JPH03210315A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin composition which can be cured under mild conditions and excels in heat resistance, flame retardancy and adhesion by mixing a cyclophosphazene derivative having formylphenoxy and methylolphenoxy groups in a specified ratio with an at least difunctional amine as essential components. CONSTITUTION:A cyclophosphazene derivative (A) of formula I (wherein the CHO group and the CH2OH group may be in any position on the benzene ring, n is 3 or 4, p + q = 2, p>0, q>0, and pn and qn are each a positive integer) or a mixture thereof with a formylphenoxycyclophosphazene derivative of formula II (wherein n is 3 or 4; and the CHO group may be in any position on the benzene ring) in a molar ratio of the formylphenoxy groups to the methylolphenoxy groups of 30:70-98:2 is mixed with an at least difunctional prim. amine (B) (e.g. phenylenediamine) as essential components to obtain a thermosetting resin composition for coating electronic and electrical components or for electrical insulation. The mixing ratio of component A to component B is 0.5-2.0 in terms of a-CHO/NH2 ratio.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel thermosetting resin composition with excellent heat resistance and flame retardancy, and more specifically, it relates to a cyclophosphazene derivative with a specific structure and a cyclophosphazene derivative with a specific structure. The composition of the present invention relates to a thermosetting resin composition having excellent heat resistance and flame retardancy, which contains a primary amine having a polyhydric acid or higher as an essential component. It is particularly useful as a

(Prior Art) In recent years, in the field of electricity, electronics, aviation, transportation machinery such as vehicles, there has been a desire to develop materials with better heat resistance as equipment becomes more efficient, smaller and lighter.

Conventionally, epoxy resins, maleimide resins, polyimide resins, etc. have been used in this field.

However, although epoxy resins have excellent mechanical and electrical properties, they do not necessarily have sufficient heat resistance.

Maleimide resin represented by N,N'-4,4'-diphenylmethane bismaleimide is an addition polymerization type, so it does not generate voids during curing and has good heat resistance, but it is difficult to dissolve the bismaleimide compound. When doing so, N,
A special highly polar solvent such as N-dimethylformamide or N-methylpyrrolidone is required, which poses hygiene and economical problems.

On the other hand, various types of soluble polyimide resins have recently been proposed, but generally speaking, the higher the solubility, the worse the heat resistance.

Furthermore, both of these maleimide resins and polyimide resins have the disadvantage that during the curing reaction, the reaction will not be completed unless they are heat-treated at a high temperature such as 250 to 350C for a long time, and the desired performance will not be exhibited. ing.

(Problems to be Solved by the Invention) The object of the present invention is to provide a coating for electrical and electronic parts that has heat resistance and flame retardance equal to or higher than that of the above-mentioned maleimide resins and polyimide resins under relatively mild heat treatment conditions. The present invention provides a thermosetting resin composition based on a cyclophosphazene derivative and a divalent or more divalent primary amine, which is particularly suitable for electrical insulation.

(Means for Solving the Problems) The present inventors have conducted various studies on the characteristics of resin compositions containing various cyclophosphazene derivatives and primary amines. When a cyclophosphazene derivative having a specific structure having a formylphenoxy group is used as the cyclophosphazene derivative, the composition can be prepared from room temperature to 250°C.
It has already been proposed that a resin with excellent heat resistance and flame retardancy can be obtained by curing at a temperature of
No. 0, hereinafter referred to as the optical invention).

Subsequently, as a result of further investigation, a primary amine was combined with a cyclophosphazene derivative in which part of the formylphenoxy group was replaced with a methylolphenoxy group, that is, a phosphazene derivative with a constant structure containing a formylphenoxy group and a methylolphenoxy group. As proposed in the above-mentioned previous invention, the curing reaction is completed under mild conditions 1-
1.The cured product has heat resistance and flame retardance that are equal to or better than those of the cured product of the composition of the earlier invention, and has better adhesion than the cured product of the composition of the earlier invention, and is suitable for electrical and electronic applications. They discovered that it was suitable as a coating material for parts or an insulating material, and completed the present invention.

That is, the gist of the present invention i-h, a cyclophosphazene derivative containing a formylphenoxy group and a methylolphenoxy group represented by the following general formula (I); , p
>0゜q>01pn and qn are positive integers, and the formyl group and methylol group may be located at any of the ortho, meta, and para positions of the benzene ring. ) or formylphenoxycyclophosphazene derivatives represented by these and general formula (II); (However, 11-3 or 4, and the formyl group may be located at any of the ortho, meta, and para positions of the benzene ring. ), in which the molar ratio of formylphenoxy groups and methylolphenoxy groups is 30=70 to 9.
8:2 (formylphenoxy group: methylolphenoxy group) and a second component that is a primary amine with a valence of 2 or higher. be.

Among the first components used in the present invention, the cyclophosphazene derivative containing a formylphenoxy group and a methylolphenoxy group represented by the general formula (1) is 0-lm- or p-(formylphenoxy- methylolphenoxy)cyclotriphosphazene, o -m-
or p-(formylphenoxy-methylolphenoxy)cyclotetraphosphazene, which is a formylphenoxycyclophosphazene derivative represented by the general formula (II) which is another optional constituent of the first component,
It can be easily obtained by reducing part of the formyl group to a methylol group with a suitable transition agent (eg, sodium borohydride, lithium aluminum hydride, etc.).

It can also be obtained by reacting a mixture of hydroxybenzaldehyde and hydroxybenzyl alcohol with cyclotrichloride or tetraphosphazene.

The formylphenoxycyclophosphazene derivative represented by the above general formula (II) is om-4 or p-(formylphenoxy)cyclotriphosphazene, 0-m-
or p-(formylphenoxy)cyclotetraphosphazene. These compounds can be obtained by reacting hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene hydroxypenzaldehyde.

The first component used in the present invention is a cyclophosphazene derivative having a formylphenoxy group and a methylolphenoxy group represented by the general formula (1) as described above alone or as a mixture, or in addition to the above-mentioned cyclophosphazene derivative as described above. By adding a formylphenoxycyclophosphazene derivative represented by the general formula (tl), the molar ratio of formylphenoxy groups to methylolphenoxy groups is 30, preferably 0 to 98:2, preferably 50:50 to 95.
:5 (formylphenoxy group: methylolphenoxy group).

In addition, the primary diamine or primary polyamine that is the second component may include primary diamines or primary polyamines, and representative examples thereof include phenylene diamine, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenylsulfone, and diaminodiphenyl sulfide. ,
Tolylenediamine, xylylenediamine, diaminobenzophenone, diaminofluorene, diaminofluorenone, diaminoanthraquinone, diaminobiphenyl, diaminonaphthalene, alkyldiaminobifenyl, alkyldiaminofluorene, triaminobenzene, triaminobiphenyl, tetraminobiphenyl, diaminopyridine , diaminopyrazine, diaminotriazine, triaminotriazine, diaminoquinoline, and other aromatic or heterocyclic amines, among which o-1m- or p-phenylenediamine, 4.4'-diaminodiphenylmethane, 4.4'- Diaminodiphenyl ether, 4°4'-diaminodiphenylsulfone, m-xylylenediamine, tolylene-2,4-diamine, 0-tolidine, 2,6-diamitupyridine, 1,5-diaminoanthraquinone, and 3,3' -diaminobenzidine and the like are preferred, but are not limited thereto.

The mixing ratio of the first component and the second component is 0.5 to 2.0 ('-CHO
/-NH2) is suitable, preferably 0.8 to 1.2
It is.

When reacting the cyclophosphazene derivative as the first component and the primary amine as the second component, the solvent to be used is a solvent that dissolves both of them, such as ethers, ketones, esters, halogenated hydrocarbons, etc. The use of solvents is possible. Of course, it is also possible to use special highly polar solvents such as N,N-dimethylformamide and N-methylpyrrolidone.

Although the curing reaction of the resin composition of the present invention proceeds easily at room temperature, in order to complete the reaction, it is appropriate to heat it at 50 to 250 C, preferably 150 to 250 C, for 1 minute to 20 hours.

(Effects of the Invention) The composition of the present invention is soluble in general-purpose solvents, the curing reaction is completed under relatively mild conditions, and the cured product has excellent heat resistance, flame retardance, and electrical properties, and is suitable for metals, glass, etc. It has strong adhesion to the like, and has a thermal decomposition starting temperature of 350C or higher.
In some cases, it provides a cured product that exhibits extremely high thermal stability, such as 500C or higher.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these.

Note that the JIS K 5400 substrate eye test was used to evaluate the adhesion.

Example 1 1) Synthesis of p-(formylphenoxymerolphenoxy)cyclotriphosphazene p-(formylphenoxy)cyclotriphosphazene 50? 300+++A
11' in tetrahydrofuran and stirred at room temperature. For hydrogenation, sodium boronate was added. 3 (＞
Add ml of methanol and then! ! Stirring was continued for 12 hours at room temperature.

Then, add hydrochloric acid to neutralize the contents 1. , Separation 1 - After thoroughly washing the solid substance with water, it was vacuum dried to obtain the desired product.

As a result of NMR analysis, it was found that it was p-(formylphenoxy-methylolphenoxy)cyclotriphosphazene, which had an average composition of 7 formylphenoxyl groups and 76% methylolphenoxy groups and 24% methylolphenoxy groups.

2) Curing reaction: The p-(formylphenoxy-methylolphenoxy)cyclotriphosphazene 288P synthesized in 1) above was dissolved (dissolved) in 801yIl of dioxane.

After mixing solution A and solution B at room temperature, it was immediately applied uniformly on an aluminum plate, and the solvent was slowly evaporated at room temperature. Next, it was heat treated at 80C for 1 hour and then at 200C for 6 hours, resulting in a coating that could not be easily peeled off. The film thickness was approximately 80 μm, and the evaluation score in the substrate eye test was 10.

When the electrical properties of this material were measured, the surface resistivity (ρs) was 1.5 x 1015 (Ω), and the volume resistivity (ρv) was 1.4 x 10'5 (Ωφ100) (both 100vD, C11 minutes). value), dielectric breakdown strength 63
(kv/w) (25m (25 plates, measured value 4.2-6.
0kv, pressurization rate 0.5kv/5ec).

Example 2 In Example 1-2), instead of applying the mixed solution of solution A and solution B on an aluminum plate, it was applied a little thicker on a glass plate coated with a small amount of mold release agent, and the same process was carried out. The cured product/glass plate obtained by post-treatment is soaked in water,
A thin film of the cured product was carefully peeled off with tweezers and dried in vacuum.

The thermal properties of the thin film approximately 300 μm thick thus obtained were measured.

The shrinkage temperature measured by the TMA method was 288C, and the linear expansion coefficient was 8.55X10 (1/C) (10 (average value from 1 to 250C)).

On the other hand, when the heating loss was measured using the TGA method (in air,
Temperature increase rate: 1o'c/=), decomposition start temperature, 10%, 2
The temperatures showing 0%, 30%, 40% and 50% weight loss are:
They were 530.560.700.780.810 and 840 tl', respectively. In other words, it was found that this cured product exhibited extremely high thermal stability.

Example 3 The water absorption rate (E-24150, D-24/23
), it was determined to be 2.6.

Example 4 In Example -1), 1.1? Replacement of sodium borohydride φ1 of r, 04? The same operation was repeated except that sodium boronate was used for the hydrogenation of p-(polmylphenoxy), which had an average composition of 92% formylphenoxy groups and 8% methylolphenoxy groups.
Cyclotriphosphazene/p-(formylphenoquine-
A mixture of methylolphenoxy)cyclotriphosphazene was obtained.

Next, 30 ml of a dioxane solution containing the above mixture 101
/ and 30 ml of a dioxane solution containing 6.9 F of 4,4'-diaminodiphenylmethane were mixed at room temperature, and immediately applied on an aluminum plate, and after evaporating the solvent at room temperature, the mixture was heated at 150 C for 1 hour. Cured product with good adhesion after heat treatment at 200C for 1 hour (thickness: approx. 100μm)
/An aluminum plate was obtained. The evaluation score for the foundation test was 10. In addition, the surface resistivity is 1.0×1015 (Ω),
The volume resistivity is 3. It was 1×1016 (Ω·crn).

30ml of dioxane solution containing 10F of the above cyclotriphosphazene mixture and 69ml of 4,4'-diaminodiphenylmethane. 30 ml of dioxane solution containing the above were mixed at room temperature, applied on a glass plate coated with a small amount of mold release agent, and after evaporating the solvent at room temperature, heat treatment was performed at 150C for 1 hour, then at 200C for 1 hour. A thin film with a thickness of approximately 50 μm was peeled off from the cured product/glass plate obtained.

When we investigated the thermal properties of this thin film, we found that the shrinkage temperature was 310C.
1 linear expansion coefficient 5.0X10 (]/C) (2s~25
0C). Also, the water absorption rate (E-
24150, D-24/23) was 1.8.

Example 5 1) Synthesis of m-(formylphenoxy-methylolphenoxy)cyclotetraphosphazene: In Example 1-1), p-(formylphenoxy)
Instead of cyclotriphosphazene 5054, m-(formylphenoxy)cyclotetraphosphazene 5ofP
Using 1.1? Hydrogenation of 2.0? instead of sodium boronate Exactly the same operation as in Example 1-1) was repeated except for using sodium boronate for hydrogenation of m-(formylphenoxy- methylolphenoxy)cyclotetraphosphazene was obtained.

2) Curing reaction: Combined with the above, a mixed solution of tetrahydrofuran/monochlorobenzene (1/1 by volume) containing 28.9P of m-(pormylphenoxy-methylolphenoxy)cyclotetraphosphazene IQQmA! and 150 m of a tetrahydrone run/monochlorobenzene mixed bath containing 5.5 l of p-phenylene diamine were mixed at room temperature, applied on an aluminum plate, and after evaporating the solvent at room temperature, 1
Heat treatment was performed at 50C for 1 hour and then at 220C for 1 hour to obtain a cured product (thickness: approximately 80 μm)/aluminum plate. The cured product tightly adhered to the aluminum plate and could not be easily peeled off, and the evaluation score in the base grain test was 10.

Also, the surface resistivity was 2.3 x 1015 (Ω), and the volume resistivity was 1.9 x 1016 (Ω, leap).Example 6 Instead of applying the mixed solution on the aluminum plate in Example 5-2), , a small amount of mold release agent was applied on a wet glass plate, and the same post-treatment was performed to obtain a thickness of about 240 mm.
Thermal properties were measured for micrometer thin films.

The shrinkage leakage measured by TMA method is 290C, and the coefficient of linear expansion is 4. I X 10-” (1/'C) <25~25
0C).

Patent IAf + person Maruzen Petrochemical Co., Ltd. Continued Supplementary Positive book Heisei 2 years February lambda day 1990 Patent Application No. 5899 2. Name of the invention thermosetting resin composition 3゜ person who makes corrections Relationship with the incident

Claims (5)

[Claims] (1) Cyclophosphazene derivative containing a formylphenoxy group and a methylolphenoxy group represented by the following general formula (I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, n = 3 or 4, p+q=2, p>0, q>
0, pn and qn are positive integers, and the formyl group and methylol group may be located at any of the ortho, meta, and para positions of the benzene ring. ) or these and the general formula (I
Formylphenoxycyclophosphazene derivative represented by I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (However, n = 3 or 4, and the formyl group is either ortho, meta, or para of the benzene ring. ) in which the molar ratio of formylphenoxy groups and methylolphenoxy groups is 30:70 to 98:
2 (formylphenoxy group: methylolphenoxy group)
1. A thermosetting resin composition comprising, as essential components, a first component which is a primary amine having a valence of two or more, and a second component which is a primary amine having a valence of two or more. (2) The thermosetting material according to claim 1, wherein the molar ratio of formylphenoxy groups and methylolphenoxy groups in the cyclophosphazene derivative as the first component is 50:50 to 95:5 (formylphenoxy groups: methylolphenoxy groups). Resin composition. (3) The primary amine of divalent or higher valence as the second component is o-, m
- or p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, m-xylylenediamine, tolylene-2,4-diamine, o-
The thermosetting resin composition according to claim 1 or 2, which is an aromatic diamine or a heterocyclic diamine selected from the group consisting of tolidine and 2,6-diaminopyridine. (4) The mixing ratio of the first component and the second component is 0.5 to 2.0 (-CH
The thermosetting resin composition according to any one of claims 1 to 3, which is O/-NH_2). (5) The thermosetting resin composition according to any one of claims 1 to 4, which is used for coating electronic or electrical parts or for electrical insulation.