JPS636014A - Production of flame-retarding resin composition for laminate - Google Patents

Abstract

PURPOSE:To obtain a flame-retarding resin composition for laminates, which can impart excellent flame retardancy to a laminate even when used in a small amount, by reacting a brominated bisphenol A diglycidyl ether successively with a specified phosphate ester and an aromatic amine. CONSTITUTION:Brominated bisphenol A diglycidyl ether (A) (the number of moles of epoxy groups contained is a) is reacted with a phosphoric ester (B) of formula I (wherein m is 1 or 2, R1 is 1-6C alkyl, phenyl, formula II, formula III or the like, p is 1-3C alkyl, r is 1-3 and X is Cl or Br) (the number of moles of hydroxyl groups contained is b), e.g., formula VI, at a ratio satisfying a>b. The product is mixed with an aromatic amine (the number of moles of -NH groups contained is c) of formula V (wherein R3 is H or a 1-3C alkyl), e.g., formula VI, in such an amount as to satisfy a-b=c 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, due to a wide variety of required characteristics, especially dimensional accuracy, demands for low-temperature punching or no-heat punching, and further demands in terms of price 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, there are known low molecular weight additive flame retardants that do not have reactivity and reactive flame retardants that have reactivity. However, when additive flame retardants are used, the heat resistance, chemical resistance, and electrical properties of the laminate deteriorate.
Furthermore, interlayer adhesion is significantly reduced due to a decrease in the crosslinking density of the resin. In particular, regarding punchability, interlayer delamination during punching,
Powder may fall and the die may become clogged.

- When using method 1 reactive flame retardant, although the above-mentioned drawbacks 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. In addition, since the reactivity is high, the storage stability of the compounded resin and coating base material becomes poor.

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, both are used in combination, taking into consideration their respective advantages and disadvantages, due to a wide variety of requirements for characteristics. In addition, the combination of both, particularly the combination of halogen (Br is often used in practice) and P, has advantages from other aspects as well. In other words, it is better to use multiple elements that have flame retardant effects (halogen, P, N, B, etc.) in combination than to use them alone.
Their mutual effect increases the flame retardant effect, and as a result, the total amount of flame retardant resin and flame retardant used can be reduced. Furthermore, since the additive flame retardant has an excellent plasticizing effect, the combination thereof can improve flexibility and punchability.

However, to give an example of the most frequently used composite system of Br and P, conventional Br-based systems have been put into practical use in both the additive type and reactive type as mentioned above, but P-based systems have Only the additive type has been put into practical use. Therefore, Br
Even if it were possible to find a blending ratio that exhibits the optimum flame retardant effect in a composite system of P and P, the amount 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 be said that a compound system with a high flame retardant effect was necessarily selected.

As a result, the amount used to ensure flame retardancy increases, resulting in a problem of lower characteristics and higher costs.

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 excellent flame retardant properties. The object of the present invention is to provide a flame-retardant resin composition for laminates 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-mentioned object, and its first invention consists of brominated bisphenol A diglycidyl ether (containing number of moles of epoxy groups a) and −
Mathematical formula [■]■ () (O+-, I P-(0-几,) m...
・・・・・・・・・ CI) is an integer of 1 to 3, 几 is selected from the group of alkyl having 1 to 3 carbon atoms) phosphoric acid ester (number of moles of hydroxyl group contained b) , a >
After reacting with a composition such that b is obtained, the aromatic amine represented by the formula (n) R1 R1 (where 几 is a fulkyl group having 1 to 3 H1 carbon atoms) (the number of moles of 1NH it contains) C),
This is a method for producing a flame-retardant resin composition for a laminate, characterized by adding and reacting so that a-b=c.

Further, the second invention provides, in the first invention, −mathematical formula (I
In place of the aromatic amine represented by formula (t), an aromatic amine represented by the formula (I[l) is used, and the third invention is the case in which the aromatic amine represented by the formula (II) is used in the first invention. This is a case where an aromatic amine represented by the formula [■] is used instead of the aromatic amine represented by the formula [■].

In either case, the amount added is the same as in the first invention.

The hydroxyl group of the phosphoric acid ester represented by the general formula (1) has a very high reactivity with the epoxy group, and even without a catalyst, the hydroxyl group of the phosphoric acid ester has a
If heated above 0"C, the reaction will occur in a short time. Due to this reactivity, the phosphoric acid ester will bond to the brominated epoxy resin which has been polymerized to some extent, so it will not react with conventional additive type phosphoric acid esters. It is possible to increase the amount of phosphoric acid ester used relatively freely without exposing its various drawbacks.In this way, the amount of phosphoric acid ester used can be increased to the point where the mutual effect of Br and P can be effectively exerted. It can be increased.

Further, after reacting the brominated bisphenol A dik 1J cidyl ether with the phosphoric acid ester, -formula'
(2) Alternatively, by adding an aromatic amine represented by formula (III) or (IV) in an amount equivalent to the amine equivalent to the remaining epoxy group, C1 is bonded to the remaining epoxy group. - The aromatic amine represented by formula (n) or formula [111) or (IV] retains the ability to be methylolated at the ortho position with respect to the -NH group by formaldehyde, and is not suitable for blending into phenol resins. In this way, by combining the entire reaction composition with the phenolic resin, which is the main ingredient, it is difficult to easily promote the bonding with the phenolic resin during curing. It is possible to completely overcome the drawbacks similar to those of refueling agents.

Regarding the usage amount of the phosphoric acid ester represented by the general formula CI), "C" means that when the number of moles of hydroxyl groups in the phosphoric ester becomes larger than the number of moles a of the epoxy groups in the brominated bisphenol A diglycidyl ether, the remaining hydroxyl groups reacts with the aromatic amine added later, leaving a low-molecular-weight phosphate ester amine salt in the system, which is undesirable because the disadvantages of additive-type flame retardants are inherent.Also, If the amount of P contained in the phosphoric acid ester is less than 24 compared to the amount of Br contained in the brominated bisphenol A diglycidyl ether, the effect on flame retardancy will be reduced.

Within the above range, C, brominated bisphene/-/I/
As the amount of phosphate ester increases with respect to A diglycidyl ether, the number of ends where the reaction ends between the epoxy group and the phosphoric ester increases, and the flexibility effect of the phosphoric ester is also added. Improves flexibility. moreover,
This tendency increases because the number of epoxy groups that can react with tertiary amines also decreases.

The number of hydroxyl groups (mwt or 2) in the phosphoric ester represented by the general formula (I) is not particularly limited, and a single structure in which m=1 or 2 or a mixture thereof can be used. - In general formula CI), m=5
When the amount of phosphoric acid ester used, represented by 1, increases, the average molecular weight of the reaction system becomes relatively low, and the flexibility improves. Furthermore, when the amount of phosphoric acid ester used, which is represented by m w 2, increases, the average molecular weight of the reaction system increases, and although the flexibility slightly decreases, the interlayer adhesion improves.

In addition, the phosphoric esters that can be used include alkyl phosphoric esters in which 几 is an alkyl group having 1 to 6 carbon atoms;
Further, R1 is a phenyl group.

1-3 substituted alkyl (1-3 carbon atoms) phenyl group, 1
The bromo compound for ~34 is a phosphoric acid ester which is a chlorophenyl group. They can be used as a single structure, a composite of the above structures, or a mixture thereof.

In alkyl phosphate esters, as the number of carbon atoms in the alkyl group increases, flexibility improves, but the flame retardant effect tends to decrease. If the number of carbon atoms exceeds 6, the solubility in a phenol resin solution containing a large amount of methanol decreases, making it unsuitable as a flame retardant resin for laminates. In the phenyl phosphate ester, the number of carbon atoms in the alkyl group substituted by the phenyl group is also limited to 3 or less for the same reason as described above. Furthermore, when the phenyl group is substituted with 8r or C1, C exhibits a more remarkable effect on flame retardancy.

From the above characteristic trends, the total amount of phosphoric ester represented by the general formula CI), the number of substituents (m), the structure of the substituent R, and By adjusting their mixing ratio, a flame-retardant resin with predetermined characteristics can be obtained.

In the reaction system of the brominated bisphenol A diglycidyl ether of the present invention and the phosphoric ester represented by the general formula [I], the reaction proceeds in a short time without a catalyst when the temperature is raised to 40 to 50°C or higher, so especially Does not require a catalyst. - general formula CI)
Since the phosphoric acid ester represented by is a relatively strong acid, if it remains, as mentioned above, the general formula (
II) or the aromatic amine represented by formula CI], CI'll'), it easily forms an acid amide, leaving a low molecular weight substance. However, the degree of reaction can be confirmed by the following method, and it can be proven that most of the phosphoric acid ester has completed the reaction with the brominated bisphenol A diglycidyl ether.

That is, a certain amount of a mixture of brominated bisphenol A diglycidyl ether and a phosphoric acid ester represented by the general formula CI) was taken, diluted with 10 times the amount and 5 times the amount with distilled water, and after stirring, the aqueous layer was phase-separated. Measure the pH of. -Depending on the structure and usage amount of the phosphoric acid ester represented by the general formula CI], those with a pH of L to 3 at the time of blending have a pH of -6,8 after the reaction.
~7.0! Therefore, it is considered that the hydroxyl groups of the phosphoric acid ester are almost completely consumed by the reaction.

After their reaction, - formula (II) or formula [1■], (I
An aromatic amine represented by V) is added, but the ortho-position of the -NH group is unsubstituted and has room for reaction with formaldehyde.

This allows formaldehyde to undergo methylolization, facilitates bonding with the phenolic resin, and binds the entire reaction system to one of the skeletons of the phenolic resin, thereby suppressing drawbacks as an additive flame retardant. It is something.

- The amount of the aromatic amine represented by formula (II) or formula (It) [v]
When the number of moles of the -NH group is made larger than the number of moles of the epoxy group remaining after the reaction of the diglycidyl ether and the phosphoric acid ester represented by the general formula CI), due to the action of the remaining -NH1 group, , the storage stability of a blended solution with a phenolic resin deteriorates, and in extreme cases, it may become cloudy immediately after blending. In addition, the amount of aromatic amine added is
If the temperature is less than the residual epoxy group, the storage stability of the mixed solution with the phenol resin and the coated substrate will deteriorate due to the action of the residual epoxy group. Therefore, the amount of the aromatic amine represented by formula [■] or formulas (III) and (IV) to be added is determined by the number of moles of monoNH2 group contained and the brominated bispheno-/I/A diglycidyl in the preceding stage. It is preferable that the number of moles of the epoxy group remaining after the reaction of the ether and the phosphoric acid ester represented by the general formula (I) be equal, so that the epoxy group and the -NH group are completely reacted.

The flame retardant resin of the present invention can be used alone or in combination with a relatively small amount of additive flame release agent such as triphenyl phosphate or brominated diphenyl ether, but in either case, the flame retardant resin 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 60 liter toluene solution of brominated bisphenol A diglycidyl ether with a bromine content of 48 or more and an epoxy equivalent of 400. □.

Phosphate ester represented by (weight ratio A/B = 1/1) 7
3? was charged into a Mitsuro flask and reacted at 80°C for 2 hours (reactant 1).

51 samples of the solution were taken at the time of blending and at the end of the reaction, and the total amount was 50.
Distilled water was added so that the p
When H was measured, they were 2.3 and 7.0, respectively.

Further, when the epoxy equivalent was measured by the tetraethylamsonium bromide-perchloric acid method, the epoxy equivalent weight of the entire solution was 1020 and 700 at the time of blending and after completion of the reaction, respectively.

78? and further reacted at 80″C for 1 hour (Reactant 2).

Additionally, a tung oil-modified phenol resin was separately obtained in the following manner. Tung oil 720 in a Mitsuro flask? , m-cresol 58
0%, para-toluenesulfonic acid 0.74P was added,
After reaction at 80°C for 1 hour, phenol 5005', 86
4 Paraform 450? , 359 - of 25% aqueous ammonia was added, the reaction was further advanced at 80°C, and when the curing time reached 6 minutes on a 160'C heating plate, it was dehydrated and concentrated, and methanol was added afterwards to reduce the resin content to 50%. Adjusted to oyster.

This tung oil modified phenolic resin and the reactant (2) were mixed at a solid content ratio of tung oil modified phenolic resin/reactant (21-8
Mix and dissolve in a ratio of 0/20 and apply this varnish to 11 mils kraft paper. Furthermore, Example 1
Using a varnish in which reactant 3 and tung oil-modified phenolic resin were mixed in the same ratio as in Example 1, a thickness of 1.6
A single-sided copper-clad paper-based phenolic resin laminate of TAM was obtained.

Example 3 Using 77 g of phosphoric acid ester (weight ratio E/F-1/1), a single-sided copper-clad paper board with a thickness of 1.6 mm was prepared in the same manner as in Example 1. A phenolic resin laminate was obtained.

Example 4 Phosphate ester (weight ratio G/H-1/1) 50
It was coated and dried to give a good finish.

One sheet of 35μ thick copper foil with adhesive and the coated dry paper base material 8
The sheets were combined and heated and pressed to obtain a phenolic resin laminate with a copper clad paper base on one side and a thickness of 1.6 mm.

Example 2 Brominated bisphenol A diglycidyl ether toluene solution L532 similar to Example 1? Phosphate ester (
Weight ratio C/D=l/1)97? was put into a Mitsuro flask and reacted in the same manner as in Example 1. After checking the pH, 961 ml of amine was added and reacted in the same manner as in Example 1.
Reactant 3).

534? , CH.

Oh.

Aromatic amine 36? A 1.6 m thick single-sided copper-clad paper-based phenolic resin laminate was obtained in the same manner as in Example [1].

Comparative Example 1 Tung oil-modified phenolic resin used in Example 1 and a 60 ml toluene solution of brominated bisphenol A diglycidyl ether with a bromine content of 48 or more and an epoxy equivalent of 400 were mixed at a solid content ratio of tung oil-modified phenolic resin/brominated bisphenol. A diglycidyl ether was mixed and dissolved in a ratio of 80/20, and using this varnish, a phenolic resin laminate having a thickness of 1.6 nm and having a copper clad paper base on one side 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 the previous oil-modified phenol resin/brominated bisphenol diglycidyl ether/triphenyl phosphate = 60/
The varnishes were mixed and dissolved at a ratio of 30/lO, and using this varnish, a phenolic resin laminate having a thickness of 1.6 shoes and having a copper-clad paper base on one side 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.

From the test results above and beyond the effects of the invention, it can be seen that the present invention can reduce the amount of flame retardant used and improve the low-temperature punchability of the laminate. Furthermore, the storage stability of the flame retardant resin solution and coating substrate is improved, and its industrial value is extremely large.

Claims (1)

[Claims] 1. Brominated bisphenol A diglycidyl ether (
Number of moles of epoxy groups contained a) and general formula [I] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼・・・・・・・・・
...[I] (However, m = 1 or 2, R_1 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 is 1 An integer of ~3, R_
2 is an alkyl group with 1 to 3 carbon atoms), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (r is an integer from 1 to 3, X is Cl or Br), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (p + r ≦5)) represented by phosphoric acid ester (number of moles of hydroxyl groups contained b) in a proportion such that a>b, general formula [II] ▲ Numerical formula, chemical formula, There are tables, etc. ▼・・・・・・・・・
...[II] (However, R_3 is H, an alkyl group having 1 to 3 carbon atoms) aromatic amine (the number of moles of NH contained C) is set so that a-b=c. A method for producing a flame-retardant resin composition for laminates, which comprises adding and reacting the composition. 2. Brominated bisphenol A diglycidyl ether (
Number of moles of epoxy groups contained a) and general formula [I] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼・・・・・・・・・
...[I] (However, m=1 or 2, R_1
is an alkyl group with 1 to 6 carbon atoms, ▲ has mathematical formulas, chemical formulas, tables, etc. ▼, ▲ has numerical formulas, chemical formulas, tables, etc. ▼ (p is an integer of 1 to 3, R_2 is an alkyl group with 1 to 3 carbon atoms ),
▲There are mathematical formulas, chemical formulas, tables, etc.▼ (r is an integer from 1 to 3, X is Cl or Br), ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (selected from the group of (p+r≦5)) After reacting phosphoric acid ester (number of moles of hydroxyl groups b) in a proportion such that a>b, formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・・
...[III] A flame-retardant resin composition for a laminate, characterized in that an aromatic amine represented by (containing -NH) c is added and reacted so that a-b=c. Production method. 3. Brominated bisphenol A diglycidyl ether (
Number of moles of epoxy groups contained a) and general formula [I] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼・・・・・・・・・
...[I] (However, m=1 or 2, R_1 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 is An integer of 1 to 3, R_2 is an alkyl group with 1 to 3 carbon atoms), ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (r is 1 to 3
, where X is an integer of Cl or Br), ▲Mathematical formula, chemical formula, table, etc. ▼(p+r≦5)) is a phosphoric acid ester (number of moles of hydroxyl groups contained b), a> After reacting with a mixture that gives b, the formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
IV] Aromatic amine represented by (number of moles of -NH contained c)
A method for producing a flame-retardant resin composition for a laminate, which comprises adding and reacting so that a-b=c.