JPH0794606B2 - Thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a thermosetting resin composition having excellent heat resistance, mechanical properties, and processability.

(Prior Art) Polyimide resins have excellent heat resistance, chemical resistance, and other excellent properties, and are particularly useful at high temperatures such as films, wire coatings, laminates, paints, adhesives, and molded products. There are uses.

Of the polyimide resins, those obtained by polymerizing a maleimide compound alone are excellent in thermal properties, but their mechanical strength is inferior due to their molecular structure. At present, the mechanical strength is improved even if the physical properties are sacrificed to some extent.
On the other hand, organic solvent-soluble polyether imides are attracting attention as high-performance engineering plastics that can be injection-molded, and have been used in various applications such as films and molding materials. However, due to their thermoplasticity, their reliability at high temperatures is somewhat high. There was an inferior drawback.

(Problems to be Solved by the Invention) The present invention has been made in view of these drawbacks, and is intended to provide a thermosetting resin composition having excellent heat resistance, mechanical properties, and processability. is there.

[Structure of Invention] (Means and Actions for Solving Problems) As a result of intensive studies conducted by the present inventors in order to achieve the above-mentioned object, the thermosetting resin composition having the composition described below has heat resistance. ,
The inventors have found that they have excellent mechanical properties and workability, and completed the present invention.

That is, the present invention provides (A) general formula (However, in the formula, R ¹ is , N is an integer of 2 or more, respectively), and an organic solvent-soluble polyetherimide represented by the formula (B) (a) (However, in the formula, R ² is an n-valent organic group, X ¹ and X ² are the same or different one atom or group selected from a hydrogen atom, a halogen atom or an organic group, and n is an integer of 2 or more. And (b) a general formula (Wherein R ³ represents a hydrogen atom, a halogen atom or an atom or a group selected from an organic group, and m represents an integer of 1 to 5, respectively), and an addition reaction product with an aminophenol, and ( C) General formula (However, R ^{4 to} R ^{7 in the} formula represent the same or different atoms or groups selected from a hydrogen atom or an alkyl group), which is a thermosetting resin composition.

Examples of the (A) organic solvent-soluble polyetherimides used in the present invention include "ULTEM" (GE Corporation, polyetherimide trade name). This is represented by the above-mentioned general formula, and is obtained by a polyether formation reaction (aromatic nucleophilic substitution polymerization accompanied by elimination of a nitro group), and dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, etc. It is soluble in aprotic organic solvents. Here, as the polyamines for synthesizing the nitro group-containing polyimide intermediate, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diamino-3,3'-dichlorodiphenylmethane and the like can be mentioned.

The (B) addition reaction product used in the present invention is obtained by reacting (a) polymaleimides with (b) aminophenols. (B) Examples of the polymaleimides include ethylene bismaleimide, hexamethylene bismaleimide, m- or p-phenylene bismaleimide, 4,
4'-diphenylmethane bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 4,4'-dicyclohexylmethane bismaleimide, m- or p-xylylene bismaleimide, 4,4 ' -Diphenylcyclohexane bismaleimide, 4,4'-diphenylene bismaleimide, poly (phenylmethylene) polymaleimide and the like. Further, as (b) aminophenols, o-, m- or p-
Examples include aminophenol, aminocresol containing various substituent isomers, aminoxylenol, aminochlorophenol, aminopromphenol, aminocatechol, aminoresorcin, aminobis (hydroxyphenol) propane, aminooxybenzoic acid and the like. From these polymaleimides and aminophenols, one or more compounds are selected and reacted to obtain an addition reaction product. As for the mixing ratio of the polymaleimides and the aminophenols, it is desirable to mix 0.1 to 1 mol of the aminophenols with respect to 1 equivalent of the maleimide group of the polymaleimides. If this amount is less than 0.1 mol, the processability and mechanical strength of the resin composition will deteriorate, and if it exceeds 1 mol, the amino groups will be excessive and the heat resistance and stability of the resin composition will decrease, which is preferable. Because there is no. The temperature of the addition reaction is generally 50 to 200 ° C, more preferably 80 to 180 ° C, and the reaction time is several minutes to several 1
Within the range of 0 hours, it can be arbitrarily selected depending on the reaction components and the reaction temperature. Further, these reaction components may be melt-reacted without a solvent, but may be reacted in a solvent. When the reaction is carried out in a solvent, dimethylformamide, dimethylacetamide, N-methyl-2-
Other polar solvents such as pyrrolidone, acetone, methyl ethyl ketone, dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, low boiling point solvents such as cyclohexane, and the like,
One kind or a mixture of two or more kinds is used. The (B) addition reaction product thus obtained is blended with (A) the organic solvent-soluble polyetherimides, but the total amount of the organic solvent-soluble polyetherimides and the addition reaction product [(A) + (B)]. In contrast, organic solvent-soluble polyetherimides 5-80
It is desirable to add 95% to 20% by weight of the addition reaction product. This is because if the addition amount of the addition reaction product exceeds 95% by weight, the mechanical strength will decrease, and if it is less than 20% by weight, the processability will decrease, which is not preferable.

The imidazoles (C) used in the present invention are those represented by the above general formula. The imidazole serves as a curing accelerator for the addition reaction product, and is preferably added in an amount of 0.01 to 5% by weight based on the addition reaction product. Compounding amount
If it is less than 0.01% by weight, there is no effect in promoting curing, and if it exceeds 5% by weight, workability and heat resistance are deteriorated, which is not preferable.

The thermosetting resin composition of the present invention should be compounded with a filler and other additives unless it is against the object of the present invention to consist of organic solvent-soluble polyetherimides, addition reaction products, and imidazoles. You can As the filler, inorganic powder such as kaolin, clay, talc, calcium carbonate, silica, alumina, aluminum hydroxide is used, and other additives such as silane coupling agent, titanate coupling agent, stearic acid, carnauba wax, etc. And these can be selectively used according to need.

In carrying out the present invention, a thermosetting resin composition is usually used by dissolving it in N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide or the like. When applied to a molding material, a resin solution is poured into a large excess of water, and only the resin is separated and dried to obtain a powder material. The powder material thus obtained can be heated to 170 to 250 ° C. to be cured.

(Examples) Next, the present invention will be specifically described with reference to Examples.

In the following examples and comparative examples, "parts" and "%" mean "parts by weight" and "% by weight", respectively.

Example 1 358 g (1 mol) of 4,4'-diphenylmethane bismaleimide and 32.7 g (0.3 mol) of m-aminophenol were mixed and heat-kneaded at 140 ° C for 15 minutes to obtain an addition reaction product. Next, Ultem 1000 (GE company, trade name) 60 parts, addition reaction product 40
Part and 2E4MZ (Shikoku Kasei Co., Ltd., imidazole trade name)
One part was dissolved in 400 parts of dimethylformamide to form a uniform solution. This solution was dispersed in a large amount of water to form a powdery precipitate, which was filtered and dried under reduced pressure at 60 ° C. for 5 hours to produce a molding material. 20 molding materials obtained in this way
When placed in a mold heated to 0 ° C. and molded at a pressure of 120 kg / cm ² , a sufficient hardness was maintained when the molded product was taken out from the mold by molding for 3 minutes. Then, it was post-cured at 250 ° C. for 3 hours. Measurement of the flexural strength of the molded article at room temperature 14.2 kg / mm ^2, 250 has a strength of 10.1 kg / mm ² even in an atmosphere of ° C., even when heated for a further 20 days at 250 ° C. 11.8 kg / mm
The strength of ² (measured at room temperature) was maintained, and the effect of the present invention was confirmed.

Example 2 358 g (1 mol) of 4,4′-diphenylmethane bismaleimide and 54.5 g (0.5 mol) of m-aminophenol were added to 1,4-
It was dissolved in 275 g of dioxane and reacted by heating at 100 ° C. for 5 hours to obtain a uniform addition reaction product solution. Next, 50 parts of Ultem 1000 (described above), 50 parts of the addition reaction product, and 0.5 parts of 2MZ-AZINE (manufactured by Shikoku Kasei Co., Ltd., imidazole brand name) are N-methyl-2.
-Dissolved in a mixed solvent of pyrrolidone / dioxane = 4/1 to prepare a resin solution having a concentration of 20%. The resin solution thus obtained was treated with aminosilane glass at 120 ° C. for 10 minutes,
Further, it was dried at 170 ° C. for 5 minutes to prepare a prepreg. Nine sheets of this prepreg were stacked and press-molded at 180 ° C. and a pressure of 40 kg / cm ² for 90 minutes to obtain a laminated plate having a thickness of 1.6 mm. This laminate was post-cured at 200 ° C for 15 hours, and its bending strength was measured. As a result, it maintained a strength of 65 kg / mm ^{2 at} room temperature and a strength of 51 kg / mm ² even at 250 ° C and was heated at 250 ° C for 20 days. Even after deterioration, it was 53 kg / mm ² at room temperature. The effect of the present invention was confirmed.

Example 3 358 g (1 mol) of 4,4'-diphenylmethane bismaleimide and 43.6 g (0.4 mol) of m-aminophenol were mixed and heat-kneaded at 140 ° C for 15 minutes to obtain an addition reaction product. Next, 35 parts of Ultem 1000 (supra), 65 parts of addition reaction product and 2M
0.5 part of Z-AZINE (described above) was dissolved in a mixed solvent of N-methyl-2-pyrrolidone / dioxane = 3/1 to prepare a resin solution having a concentration of 20%. This resin solution was polished with No. 240 emery paper and then degreased with trichlene (SS41, 10
0 × 25 × 1 mm) and dried at 120 ° C. for 10 minutes and then at 170 ° C. for 5 minutes to form a coating film having a thickness of 25 μm. Two sheets of this coating film are wrapped by 10mm and sandwiched,
Press-molded under the conditions of 5kg / cm ² and 10 minutes, then at 220 ℃ for 5
Post-curing was performed for a period of time. The tensile shear adhesive strength of this sample was measured and found to be 215 kg / cm ^{2 at} room temperature and 250 ° C.
However, the strength of 180 kg / cm ² was maintained, and it was 175 kg / cm ² at room temperature even after heating and aging at 250 ° C. for 20 days.

The effect of the present invention was confirmed.

[Effects of the Invention] The thermosetting resin composition of the present invention compliments the disadvantages of polyetherimides and maleimides to each other and is excellent in heat resistance, mechanical strength, and processability. It is an extremely useful adhesive used in electric and electronic devices.

Claims (4)

[Claims] 1. A general formula (A) (However, in the formula, R ¹ is , N is an integer of 2 or more, respectively), and an organic solvent-soluble polyetherimide represented by the formula (B) (a) (However, in the formula, R ² is an n-valent organic group, X ¹ and X ² are the same or different one atom or group selected from a hydrogen atom, a halogen atom or an organic group, and n is an integer of 2 or more. And (b) a general formula (Wherein R ³ represents a hydrogen atom, a halogen atom or an atom or a group selected from an organic group, and m represents an integer of 1 to 5, respectively), and an addition reaction product with an aminophenol, and ( C) General formula (In the formula, R ^{4 to} R ⁷ represent a hydrogen atom or the same or different atom or group selected from an alkyl group), and a thermosetting resin composition. 2. A total amount of organic solvent-soluble polyetherimides (A) and addition reaction product (B) [(A) +
The thermosetting resin composition according to claim 1, wherein 5 to 80% by weight of an organic solvent-soluble polyetherimide and 95 to 20% by weight of an addition reaction product are added to (B)]. 3. In the addition reaction product, aminophenols are added in an amount of 0.1 equivalent to 1 equivalent of maleimide groups of polymaleimides.
The thermosetting resin composition according to claim 1 or 2, which is blended in an amount of 1 to 1 mol. 4. The imidazoles are added to the addition reaction product in an amount of 0.
Claims 1 to 3 in which 01 to 5% by weight is blended
Item 10. A thermosetting resin composition according to any one of items.