JPH07268214A - Polyimide resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which can be melt molded and gives a molding having high fatigue resistance by mixing a specified polyimide and polyaryletherketone with a specified polyetherimide. CONSTITUTION:100 pts.wt. resin consisting of 5-99 pts.wt. polyimide having repeating units of formula I (wherein R1 is a 2-27C aliphatic or monocyclic, condensed polycyclic or non-condensed polycyclic aromatic group) and having the molecular end blocked by reacting in the presence of particularly an aromatic dicarboxylic acid anhydride of formula II (wherein Z is a 6-15C monocyclic or polycyclic aromatic group) or an aromatic monoamine represented by the formula V-NH2 (wherein V is the same as Z) and 95-1 pts.wt. polyaryletherketone particularly having repeating units of, e.g. formula III is mixed with 1-50 pts.wt. polyetherimide particularly having repeating units of formula IV (wherein Ar and Y are each a 4-27C monocyclic or non-condensed polycyclic aromatic group) to give the objective composition A molding obtained from this composition and heat treated at 150-300 deg.C is suitable particularly for parts of which good dynamic fatigue characteristics are required.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide resin composition having good fatigue properties and an injection molded product thereof. Specifically, it relates to a polyimide resin composition having good melt moldability and excellent fatigue resistance, and an injection molded product thereof.

[0002]

2. Description of the Related Art Conventionally, in addition to its high heat resistance, polyimide has excellent mechanical strength, dimensional stability, flame retardancy, and electrical insulation properties. Widely used in fields such as transportation equipment. Conventionally, various polyimides showing excellent properties have been developed, but even if they have excellent heat resistance, they do not have a clear glass transition temperature, so when they are used as molding materials, they are processed using methods such as sintering molding. It has excellent workability, but has a low glass transition temperature, is soluble in halogenated hydrocarbon solvents and is not satisfactory in terms of heat resistance and solvent resistance. was there.

Melt-moldable polyimides and various co-polyimides having excellent mechanical properties, thermal properties, electrical properties, and chemical resistance have been developed as polyimides that solve these problems (Japanese Patent Laid-Open No. 61-61160). -143478 gazette, 62.
-205124 publication). However, the requirements for the performance of compositions containing polyimide have reached a higher level, and polyimide compositions having excellent dynamic mechanical properties such as fatigue properties have been required. A polyimide composition that sufficiently satisfies the requirements for this fatigue property is still under investigation. In particular, in the field of highly heat-resistant polyimide capable of injection molding which has been developed in recent years, there is almost no knowledge at present. For example, a polyimide resin having a repeating unit represented by the formula (1) described in the present specification has excellent heat resistance and good mechanical properties (see, for example, JP-A-63 / 63).
-7763). However, its mechanical properties are still insufficient, and it cannot be used as a substitute for metal materials used in fields requiring high heat resistance and high durability. The known carbon fiber reinforced polyimide composition cannot reach the fatigue limit of a metal material, for example, an aluminum alloy, which is required to have particularly excellent fatigue properties at high temperature.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to obtain a polyimide resin composition which can be melt-molded by injection molding or the like and has a high fatigue property and a molded product thereof under the above-mentioned circumstances. It is in.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the polyimide of the formula (1) and the repeating unit represented by the formulas (4) to (8) At least one or more of the polyallyl ether ketone having a polyimide resin composition obtained by containing a polyether imide in an amount of a specific range shows excellent melt flow moldability, and from this resin composition to fatigue characteristics They have found that an excellent injection-molded product can be obtained, and have reached the present invention.

That is, the present invention uses the formula (1)

[Chemical 11] (In the formula, R ₁ has 2 to 27 carbon atoms, and an aliphatic group, a monocyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group and / or an aromatic group are directly or A polyimide having a repeating unit represented by a tetravalent group which is a non-condensed polycyclic aromatic group interconnected by a crosslinking member.
1 to 5 per 100 parts by weight of the total amount of the resin composition consisting of 99 parts by weight and 95 to 1 parts by weight of polyallyl ether ketone.
A polyimide resin composition characterized by containing 0 parts by weight of polyetherimide and an injection molded article thereof,

Preferably, the polyimide having the repeating unit represented by the formula (1) has the formula (2) during its production.

[Chemical 12] (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
An aromatic dicarboxylic acid anhydride represented by a condensed polycyclic aromatic group and / or a divalent group which is a non-condensed polycyclic aromatic group in which aromatic groups are directly or mutually linked by a bridging member) Thing and / or formula (3)

[Chemical 13] (In the formula, V has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
In the coexistence of an aromatic monoamine represented by a condensed polycyclic aromatic group and / or a monovalent group which is a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member. Obtained by reacting with, the molecular end of the polymer is sealed,

The polyallyl ether ketone has the formula (4), the formula (5), the formula (6), the formula (7) and / or the formula (8), and the formula (4)

[Chemical 14] Formula (5)

[Chemical 15] Formula (6)

[Chemical 16] Formula (7)

[Chemical 17] Formula (8)

[Chemical 18] Is at least one selected from the group consisting of polyallyl ether ketone having a repeating unit represented by,

Further, the polyetherimide may be of formula (9), preferably of formula (10)

[Chemical 19] (In the formula, Ar and Y each have a carbon number of 4 to 27, and represent a monovalent aromatic and / or a divalent group which is a divalent non-condensed polycyclic aromatic group linked by a bridge member. )

[Chemical 20] A polyimide resin composition having a repeating unit represented by: Furthermore, a fiber-reinforced polyimide resin composition containing a fibrous reinforcing material in these polyimide resin composition, in an injection molded body obtained from these polyimide resin composition or fiber-reinforced polyimide resin composition is there.

The polyimide represented by the formula (1) used in the present invention has the formula (11)

[Chemical 21] A diamine represented by the following formula, that is, 3,3′-diaminobenzophenone, and a formula (12)

[Chemical formula 22] (In the formula, R ₁ has the same meaning as in the case of the formula (1).) And is obtained by polymerizing a tetracarboxylic dianhydride represented by the formula.

The tetracarboxylic dianhydride represented by the formula (12) is, for example, ethylene tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 '. , 4,4'-Benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'
-Benzophenone tetracarboxylic 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, 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} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone 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-hexaflupropane dianhydride, 2,2
-Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-propane dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride , 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride Etc. These may be used alone or in admixture of two or more.

Further, one or more other diamines or tetracarboxylic dianhydrides may be mixed and polymerized within a range that does not impair the properties and physical properties of the polyimide. Examples of diamines that can be mixed and used include, for example, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, o-aminobenzylamine, p-aminobenzylamine, and 3-chloro-. 1,2-phenylenediamine,
4-chloro-1,2-phenylenediamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 3,5- Diaminotoluene, 2-methoxy-1,4
-Phenylenediamine, 4-methoxy-1,2-phenylenediamine, 4-methoxy-1,3-phenylenediamine, benzidine, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxy Benzidine, 3,3 '
-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,
3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfoxide, 3,4'-
Diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide,

3,3'-diaminodiphenyl sulfone, 3,4 '
-Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,4'-
Diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
Bis [4- (4-aminophenoxy) phenyl] methane, bis [3- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2- Bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [4-
(4-Aminophenoxy) phenyl] propane, 1,3-
Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,2-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4
-Aminophenoxy) phenyl] butane, 1,4-bis [4- (4-aminophenoxy) phenyl] butane, 2,
2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3-
Methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3-methylphenyl] propane, 2
-[4- (4-aminophenoxy) phenyl] -2-
[4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4 -(4-Aminophenoxy) phenyl] -1,1,1,
3,3,3-hexafluoropropane, 2,2-bis [3-
(4-Aminophenoxy) phenyl] -1,1,1,3,3,3-
Hexafluoropropane, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3 -Aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1
, 3-bis (4-aminobenzoyl) benzene, 1,4-
Bis (4-aminobenzoyl) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 3,3'-bis (4
-Aminophenoxy) biphenyl,

Bis [4- (4-aminophenoxy) phenyl] ketone, bis [3- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) ketone
Phenyl] sulfide, bis [3- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (4
-Aminophenoxy) phenyl] sulfone, bis [3-
(4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether,
Bis [3- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, bis [3- (4-aminophenoxy) phenyl] ether, 1,3-bis [4- (4-Aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4 -Aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,
4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3 -Aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4'-bis (3-Aminophenoxy) -3-methylbiphenyl, 4,4'-bis (3
-Aminophenoxy) -3,3'-dimethylbiphenyl, 4,
4'-bis (3-aminophenoxy) -3,5-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,
3 ', 5,5'-tetramethylbiphenyl, 4,4'-bis (3-
Aminophenoxy) -3,3'-dichlorobiphenyl, 4,4 '
-Bis (3-aminophenoxy) -3,5-dichlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ',
5,5'-tetrachlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3'-dibromobiphenyl, 4,4'-
Bis (3-aminophenoxy) -3,5-dibromobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,
5'-tetrabromobiphenyl, bis [4- (3-aminophenoxy) -3-methoxyphenyl] sulfide,
[4- (3-aminophenoxy) phenyl] [4- (3
-Aminophenoxy) -3,5-dimethoxyphenyl] sulfide, bis [4- (3-aminophenoxy) -3,5
-Dimethoxyphenyl] sulfide,

Bis [4- (3-aminophenoxy) phenyl] methane, bis [3- (3-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1 , 2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4-
(3-Aminophenoxy) phenyl] propane, 1,2-
Bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 1,1-bis [4- (3-aminophenoxy) phenyl] butane, 1,2-bis [4-
(3-aminophenoxy) phenyl] butane, 1,3-bis [4- (3-aminophenoxy) phenyl] butane,
1,4-bis [4- (3-aminophenoxy) phenyl]
Butane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,3-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-amino Phenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3- Hexafluoropropane, 4,4'-bis (3-aminophenoxy) biphenyl,
3,3′-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [3- (3-aminophenoxy) phenyl] ketone,
Bis [4- (3-aminophenoxy) phenyl] sulfide, bis [3- (3-aminophenoxy) phenyl]
Sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [3- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (3 -Aminophenoxy) phenyl] sulfone and the like can be used, and these can be used alone or in combination of two or more.

The polyimide obtained by using these diamine component and tetracarboxylic dianhydride as monomer components is a polyimide mainly having a repeating structural unit of the formula (1), and a polyimide mainly having a repeating structural unit of the formula (1). However, a polyimide whose polymer molecule terminal is not substituted or substituted with a group having no reactivity with amine or dicarboxylic acid anhydride is also included. Polyimide which is unsubstituted or substituted with a group having no reactivity with amine or dicarboxylic acid anhydride at the end of the polymer molecule is

The diamine represented by the formula (11), that is, 3,3'-diaminobenzophenone, is used, and this and the tetracarboxylic dianhydride represented by the formula (12) are combined with the formula (2).

[Chemical formula 23] (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
An aromatic dicarboxylic acid anhydride represented by a condensed polycyclic aromatic group and / or a divalent group which is a non-condensed polycyclic aromatic group in which aromatic groups are directly or mutually linked by a bridging member) Thing and / or formula (3)

[Chemical formula 24] (In the formula, V has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
The presence of an aromatic monoamine represented by a condensed polycyclic aromatic group and / or a monovalent group which is a non-condensed polycyclic aromatic group in which aromatic groups are directly or cross-linked with each other by a bridge member) It can be reacted below.

Examples of the dicarboxylic acid anhydride represented by the formula (2) include phthalic anhydride, 2,3-benzophenone dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride and 2,3-dicarboxyphenylphenyl. Ether anhydride, 3,4-dicarboxyphenylphenyl ether anhydride, 2,3-biphenyldicarboxylic acid anhydride, 3,4-biphenyldicarboxylic acid anhydride, 2,3-dicarboxyphenylphenylsulfone anhydride, 3, 4-dicarboxyphenyl phenyl sulfone anhydride, 2,3-dicarboxyphenyl phenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic acid anhydride, 2,3-naphthalenedicarboxylic acid Acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-ant Senjikarubon acid anhydride, 1,9 - anthracene dicarboxylic acid anhydride and the like. These dicarboxylic acid anhydrides may be substituted with a group having no reactivity with the amine or the dicarboxylic acid anhydride, and may be used alone or in combination of two or more kinds. Among these dicarboxylic acid anhydrides, phthalic anhydride is most preferable from the viewpoint of performance and practical use of the obtained polyimide.

When dicarboxylic acid anhydride is used, the amount thereof is 0.001 to 1.0 mol ratio per mol of 3,3'-diaminobenzophenone represented by the formula (11). If it is less than 0.001 mol, the viscosity is increased during high temperature molding, which causes deterioration of moldability. On the other hand, if it exceeds 1.0 mol, the mechanical properties will deteriorate. The preferred amount used is 0.01 to 0.5 mol.

Examples of the aromatic monoamine represented by the formula (3) include aniline, o-toluidine and m-.
Toluidine, p-toluidine, 2,3-xylidine, 2,6
-Xylidine, 3,4-xylidine, 3,5-xylidine,
o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline,
p-bromoaniline, o-nitroaniline, p-nitroaniline, p-nitroaniline, o-aminophenol, m-aminophenol, p-aminophenol, o
-Anisidine, m-anisidine, p-anisidine, o-
Phenedine, m-phenedine, p-phenedine, o-aminobenzaldehyde, m-aminobenzaldehyde,
p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl,
4-aminobiphenyl, 2-aminophenyl phenyl ether, 3-aminophenyl phenyl ether, 4-aminophenyl phenyl ether, 2-aminobezophenone, 3-aminobezophenone, 4-aminobezophenone, 2-amino Phenylphenyl 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-
Examples thereof include naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like. These aromatic monoamines may be substituted with a group having no reactivity with the amine or the dicarboxylic acid anhydride, and may be used alone or in combination of two or more kinds.

When an aromatic monoamine is used, its amount is 1% by weight of the tetracarboxylic acid dianhydride represented by the formula (12).
The molar ratio is 0.001 to 1.0. If it is less than 0.001 mol, the viscosity is increased during high temperature molding, which causes deterioration of moldability. Further, if it exceeds 1.0 mol, mechanical properties are deteriorated. The preferred amount used is 0.01 to 0.5 mol.

The polyimide resin of the present invention can be manufactured by any known method. That is, 1) synthesize a polyamic acid in an organic solvent and remove the solvent by decompression, or isolate the polyamic acid from the obtained polyamic acid solution by a method such as using a poor solvent, and then heat the polyamic acid. To obtain a polyimide by imidization. 2) A polyamic acid solution is obtained in the same manner as in 1), a dehydrating agent typified by acetic anhydride is further added, and a catalyst is optionally added to chemically imidize the polyimide, and then a polyimide is prepared by a known method. The method of isolating, washing and drying if necessary. 3) A method in which a polyamic acid solution is obtained in the same manner as in 1), and then the solvent is removed by reduced pressure or heating, and at the same time, thermal imidization is performed. 4) A method in which raw materials are charged in an organic solvent and then heated to simultaneously perform the synthesis of polyamic acid and the imidization reaction, and to make a catalyst, an azeotropic agent, a dehydrating agent, etc. coexist as necessary. And so on.

In the production, it is particularly preferable to carry out the reaction in an organic solvent. Examples of the organic solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethanebis (2-
Methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, Dimethyl sulfoxide, dimethyl sulfone, tetramethyl urea, hexamethyl phosphoramide, phenol, o-
Examples include cresol, m-cresol, p-cresol, m-cresylic acid, p-chlorophenol, anisole and the like. These organic solvents may be used alone or in combination of two or more.

In these methods, diamines, tetracarboxylic acid dianhydrides and dicarboxylic acid anhydrides or aromatic monoamines are added to and reacted in an organic solvent as follows: (a) tetracarboxylic acid dianhydride Method of continuing reaction by adding dicarboxylic acid anhydride or aromatic monoamine after reacting diamines, (b) adding dicarboxylic acid anhydride to diamines and reacting, and then adding tetracarboxylic acid dianhydride And continue to react, or
A method in which an aromatic monoamine is added to a tetracarboxylic dianhydride to cause a reaction, and then a diamine is added to continue the reaction,
(C) Any addition method such as a method of simultaneously adding tetracarboxylic dianhydride, diamine and dicarboxylic acid anhydride or aromatic monoamine to cause a reaction may be used. Polymerization / imidization reaction temperature is usually 300
It is below ℃. The polymerization / imidization reaction pressure is not particularly limited, and can be carried out at normal pressure. The polymerization / imidation reaction time varies depending on the type of diamine, the type of tetracarboxylic dianhydride, the type of solvent and the reaction temperature, and is usually 4 to
24 hours is enough. By the above method, a polyimide having a repeating unit represented by the formula (1) can be obtained.

In particular, the present invention is characterized in that the polyetherimide resin is contained in the polyimide resin represented by the formula (1) and the polyallyl ether ketone in an amount within a specific range. The injection-molded article obtained from this polyimide resin composition has improved fatigue characteristics.

The polyallyl ether ketone used in the present invention is at least one selected from the group consisting of polyallyl ether ketones represented by the formulas (4) to (8). Formula (4)

[Chemical 25] Formula (5)

[Chemical formula 26] Formula (6)

[Chemical 27] Formula (7)

[Chemical 28] Formula (8)

[Chemical 29]

The polyetherimide resin used in the polyimide-based composition of the present invention is represented by the formula (9) having an ether bond and an imide bond as essential bond units.

[Chemical 30] (In the formula, Ar and Y each have a carbon number of 4 to 27, and represent a monovalent aromatic and / or a divalent group which is a divalent non-condensed polycyclic aromatic group linked by a bridge member. ) Is a main structural unit having a repeating unit represented by.

For example, as a polyetherimide resin,
In equation (9),

[Chemical 31]

[Chemical 32]

[Chemical 33]

[Chemical 34]

[Chemical 35]

[Chemical 36]

[Chemical 37] Etc. You may use these individually or in mixture of 2 or more types.

Particularly preferred polyetherimide resins have the formula (10)

[Chemical 38] It has a repeating unit represented by

In the polyimide resin composition of the present invention, the content of these polyetherimide resins is 5 to 99 parts by weight of the polyimide resin represented by the formula (1) and 95 to 1 parts by weight of the polyaryletherketone. And more preferably a polyimide resin 20 to 99.
1 to 100 parts by weight of the total amount of the resin composition consisting of 80 parts by weight and 80 to 1 parts by weight of polyaryletherketone.
The amount is 50 parts by weight, preferably 5 to 30 parts by weight, and more preferably 5 to 25 parts by weight. Furthermore, the polyimide resin composition of the present invention is carbon fiber, glass fiber, aromatic polyamide fiber, potassium titanate fiber, metal fiber,
It is also possible to use a fibrous reinforcing material such as polon fiber, silicon carbide fiber, asbestos, rock wool or the like to prepare a molding material. In this fiber reinforced composition, the content of the fibrous reinforcing material is 1 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the composition composed of polyimide, polyaryl ether ketone and polyether imide. Is. Fibers維状amount of reinforcement is not sufficient reinforcing effect can be obtained with less than 1 part by weight, exceeding 100 parts by weight injection molding of polyimide resin composition itself is lowered,
A good injection molded product cannot be obtained.

Further, the molded product of the present invention is used in the range of 150 to 300.
The heat treatment at ° C can improve the durability of the molded product. The temperature is suitably 150 to 300 ° C, more preferably 180 to 280 ° C. Further, as a method of adding the fibrous reinforcing material, a generally known method is used, but after preliminarily kneading the polyimide powder and the reinforcing material 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 pellets or powdery mixture using a melt mixer, a heat roll or the like.

As the molding method of the polyimide resin composition of the present invention, a known molding method such as an injection molding method, an extrusion molding method, a compression molding method and a rotational molding method is used for practical use. Since the polyimide resin has a characteristic of having an excellent melt fluidity, the injection molding method is most preferable from the viewpoint of work efficiency.

Other thermoplastic resins such as polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, polyethersulfone, polyphenylene sulfide, polyamide imide, modified polyphenylene oxide, polyimide, poly It is also possible to mix an appropriate amount of ether nitrile, a fluororesin and a thermosetting resin according to the purpose. Further, one or more solid lubricants such as molybdenum disulfide, graphite, boron nitride, lead monoxide, and lead powder can be added to the polyimide resin composition of the present invention. Furthermore, to the extent that the object of the present invention is not impaired with respect to the polyimide resin composition of the present invention, an antioxidant, a heat stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant aid,
One or more usual additives such as antistatic agents and coloring agents can be added.

The injection-molded article obtained from the polyimide resin composition of the present invention can be formed into any shape by changing the shape of the mold, but particularly excellent dynamic fatigue properties are required. It is preferably applied to valve lifters and impellers around automobile parts.

[0036]

EXAMPLES The present invention will now be described in detail with reference to Examples and Comparative Examples. Synthesis Example 1 A reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube was charged with 2.12 kg (10 mol) of 3,3′-diaminobenzophenone and 29.7 kg of N, N-dimethylacetamide at room temperature. In a nitrogen atmosphere, 3.12 kg (9.7 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was added portionwise while paying attention to the rise of the solution temperature, and the mixture was stirred at room temperature for about 20 hours. To this polyimide acid solution, 222 g (1.5 mol) of phthalic anhydride was added at room temperature under a nitrogen atmosphere, and the mixture was further stirred for 1 hour. Then 2.02 kg (20 mol) of triethylamine and 3.06 kg (30 mol) of acetic anhydride were added dropwise to this solution. Approximately 1 hour after the completion of dropping, yellow polyimide powder began to precipitate. The mixture was further stirred at room temperature for 10 hours and filtered.
Furthermore, it was dispersed and washed in methanol, filtered, and dried at 180 ° C. for 2 hours to obtain 4.7 kg of polyimide powder. The logarithmic viscosity of this polyimide powder was 0.46 dl / g. Here, the logarithmic viscosity was 3 after heating and dissolving in a mixed solvent of parachlorophenol / phenol (weight ratio 90/10) with a concentration of 0.5g / 100ml.
It is a value measured by cooling to 5 ° C.

Synthesis Example 2 A reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube was charged with 2.03 kg (9.7 mol) of 3,3'-diaminobenzophenone and 29.7 kg of N, N-dimethylacetamide. ,
3.22Kg (10 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was added in portions at room temperature under a nitrogen atmosphere while paying attention to the rise of the solution temperature, and stirred at room temperature for about 20 hours. It was To this polyimide acid solution, 140 g (1.5 mol) of aniline was added at room temperature in a nitrogen atmosphere, and the mixture was further stirred for 1 hour. Then 2.02 Kg (20 mol) of triethylamine and 3.06 Kg (30 mol) of acetic anhydride were added dropwise to this solution. Approximately 1 hour after the completion of dropping, yellow polyimide powder began to precipitate. The mixture was further stirred at room temperature for 10 hours and filtered.
Furthermore, it was dispersed and washed in methanol, filtered, and dried at 180 ° C. for 2 hours to obtain 4.7 kg of polyimide powder. The logarithmic viscosity of this polyimide powder was 0.46 dl / g. Here, the logarithmic viscosity is 35 g after being dissolved by heating in a mixed solvent of parachlorophenol / phenol (weight ratio 90/10) at a concentration of 0.5 g / 100 ml.
It is the value measured by cooling to ℃.

Examples 1 to 5 and Comparative Examples 1 to 4 Polyimide powder having a logarithmic viscosity of 0.46 dl / g and polyallyl ether ketone (PEEK450P: PEEK450P: ICI) and polyetherimide (Uldem 1000: GE)
Were evenly mixed with a Henschel mixer, and melt-kneaded (420 ° C.) using a twin-screw extruder (carbon fiber was supplied from side feed) to obtain pellets. Using this pellet, ASTM No. 1 dumbbell tensile test pieces were molded (400-
420 ° C.), and the following evaluation was performed using this test piece. -Tensile strength: Performed according to ASTM D-638.-Fatigue life at room temperature: Fatigue life at room temperature was measured as one of the durability evaluations. Frequency 30Hz, stress ratio 0, stress 1
It was carried out under the condition of 3 kg / mm ² or 5.5 kg / mm ² , and the number of repetitions until breakage was defined as the life. High temperature fatigue limit: 1 as one of the durability evaluation at high temperature
The fatigue limit at 00 ° C was determined. The fatigue limit is the stress at which the material is just fractured after being repeatedly fatigued 10 ⁷ times.
The conditions were 5 Hz and a stress ratio of 0, and an SN diagram (stress-life curve) was prepared, from which the stress at the 10 ⁷ times life was determined. The evaluation results of the molded products obtained in Examples 1 to 5 and Comparative Examples 1 to 4 are summarized in Tables 1 and 2.

Example 6, Comparative Example 5 The powders in Table 1 were uniformly mixed in a Henschel mixer,
Using a twin-screw extruder, pelletizing at 400 ° C,
The test piece preparation and evaluation were performed in the same manner as in Example 1 below. The evaluation results of the molded products obtained in Example 6 and Comparative Example 5 are summarized in Tables 1 and 2.

Example 7 Evaluation was carried out in the same manner as in Example 1 except that aniline was used as the polyimide end-capping agent and the obtained polyimide powder had a logarithmic viscosity of 0.51 dl / g.

Example 8 PEK 2 manufactured by ICI was used as the polyallyl ether ketone used.
Evaluation was performed using the same method as in Example 1 except that 20P was used.

Example 9 PEKEKK manufactured by BASF Corporation as the polyallyl ether ketone used
Evaluation was performed using the same method as in Example 1 except that A 1000 was used.

Example 10 The test piece obtained in Example 1 was heat-treated at 220 ° C. for 5 hours, and the heat-treated test piece was used for the same evaluation as in Example 1.

Example 11 Evaluations were made in the same manner as in Example 1 except that glass fibers were used as the fibers.

Comparative Example 6 Aniline was used as the terminal blocking agent for the polyimide used,
Evaluation was performed by using the same method as in Comparative Example 3 except that the obtained polyimide powder having an inherent viscosity of 0.51 dl / g was used.

Comparative Example 7 Evaluation was carried out in the same manner as in Comparative Example 3 except that glass fiber was used as the fiber used.

The results of Examples 7 to 11 and Comparative Examples 6 to 7 are shown in Tables 1 and 2.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

EFFECTS OF THE INVENTION According to the method of the present invention, a polyimide resin composition having excellent fatigue resistance and an injection molded article are provided.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiyuki Kataoka 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals, Inc. (72) Nobuhiro Takizawa 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Hiroyuki Furukawa 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (8)

[Claims] 1. Formula (1): (In the formula, R ₁ has 2 to 27 carbon atoms, and an aliphatic group, a monocyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group and / or an aromatic group is directly or crosslinked. A polyimide having a repeating unit represented by a tetravalent group which is a non-condensed polycyclic aromatic group interconnected by a member.
1 to 5 per 100 parts by weight of the total amount of the resin composition consisting of 99 parts by weight and 95 to 1 parts by weight of polyallyl ether ketone.
A polyimide resin composition comprising 0 parts by weight of polyetherimide. 2. A polyimide having a repeating unit represented by the formula (1) according to claim 1 is produced by the formula (2): (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
An aromatic dicarboxylic acid anhydride represented by a condensed polycyclic aromatic group and / or a divalent group which is a non-condensed polycyclic aromatic group in which aromatic groups are directly or mutually linked by a bridging member) And / or formula (3) (In the formula, V has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
In the coexistence of an aromatic monoamine represented by a condensed polycyclic aromatic group and / or a monovalent group which is a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member. The polyimide-based resin composition according to claim 1, which is obtained by reacting the polymer with the polymer having a molecular terminal blocked. 3. The polyallyl ether ketone is a polyallyl ether ketone having a repeating unit represented by formula (4), formula (5), formula (6), formula (7) and / or formula (8). The polyimide resin composition according to claim 1 or 2. Formula (4) Formula (5) Formula (6) Formula (7) Formula (8) 4. The polyetherimide has the formula (9): (In the formula, Ar and Y each have a carbon number of 4 to 27, and represent a monovalent aromatic and / or a divalent group which is a divalent non-condensed polycyclic aromatic group linked by a bridge member. The polyimide resin composition according to claim 1, which has a repeating unit represented by the formula (1). 5. The polyetherimide has the formula (10): The polyimide resin composition according to claim 1 or 2, which has a repeating unit represented by: 6. The polyimide resin composition according to claim 1, which is heat-treated at 150 ° C. to 300 ° C. 7. A fiber-reinforced polyimide resin composition, wherein the polyimide resin composition according to claim 1 further contains a fibrous reinforcing material. 8. An injection-molded article obtained from the polyimide resin composition according to claim 1.