JPH01152129A - thermosetting resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel thermosetting resin composition that has excellent mechanical strength without impairing heat resistance.

[Conventional technology]

Thermosetting resins having an imide structure have been widely used in industry since they have excellent electrical insulation properties, heat resistance, and dimensional stability of molded products.

However, although the thermosetting resin obtained by thermally polymerizing aromatic bismaleimide alone is a material with excellent heat resistance, it has the drawback of being extremely brittle and lacking in flexibility. As a method to improve this drawback, there have been attempts to use thermosetting resin compositions consisting of aromatic bismaleimide and aromatic diamine. For example, N,N'-4,4'-diphenylmethane bismaleimide and 4 , 4°-diaminodiphenylmethane (manufactured by Loos-Boulin, trade name Kelimide) has been put into practical use and is widely used in impregnated varnishes, laminates, molded products, etc. (Japanese Patent Publication No. 46-23250 ).

However, these thermosetting resin compositions did not have sufficient heat resistance (and were also unsatisfactory in terms of impact resistance and flexibility).

[Problems to be Solved by the Invention] An object of the present invention is to provide a thermosetting resin composition having α-wave strength and heat resistance.

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors found that a thermosetting resin composition comprising N,N'-4,4'-diphenylmethane bismaleimide and a specific aromatic amine resin is particularly effective. The present invention was completed based on this discovery.

That is, the thermosetting resin composition of the present invention contains 100 parts by weight of N,N'-4,4'-diphenylmethane bismaleimide represented by formula (I) and an aromatic binder represented by formula (If). (It) (wherein A represents a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenyl ether group, or a naphthylenyl group, and R1 is a halogen atom, a hydroxyl group, a lower alkoxy group having up to 4 carbon atoms, or a lower lower alkoxy group having up to 5 carbon atoms) represents an alkyl group, and R1 may be the same or different from each other and may form a ring; Il represents 1 or 2; m represents an integer of 0 to 3; This is a thermosetting resin composition consisting of 5 to 100 parts by weight of an amine resin (indicating an integer of ).

N,N'-4,4'-diphenylmethane bismaleimide represented by the above formula (I) is prepared by a commonly known method.
It can be easily produced by condensing and dehydrating °-diaminodiphenylmethane and maleic anhydride.

The specific aromatic amine resin (H) used in the present invention has the general formula (IV) R"0CHz A CHzOR" (■)
(In the formula, A represents a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenyl ether group, or a naphthylenyl group, and Rz represents a hydrogen atom, an acyl group, or a lower alkyl group having 4 or less carbon atoms.) For 1 mole of the aralkyl alcohol derivative, the general formula (I may be the same or different, may form a ring, j! represents 1 or 2, m
It is a novel resin obtained by reacting an aromatic amine compound represented by .theta. to 3 in a proportion of 1 to 15 moles (Japanese Patent Application No. 252,517/1982).

A of the aralkyl alcohol derivative represented by the general formula (IV) as a raw material is as follows, and R1 is a hydrogen atom, an acyl group, or an alkyl group. Specifically, α9. α゛-dihydroxy-〇-xylene, α,α′-dihydroxy-m-xylene, α,α1-dihydroxy-p-xylene, α,α1-
Diacetoxy〇-xylene, α, α9-diacetoxy m-xylene, α, α9-diacetoxy p-xylene, α, α1-dipropionoxy p-xylene, α,
α”-di-n-butyroxy-p-xylene, α, α°
-dimethoxy〇-xylene, α, α9-dimethoxy m-xylene, α, α1-dimethoxy p-xylene,
α, α°-Jetoxy-m-xylene, α, α1-Jetoxy-m-xylene, α, α”-Jetoxy-p-xylene, α, α゛-diisopropoxy-xylene,
α. α1-diisopropoxy-m-xylene, α, α1
-diisopropoxy p-xylene, α, αゝ-gin
-Propoxy p-xylene, α, α′-di-n-butoxy m-xylene, α, α9-di-n-butoxy p-xylene
-xylene, α, α1-di5ec-butoxy p-xylene, α, α1-diisobutoxy p-xylene, 4
．． 4”-dihydroxymethyldiphenyl ether, 4.
4'-dihydroxymethyldiphenyl, 2.6-cyhydroxynaphthalene, 4.4'-diacetoxymethyldiphenyl ether, 4.4'-diacetoxymethyldiphenyl, 2.6-diacedoxymethylnaphthalene, 4.4
'-Methoxymethyldiphenyl ether, 4.4'-methoxymethyldiphenyl, 4.4'-jethoxymethyldiphenyl ether, 4.4'-diisopropoxymethyldiphenyl, 4.4'-diisobutoxymethyldiphenyl ether, α, α9- dimethoxy-2-methyl-P
-xylene, α, α1-dimethoxy-3-methyl-m-
Xylene, α, α゛-dihydroxy-2.5-dimethyl-p-xylene, α, α9-dimethoxy 2.5-dimethyl-p-xylene, α, α゛-dimethoxy-2.4-
Examples include dimethyl-1,3-xylene, α,α゛-dimethoxy-2,4-dimethyl-1,5-xylene, and the like. Among them, the more preferable compounds are α, α
1-dimethoxy p-xylene.

In addition, R1 of the aromatic amine compound represented by -sujirin (I[[) is a halogen atom, a hydroxyl group, a lower alkoxy group having 4 or less carbon atoms, or a lower alkyl group having 5 or less carbon atoms, There are 1 or 2 amino groups, which may be the same or different from each other and may form a ring. Specifically, aniline, 0-toluidine, m
-toluidine, p-)luidine, 0-ethylaniline,
m-ethylaniline, p-ethylaniline, 0-isopropylaniline, m-isopropylaniline, p-isopropylaniline, 0-n-propylaniline, o-t
ert-butylaniline, p-tert-butylaniline, on-butylaniline, p-5eC-butylaniline, 2,3-xylidine, 2,4-xylidine,
2.6-xylidine, 3.4-xylidine, 3.5-xylidine, 2-methyl-3-ethylaniline, 2-methyl-4-isopropylaniline 7.2.6-ethylaniline, 2-ethyl-5 -tart-butylaniline, 2
．． 4-diisopropylaniline, 2,4.6-)limethylaniline, 4-chloroaniline, 4-bromoaniline, 4-fluoroaniline, 3-chloroaniline, 3-
Bromoaniline, 3.4-dichloroaniline, 3-chloro-〇-toluidine, 3-chloro-P-toluidine, 2
．． 6-dimethyl-4-chloroaniline, 0-aminophenol, m-aminophenol, P-aminophenol, 2-amino-4-cresol, 4-amino-2-te
rt-butylphenol, 2,6-dimethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-amino-1,3-resorcin, 4-amino-1,
3-resorcin, 2-aminohydroquinone, 2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline, 2-isopropoxyaniline, 2,4-dimethoxyaniline, 0-phenylenediamine, m-phenylenediamine, p-phenylene Diamine, 2.4-diaminotoluene, 2.6-diaminotoluene, 2.4-diaminoethylbenzene, 2.6-diaminoethylbenzene, 2.4-diaminoisopropylbenzene, 2.4-diamino-tert-butylbenzene, 2 , 6-diamino-tert-butylbenzene, 2,4-diamino-1,
Examples include 3-dimethylbenzene, 1,1-dimethyl-4-aminoindan, and 1,1-dimethyl-4,6-diamitindane. In addition, suitable compounds are aniline, toluidines, xylidines, aminophenols and diamines, and particularly preferred is aniline.

The reaction between the aralkyl alcohol derivative (IV) and the aromatic amine compound (I[[) is carried out in the presence of an acid catalyst such as hydrochloric acid, with 1 to 15 moles of the aromatic amine compound, preferably 1. A condensation reaction is carried out in a proportion of 1 to 10 moles at a temperature of 170 to 240'C for 10 to 40 hours. After the reaction is complete, the reaction mixture is neutralized using an alkali represented by caustic soda, and after washing with water, the excess is removed. The aromatic amine resin of formula (If) can be obtained by removing the aromatic amine compound under reduced pressure.

The molecular weight range of the aromatic amine resin obtained is 300 to 60
, 000, and the softening point range of the resin is from liquid at room temperature to about 250°C (ring and ball softening point according to JIS-2548).

A thermosetting resin composition is obtained from N,N'-4,4"-diphenylmethane bismaleimide represented by the above formula (I) and an aromatic amine resin represented by the formula (■). In this case,
Various methods listed below can be used.

(I) A pulverized mixture of bismaleimide and aromatic amine resin in a solid-solid state, a solid-liquid mixture, or a prepolymer by heat treatment, and then pulverized into pellets or powder. In this case, the heating conditions are preferably those that partially cure the prepolymer stage, generally at a temperature of 70 to 220°C for 5 to 240 minutes, preferably at a temperature of 80 to 200''C for 10 to 180 minutes. It is appropriate to do so.

(2) Bismaleimide and aromatic amine resin are dissolved in an organic solvent, then discharged into a poor solvent, and the precipitated crystals are filtered and dried to form pellets or powder, or after being dissolved in an organic solvent, heat treatment is performed. After partially curing to the stage of prepolymer, it is discharged into a poor solvent, and the precipitated crystals are filtered and dried to form pellets or powder. The conditions in this case also conform to (I).

The organic solvent that can be used is limited in that it does not substantially react with both components, but it is also desirable that it be a good solvent for the re-reacted components. Usually, reaction solvents used include halogenated hydrocarbons such as methylene chloride, dichloroethane, and trichloroethylene, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and diisopropyl ketone, ethers such as tetrahydrofuran, dioxane, and methyl cellosolve, benzene, toluene, and chlorobenzene. aromatic compounds, aprotic polar solvents such as acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. etc.

The amount of the aromatic amine resin represented by formula (II) is 5 to 100 parts by weight based on 100 parts by weight of N,N'-4,4''-diphenylmethane bismaleimide represented by formula (I).
1 part, preferably 10 to 811 parts.

If the amount of aromatic amine resin is less than 5 parts by weight, the cured product will be extremely brittle and will not have satisfactory bending strength, and if it is more than 100 parts by weight, the heat resistance of the cured product will be poor.

If necessary, the following components can be added to the thermosetting resin composition of the present invention within a range that does not impair the object of the present invention.

(b) Curing accelerators, such as radical polymerization initiators such as azo compounds and organic peroxides, ionic catalysts such as tertiary amines, quaternary ammonium salts, imidazoles, and boron trifluoride/amine salts. .

(b) Powdered reinforcing agents and fillers, such as metal oxides such as aluminum oxide and magnesium oxide, metal hydroxides such as aluminum hydroxide, metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth powder, and bases. Magnesium silicate, fired clay, fine powder silica, fused silica, crystalline silica, carbon black, kaolin, fine powder mica, quartz powder, metal hydroxides such as aluminum hydroxide, graphite, asbestos, molybdenum disulfide, dioxide such as antimony. Furthermore, fibrous reinforcing materials and fillers include inorganic fibers such as glass fiber, rock wool, ceramic fiber, alumina fiber, and potassium titanate fiber, and organic fibers such as carbon fiber and aromatic polyamide.

(c) Furthermore, various synthetic resins can be blended for the purpose of improving the properties of the resin in the final coating film, adhesive layer, resin molded product, etc. For example, thermosetting resins such as phenol resin, epoxy resin, melamine resin, silicone resin, polyamide, polycarbonate, polysulfone, polyether sulfone, polyether ether ketone, modified polyphenylene oxide, polyphenylene sulfide, polyetherimide, fluororesin, etc. It is.

The thermosetting resin composition of the present invention is molded by a known molding method such as a compression molding method, a transfer molding method, an extrusion molding method, or an injection molding method, and is put into practical use.

〔Example〕

The present invention will be explained below using examples.

Synthesis Example 1 In a reaction vessel equipped with a stirrer, a thermometer, and a Dean-Stark azeotropic distillation trap, 1116 g of aniline (I
665 g (4,0 mol) of α, α”-dimethoxy-p-xylene as an aralkyl alcohol derivative represented by -Tsuriyo (IV) and 3 as a catalyst.
626 g (6.0 mol) of 5% aqueous hydrochloric acid solution was charged, and the temperature was raised while bubbling nitrogen gas. From an internal temperature of about 110"C, water distilled into the trap was removed from the system. When the temperature was further raised, Distillation of methanol was observed from about 130°C, and the temperature continued to rise without distilling off the methanol produced.
After reaching 70°C, it was kept constant for 3 hours. After almost no methanol was generated, the temperature was continued to rise and the reaction was carried out at 190-200''C for 12 hours.

Then, the internal temperature was lowered to 95°C by cooling, and 15%
It was added to 1,680 g of a caustic soda aqueous solution and neutralized by stirring. After standing still, the lower aqueous layer was separated and removed, and 30% of saturated saline solution was added.
00 g was added and washed and separated. Next, the mixture was heated and dehydrated under a nitrogen stream, and then filtered under pressure to remove inorganic salts and the like. This was vacuum concentrated under a vacuum of 2 to 3 mmHg to recover 519 g of unreacted aniline.

The remaining amount was discharged to obtain 945 g of light yellowish brown aniline resin.

As a result of compositional analysis of the aromatic amine resin obtained as described above by high performance liquid chromatography, it was found that
I) n=o is 28, n=1 is 16.8, n=2 is 1O
05, n=3 is 7.8, n≧4 is 36.9 (mol%)
Met.

In addition, the amine equivalent (perchloric acid-glacial acetic acid method) of this resin is 0.578 equivalent/(I00g), and it is -2 in JIS-2.
The softening point measured using a ring and ball softening point measuring device manufactured by No. 548 was 68°C, and the average molecular weight was 960.

Synthesis Example 2 745 g (8.0 mol) of aniline, 664 g (4.0 mol) of α,α゛-dimethoxy-p-xylene, and 420 g (4.0 mol) of 35% aqueous hydrochloric acid solution as a catalyst.
Using this, the reaction was carried out in the same manner as in Synthesis Example 1 to obtain 747 g of a pale yellowish brown aniline resin.

As a result of compositional analysis of the aromatic amine resin obtained as described above by high performance liquid chromatography, it was found that
), n-0 is 17.0, n=1 is 14.5, n-2 is 1
3.2, n≧3 was 55.2 (mol%).

In addition, the amine equivalent of this resin is 0.520 equivalent/(I0
0g), and the softening point is 61", and the C1 average molecular weight is 210.
It was 0.

Synthesis Example 3 244.4 g (2.0 mol) of 2,4-diaminotoluene was used as an aromatic amine compound represented by the general formula (I[[), and 209 g (2.0 mol) of 35% hydrochloric acid was used as a catalyst. The reaction was carried out in the same manner as in Example 1 except that 1
32 g of reddish brown oily diaminotoluene resin was obtained.

As a result of compositional analysis of the aromatic amine resin obtained as described above by high performance liquid chromatography, it was found that
In I), n-0 was 44.5, n=1 was 29.7, n=2 was 14.6, and n≧3 was 11.2 (mol%).

Further, the amine equivalent of this resin was 1.204, the softening point was 46°C, and the average molecular weight was 550.

Synthesis Example 4 -i Using 121.1 g (I, 3 mol) of aniline as the aromatic amine compound represented by the formula (III), α, α° − as the aralkyl alcohol derivative represented by the binding margin (mV) Dihydroxy-m-xylene 138.2g
(I, 0 mol) and 33 g of concentrated sulfuric acid (
The reaction was carried out in the same manner as in Synthesis Example 1 except that 0,325 mol) was used, and 151 g of a pale yellowish brown aniline resin was obtained.

The equivalent weight of the aromatic amine resin obtained as above is 0.4
96, the softening point measured using a ring and ball softening point measuring device according to JIS-2548 was 118°C, and the average molecular weight was 6,500.

Synthesis Example 5 In a reaction vessel, 109 g (I, 0 mol) of P-aminophenol as an aromatic amine compound represented by general formula (III), α as an aralkyl alcohol derivative represented by -Tsuriyo (IV), 110.2 g (0.5 mol) of α°-diacetoxy-p-xylene, 6.8 g (0.05 mol) of zinc chloride as a catalyst and 19 g (0.1 mol) of p-toluenesulfonic acid were charged, The reaction, which was carried out under reduced pressure using a water jet pump, started at about 130°C and was raised to 170'C in 3 hours. During the process, acetic acid produced was collected in a cryogenic trap. After holding at the same temperature for 3 hours, the reaction temperature was further increased to 200℃, and
Aging was completed at ℃ for 1 hour. After cooling to 95°C, add 300 ml of toluene, stir and dissolve, add 20.2 g of triethylamine, and add 20 ml of water.
After adding 0 ml of the mixture and stirring, the mixture was allowed to stand and the lower aqueous layer was separated and removed. After washing and separating once more with 200 sl of water, the mixture was concentrated in vacuo to remove toluene and unreacted p-aminophenol. 138 g of a co-condensed resin of p-aminophenol was obtained as a brown resin with residual aroma.

The aromatic amino resin obtained as described above had an amine equivalent of 0.525, a softening point measured using a ring and ball softening point measuring device according to JIS-2548, and an average molecular weight of 2,200. Ta.

Synthesis Examples 6-14 Type 8 of aromatic amine compound represented by general formula (III)
,-71 The type and amount of the aralkyl alcohol derivative represented by formula (IV), the type and amount of the catalyst, and the reaction conditions are listed.
The reaction was carried out in the same manner as in Synthesis Example 1 except as shown in 1.
Various aromatic amine resins as shown in Table 1 were obtained.

Examples 1 to 4 N,N'-4,4°-diphenylmethane bismaleimide and the aromatic amine resin obtained in Synthesis Example 1 were placed in a stainless steel reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, respectively. Charge the parts by weight shown in Table 2 and heat to 180℃ for 20 minutes.
Melt by heating for 15 minutes, and further at 150℃ under reduced pressure (I0~15w
After defoaming for 30 minutes (mHg), the mixture was cooled to room temperature to obtain a resin composition solidified into a brown transparent glass shape.

After filling the composition into a mold heated to 180°C while heating and melting it, 50Kg/ca was heated at 200°C for 3
Hold for 0 minutes, compression mold, take out the primary molded product, and post-cure for 4 hours in an open air at 250°C to obtain a cured test piece measuring 127 mm long, 12.7 mm wide, and 6.41 mm thick. Ta.

The thermal deformation temperature of this test piece was set to STM-D-648, and a bending test was conducted according to ASTM-D-790, and the thermal decomposition onset temperature was measured in air at a heating temperature of 10°C/win. The results shown in Table 2 were obtained.

Examples 5 to 17 and Comparative Examples 1 to 2 100 parts by weight of N,N'-4,4°-diphenylmethane bismaleimide and the aromatic amine resin shown in Table 2 were added to the table.
Using the parts by weight shown in Table 2, the same handling as in Examples 1 to 4 was carried out, and the results shown in Table 2 were obtained.

Comparative Example 3 The same operations as in Examples 1 to 4 were carried out, except that N,N'-4,4''-diphenylmethane bismaleimide and 4,4'-diaminodiphenylmethane were used in the parts by weight shown in Table 2. -2 result was obtained.

Comparative Example 4 Kelimide-1050 was used instead of the resin composition of the present invention.
(Polyamino bismaleimide resin manufactured by Nippon Polyimide ■)
Molded products were made in the same manner as in Examples 1 to 4 using the following methods, and various physical properties were measured. The results are shown in Table-2.

From the results shown in Table 2, the thermosetting resin composition according to the present invention has high bending strength and bending elastic modulus, and has excellent heat resistance, with a heat distortion temperature of 290°C or higher and a thermal decomposition onset temperature of 340°C or higher.

〔Effect of the invention〕

The thermosetting resin of the present invention has excellent mechanical strength and heat resistance, and is expected to be widely used in electrical and electronic fields, and mechanical fields such as aircraft and vehicles, where higher heat resistance is required in recent years. , the industrial use effect is great.

Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 100 parts by weight of N,N'-4,4'-diphenylmethane bismaleimide represented by formula (I) ▲Mathematical formulas, chemical formulas, tables, etc. General aromatic formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, A represents a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenyl ether group, or a naphthylenyl group, and R^1 represents a halogen atom, a hydroxyl group, a lower alkoxy group having 4 or less carbon atoms, or a lower alkyl group having 5 or less carbon atoms, and R^1 may be the same or different from each other, and may form a ring. l is 1 or 2
, m represents an integer of 0 to 3, and n represents an integer of 0 to 300. ) A thermosetting resin composition comprising 5 to 100 parts by weight of an amine resin.