+_1
A method for producing a flame-retardant resin composition for a laminate, which comprises reacting an aromatic amine represented by n=1 to 3). 2. Brominated bisphenol A diglycidyl ether and general formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [R_1, R_2 = -CH_2-, C_2H_4- ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ To be elected. m, n = an integer of 1 to 6] After reacting the brominated bisphenol A alkyl oxide adduct diglycidyl ether represented by tertiary amine as a catalyst, the reaction product obtained by reacting triphenylphosphite with A method for producing a flame-retardant resin composition for a laminate, which comprises reacting formaldehyde and then reacting an aromatic amine represented by formula (3). 3. Brominated bisphenol A diglycidyl ether and general formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [R_1, R_2 = -CH_2-, C_2H_4- ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ To be elected. m, n = an integer of 1 to 6] After reacting the brominated bisphenol A alkyl oxide adduct diglycidyl ether represented by tertiary amine as a catalyst, the reaction product obtained by reacting triphenylphosphite with , formaldehyde is reacted, and general formula (4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (
4) A method for producing a flame-retardant resin composition for a laminate, which involves reacting an aromatic amine represented by the following.