JPH11181280A - Polyimide-based resin composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soluble and thermoplastic polyimide resin composition, and to provide a production method and an injection molding product thereof. SOLUTION: This polyimide resin composition comprises 100 pts.wt. soluble and thermoplastic polyimide having a repeating structural unit of the formula (Ar has 4-27 carbon atoms and is a tetravalent group selected from an aliphatic, a monocyclic aliphatic, a condensed polycyclic aliphatic, a monocyclic aromatic and a condensed polycyclic aromatic groups and an uncondensed polycyclic aromatic group having aromatic groups mutually bonded directly or through cross linking members) as an essential structural unit, and >=0.3 dl/g logarithmic viscosity, and 5-65 pts.wt. at least one kind selected from a carbon fiber, a glass fiber, an aromatic polyamide fiber and a potassium titanate fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a soluble and thermoplastic polyimide resin composition, a method for producing the same, and an injection molded article thereof. Specifically, a polyimide resin composition comprising at least one selected from polyimide and carbon fiber, glass fiber, aromatic polyamide fiber, and potassium titanate fiber, which is soluble in a general-purpose organic solvent and has thermoplasticity, and production thereof The present invention relates to a method, and also to their injection-molded articles.

[0002]

2. Description of the Related Art Conventionally, in addition to its high heat resistance, polyimide has excellent mechanical strength and dimensional stability, and has physical properties such as flame retardancy, electrical insulation and radiation resistance. Widely used in the fields of industrial equipment, transportation equipment and the like. Conventionally, various polyimides exhibiting excellent properties have been developed, but even if they have excellent heat resistance, they do not have a clear glass transition temperature. It had advantages and disadvantages in terms of its performance, such as that it had to be used for processing, and its workability was excellent but its glass transition temperature was low.

In recent years, general formula (3)

Embedded image With regard to the polyimide having the basic skeleton of (1), a polyimide capable of injection and extrusion molding by adjusting the polymer molecular weight by sealing the terminal of the reactive polymer has been found (JP-A-02-018419). However,
Although this polyimide also had thermoplasticity, it could not be impregnated with a fibrous reinforcing material or the like because it did not dissolve in a general-purpose solvent.

Further, equation (4)

Embedded image Is a polyetherimide having both melt moldability and solvent solubility. In the case of this resin, the basic skeleton contains an alkyl group having poor thermo-oxidative stability. From things
There is a problem in heat resistance, and there is also a problem in water absorption and moisture absorption. Therefore, the resin composition using this polyetherimide resin has the same problem.

Accordingly, a solvent-soluble polyimide resin composition which has sufficiently solved the problems of heat resistance, water absorption and moisture absorption has not been found yet.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyimide resin composition having solubility and thermoplasticity, a method for producing the same, and an injection molded article thereof.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a polyimide having a specific structure and a molecular weight is soluble and has thermoplasticity. We found that we gave things and completed the present invention.

That is, the present invention provides a compound represented by the general formula (1):

Embedded image [Wherein, Ar has 4 to 27 carbon atoms and an aliphatic group;
Monocyclic aliphatic group, condensed polycyclic aliphatic group, monocyclic aromatic group, condensed polycyclic aromatic group, non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member A tetravalent group selected from the group consisting of group groups; 100 parts by weight of a soluble and thermoplastic polyimide having at least one of the repeating structural units represented by the formula (1) as an essential structural unit, and having a logarithmic viscosity of 0.3 dl / g or more, and 5 to 65 parts by weight of carbon Fiber, glass fiber, relates to a polyimide resin composition containing at least one selected from aromatic polyamide fiber and potassium titanate fiber,
Further, among them, the general formula (2)

Embedded image [Wherein, Ar has 4 to 27 carbon atoms and an aliphatic group;
Monocyclic aliphatic group, condensed polycyclic aliphatic group, monocyclic aromatic group, condensed polycyclic aromatic group, non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member A tetravalent group selected from the group consisting of group groups; 100 parts by weight of a soluble and thermoplastic polyimide having at least one of the repeating structural units represented by the formula (1) as an essential structural unit, and having a logarithmic viscosity of 0.3 dl / g or more, and 5 to 65 parts by weight of carbon Fiber, glass fiber, relates to a polyimide resin composition containing at least one selected from aromatic polyamide fiber and potassium titanate fiber,
Further, after dissolving a soluble and thermoplastic polyimide having a repeating structural unit represented by the general formula (1) in a specific organic solvent, carbon fiber, glass fiber, aromatic polyamide fiber, potassium titanate fiber More specifically, the present invention relates to a method for producing a polyimide resin composition, in which at least one selected from the following is mixed, and then the solvent is removed to obtain a resin composition. Organic solvent that dissolves a soluble, thermoplastic polyimide having a structural unit is a halogen-based hydrocarbon solvent, an amide-based solvent, a method for producing a polyimide resin composition that is a phenol-based solvent,
Further, the present invention relates to an injection molded article obtained from these polyimide resin compositions.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The polyimide resin composition of the present invention contains at least one kind of a repeating structural unit represented by the above general formula (1) as an essential structural unit, and has a logarithmic viscosity of 0.3 dl. / G or more soluble,
And 100 parts by weight of a thermoplastic polyimide and 5-6
A polyimide resin composition containing 5 parts by weight of at least one selected from carbon fiber, glass fiber, aromatic polyamide fiber and potassium titanate fiber, and a method for producing the same.

When producing a soluble and thermoplastic polyimide having a repeating structural unit represented by the general formula (1) used herein, the general formula (5)

Embedded image Bis (aminophenoxy) -thiophenyl-
Benzene compounds and general formula (6)

Embedded image [Wherein, Ar has 4 to 27 carbon atoms and an aliphatic group;
Monocyclic aliphatic group, condensed polycyclic aliphatic group, monocyclic aromatic group, condensed polycyclic aromatic group, non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member A tetravalent group selected from the group consisting of group groups; ] Are used.

The bis (aminophenoxy) -thiophenyl-benzene compounds represented by the general formula (5) used herein are specifically 1,3-bis (3-aminophenoxy) -2-thiophenyl-benzene 1,3-bis (3-aminophenoxy) -4-thiophenyl-benzene, 1,3-bis (3
-Aminophenoxy) -5-thiophenyl-benzene,
1,3-bis (4-aminophenoxy) -2-thiophenyl-benzene, 1,3-bis (4-aminophenoxy) -4-thiophenyl-benzene, 1,3-bis (4
-Aminophenoxy) -5-thiophenyl-benzene,
1,4-bis (3-aminophenoxy) -2-thiophenyl-benzene, 1,4-bis (3-aminophenoxy) -3-thiophenyl-benzene, 1,4-bis (4
-Aminophenoxy) -2-thiophenyl-benzene,
1,4-bis (4-aminophenoxy) -3-thiophenyl-benzene, and the like.
1,3-bis (3-aminophenoxy) -5-thiophenyl-benzene is desirable, and a polyimide represented by the general formula (2) can be obtained using this diamine compound.

The tetracarboxylic dianhydride represented by the general formula (6) used herein is, for example, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid. Acid dianhydride, 2,2 ', 3
3′-benzophenonetetracarboxylic dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride Anhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4
-Dicarboxyphenyl) sulfone dianhydride, 1,1-
Bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,1 3,3,3-hexafluoropropane dianhydride, 1,3-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] Benzene dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, 2,2
-Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4-
(1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4 ′
-Bis [4- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, 4,4'-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4 -(1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [3- (1,2
-Dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, bis {4-
[3- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, 2,2-bis {4- [4-
(1,2-dicarboxy) phenoxy] phenyl}-
1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3 , 3,3
-Hexafluoropropane dianhydride, 2,3,6,7-
Naphthalenetetracarboxylic dianhydride, 1,4,5,8
-Naphthalenetetracarboxylic dianhydride, 1,2,5
6-naphthalenetetracarboxylic dianhydride, 1,2,2
3,4-naphthalenetetracarboxylic dianhydride, 3,
4,9,10-perylenetetracarboxylic dianhydride,
2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-anthracenetetracarboxylic dianhydride and the like 1,2,3,4-butanetetracarboxylic dianhydride,
1,2,3,4-cyclobutanetetracarboxylic dianhydride is exemplified.

There is no problem if one or more other diamines are mixed and polymerized as long as the properties and physical properties of the polyimide are not impaired. Examples of the diamine that can be used in combination include, for example, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 4,4′-diaminodiphenyl ether,
3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, bis (3-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis ( 3-aminophenyl) sulfoxide,
Bis (4-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, (3-aminophenyl) (4- Aminophenyl) sulfone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4 ′
-Diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
3,4′-diaminodiphenylmethane, bis [4- (3
-Aminophenoxy) phenyl] methane, bis [4-
(4-aminophenoxy) phenyl] methane, 1,1-
Bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4
-(3-aminophenoxy) phenyl] propane, 2,
2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy)
Phenyl] butane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) ) Phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3- Bis (4-aminophenoxy)
Benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-amino Phenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl]
Ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy)
Phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4-
(3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone,
Bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy)
Benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4- (4
-Amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) phenoxy-α , Α
-Dimethylbenzyl] benzene, 1,3-bis [4-
(4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3 -Bis [4- (4-
Amino-6-fluorophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-
Cyanophenoxy) -α, α-dimethylbenzyl] benzene, 3,3′-diamino-4,4′-diphenoxybenzophenone, 4,4′-diamino-5,5′-diphenoxybenzophenone, 3,4′- Diamino-4,5 '
-Diphenoxybenzophenone, 3,3'-diamino-
4-phenoxybenzophenone, 4,4'-diamino-
5-phenoxybenzophenone, 3,4'-diamino-
4-phenoxybenzophenone, 3,4'-diamino-
5'-phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4 '
-Diamino-5,5'-dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibiphenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 4,4'-diamino-5 Biphenoxybenzophenone, 3,4'-diamino-4-biphenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone, 1,3-bis (3-amino-
4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene,
1,3-bis (4-amino-5-phenoxybenzoyl) benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino-4-biphenoxybenzoyl) Benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5- Biphenoxybenzoyl) benzene, 2,6-bis [4-
(4-amino-α, α-dimethylbenzyl) phenoxy] benzonitrile, 2,6-bis [4- (4-amino-α, α-bistrifluoromethylbenzyl) phenoxy] benzonitrile, 2,6-bis [ 4- (4-aminophenoxy) phenoxy] benzonitrile, 2,6-bis [4- (4-aminobenzoyl) phenoxy] benzonitrile, 3,3′-diamino-4,4′-diphenoxybenzophenone, 4'-diamino-5,5'-diphenoxybenzophenone, 3,4'-diamino-4,
5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino- 5-phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,
4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibiphenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 4,4'-diamino- 5-biphenoxybenzophenone, 3,4'-diamino-4-biphenoxybenzophenone, 3,4'-diamino-5-biphenoxybenzophenone, 3,3'-diamino-4,
4'-dimethoxybenzophenone, 4,4'-diamino-5,5'-dimethoxybenzophenone, 3,4'-diamino-4,5'-dimethoxybenzophenone, 3,
3'-diamino-4-methoxybenzophenone, 4,
4'-diamino-5-methoxybenzophenone, 3,
4'-diamino-4-methoxybenzophenone, 3,
4'-diamino-5-methoxybenzophenone, 1,3
-Bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) benzene, 4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-
Bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5
Biphenoxybenzoyl) benzene, 1,4-bis (4
-Amino-5-biphenoxybenzoyl) benzene,
1,3-bis (3-amino-4-methoxybenzoyl)
Benzene, 1,4-bis (3-amino-4-methoxybenzoyl) benzene, 1,3-bis (4-amino-5-
Methoxybenzoyl) benzene, 1,4-bis (4-amino-5-methoxybenzoyl) benzene, and the like.

The polyimide obtained by using the aromatic diamine component and the aromatic tetracarboxylic dianhydride as monomer components is mainly a polyimide having a repeating structural unit represented by the general formula (1). It may be substituted with a group having no reactivity with dicarboxylic anhydride.

The polyimide having an aromatic ring substituted at its terminal with a group having no reactivity with an amine or a dicarboxylic anhydride can be obtained by preparing an aromatic diamine represented by the general formula (5):
Mainly reacting the tetracarboxylic dianhydride represented by the general formula (6) in the presence of an aromatic dicarboxylic anhydride or an aromatic monoamine to thermally or chemically imidize the resulting polyamic acid It is obtained by doing.

The dicarboxylic anhydride and monoamine used here are conventionally known compounds. Specific dicarboxylic anhydrides include phthalic anhydride, 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4- Dicarboxyphenylphenyl ether anhydride, 2,3-biphenyldicarboxylic anhydride, 3,4-biphenyldicarboxylic anhydride, 2,3-dicarboxyphenylphenylsulfone anhydride, 3,4-dicarboxyphenylphenylsulfone anhydride Product, 2,3-dicarboxyphenylphenyl sulfide anhydride, 3,4-dicarboxyphenylphenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-
Examples thereof include naphthalenedicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride, 2,3-anthracenedicarboxylic anhydride, and 1,9-anthracenedicarboxylic anhydride. These dicarboxylic anhydrides may be substituted with a group having no reactivity with amine or dicarboxylic anhydride.

Of these dicarboxylic anhydrides, phthalic anhydride is most preferable from the viewpoint of properties and practicality of the polyimide from which phthalic anhydride can be obtained. In the case of using phthalic anhydride, there is no problem if a part of the phthalic anhydride is replaced with another dicarboxylic anhydride as long as the good physical properties of the polyimide are not impaired.

The amount of the dicarboxylic anhydride used is 0.001 per mole of the aromatic diamine represented by the formula (5).
To 1.0 mole ratio, and the preferred amount is 0.01 to
0.5 mole.

When an aromatic monoamine is used,
Examples of the aromatic monoamine include aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,6-xylidine, 3,4-xylidine,
3,5-xylysine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline,
m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline,
o-aminophenol, m-aminophenol, p-aminophenol, o-anisidine, m-anisidine, p
-Anisidine, o-phenezine, m-phenezine, p-
Phenezine, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-
Aminobenzonitrile, m-aminobenzonitrile, p
-Aminobenzonitrile, 2-aminobiphenyl, 3-
Aminobiphenyl, 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether, 4-aminophenylphenyl ether, 2
-Aminobenzophenone, 3-aminobenzophenone,
4-aminobenzophenone, 2-aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide, 4-aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfone, 4-aminophenylphenyl sulfone,
α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 2-amino-1-naphthol, 4-
Amino-1-naphthol, 5-amino-1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-
Examples thereof include 2-naphthol, 1-aminoanthracene, 2-aminoanthracene, and 9-aminoanthracene. These aromatic monoamines may be substituted with a group having no reactivity with amine or dicarboxylic anhydride.

The amount of the aromatic monoamine used is 0.001 to 1.0 mole ratio per 1 mole of the tetracarboxylic dianhydride represented by the general formula (6), and the preferred amount is 0.01 to 1.0. 0.5 mole.

The method for producing the polyimide of the present invention includes:
Although all methods capable of producing polyimide can be applied including known methods, it is particularly preferable to carry out the reaction in an organic solvent. The solvent used in such a reaction is preferably N, N-dimethylacetamide, and other usable solvents include, for example, N, N-dimethylformamide, N, N-diethylacetamide, N, N-dimethylacetamide. Dimethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether,
1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyrroline, picoline, dimethylsulfoxide,
Examples include dimethyl sulfone, tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, m-cresylic acid, p-chlorophenol, anisole, benzene, toluene, xylene and the like. These organic solvents may be used alone or as a mixture of two or more.

According to the method of the present invention, an organic solvent represented by the general formula (5)
A method of adding and reacting an aromatic diamine of formula (4), a tetracarboxylic dianhydride, an aromatic dicarboxylic anhydride or an aromatic monoamine of the general formula (6) includes (a) aromatic tetracarboxylic dianhydride and aromatic A method of adding an aromatic dicarboxylic acid anhydride or an aromatic monoamine and then continuing the reaction after reacting the aromatic diamine, (ii) reacting the aromatic diamine by adding the aromatic dicarboxylic acid anhydride to the aromatic diamine, A method in which tetracarboxylic dianhydride is added and the reaction is further continued. (C) After an aromatic monoamine is added to aromatic tetracarboxylic dianhydride and reacted, an aromatic diamine is added and the reaction is further continued. And (d) a method of simultaneously adding and reacting an aromatic tetracarboxylic dianhydride, an aromatic diamine, an aromatic dicarboxylic anhydride or an aromatic monoamine. Gerare, really no problem with any of the addition method.

The reaction temperature is usually 250 ° C. or lower, preferably 50 ° C. or lower. The reaction pressure is not particularly limited, and the reaction can be sufficiently performed at normal pressure. The reaction time varies depending on the type of aromatic tetracarboxylic dianhydride, the type of solvent and the reaction temperature, and usually 4 to 24 hours is sufficient. Further, by heating the obtained polyamic acid to 100 to 400 ° C. to imidize or chemically imidizing using an imidizing agent such as acetic anhydride, a polyimide having a repeating structural unit corresponding to the polyamic acid is obtained. can get.

Further, an aromatic diamine of the general formula (5) and a tetracarboxylic dianhydride of the general formula (6), and further, when the terminal of the polyimide has an aromatic ring, an aromatic dicarboxylic anhydride or an aromatic monoamine Are suspended or dissolved in an organic solvent and then heated, and imidation is carried out simultaneously with the production of the polyamic acid, which is a precursor of the polyimide, to obtain the desired polyimide.

By the above method, a polyimide represented by the general formula (1) is obtained. In particular, in the present invention, the logarithmic viscosity of the polyimide represented by the general formula (1) is 0.30 dl.
The role of the polyimide resin of / g or more is particularly important. When the logarithmic viscosity is less than 0.30 dl / g, the mechanical strength of the polyimide resin itself cannot be said to be sufficient, and moreover, the resin composition does not have satisfactory physical properties.

The polyimide resin composition of the present invention is prepared by adding carbon fiber, glass fiber, aromatic polyamide fiber, and the like to 100 parts by weight of the polyimide resin represented by the general formula (1) having a logarithmic viscosity of 0.30 dl / g or more. The reinforcing material such as potassium titanate fiber is 5 to 65 parts by weight, preferably 10 to 5 parts by weight.
It is prepared by adding 0 parts by weight. If the amount of the reinforcing material is less than 5 parts by weight, a sufficient reinforcing effect cannot be obtained. On the other hand, if the amount exceeds 65 parts by weight, a favorable molded product cannot be obtained when melt molding such as injection molding is performed.

As a method of adding a reinforcing material, a generally known method is used. The polyimide powder and the reinforcing material are preliminarily kneaded using a mortar, a Henschel mixer, a drum blender, a tumbler blender, a ball mill, a ribbon blender or the like. The most common method is to obtain a pellet or a powdery mixture using a melt mixer, a hot roll or the like,
This technique can be performed in the present invention.

However, it is also possible to realize the pre-kneading state by utilizing the solvent solubility which is a feature of the polyimide represented by the general formula (1). That is, a predetermined amount of the polyimide represented by the general formula (1) is dissolved in a halogenated hydrocarbon-based solvent, an amide-based solvent, a phenol-based solvent, or the like, and then a predetermined amount of a reinforcing material is added and dispersed under stirring. . Thereafter, the solution is discharged into a poor solvent for precipitating polyimide under high-speed stirring. The polyimide powder precipitated by such an operation is in a pre-kneaded state in which the reinforcing material is uniformly dispersed. In carrying out this method, the solvent for dissolving the general formula (1) is specifically dichloromethane, chloroform, 1,2-dichloroethane,
1,1,2-trichloroethane, dibromomethane, tribromomethane, 1,2-dibromoethane, 1,1,2-
Tribromoethane, N, N-dimethylformamide,
N, N-dimethylacetamide, N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, phenol, cresol, xylenol, halogenated phenol, halogen Cresol, dimethyl sulfoxide, dimethyl sulfone, and the like are considered. In this case, the concentration of the polyimide solution is 5 to 50 wt%, but from the viewpoint of working mechanical viscosity, it is preferably 15 to 40 wt%.
%. Further, as a poor solvent for precipitating polyimide, methanol, ethanol, propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, and the like are considered, the amount to be used is 5 to 30 times the total composition weight, Preferably 10
20 times.

As the fibrous reinforcing material used in the present invention, various materials are used, for example, glass fiber, carbon fiber, potassium titanate fiber, aromatic polyamide fiber, silicon carbide fiber, alumina fiber, boron fiber, and ceramic. Examples thereof include generally known inorganic fibers and organic fibers such as fibers. Particularly preferably used are glass fibers, carbon fibers, potassium titanate fibers, and aromatic polyamide fibers.

As the glass fiber, a molten glass is quenched while being drawn by various methods to form a thin fiber having a predetermined diameter, a strand in which single fibers are bundled with a sizing agent,
Any of rovings in which strands are uniformly aligned to form a bundle can be used. These glass fibers, in order to have an affinity with the polyimide resin of the present invention, use those treated with a silane coupling agent such as aminosilane and epoxysilane, chromic chloride, and a surface treatment agent according to other purposes. be able to. The length of the glass fiber greatly affects the physical properties of the obtained molded article and the workability during the production of the molded article. In general, the longer the glass fiber length, the better the physical properties of the molded product, but the worse the workability during the production of the molded product. For this reason, the length of the glass fiber in the present invention is 0.1 to 6 mm, preferably 0.3 to 6 mm.
Those having a range of 4 mm are preferable because the physical properties and workability of the molded article are balanced.

Examples of the carbon fibers include high elasticity and high strength fibers obtained by carbonizing polyacrylonitrile or petroleum pitch as a main raw material. As the carbon fiber, one having an appropriate diameter and an aspect ratio (ratio of length / diameter) is used depending on the reinforcing effect and the mixing property. The carbon fiber preferably has a diameter of usually 5 to 20 μm, particularly preferably about 8 to 15 μm. The aspect ratio is preferably from 1 to 600, and particularly preferably from about 100 to 350 from the viewpoint of the mixing property and the reinforcing effect. If the aspect ratio is small, there is no reinforcing effect, and if the aspect ratio is large, the mixing property is poor and a good molded product cannot be obtained. In addition, the surface of the carbon fiber various treatment agents, for example, epoxy resin, polyamide resin, polycarbonate resin,
Those treated with a polyacetal resin or the like, or those using a known surface treating agent according to other purposes, are also used. Further, potassium titanate fiber is a kind of high-hardness fiber (whisker) and has a chemical composition of K ₂ O ·
A _{6TiO 2, K 2 O · 6TiO} 2 · 1 / 2H 2 O needle-like crystals having a basic, representative melting point from 1,300 to 1,350 ° C.
It is. The average fiber length is 5 to 50 μm, and the average fiber diameter is 0.
Those having an average fiber length of 20 to 30 μm and an average fiber diameter of 0.1 to 0.3 μm are preferred. The potassium titanate fiber can be usually used without treatment, but in order to maintain affinity with the polyimide resin of the present invention, aminosilane, silane coupling agent such as epoxysilane, chromic chloride, and other surface treatment agents according to the purpose Can be used.

Further, the aromatic polyamide fiber is a heat-resistant organic fiber which has been relatively newly developed.
As a typical example, Equation (7), Equation (8), or (9)

Embedded image

Embedded image Example) DuPont trademark: Kevlar

Embedded image Example) DuPont trademark: Nomex, Teijin trademark: Con
ex. In addition, there are aromatic polyamide fibers having various skeletons depending on the ortho, meta, and para position isomeric structures. Among them, those having a para-position to para-position bond of the formula (7) have a high softening point and a high melting point, and as heat-resistant organic fibers Most preferred in the present invention.

The fibrous reinforcing material in the present invention is used in an amount of 5 to 65 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the polyimide resin represented by the general formula (1). If the amount is less than 5 parts by weight, the reinforcing effect characteristic of the present invention cannot be obtained. Conversely, if it is used in an amount exceeding 65 parts by weight, the fluidity of the composition at the time of molding becomes poor, and it becomes difficult to obtain a satisfactory molded product.

When the polyimide of the present invention is subjected to melt molding, other thermoplastic resins such as polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, polyethersulfone, and the like can be used without impairing the object of the present invention. It is also possible to mix appropriate amounts of polyether ketone, polyphenyl sulfide, polyamide imide, polyether imide, modified polyphenylene oxide, polyimide other than the present invention, etc. according to the purpose. Further, the following fillers and the like used in ordinary resin compositions may be used as long as the object of the invention is not impaired. That is, abrasion resistance improvers such as graphite, carborundum, silica stone powder, molybdenum disulfide, and fluorine-based resin, reinforcing agents such as glass fiber and carbon fiber, and flame retardant improvement such as antimony trioxide, magnesium carbonate, and calcium carbonate. Agents, clay, mica, etc., electrical property improvers, asbestos, silica, graphite and other tracking resistance improvers, barium sulfate, silica, calcium metasilicate and other acid resistance improvers, iron powder, zinc powder, aluminum powder, copper Thermal conductivity improver such as powder, other glass beads,
Glass spheres, talc, diatomaceous matter, alumina, shirasubarun, hydrated alumina, metal oxides, coloring agents and the like.

The polyimide of the present invention may be in the form of fibers in addition to various molding materials and films.

[0036]

The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples. The properties of the polyimide were measured by the following methods. Tg, Tc, Tm: DSC (Shimadzu DE-40 series,
DSC-41M). 5% weight loss temperature: DTG (Shimadzu DT-40) in the air
Series, DTG-40M). Logarithmic viscosity (ηinh): 0.5 parts of polyimide powder in a mixed solvent of p-chlorophenol / phenol (weight ratio 9/1)
Measured at 35 ° C. after dissolving at a concentration of g / 100 ml. Injection molded product tensile test: The tensile test is ASTM D3039.
It measured based on. The measurement conditions were room temperature (18 to
(At 25 ° C.) an atmosphere having a moisture absorption rate of 0.2% or less (RT / DRY) and an atmosphere having a high temperature (100 ° C. and 150 ° C.) moisture absorption rate of 0.6 ± 0.1% (HOT / WET).

A synthesis example of a diamine compound which is a raw material of the polyimide used in the present invention and a synthesis example of a polyimide obtained from the diamine compound are shown below. Synthesis Examples 1 to 1, Synthesis of 1,3-bis (3-aminophenoxy) -thiophenyl-benzene 1,3-dimethylimidazolidinone in a four-necked flask equipped with a thermometer, a reflux condenser, a nitrogen inlet tube, and a stirrer (DMI) 501.7 g, thiophenol 221.5 g
(2.01 mol), 135.2 g of potassium hydroxide (2.
41 mol) and 308 g of toluene, and the mixture was heated to 130 ° C. with stirring and then azeotropically dehydrated at 130 ° C. for 2 hours. Thereafter, a solution of 438 g (1.34 mol) of 1,3-bis (3-aminophenoxy) -5-chlorobenzene and 1022 g of DMI was added dropwise at 130 ° C. over 2 hours. Further, the temperature was gradually raised to 180 ° C. over 4 hours, and aging was performed at 180 ° C. for 8 hours. At this stage, when analyzed by high performance liquid chromatography, the peak of 1,3-bis (3-aminophenoxy) -5-chlorobenzene as the raw material disappeared, and instead, the area fraction was 83%.
A new peak was expressed. After completion of the reaction, the inorganic salts were removed by cooling to room temperature and filtering, and DMI was distilled off using an aspirator. About 50 collected residue
Drained into 0 ml water and stirred vigorously to separate brown oil into lower layer. After recovering this brown oily substance, 500 m
and a 36% aqueous hydrochloric acid solution was added dropwise with stirring to obtain a brown aqueous solution. Further, an appropriate amount of sodium chloride was added to this aqueous solution to precipitate a brown hydrochloride. The obtained hydrochloride was redissolved in water, decolorized with activated carbon, further concentrated and crystallized, whereby a white hydrochloride was precipitated. The hydrochloride was separated by filtration and analyzed for purity by high performance liquid chromatography to find 98.3%. In addition, this hydrochloride is added to water 50
After heating and dissolving in 0 ml, an appropriate amount of aqueous ammonia was dropped and charged.
When neutralized, it separated into two layers. 500 ml of diethyl ether was added to this two-layer solution, and the oil layer side was extracted. Thereafter, diethyl ether was distilled off with an evaporator, and the oily substance was allowed to stand at room temperature, whereby a pale orange precipitate was obtained. The precipitate is dried under reduced pressure at 60 ° C.
90 g of 1,3-bis (3-aminophenoxy) -5
Thiophenyl-benzene was obtained. Yield 54%. The analysis results of the diamine compound 1,3- (3-aminophenoxy) -5-thiophenyl-benzene obtained here are shown below. [Melting point] 68.4-70.9 ° C [Purity] 99.0% (high-performance liquid chromatography) [Elemental analysis] Theoretical value of CHNS (%) 71.97 5.04 7.00 8.00 Actual measurement Value (%) 72.02 5.16 6.85 8.24

Synthesis Example 2 Synthesis of Polyimide 20.03 g (0.05 mol) of 1,3-bis (3-aminophenoxy) -5-thiophenyl-benzene was placed in a vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube. ),
15.47 g (0.048 mol) of 3,3′4,4′-benzophenonetetracarboxylic dianhydride, 0.592 g (0.004 mol) of phthalic anhydride, 0.70 g of γ-picoline, 146.8 g of m-cresol And heated to 150 ° C. while stirring under a nitrogen atmosphere. Thereafter, the reaction was carried out at 150 ° C. for 4 hours, during which time about 1.8 ml of water was distilled out. After completion of the reaction, the mixture was cooled to room temperature and discharged into about 1 L of methanol, and then the polyimide powder was separated by filtration. This polyimide powder was washed with methanol, and then dried under reduced pressure at 50 ° C. for 24 hours and under reduced pressure at 160 ° C. for 12 hours to obtain 33.54 g of polyimide powder.
(Yield 97.8%). The logarithmic viscosity of the thus obtained polyimide powder was 0.53 dl / g, and the weight average molecular weight (Mw) by GPC was 138,000. DSC measurement of this polyimide powder revealed a glass transition temperature (Tg) of 167 ° C. The 5% weight loss temperature of this polyimide powder was 519 ° C. Was measured infrared absorption spectrum of the polyimide powder, 1780 cm ^-1 and 1720 cm ^-1 imide characteristic absorption bands
Near absorption was noticed. The elemental analysis values of the obtained polyimide powder were as follows. CH N S calculated value (%) 71.71 3.24 4.08 4.67 measured value (%) 71.53 3.19 4.10 4.55 The flow onset temperature of this polyimide powder is raised. When measured using a tester, flow was observed at 235 ° C., and the melt viscosity at 300 ° C. was 26100.
Poise. The polyimide powder obtained here is chloroform, dichloromethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, N, N-
It was soluble in dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, m-cresol and the like. Furthermore, the moisture absorption of the polyimide powder obtained here was 0.56%.
Met.

Synthesis Examples 3 to 5 Using the diamine compounds and tetracarboxylic dianhydrides shown in Table 1, polyimide powders were synthesized in exactly the same manner as in Synthesis Example 2. Table 1 lists diamine compounds and tetracarboxylic dianhydrides, and shows the yield, logarithmic viscosity of polyimide powder, glass transition temperature, 5% weight loss temperature, and moisture absorption. The polyimides obtained in Synthesis Examples 3 and 4 were soluble in the same solvent as the polyimide obtained in Synthesis Example 2, but the polyimide obtained in Synthesis Example 5 was insoluble in these solvents.

Example 1 After dissolving the polyimide obtained in Synthesis Example 2 in N, N-dimethylformamide (DMF) at a concentration of about 30% by weight, 40 parts by weight of carbon fiber was added to 100 parts by weight of the polyimide powder. (HTA-C6 manufactured by Toho Rayon Co., Ltd.) was dispersed under stirring. This polyimide resin composition solution was discharged into methyl ethyl ketone in an amount about 15 times the weight of the polyimide powder under high-speed stirring. The obtained resin composition was dried at 200 ° C. for about 4 hours under a nitrogen stream to obtain a polyimide / carbon fiber mixture. The obtained resin mixture has a diameter of 30 mm.
After melt-kneading with a single screw extruder, the strand was air-cooled and cut to obtain pellets. An Aburg injection molding machine (injection pressure 500 kg / c)
m ² , cylinder temperature 350 ° C., mold temperature 150 ° C.) to obtain a JIS standard No. 1 dumbbell test piece. As described above, the tensile test of the test piece was performed at room temperature and under drying (RT / DR).
Y) and high temperature (100 ° C, 150 ° C)
T.WET). Table 2 shows the results. From the results here, the tensile strength in HOT / WET is RT / DR.
It can be seen that the tensile strength in Y is maintained at about 70% of the tensile strength.

Example 2.3 Test pieces were prepared in the same manner as in Example 1 using the polyimide powder obtained in Synthesis Examples 3 and 4. The same tensile test as in Example 1 was performed using the obtained test piece. Table 2 shows the results. The results here show that the tensile strength in HOT / WET is maintained at about 70% of the tensile strength in RT / DRY.

Comparative Example 1 Since the polyimide powder obtained in Synthesis Example 5 was insoluble in DMF, a resin mixture having the same ratio as in Example 1 was prepared using a drum blender mixer (manufactured by Kawada Seisakusho). Hereinafter, a test piece was prepared in the same manner as in Example 1, and a similar tensile test was performed. Table 2 shows the results. From these results, the polyimide has a higher moisture absorption than the polyimide resin composition obtained in the above example, and the tensile strength in HOT / WET is about 60% of the tensile strength in RT / DRY.
It turns out that it is about.

COMPARATIVE EXAMPLES 2.3 With respect to the polyimide obtained in Synthesis Example 1, a resin composition test piece outside the composition range of the present invention was prepared and subjected to the same tensile test as in the above Examples. Table 2 shows the results. Compared with the case where the carbon fiber is used within the scope of the present invention, the tensile strength is lowered even at room temperature when the amount used is outside the small range,
In addition, injection molding was impossible when used outside the range where the amount used was large.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

As described above, the polyimide resin composition according to the present invention comprises:
In addition to various properties such as high heat resistance inherent to the polyimide resin, it also has more physical properties than before, such that high mechanical properties are maintained even under high temperature and high humidity. In addition, also in the manufacturing method thereof, by utilizing the solvent solubility of the present polyimide itself, mixing in a polyimide / reinforcement solution became possible.

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Claims (5)

[Claims] 1. A compound of the general formula (1) [Wherein, Ar has 4 to 27 carbon atoms and an aliphatic group;
Monocyclic aliphatic group, condensed polycyclic aliphatic group, monocyclic aromatic group, condensed polycyclic aromatic group, non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member A tetravalent group selected from the group consisting of group groups; 100 parts by weight of a soluble and thermoplastic polyimide having at least one of the repeating structural units represented by the formula (1) as an essential structural unit, and having a logarithmic viscosity of 0.3 dl / g or more, and 5 to 65 parts by weight of carbon A polyimide resin composition containing at least one selected from fibers, glass fibers, aromatic polyamide fibers and potassium titanate fibers. 2. A compound of the general formula (2) [Wherein, Ar has 4 to 27 carbon atoms and an aliphatic group;
Monocyclic aliphatic group, condensed polycyclic aliphatic group, monocyclic aromatic group, condensed polycyclic aromatic group, non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member A tetravalent group selected from the group consisting of group groups; 100 parts by weight of a soluble and thermoplastic polyimide having at least one of the repeating structural units represented by the formula (1) as an essential structural unit, and having a logarithmic viscosity of 0.3 dl / g or more, and 5 to 65 parts by weight of carbon A polyimide resin composition containing at least one selected from fibers, glass fibers, aromatic polyamide fibers and potassium titanate fibers. 3. After dissolving a soluble and thermoplastic polyimide having a repeating structural unit represented by the formula (1) in a specific organic solvent, carbon fiber, glass fiber, aromatic polyamide fiber, titanic acid The method for producing a polyimide resin composition according to claim 1, wherein at least one selected from potassium fibers is mixed, and then the solvent is removed to obtain a polyimide resin composition. 4. An organic solvent for dissolving a soluble and thermoplastic polyimide having a repeating structural unit represented by the formula (1) is a halogen-based hydrocarbon solvent, an amide-based solvent, or a phenol-based solvent. A method for producing the polyimide resin composition according to claim 3. 5. An injection molded article obtained from the polyimide resin composition according to claim 1.