JPS633016A - Production of flame-retardant resin composition for laminated sheet - Google Patents

Abstract

PURPOSE:To obtain a flame-retardant resin composition for laminated sheet and having excellent flame-retardancy, flexibility and storage stability, by reacting a brominated bisphenol A diglycidyl ether with a specific phosphoric acid ester. CONSTITUTION:The objective flame-retardant resin for laminated sheet can be produced by reacting (A) a brominated bisphenol A diglycidyl ether with (B) one or more kinds of phosphoric esters of formula I (R1 is 1-6C alkyl, group of formula II, etc.; m is 1 or 2). Preferably the amount of epoxy group is larger than that of hydroxyl group of the phosphoric ester and the amount of P of the phosphoric acid ester is >=2% of the amount of Br of the brominated bisphenol A diglycidyl ether.

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, which has excellent bag resistance, flexibility, and storage stability.

BACKGROUND OF THE INVENTION In recent years, there has been an increasing demand for flame retardant printed circuit boards used in household electric appliances, including safety measures.

At the same time, requirements for a wide variety of required properties (particularly dimensional accuracy requirements, low-temperature punching performance or no-heat punching performance), as well as price requirements, are becoming stricter year by year. Therefore, there is a need for a flame retardant resin and flame retardant for laminated plates that have excellent low-temperature punching properties and no-heat punching properties and have minimal deterioration. It has been difficult to completely satisfy the above objectives with oil and fuel.

That is, as conventional flame retardant lubricants and flame retardants, we use additive-type flame retardants with low molecular weight and no reactivity.

Reactive flame retardants are known1. However, if an additive flame retardant is used, the heat resistance, chemical resistance, and electrical properties of the laminate will decrease, and the crosslinking density of the resin will decrease, resulting in a significant decrease in interlayer density (especially 1m, for punching, there may be peeling between A, powder falling from the punching, or clogging of the die).

When a reactive flame retardant is used, the above disadvantages are less, but due to the increased crosslinking density of the resin when it is made into a laminate, the softening point of the laminate moves to the high temperature side, making it unsuitable for low temperature or non-heat punching. , Also, due to its high reactivity,
The storage stability of the compounded resin and coating base material 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 brominated epoxy resin.

In reality, both are used in combination, taking into consideration the strengths and weaknesses of each. Also,
The combination of both, especially the combination of halogen (Br is often used in practice) and P (another lateral force), is also advantageous.

In other words, elements that have a flame retardant effect (halogen, P, N, B, etc.)
Compared to using them alone, when using multiple of them together, their synergistic effect increases the flame retardant effect,
As a result, the total amount of flame retardant resin and flame retardant used can be reduced. Further, since the additive flame retardant has an excellent plasticizing effect, by using it in combination, it is possible to improve the flexibility and punching property.

However, to take an example of the most frequently used composite system (Br and PO), conventional Br-based systems have been put into practical use as both additive and reactive types, as mentioned above, but P-based systems have been put into practical use. (Additional type sword) has not been put into practical use. 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 drawbacks of additive flame retardants, C
Usage cannot be increased easily.

Problems that the invention seeks to solve Conventional flame retardant resins and flame retardants have various limitations in terms of properties, so it is necessary to change the ratio of halogen, P, N, etc. in order to obtain the optimum flame retardant effect. The degree of freedom was very narrow, and it could not be said that the combination system with the highest flame retardant effect was necessarily selected. As a result, the amount used to maintain flame retardancy of 1 increased, resulting in lower custom orders and cost issues.

The present invention solves the above-mentioned problems of conventional flame retardant oils and flame retardants, and has excellent flame retardancy and other properties so that it can exhibit flame retardant effects even when used in small amounts. An object of the present invention is to provide a flame-retardant resin composition for a laminate that has excellent flexibility of the laminate and storage stability of the resin without reducing the properties of the laminate.

Means to solve problems 〉°.

The present invention relates to brominated bisphenol A diF IJ cidyl ether and the general formula (HO(P+O-R+) 3 m (however, --
1 or 2) ......[Eng.] Less Il phosphate ester blFL! : A method for producing a resin composition for pickling, which is characterized by reacting (here, R+ is a carbon number of 1 ptll to 30
)'%tX, R1 is an alkyl group having 1 to 3 carbon atoms)
, (selected from the group of integers from r to 3, Xr≦5).

Phosphate ester represented by the general formula [E]) The water Q2 group has very high reactivity with epoxy groups, and even with a non-releasable solvent, it reacts in a short time if the temperature is lowered to 40 to 50°C or higher. do. Due to this reactivity, the phosphoric acid ester binds to the brominated epoxy resin, which has been polymerized to some extent.
It is possible to increase the amount of phosphoric ester used relatively freely without making the various drawbacks of the additive type phosphoric ester mentioned above obvious. In this way, the amount used can be increased to the point where the mutual effect of Br and P can be effectively exerted.

There are no particular restrictions on the effect of the phosphate ester represented by the general formula [E], but if there are many residual hydroxyl groups due to the phosphate ester, the pH of the phenol resin solution blended for the laminate is on the acidic side, promoting the condensation reaction of the phenol resin, and increasing the speed of the curing reaction when making Fukujen boards, but it becomes somewhat difficult to control. Therefore, for normal purposes, it is desirable to have a blended system in which the epoxy groups are present in a larger amount than the hydroxyl groups of the phosphoric ester, so that the phosphoric ester is completely reacted.

Furthermore, if the amount of P contained in the phosphoric acid ester is less than 2% with respect to the Br contained in the brominated bisphenol A diglycidyl ether, the effect on flame retardancy will decrease.

Within the above range, for brominated bisphenol A diglycidyl ether, the amount of phosphate ester increases (and the number of ends where the reaction ends between the epoxy group and the phosphate ester increases, In addition, the flexibility effect of the mono-diphosphate ester is added, and the flexibility is improved.

The number of hydroxyl groups (,, -1 or 2) of the phosphoric acid ester represented by the general formula [I] is not particularly limited to 1-2, and m-1 or 2 may be used as a single structure or a mixture thereof. Can be used for convenience. In general formula [I] 1:, as the amount of the phosphoric acid ester represented by C-1 increases, the average molecular weight of the reaction system becomes relatively low and the flexibility improves. Furthermore, as the amount of phosphoric acid ester (m=2) used increases or decreases, the average molecular weight of the reaction system increases, and although the flexibility decreases slightly, the interlayer flexibility improves.

In addition, as a phosphoric acid ester that can be used for one more time, R175
f, an alkyl phosphate ester which is an alkyl group having 1 to 6 carbon atoms; Alternatively, it 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 an alkyl phosphate ester, as the number of carbon atoms in the alkyl group increases, the p flexibility increases.

There is a tendency for the flame retardant effect to decrease. If the number of carbon atoms exceeds 6, the disintegration into phenolic resin solutions containing a large amount of methanol will decrease, making it unsuitable for use in laminates (as a fat). The number of carbon atoms in the alkyl group is also limited to 3 or less for the same reason as above.Furthermore, when the phenyl group is substituted with Br or at, an even more remarkable effect on flame retardancy is exhibited. Go down.

From the characteristic tendency of
With respect to diglycidyl ether, the total amount of phosphoric ester represented by the general formula CD and the number of substituents (,,),
By adjusting the structure of the substituent R3 and the mixing ratio thereof, a flame-retardant resin having predetermined characteristics can be obtained.

The reaction thread of the brominated bisphenol A diglycidyl ether of the present invention and the phosphoric acid ester represented by the general formula Does not require a catalyst.

Since the phosphoric acid ester represented by the general formula [E] is a relatively strong acid, if it remains, the condensation reaction rate of the diphenol resin will be affected as described above.

However, the degree of reactivity can be confirmed by the following method, and
This proves that most of the phosphate esters have completed the reaction.

That is, a certain amount of a mixture of brominated bisphenol A diglycidyl ether and a phosphoric acid ester represented by the general formula [E] was collected, diluted with distilled water to a 10-fold volume, stirred, and the pH of the aqueous layer separated into multiple phases was determined. Measure. - Although it depends on the structure and usage amount of the phosphoric acid ester represented by the general formula (Il), those with a pH of 1 to 3 at the time of blending have a pH of 6.8 after the reaction.
7.0, it is considered that the hydroxyl groups of the phosphoric acid ester are almost completely consumed by the reaction.

The flame retardant resin of the present invention can be used alone or in combination with a relatively small amount of additive flame retardant such as triphenyl phosphate or brominated diphenyl ether. In the case of fire retardant resin and clutter
It would be possible to reduce the total usage of t.

Example Next, Example 8r of the present invention will be explained.

Example 1 Brome-containing'! 60% toluene solution of brominated bisphenol A diglycidyl ether with 54B% niboxy equivalent of 400 1532s' and a phosphoric acid ester represented by the formula (weight ratio a/b -1/1)
73f was put into a Mitsuro flask and reacted at 80°C for 2 hours (0 reactants 1). 52 samples of the solution were taken at the time of blending and at the end of the reaction.
Distilled water was added so that the pF of the aqueous phase was stirred and the two phases were separated.
t was 2.3 at the time of blending and 7.0 at the end of the reaction.

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

Tung oil 720r-, I-cresol 5 in Mitsuro flask
Phenol 5002.86
% paraform 4509.25 ratio Aqueous ammonia 352% was added, the reaction proceeded at 80°C, and when the reaction material had hardened on a 160°C hot plate for 6 minutes, it was dehydrated and concentrated, and then methanol was added to the blade. Adjusted to 50% for the month.

This tung oil-modified phenol resin and the reactant (1) were mixed in a solid content ratio of tung oil-modified phenol resin/reactant (1) -
The varnish was mixed and dissolved at a ratio of 80/2 o, and the varnish was coated on 11 mils kraft paper for five coats to give a resin-coated S content of 50% and dried.

One sheet of 35 μ thick steel foil with adhesive and the coated dry paper base material 8
Combine the sheets and press with zero force to get 1.6! I used IIIJI's single-sided steel-clad paper-based phenolic resin laminate.

Example 2 Bromine content 48 mm, epoxy equivalent 4 (] O lipromated bisphenol A jig 1) 60% toluene solution of cidyl ether 1532 f and 2 HO-ko-Q) ...... [. ] and formula
(HOO12>-o-IQl, ---c, 1)-c, phosphoric acid ester (weight ratio c/a-1/1) 97r
was charged into a Mitsuro flask and reacted at 80°C for 2 hours (reactant 2). When the pH of the solution was measured in the same manner as in Example 1, it was 2.6 at the time of blending and 7.0 at the end of the reaction.

Hereinafter, using the same blending amount and method as in Example 13'lJ 1, a phenolic resin laminate having a thickness of 1.64 mm and having a single-sided steel clad paper base was obtained.

Example 3 A 60 ratio toluene solution of brominated bisphenol A diglycidyl ether with a bromine content of 48% and an epoxy equivalent of 400 (1532f) and L+0? ”.

Formula HO-) words...(e) and formula (HO
107 phosphoric acid esters (fJfL ratio o/f-1/1) represented by S・B-O-o...Cf') were charged into a Mitsuro flask and reacted at 80°C for 2 hours. (Reactant 3). The thickness was 1.6fi using the same 7 method as in Example 1.
A single-sided steel-clad paper-based phenolic resin laminate was obtained.

Example 4 A 60% toluene solution of prophylated bisphenol A diglycidyl ether with a bromine content of 48% and an epoxy equivalent of 400 (1532f) and a phosphoric acid ester represented by the formula 1 (heavy Jl ratio f/h-171)
534? was charged into a Mitsuro flask and reacted at 80°C for 2 hours (Reactant 4). Thereafter, in the same manner as in Example 1, a 1.6 wn thick single-sided steel-clad paper-based phenolic resin laminate was obtained.

Comparative Example 1 A 60% toluene solution of the tung oil-modified phenol resin used in Example 1 and brominated bisphenol A diglycidyl ether with a bromine content of 48 Yu and an epoxy equivalent of 400 was mixed with the solid content ratio of tung oil-modified phenol resin/brominated resin. Bisphenol 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 mm 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 brominated bisphenol A diglycidyl ether used in 1. and triphenyl phosphate 5' sulfate were added in a solid* ratio to tung oil modified phenol H1y.
1/brominated bisphenol diglycidyl k:r--
Example 1 was prepared using this varnish.
A single-sided copper-clad paper base phenolic resin laminate with a thickness of 1.6 strips was obtained in the same manner as above.

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

It is.

Claims (1)

[Claims] Brominated bisphenol A diglycidyl ether and the general formula [I] ▲There are numerical formulas, chemical formulas, tables, etc.▼ (However, m = 1 or 2) ・・・・・・・・・ [I ] A method for producing a flame-retardant resin composition for a laminate, characterized by reacting the composition with at least one phosphoric acid ester represented by the formula (where R_1 is an alkyl group having 1 to 6 carbon atoms, There are chemical formulas, tables, etc. ▼ (However, p is an integer of 1 to 3, R_1 is an alkyl group having 1 to 3 carbon atoms), ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (However, r is 1
~3 integer, X is Cl or Br) ▲Mathematical formula, chemical formula,
There are tables, etc. (selected from the group p+r≦5).