JPS62116662A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To provide a thermosetting resin compsn. having excellent heat resistance, mechanical characteristics and processability, consisting of specified org. solvent-soluble polyimides, a specified addition reaction product and imidazoles. CONSTITUTION:A thermosetting resin compsn. consists of org. solvent-soluble polyimides (A) composed of a benzophenonetetracarboxylic acid (derivative) of formula I (wherein R<1> is a group of formula II, III, IV, V or VI; n is an integer of at least 2), an addition reaction product (B) of polymaleimides (a) of formula VII (wherein R<2> is an n-valent org. group; X<1>, X<2> are each H, halogen, an org. group; n is an integer of at least 2) and aminophenols (b) of formula VIII (R<3> is H, halogen, an org. group; m is an integer of 1-5) and imidazoles (c) of formula IX (wherein R<4>-R<7> are each H, an alkyl). The compsn. has excellent heat resistance, mechanical strength and processability and is very useful as a material for laminated sheets, molding materials, adhesives, electrical equipment, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention 1] The present invention relates to a thermosetting resin composition having excellent heat resistance, mechanical properties, and processability.

[Technical background of the invention and its problems] Polyimide has a high degree of heat resistance, chemical resistance, and other excellent properties, and is particularly suitable for use in films, wire coatings, laminates, It is used as paint, adhesive, molded products, etc.

Among these, homopolymers of maleimide compounds have excellent thermal properties, but their molecular structure inevitably leads to inferior mechanical strength, so by copolymerizing with other materials, the thermal properties must be sacrificed to some extent. However, the current situation is that mechanical strength is being improved. On the other hand, Vespel, which is marketed as an aromatic polyimide,
Polyimide 2080'' etc. have poor mechanical and thermal properties, so they are used in various applications such as films and wire coatings, but they have difficulties in processability and require relatively high temperatures and pressures for molding, laminating, and adhesion. In the field of molding, molding, etc., processing equipment for general thermosetting resins such as phenolic resins and epoxy resins currently on the market cannot be used as is, and special construction is required. In the fields of lamination, adhesion, etc., it was only used in some areas.

[Object of the invention] The object of the present invention has been made in view of the above-mentioned drawbacks, and
The aim is to provide a thermosetting resin composition that is excellent in heat resistance, mechanical properties, and processability.

SUMMARY OF THE INVENTION In order to achieve the above-mentioned object, the present inventor has conducted extensive research and has discovered that a thermosetting resin composition having the composition described below has heat resistance,
Although the mechanical properties and processability are poor, the inventors have discovered that the above objects can be achieved and have completed the present invention. That is, the present invention provides benzif, [nontetracarboxylic acid or (other!'＋'
+7 organic solvent-soluble polyimides, (B) (
b) General formula (however, in the formula, R2 is n-valent +M m, ×1 and ×
2 is the same or different 1 m atom or base selected from a hydrogen atom, a halogen atom, or an organic group, and n is an integer of 2 or more);
(b) With amine phenols represented by the general formula (in which R3 represents an atom or group selected from a hydrogen atom, a halogen atom, or an organic group, and m represents an integer of 1 to 5) It is characterized by consisting of an addition reactant, and (C) imidazoles represented by the general formula (wherein R4 to R7 represent atoms or groups selected from hydrogen atoms or alkyl groups that are different but appear to be the same) It is a thermosetting resin composition.

As the organic solvent soluble polyimide (A) used in the present invention, for example, Upjohn's polyimide "2080"
(Product name) etc. This compound is represented by the above-mentioned general formula (7), and is obtained by reacting benzif-1-nontetracarboxylic acid or its derivative with polyamines or polyisocyanates by a conventional method, and dimethylformamide, dimethylacetamide, N- Aprotic compounds such as methyl-2-pyrrolidone are soluble in solvents.

Here, the polyamines include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether,
Examples include 4.41-diaminodiphenylsulfone, 4.4'-diamino-3,3'-dichlorodiphenylmethane, and examples of polyisocyanates include 4.4'-diphenylmethane diisocyanate, 2.4-t-lylene diisocyanate, 2. .6-Drylene diisocyanate and the like.

The addition reaction product (B) used in the present invention is produced by reacting (a) polymaleimides with (b) aminephenols.
It is something that can be done. (a) Polymaleimides include, for example, ethylene bismaleimide, hexamethylene bismaleimide, m- or 0-phenylene bismaleimide, 4.4'-Schiff1nylmethane hismaleimide, 4.4
'-diphenyl ether maleimide, 4,4'-diphenylsulfone bismaleimide, 4,4'-dicyclohexylmethane bismaleimide, m- or p-xylylene bismaleimide, 4,4'-diphenylcyclohekirin bismaleimide, 4, Examples include 4'-diphenylenebismaleimide and poly(phenylmethylene)polymaleimide. Also, as (oral) aminophenols,
o-, m- or p-amine phenol and amine cresol, aminoxylenol containing various substituent isomers, aminochlorophenol, aminobromophenol,
Examples include aminocatechol, amylzorcin, aminobis(hydroxyphenol)propane, aminooxybenzoic acid, and the like. One or more of these polymaleimides and amine phenols are selected and reacted to obtain an addition reaction product. Regarding the blending ratio of the polymaleimide and the amine phenol, it is preferable that 0.1 to 1 mole of the aminophenol is blended per equivalent of the maleimide group of the polymaleimide. If the amount is less than 0.1 mol, the processability and mechanical strength of the resin composition will deteriorate, which is not preferable. Moreover, if it exceeds 1 mole, the amino groups will be excessive and the heat resistance and stability of the resin composition will deteriorate, which is not preferable. The addition reaction temperature is generally 50 to 200°C, more preferably 80°C.
~180°C, and the reaction time can be arbitrarily selected depending on the temperature within the range of several minutes to several tens of hours. Further, these reaction components may be melt-reacted without a solvent, but they can also be reacted in a solvent. In addition to polar solvents such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, dioxinane, ethylene glycol monomethyl ether, and ethylene glycol 7-methyl ether can be used as a solvent when reacting in a solvent. Examples include low boiling point solvents such as acetate and cyclohexane, which may be used singly or in combination of two or more. This is how it is obtained (B
) The addition reaction product is blended with the (A) right □ solvent-soluble polyimide term, but the total ffi of the organic solvent-soluble polyimides and the addition reaction product [(A) + (B) 1, the organic solvent-soluble polyimide It is preferable to mix 5 to 80% by weight of the above and 95 to 20% by weight of the addition reaction product. If the content of the addition reactant exceeds 95% by weight, the mechanical strength will decrease, which is undesirable. Moreover, if the 20i content is less than 1%, the processability will deteriorate, which is undesirable.

The imidazoles (C) used in the present invention are those represented by the above general formula. The imidazole acts as a curing accelerator for the addition reaction product, and is blended in an amount of 0.5 to 5% by weight based on the addition reaction product.

If the amount is less than 0.5% by weight, it will not be effective in accelerating curing, and if it exceeds 5% by weight, workability and heat resistance will decrease, which is not preferable.

The thermosetting resin composition of the present invention is composed of a line-specific solvent-soluble polyimide, an addition reaction product, and an imidazole, but fillers and other additives may be blended as long as they do not contradict the purpose of the present invention. Inorganic powders such as kaolin, clay, talc, DEW calcium, silica, alumina, and aluminum hydroxide are used as fillers, and other additives include silane coupling agents, titanate coupling agents, and stearic acid. , carnauba wax, etc., and these can be selectively used as required.

When carrying out the present invention, the thermosetting resin composition is usually used after being dissolved in, for example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, or the like. In addition, when applying it to molding materials, pour the resin solution into a large excess of water, separate and dry only the resin, and make 1q of powder material.
I can do that.

The thus prepared material can be cured by heating to 170 to 250°C.

[Embodiments of the invention] Next, the present invention will be specifically explained using examples.

In the following Examples and Comparative Examples, "parts" and "%J" mean "parts by weight J" and "%J by weight."

Example 1 358 g of 4.4'-diphenylmethane bismaleimide (
1 mol) and 32.7 g (0.3 mol) of m-7 minophenol were mixed and heated and kneaded at 140°C for 15 minutes to obtain an addition reaction product. 60 parts of polyimide 2080 (%J, trade name, manufactured by Upjohn Co., Ltd.), 40 parts of the addition reaction product, and 1 part of 2 parts 4MZ (imidazole, trade name, manufactured by Shikoku Kasei Co., Ltd.) were dissolved in 400 parts of dimethylborumamide, and a homogeneous mixture was dissolved. It was made into a 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.

The molding material obtained in this way was put into a mold heated to 200'C and molded at a pressure of 120k (J/cm2).
It maintained sufficient hardness when removed from the mold after being molded for a few minutes. Thereafter, it was post-cured at 250° C. for 3 hours.

When we measured the bending strength of the molded product, it was 15.1k at seedling temperature.
g/mm2.11.2kg/mm even in an atmosphere of 250℃
mm2, and after further heating at 250°C for 20 days, the strength was maintained at 613.2k (1/l11m2 (measured at room temperature), demonstrating the effectiveness of the present invention.

Example 2 358 g of 4.4'-diphenylmethane bismaleimide (
1 mol) and m-aminephenol 54.5 g (0
, 5 mol) in 275 g of 1,4-dioxane,
The reaction was heated at 00°C for 5 hours to form a homogeneous addition reactant solution. Next, 50 parts of polyimide 2080 (supplemented), 50 parts of addition reaction product, 0.5 part of J5 and 2MZ-△ZINE (imidazole, trade name, manufactured by Shikoku Kasei Co., Ltd.) were added to N-methyl-2-pyrrolidone/dioxane = 47' A resin solution having a concentration of 20% was prepared by dissolving the resin in 1 of mixed solvent.

A glass cloth (250 x 250 x o, 18 mm
) for 10 min at 120'C and 5 min at 170'C.
A prepreg was prepared by drying for a minute. Nine sheets of this prepreg were stacked at 180℃ and a pressure of 40kg/am2.
Press molding was performed for 0 minutes to obtain a laminate with a thickness of 1.6 mm.

When this laminate was cured at 200°C for 15 hours and its bending strength was measured, it was 68 kg/m at room temperature.
m2.It maintains a strength of 53kg/mm2 even at 250℃, and even after heat deterioration at 250℃ for 20 days, it has a strength of 53kg/mm2 when measured at room temperature.
It was 5 kg/mm2. The effects of the present invention were recognized.

Example 3 358 g of 4.4'-diphenylmethane bismaleimide (
1 mol) and m-aminophenol 43.6! I+ (
0.4 mol) were mixed and heated and kneaded at 140°C for 15 minutes to obtain an addition reaction product of 11. Next, polyimide 2080 (
above) 35 parts, addition reactant 65 parts, and 2MZ-AZ
0.5 part of INE (mentioned above) was dissolved in a mixed solvent of N-methyl-2-pyrrolidone/dioquine = 3/d to give a concentration of 2.
A 0% resin solution was prepared. This resin solution was applied to a mild steel plate (SS41.100x 25x i mm) that had been polished with No. 240 emery paper and degreased with Triclean.
It was dried at 120°C for 10 minutes and at 170°C for 5 minutes to form a coating film with a thickness of 25 parts and 1 part. 10 pieces of these two coating films
Wrap and sandwich the whole thing at 200℃, s
kg/cm 2. Press molded for 40 minutes, and then
Post-curing was carried out at 20° C. for 5 hours. When the tensile shear joint strength of this material was measured, it was found to be 220 at room temperature.
kfl/cm2. Even at 250℃ 185k (1/a
It maintained a strength of 180 ko/cm2 when measured at room temperature even after heat deterioration at 250°C for 20 days. The effects of the present invention were recognized.

[Effects of the Invention] The thermosetting resin composition of the present invention compensates for the drawbacks of aromatic polyimides and maleimides, and has excellent heat resistance, mechanical strength, and processability, and is suitable for use in laminates, molding materials, It is an extremely useful adhesive used in electrical equipment, etc.

Claims (1)

[Claims] 1 (A) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R_1 in the formula ▲ There are ▲ mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
Organic solvent-soluble polyimides consisting of benzophenonetetracarboxylic acid or its derivatives, represented by (B) b) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R^2 represents an n-valent organic group, and X^1 and
^2 represents the same or different one atom or group selected from a hydrogen atom, a halogen atom, or an organic group, and n represents an integer of 2 or more, respectively) and (b) General formula ▲ Numerical formula , chemical formulas, tables, etc. ▼ (However, in the formula, R^3 represents an atom or group selected from a hydrogen atom, a halogen atom, or an organic group, and m represents an integer from 1 to 5.) addition reaction product with phenols,
and (C) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R^4 to R^7 represent the same or different atoms or groups selected from hydrogen atoms or alkyl groups) A thermosetting resin composition comprising imidazoles. 2 Organic solvent soluble polyimide (A) and addition reaction product (
5 to 80% by weight of organic solvent soluble polyimides and 95% by weight of addition reaction product based on the total amount of B) [(A)+(B)]
20% by weight of the thermosetting resin composition according to claim 1. 3 In the addition reaction product, 0.1 to 1 aminophenol is added to 1 equivalent of maleimide group of polymaleimide.
The thermosetting resin composition according to claim 1 or 2, which is blended in molar amounts. 4. The thermosetting resin composition according to any one of claims 1 to 3, wherein the imidazole (C) is blended in an amount of 0.5 to 5% by weight based on the addition reaction product (B).