JPH02185526A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. having low viscosity and good workability and providing a molded item with excellent heat resistance and adhesiveness by incorporating a specified arom. diamine and a specified polymaleimide compd. CONSTITUTION:A thermoplastic resin compsn. is obtd. by incorporating an arom. diamine compd. (A) of formula I (wherein Ar is an arom. residue; R1, R2, R3 and R4 are each an allyl or H and at least one of them is allyl) [e.g. a compd. of formula II, III or IV (R1 to R4 are as described above)] and a polymaleimide compd. (B) having two or more maleimide groups in the molecule [e.g. N,N'-4,4'-diphenylmethanebismaleimide). This resin compsn. exhibits low viscosity and excellent workability, provides a molded item with excellent heat resistance and adhesiveness and is useful for casting, impregnation, lamination and molding materials.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a thermosetting resin composition, and more particularly to a thermosetting resin composition having excellent processability, heat resistance, mechanical properties, and adhesive properties.

<Prior Art> Thermosetting resins are used as casting, impregnating, laminating, and molding materials for various electrical insulation materials, structural materials, and the like.

In recent years, the conditions for using materials in various applications have become stricter, and in particular, the heat resistance of materials has become an important characteristic.

Conventionally, thermosetting polyimide resins and heat-resistant epoxy resins have been used for such purposes.

<Problems to be Solved by the Invention> Conventionally, a resin composition using an aromatic bismaleimide and an aromatic diamino has been proposed as a thermosetting polyimide resin [Japanese Patent Publication No. 46-28250] Showa 6
8-48884].

However, both components of this polyimide resin are solid at room temperature, the mixture melts only under high temperature conditions, and the viscosity of the melt is high, making casting and impregnation difficult. In addition, due to the low curing reactivity, high temperature and long molding conditions are required in order to obtain sufficient heat resistance, and furthermore, there are problems with the cured physical properties at high temperatures and heat deterioration resistance of the obtained cured product. Ta.

In addition, although heat-resistant epoxy resins have excellent moldability, they are insufficient in high heat resistance performance such as mechanical properties at high temperatures, electrical properties, and long-term heat deterioration resistance.

<Means for Solving the Problems> Against this background, the present inventors conducted intensive studies on resin compositions with excellent heat resistance and processability. The present inventors have discovered that a single-fat composition consisting of a diamine compound and a polymaleimide compound is suitable for the above purpose, and have completed the present invention.

That is, the present invention includes (A) the following general formula [13] and unsubstituted compounds. In particular, Ar is [wherein Ar represents an aromatic residue and Rle R2*R
8* R4 each independently represents an allyl group or hydrogen,
R1* R2* At least one of R8 and R4 is an allyl group. ] This is a thermosetting resin composition comprising an aromatic diamine compound in which the amino group is allylated and (B) a polymaleimide compound having two or more maleimide groups in the molecule.

To explain in more detail the diamine compound in which the amino group is allylated, that is, the aromatic diamine compound represented by the general formula El) used in the present invention, Ar is a mononuclear or polynuclear divalent aromatic residue. The aromatic nucleus is substituted with a lower alkyl group, a halogen, or a lower alkoxy group to represent H8 F8 〇- or -8-, and R5* R6* R? In most cases, particularly excellent heat resistance can be obtained.

On the other hand, in the case where Ar is C, B represents 10- or -8-, and (Special (ti) or CCO ◎)' represents 1゜], only excellent heat resistance is achieved. These compounds have excellent bending strength and excellent toughness.
It is easily synthesized by various methods. For example, there is a method using a dehydrohalogenation reaction between an aromatic diamine compound and an allyl halide compound.

Examples of aromatic diamines used as raw materials for this reaction include 4.4'-diaminodiphenylmethane, 8.8
'-Diaminodiphenylmethane, 4.4'-Diaminodiphenyl ether, 8.4'-Diaminodiphenyl ether, 4.4'-Diaminodiphenylpropane, 4.4
'-Diamino diphenyl sulfone, 8.8'-diaminodiphenylsulfone, 4.4'-diaminobenzophenone B, B/-diaminobenzophenone, 2゜4-
Toluene diamine, 2.6-) toluene diamine, m-phenylene diamine, p-phenylene diamine, benzidine, 4.4'-sia [fudiphenyl sulfide, 8.
8'-dichloro-4,4'-diaminodiphenyl sulfone, 8.8'-dichloro-4,4'-diaminodiphenylpropane, 8.8'-dimethyl-4,4'-diaminodiphenylmethane, 8.8 '-dimethoxy-4,4'
-diabemia)enyl, 3,8'-dimethyl-4,4'-diaminobiphenyl, 1,8-bis(4-aminophenoxy)
Benzene, 1.8-bis(8-aminophenoxy)benzene, 1.4-bis(4-aminophenoxy)benzene, 2.2-bis(4-aminophenoxyphenyl)propane, 4.4'-bis(4 -aminophenoxy)diphenylsulfone, 4.4'-bis(8-aminophenoxy)diphenylsulfone, 9.9'-bis(4-aminophenyl)anthracene, 9°9'-bis(4-aminophenyl)fluorene, 3.8'-dicarboxy-4
, 4'-diaminodiphenylmethane, 2,4-diaminoanisole, bis(8-aminophenyl)methylphosphine oxide, 8,8'-diaminobenzophenone,
0-Toluidine sulfone, 4,4'-methylene-bis-chloroaniline, tetrachlorodiaminodiphenylmethane, m-xylylenediamine, p-xylylenediamine, 4,4'-diaminostilbene, 5-amino-
1-(4'-aminophenyl-1,8,8-trimethylindane, 6-amino-1-(4'-aminophenyl)
-1゜8.8-trimethylindan, 5-amino-6-
Methyl-1-(8'-amino-4'-methylphenyl)
"-1e 8-8) Limethylindane, 7-amino-6-methyl-1-(8'-amino-4'methylphenyl)-1,8,8-trimethylindane, 6-amino-
5-methyl-1-(4'-amino-8-methylphenyl)-1,8,8-trimethylindane, 6-amino-2-methyl-1-(4'-amino-8'-methylphenyl)-1, Examples include 8,8-trimethylindane.

In particular, ethers with two benzene nuclei such as diaminodiphenylmethanes and diaminodiphenyl ethers, and those with three or four benzene nuclei such as bis(aminophenoxy)benzenes and bis(aminophenoxyphenyl)propanes. By using an aromatic diamine compound connected by a bond, the above-mentioned preferred aromatic diamine compound can be obtained.

In addition, R1 e R2* R8* in general formula [11]
R4 is as described above, that is, the aromatic diamine compound of the present invention is a compound having 1 to 4 allyl groups per molecule. Each of them can be used alone or as a mixture in the present invention. Preferably, it is an allylated aromatic diamine compound having an average of 1.5 to 2.5 allyl groups per molecule. This is because in this case, the highest heat resistance can be obtained.

In the reaction between the aromatic diamine compound and the allyl halide compound described above, the number of allyl groups in the molecule can be appropriately selected by changing conditions such as the amount of allyl halide to be reacted and the reaction time. .

The allylated aromatic diamine compound used in the present invention obtained in this way is liquid at around room temperature and can be easily mixed with the polymaleimide compound.

Further, the polymaleimide compound used in the present invention is a compound containing two or more maleimide groups represented by the general formula (1) in the molecule.

(In the formula, R represents a water atom or a lower alkyl group.) Specific examples thereof include N,N'-diphenylmethane bismaleimide, N,N'-diphenylmethane bismaleimide,
N,N'-phenylene bismaleimide, N,N'-diphenyl ether bismaleimide, N,N'-diphenylsulfone bismaleimide, N,N'-dicyclohexylmethane bismaleimide, N,N'-xylene bismaleimide, N , N'-1-lylene bismaleimide, N, N'
-xylylene bismaleimide, N,N'-diphenylcyclohexane bismaleimide, N,N'-dichlorodiphenylmethane bismaleimide, N,N'-diphenylcyclohexane bismaleimide, N,N'-diphenylmethane bismethylmaleimide, N,N' -diphenyl ether bismethylmaleimide, N,N'-diphenylsulfonebismethylmaleimide, N,N'-bis(aminophenoxybenzene)bismaleimide, N,N'-bis(
aminophenoxy) bisphenol A bismaleimide (
Each includes isomers. ), N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N,
NL hexamethylene bismethylmaleimide and these N
, a prepolymer having an N, N' bismaleimide skeleton at the end obtained by adding an N'-bismaleimide compound and a diamine, and a maleimide or methylmaleimide of an aniline/formalin polycondensate. Special C12) N,N'-diphenylmethane bismaleimide, N,N
'-Diphenyl ether bismaleimide is preferred.

In addition, other aromatic diamines, allyl ether compounds, alkenylphenol compounds,
Cyanoether compounds and the like can be added. Further, other thermosetting resins (for example, phenol resins, epoxy resins, etc.) can also be blended in appropriate amounts depending on the purpose.

The quantitative ratio of each component in the resin composition of the present invention can be appropriately selected depending on the intended use, desired heat resistance, and the like.

However, quantitatively, the ratio of the number of allylated aromatic diamine compounds to the number of double bonds of the polymaleimide compound is 1.
/8 to 1/2 is desirable, more preferably 1/6
~1/4.

Describing the method of thermosetting the resin composition of the present invention,
Curing is easily possible without a catalyst, but organic peroxides,
It is also possible to carry out thermal curing using a polymerization initiator such as a phosphine compound or an azo compound. Examples of such polymerization initiators include benzoyl peroxide, dicumyl peroxide, triphenylphosphine, azobisisobutyronitrile, tertiary amines, quaternary ammonium salts, and imidazoles.

The superfat composition of the present invention exhibits excellent heat-resistant mechanical properties when combined with a fiber base material, but the base material at that time can be inorganic fiber base materials such as glass fiber, fine carbon fiber, alumina fiber, or aramid fiber. Mention may be made of organic fiber substrates such as fibers.

Furthermore, the resin composition of the present invention can be combined with extenders, fillers, pigments, etc., if necessary. For example, silica, calcium carbonate, antimony trioxide, kaolin, titanium dioxide, zinc oxide, mica, pallite, carbon black, polyethylene powder, polypropylene powder, aluminum powder, iron powder, copper powder, etc. are used for molding, lamination, adhesives, Used for composite materials, etc. Depending on the purpose, other known thermosetting resins such as alkenyl group-containing resins, triazine group-containing resins, unsaturated polyester resins, epoxy resins, silicone resins, phenol resins, etc. may be added.

<Effects of the Invention> The thus obtained resin composition of the present invention provides molded products with low viscosity, excellent workability, and excellent heat resistance and adhesive properties.

It is also useful as a material for casting, impregnation, lamination, and molding.

EXAMPLES Next, Examples will be shown to explain the present invention in detail, but the present invention is not limited thereto.

[Synthesis of compound of structural formula [IV]]

Reference Example 1 11 equipped with a stirrer, reflux condenser, thermometer, and dropping funnel
4.4'-diaminodiphenylmethane 99.2 f (0.5 mol) and dimethyl sulfoxide 884 f were placed in a 4-tube flask, and after dissolving at room temperature, 48% aqueous sodium hydroxide solution 70.81 (0.85 mol) was added. Allyl chloride 65.1 f (0,
85 mol) was added dropwise over 2 hours, and 50 mol was added for 4 hours after dropping.
It was incubated at °C and left at room temperature overnight. Toluene 800
F.

Pour 500f of water, separate the organic layer, and add 500f of 15% salt solution.
Wash the organic layer twice with 00 fI and twice with 500 fI water,
Dehydration was performed using magnesium sulfate. The solvent was distilled off under reduced pressure to obtain liquid allylated diaminodiphenylmethane96. I got Of.

The average number of allyl groups was determined by LC to be 1.7 per molecule of diaminodiphenylmethane. Also, the viscosity is 1,
It was a liquid material with a temperature of 4 Stokes/25°C.

Reference Example 2 The amounts of allyl chloride and 48% sodium hydroxide in Reference Example 1 were 88.0 g (1.15 mol) and 95.8 g, respectively.
9 (1.15 mol) Perform the same operation except for changing 2 to obtain an allyl compound 144 with an average number of allyl groups of 2.8.
I got f. It was a liquid with a viscosity of 1.1 stix and 725°C.

Reference Example 3 The amounts of allyl chloride and 48% sodium hydroxide in Reference Example 1 were 168.5 f (2.2 mol) and 185.2 mol, respectively.
The same operation was performed except that f (2.22 mol) was changed to obtain an allyl compound 156F having an average number of allyl groups of 8.0. It was a liquid with a viscosity of 0.8 Stix/25°C.

Reference example 4 11 equipped with a stirrer, reflux condenser, thermometer, and dropping funnel
156 allylated product of diaminodiphenylmethane having an average number of allyl groups of 8.0 obtained in Reference Example 8
f1 methylene chloride 400F,) ethylamine 152v
(1.5 mol) was prepared and dissolved at room temperature, then allyl chloride 115f (1.5 mol) was added dropwise at 25 to 40°C over 2 hours, and the temperature was kept at 40°C for 48 hours after the dropwise addition. The by-product triethylamine hydrochloride was separated by furnace, the salt was washed with 400 f of methylene chloride, and the mixture was concentrated to obtain a crude product.

The crude product was dissolved in 400f of toluene, washed with 500f of a 10% aqueous sodium hydroxide solution, and then washed 8 times with 500y of water to remove triethylamine hydrochloride in the crude product. After drying the organic layer with anhydrous magnesium sulfate,
Concentrate under reduced pressure to obtain an allyl compound 17 with an average number of allyl groups of 8.9.
I got 0f. It was a liquid with a viscosity of 1.8 Stokes and a temperature of 725°C.

[Synthesis of compound of structural formula [V]]

Reference example 5 1n equipped with a stirrer, reflux condenser, thermometer, and dropping funnel
8.4'-diaminodiphenyl ether 100.1 F (0.5 mol) and dimethyl sulfoxide 884 f were placed in a 4-tubular flask, and after dissolving at room temperature, 48% aqueous sodium hydroxide solution 88.4 f (1,0 mol) was added. Allyl chloride 76.5 f (1
, Omol) was added dropwise over 2 hours, kept warm at 50°C for 4 hours after dropping, and left at room temperature overnight. Toluene 800
F.

Pour 500F of water, separate the organic layer, and add 500F of 15% saline solution.
The organic layer was washed twice at 00F and twice at 500F water, and dehydrated using magnesium sulfate. The solvent was distilled off under reduced pressure to obtain liquid allylated 8,4'-diaminodiphenyl ether 180f.

The average number of allyl groups was 2.0 per molecule of 8.4'-cyaelectronodiphenyl ether, and the viscosity was 8.7 stoix at 725°C.

[Synthesis of compound of structural formula [VI]] Reference Example 6 In the same manner as in Reference Example 1, 48% of 1,3-bis(4-aminophenoxy)benzene was used as a 10011 dehydrochlorination agent.
By changing the dropping amount of sodium hydroxide water bath liquid 87.2y1 allyl chloride to 81f, liquid allyl 1
, 128g of 8-bis(4-aminophenoxy)benzene
was gotten.

The average number of allyl groups was 2.0 per molecule of 1.3-bis(4-aminophenoxy)benzene, and the liquid material had a viscosity of 60 Stokes/25°C.

Reference Example 7 In the same manner as in Reference Example 1, 100f of 1,3-bis(4-aminophenoxy)benzene was added to 48% as a dehydrochlorination agent.
Aqueous sodium hydroxide solution 128f1 By changing the lower amount of asiallyl chloride to 260f and reacting at 50°C for 48 hours, an allyl compound with an average number of allyl groups of 8.2 1O7f
I got it. It was a liquid at 28 strokes/25°C.

[Synthesis of compound of structural formula [■]] Reference Example 8 In the same manner as in Reference Example 4, 1,8-bis(8-aminophenoxy)benzene was heated to 10°F and the solvent was dimethylformamide 8 B 4 f1 dehydrochloric acid. Triethylamine 107F as an agent.

By adding allyl chloride 161jF and reacting at 40°C for 24 hours, liquid allylated 1,8-bis(
8-aminophenoxy)benzene 126f was obtained.

The average number of allyl groups was 2.0 per molecule of 1.3-bis(8-aminophenoxy)benzene, and the viscosity was 70 stix at 725°C.

Reference Example 9 In the same manner as in Reference Example 8, the reaction was carried out at 40°C for 48 hours to obtain 187 g of an allyl compound having an average number of allyl groups of 2.8.18 stix/25°C and a viscosity.

Examples 1 to 4 The average molecular weight was calculated based on the average number of allyl groups of the allylated diaminodiphenylmethane obtained in Reference Examples 1 to 4, and N,N'-diphenylmethane bismaleimide (Be5tlex 181BH-180 manufactured by Sumitomo Chemical) and , after blending at a charging molar ratio of 1:2 (allylated diamine corresponds to 1/4 to maleimide group), heated and melt-mixed at 160 to 170°C,
The mixture was defoamed and poured into a mold set in advance in an oven, held at 150°C for 1 hour, and after gelling, held at 200°C for 5 hours, taken out from the mold, and a cured product with a thickness of 2ff was created. For comparison, Keri consisting of N,N'-diphenylmethane bismaleimide and diaminodiphenylmethane
mide-601 (manufactured by 0-ne-Bourand) was difficult to cast as described above, so it was cast at 50 to 9/d at 200°C.
After press molding for 1 hour at 200°C, a cured product with a thickness of 2M was obtained by curing at 200°C for 4 hours.

Table 1 shows the physical properties of each cured product.

(Hereafter 1! Margin) <Table I> (Hereafter blank) 4-I By TMA method 1 x 2 Based on JIS K6911 1 (260°C .

Example 5 The allyl compound obtained in Reference Example 5 was blended with N,N'-diphenylmethane bismaleimide (Be5tlex@BH-180 manufactured by Sumitomo Chemical Co., Ltd.) at the blending ratio shown in Table 2, and the same procedure as in Examples 1 to 4 was carried out. A cured product having a thickness of 2wj11 was obtained by the following operation.

For comparison, N.

N'-diphenylmethane bismaleimide and 8゜4'-
Diaminodiphenyl ether was heat-melted and mixed at a molar ratio of 1:0.4, press-molded at 200°C for 1 hour at 50:9/d, and then cured at 200°C for 4 hours to form a 2m thick cured product. I got something. Table 2 shows the physical properties of each cured product.

(The following is a blank space) Table 2〉 +I By TMA method +2 According to JISK6911 +8 260℃ x 24 hrs (The following is a blank space) Examples 6 to 9 Allyl compounds obtained in Reference Examples 6 to 9 were mixed with N at the blending ratio shown in Table 8. , N'-diphenylmethane bismaleimide (
After blending with Be5tlex ■BH-180) manufactured by Juman Chemical Co., Ltd., the mixture was heated and melted at 160°C to 170°C, defoamed, and poured into a mold set in advance in an oven for 15 minutes.
The mixture was maintained at 0°C for 1 hour, and after gelation was maintained at 200°C for 5 hours, and taken out from the mold to create a cured product with a thickness of 21nl.

For comparison, N,N'-diphenylmethane bismaleimide and 1,8-bis(4-aminophenoxy)benzene (
Comparative Example 8) and 1.3-bis(8-aminophenoxy)benzene (Comparative Example 4) were heated and melted and mixed at a molar ratio of 1:0.4, and after press molding at 200°C for 1 hour at 50 kti/c4. A cured product with a thickness of 2M was obtained by curing at 200° C. for 4 hours.

The physical properties of each cured product are shown in Table 89 and Table 4.

Table 4 -Xl By TMA method Yellow 2 -X11260°cx After 24 hours JISK6911 The composition comprising the allylated aromatic diamine compound of the present invention is easy to process, and the composition comprising the corresponding aromatic diamine compound It can be seen that it has superior heat resistance and toughness compared to other materials, and also has long-term heat resistance.

(after]・margin) (29 completed)

Claims (1)

[Claims] 1) (A) The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...Formula [I] [In the formula, Ar represents an aromatic residue, R_1, R_2,
R_3 and R_4 each independently represent an allyl group or hydrogen, and at least one of R_1, R_2, R_3 and R_4 is an allyl group. ] A thermosetting resin composition comprising an aromatic diamine compound represented by the following and (B) a polymaleimide compound having two or more maleimide groups in the molecule. 2) The thermosetting resin composition according to claim 1, wherein Ar is represented by the following formula [II]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼Formula [II] [In the formula,
or -S-, R_5, R_6, R_7 and R
Each of _8 independently represents a halogen, a lower alkyl group, or hydrogen. 3) The thermosetting resin composition according to claim 1, wherein Ar is represented by the following formula [III]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼Formula [III] [In the formula, B represents -O- or -S-, Y represents ▲Mathematical formula,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
Represents ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. ]