JP3258466B2 - Polyimide resin composition and injection molded article excellent in fatigue characteristics - Google Patents

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 article thereof. More specifically, the present invention relates to a polyimide resin composition having good melt moldability and excellent fatigue resistance, and an injection molded article 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, electric insulation, etc., so that electric / electronic equipment and aerospace equipment are used. Widely used in such fields. Conventionally, various polyimides exhibiting excellent properties have been developed.Even though they have excellent heat resistance, they do not have a clear glass transition temperature, so when used as a molding material, they are processed using techniques such as sinter molding. Or that they have good workability but low glass transition temperature, are soluble in halogenated hydrocarbon solvents, and are not satisfactory in terms of heat resistance and solvent resistance. There were advantages and disadvantages in performance. For the purpose of solving these problems, first, the present inventors have studied mechanical properties,
We have developed melt-moldable polyimides and various copolyimides with excellent thermal, electrical, and chemical resistance (see
1-1143478, 62-205124,
Japanese Patent Application No. 63-270778, etc.). However, studies on dynamic mechanical properties such as fatigue properties have not been made much, and it is said that there is almost no knowledge particularly in the field of injection-moldable high heat-resistant polyimide developed recently.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyimide resin composition which can be melt-molded by injection molding or the like and has high fatigue characteristics, and an injection-molded product thereof.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, the polyimide resin composition obtained by a specific method has excellent melt flow moldability, The inventors have found that an injection molded article having excellent fatigue properties can be obtained from this resin composition, and have reached the present invention. That is, the present invention relates to (1) a compound represented by the general formula (I):

[0005]

Embedded image (Wherein X represents a group selected from the group consisting of a direct bond, an isopropylidene group, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, and a sulfonyl group;
[Formula 10] is

[0006]

Embedded image Means a tetravalent group represented by ) Have a repeating structural unit represented by the logarithm of the degree 0.48~0.54dl / g
With respect to 100 parts by weight of a polyimide having viscosity , the following formula (II)

[0007]

Embedded image Logarithmic viscosity having a repeating structural unit represented by 0.7
dl / g or more of 3-45 parts by weight of polyimide;
At least one selected from carbon fiber, glass fiber, aromatic polyamide fiber and potassium titanate fiber by weight.
A polyimide resin composition having excellent fatigue properties comprising a seed, an injection molded article thereof, and (2) a polyimide having a repeating structural unit represented by the general formula (I) having a general formula (III) [ Chemical formula 12]

[0008]

Embedded image And / or general formula (IV)

[0009]

Embedded image V—NH ₂ (IV) (wherein Z and V each have 6 to 15 carbon atoms, and a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group is Represents at least one divalent or monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups interconnected by a) and / or an aromatic dicarboxylic anhydride represented by the formula: With respect to a polymer obtained by coexisting an aromatic monoamine and having a molecular end sealed and / or 100 parts by weight of the polyimide containing the polyimide, a compound of the formula (II)

[0010]

Embedded image When producing a polyimide having a repeating structural unit represented by the following general formula (V):

[0011]

Embedded image And / or general formula (VI)

[0012]

Embedded image W—NH ₂ (VI) (wherein Y and W each have 6 to 15 carbon atoms and a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group is Represents at least one divalent or monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups interconnected by a) and / or an aromatic dicarboxylic anhydride represented by the formula: A polymer obtained by coexisting a group monoamine with a molecular end sealed and / or a polyimide containing the polyimide having a logarithmic viscosity of 0.70 dl / g or more, 3 to 45 parts by weight, and 5 to 65 parts by weight of carbon fiber,
A polyimide resin composition comprising at least one selected from glass fiber, aromatic polyamide fiber and potassium titanate fiber and having excellent fatigue properties, and an injection molded article thereof. The method for producing the polyimide represented by the formula (I) used in the present invention is described in the above-mentioned JP-A-61-143478 and the like. That is, the compound represented by the general formula (VII)

[0013]

Embedded image (Wherein X represents a group selected from the group consisting of a direct bond, an isopropylidene group, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, and a sulfonyl group.) It is obtained by reacting with tetracarboxylic dianhydride. Examples of the diamine used in this method include 2,2-bis [4- (3-aminophenoxy) phenyl] propane and 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,1. 3,3,3
-Hexafluoropropane, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4 -(3-
[Aminophenoxy) phenyl] sulfone, etc., and these may be used alone or in combination of two or more. However, other diamines may be mixed and used as long as the characteristics of polyimide are not impaired. Examples of the diamines that can be used as a mixture include, for example, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, o-aminobenzylamine, 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 '
-Dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether,
4,4'-diaminodiphenylether, 3,3'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfoxide, 3,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfoxide, 3,3'-diamino Diphenyl sulfone, 3,4 '
-Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'- Diaminodiphenylmethane, 4,4 '
-Diaminodiphenylmethane, bis [4- (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, 1,3-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
1,3,3,3-hexafluoropropane, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4
-Aminophenoxy) benzene, 4,4'-bis (4-
Aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4-
(4-aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl ether, bis [4- (4-aminophenoxy) phenyl]
Ether, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-
Aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4'-bis (3-aminophenoxy) benzoyl] benzene, 4,4'-bis (3- Aminophenoxy) -3,3'-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl, 4,4'-bis (3-aminophenoxy ) -3,3 ', 5,5'-tetrachlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,
3 ', 5,5'-tetrabromobiphenyl, bis [4-
(3-Aminophenoxy) -3-methoxyphenyl] sulfed, [4- (3-aminophenoxy) phenyl]
[4- (3-aminophenoxy) -3,5-dimethoxyphenyl] sulfide, bis [4- (3-aminophenoxy) -3,5-dimethoxyphenyl] sulfide,
1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-
Aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1
1,3,3,3-hexafluoropropane, bis [4-
(3-aminophenoxy) phenyl] ketone, bis [4
-(3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone and the like. Further, a tetracarboxylic dianhydride component represented by the general formula (VIII):

[0014]

Embedded image (R [Chemical Formula 19] is

[0015]

Embedded image Means a tetravalent group represented by ), That is, pyromellitic dianhydride and / or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are used, but the properties of polyimide are impaired. Other tetracarboxylic dianhydrides may be mixed and used as long as they are not present. Examples of the tetracarboxylic dianhydride that can be used as a mixture include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, 3,
3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride Product, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4
-Dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride,
Bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2-bis (3,4
-Dicarboxyphenyl) ethane dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy)
Benzene dianhydride, 1,4-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3
4-dicarboxyphenoxy) benzene dianhydride, 2,
3,6,7-naphthalenetetracarboxylic 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, and the like. .

The polyimide obtained by using the aromatic diamine component and the aromatic tetracarboxylic dianhydride component as monomer components is mainly a polyimide having a repeating structural unit represented by the general formula (I), and is mainly a polyimide having a general formula (I) And polyimides having an aromatic ring in which the polymer molecule end is unsubstituted or substituted with a group having no reactivity with amine or dicarboxylic anhydride. The polyimide having an aromatic ring which is unsubstituted or substituted with a group having no reactivity with an amine or a dicarboxylic anhydride at the terminal of the polymer molecule comprises a diamine represented by the general formula (VII) and a diamine represented by the general formula (VII). The tetracarboxylic dianhydride represented by the formula (VIII) is converted to a compound represented by the formula (III):

[0017]

Embedded image (Wherein Z has 6 to 15 carbon atoms each, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a bridge member. Represents at least one divalent group selected from the group consisting of groups)
And / or an aromatic dicarboxylic anhydride represented by
General formula (IV)

[0018]

Embedded image V—NH ₂ (IV) (wherein V has 6 to 15 carbon atoms each, and a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group is directly or by a bridge member. Represents at least one monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups linked to.
In the presence of an aromatic monoamine represented by the formula: The polyimide having a logarithmic viscosity of 0.70 dl / g or more represented by the formula (II) used in the present invention is represented by the following formula (IX):

[0019]

Embedded image Ie, 4,4′-bis (2-
Aminophenoxy) biphenyl and / or 4,4 ′
-Bis (3-aminophenoxy) biphenyl and / or 4,4 '-(4-aminophenoxy) biphenyl, and the following formula (X)

[0020]

Embedded image Is a polyimide obtained by polymerizing a tetracarboxylic dianhydride represented by the formula, that is, pyromellitic dianhydride. In addition, as long as the properties and physical performance of the polyimide are not impaired, one or more other diamines or tetracarboxylic dianhydrides may be mixed and polymerized. The diamines used include the diamines exemplified by the general formula (VII) and the diamines exemplified above. Acid anhydrides are also the tetracarboxylic dianhydrides exemplified above. The polyimide obtained by using the aromatic diamine component and the aromatic tetracarboxylic dianhydride as monomer components is a polyimide having a repeating structural unit of the formula (II), and a polyimide having a repeating structural unit of the formula (II). Also included are polyimides having an aromatic ring in which the polymer molecular terminal is unsubstituted or substituted with a group having no reactivity with amine or dicarboxylic anhydride.
The polyimide having an aromatic ring which is unsubstituted or substituted with a group having no reactivity with an amine or a dicarboxylic anhydride at the terminal of the polymer molecule is represented by the formula (IX):

[0021]

Embedded image Ie, 4,4'-bis (2-aminophenoxy) biphenyl and / or 4,4'-bis (3-aminophenoxy) biphenyl and / or 4,4 '-(4-aminophenoxy) ) Using biphenyl and the tetracarboxylic dianhydride represented by the above formula (X), that is, pyromellitic anhydride, by the formula (V)

[0022]

Embedded image (Wherein Y has 6 to 15 carbon atoms each, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a bridge member. Represents at least one divalent group selected from the group consisting of groups)
And / or an aromatic dicarboxylic anhydride represented by
General formula (VI)

[0023]

Embedded image W—NH ₂ (VI) (wherein W has 6 to 15 carbon atoms each, and a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group is directly or mutually linked by a bridge member. Represents at least one monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups linked to.
In the presence of an aromatic monoamine represented by the formula:

The dicarboxylic anhydrides represented by the general formulas (III) and (V) include phthalic anhydride, 2,3
-Benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic anhydride 3,4-biphenyldicarboxylic anhydride, 2,3-dicarboxyphenylphenylsulfone anhydride, 3,4-dicarboxyphenylphenylsulfone anhydride, 2,3-dicarboxyphenylphenylsulfide anhydride, 3,4 -Dicarboxyphenylphenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,
Examples thereof include 8-naphthalenedicarboxylic anhydride, 1,2-anthracene dicarboxylic anhydride, 2,3-anthracene dicarboxylic anhydride, and 1,9-anthracene dicarboxylic anhydride. These dicarboxylic anhydrides may be substituted with a group having no reactivity with amine or dicarboxylic anhydride. These can be used alone or in combination of two or more. Of these aromatic dicarboxylic anhydrides, phthalic anhydride is preferably used.

The aromatic monoamines represented by the general formulas (IV) and (VI) include, for example, aniline, o-toluidine, 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, m -Nitroaniline, o-aminophenol, p-aminophenol, m-aminophenol, o-anisidine, m-
Anisidine, p-anisidine, o-phenetidine, m-
Phenetidine, p-phenetidine, o-aminobenzaldehyde, p-aminobenzaldehyde, m-aminobenzaldehyde, o-aminobenznitrile, p-aminobenznitrile, m-aminobenznitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4 -Aminobiphenyl, 2-aminophenylphenyl ether, 3-
Aminophenylphenyl ether, 4-aminophenylphenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminobenzophenone
Aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide, 4-aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfide
Aminophenylphenylsulfone, 4-aminophenylphenylsulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 5-amino-1
-Naphthol, 2-amino-1-naphthol, 4-amino-1-naphthol, 5-amino-2-naphthol, 7
-Amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like. Usually, of these aromatic monoamines, preferably derivatives of aniline are used. These can be used alone or in combination of two or more.

There is no problem if these aromatic monoamines and / or dicarboxylic anhydrides are used alone or in combination of two or more. The amount of these compounds used is a monoamine (excess component is tetracarboxylic dianhydride) or dicarboxylic anhydride (excess component is one to several times the difference in the number of moles of diamine and tetracarboxylic dianhydride used). Diamine) may be used, but at least one component, 0.1.
Generally, it is used in an amount of about 01 mole.

The method for producing a polyimide resin in the present invention is produced by any known method. 1) Synthesizing polyamic acid in an organic solvent and isolating the polyamic acid by removing the solvent at a low temperature using a technique such as distillation under reduced pressure or by discharging the obtained polyamic acid solution to a poor solvent. After that, this is heated to imidize to obtain polyimide. 2) After preparing the polyamic acid solution in the same manner as in 1),
A method in which a dehydrating agent typified by acetic anhydride is added, and a catalyst is added as necessary to chemically imidize, and then a polyimide is isolated by a known method, followed by washing and drying as 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 decompression or heat treatment, and at the same time, thermal imidization is performed. 4) A method in which a raw material is charged into an organic solvent, and then heated to simultaneously perform synthesis of a polyamic acid and an imidization reaction, and a catalyst, an azeotropic agent, and a dehydrating agent, if necessary. And the like.

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-diethylacetamide and N, N-diethylacetamide. N
-Dimethylmethoxyacetamide, 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, pyridine, picoline, dimethylsulfoxide, dimethylsulfone, tetramethylurea, hexamethylphosphoramide,
Phenol, o-cresol, m-cresol, p-cresol, cresylic acid, o-chlorophenol, m-
Chlorophenol, p-chlorophenol, anisole and the like can be mentioned. In addition, these organic solvents alone,
Also, a mixture of two or more kinds may be used.

In the method of the present invention, the method of adding and reacting a diamine, a tetracarboxylic dianhydride, a dicarboxylic anhydride or an aromatic monoamine in an organic solvent includes the following (a) tetracarboxylic dianhydride. And reacting the diamine with a diamine and then adding dicarboxylic anhydride or aromatic monoamine to continue the reaction. (Ii) A dicarboxylic acid anhydride is added to a diamine to cause a reaction, and then a tetracarboxylic acid dianhydride is added to continue the reaction, or an aromatic monoamine is added to the tetracarboxylic acid dianhydride to react the diamine. A method of continuing the reaction by adding (C) A method in which a tetracarboxylic dianhydride, a diamine and a dicarboxylic anhydride or an aromatic monoamine are simultaneously added to cause a reaction. There is no problem using either method. The reaction temperature is usually 300 ° C. or lower, and 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 diamine, the type of tetracarboxylic dianhydride, the type of solvent, the presence or absence of a catalyst, and the reaction temperature, but usually 4 to 24 hours is sufficient. By the above method, the polyimide represented by the formula (I) and the formula (II) in the present invention is obtained. In particular, in the present invention, the role of the polyimide represented by the formula (II) having a logarithmic viscosity of 0.65 dl / g or more, preferably 0.7 dl / g or more is important. Since the polyimide has a too high molecular weight, the polyimide resin composition composed of only the polyimide and the reinforcing material has a too high melt viscosity, and a good injection molded body can be obtained with an injection molding machine generally used at present. Can not. On the other hand, an injection-molded article obtained from a polyimide resin composition comprising only the polyimide represented by the formula (I) and a reinforcing material does not have good fatigue properties.

The polyimide resin composition of the present invention has a logarithmic viscosity represented by the formula (II) of at least 0.65 dl / g, preferably 0.1 wt%, per 100 parts by weight of the polyimide resin represented by the formula (I). It is adjusted by adding 1 to 60 parts by weight, preferably 3 to 45 parts by weight of a polyimide resin of 70 dl / g or more and, as a reinforcing material, for example, carbon fiber, glass fiber, aromatic polyamide fiber, potassium titanate fiber and the like. You. Logarithmic viscosity represented by formula (II) 0.65
The amount of dl / g or more, preferably 0.70 dl / g, varies depending on the amount and type of the reinforcing material, but is 1 to 60 parts by weight, preferably 3 parts by weight, based on the polyimide resin of the formula (I).
~ 45 parts by weight is sufficient. When the amount is 3 parts by weight or less, no remarkable improvement in fatigue properties is observed, and when the amount is 45 parts by weight or more, the injection moldability of the polyimide resin composition itself deteriorates, and a good injection molded product is obtained. I can't get it. In addition, the amount of carbon fiber, glass fiber, aromatic polyamide fiber, potassium titanate fiber, etc. used as a reinforcing material is determined based on the polyimide resin having a body number viscosity of 0.70 dl / g or more represented by the formula (II). Although it depends on the type and the amount used, it is 5 to 65 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the polyimide represented by the formula (I). Carbon fiber is most preferable as the type of the reinforcing material. As a method for adding the reinforcing material, a generally known method is used.However, after preliminarily mixing 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, and the like, melting is performed. The most common method is to obtain a pellet or a powdery mixture using a mixer, a hot roll, or the like.

Further, other thermoplastic resins such as polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, and the like may be used within a range not to impair the object of the present invention.
An appropriate amount of polysulfone, polyetherimide, polyethersulfone, polyetheretherketone, polyetherketone, polyphenylenesulfide, polyamideimide, modified polyphenylene oxide, and other polyimides and thermosetting resins can be blended. The polyimide resin composition of the present invention is molded by a known molding method such as an injection molding method, an extrusion molding method, a compression molding method, and a rotational molding method, and is provided for practical use. Due to its fluidity, the injection molding method is most preferable from the viewpoint of working efficiency. The injection molded article obtained from the polyimide resin composition of the present invention can be formed into a molded article of any shape by changing the shape of a mold, but is particularly suitable for automobile parts where excellent dynamic fatigue properties are required. Is expected to be applied to valve lifters and impellers.

[0032]

The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples. In addition, the measurement of various physical properties in the example was based on the following method. Logarithmic viscosity: 0.50 g of polyimide powder is added
A mixed solvent of chlorophenol and ferol (90: 1
(0 weight ratio) Measured after heating and dissolving in 100 ml and cooling to 35 ° C. Glass transition temperature (Tg): Measured by DSC (Shimadzu DT-40 series, DSC-41M) at a heating rate of 16 ° C./min. 5% weight loss temperature: DTA-TG (Shimadzu DT-4)
0 series, 40M) in air at 10 ° C / mi.
Measured at a heating rate of n. (Synthesis Example 1) 3.68 kg (10.0 mol) of 4,4′-bis (3-aminophenoxy) biphenyl was added to a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube. 2.08 Kg of acid dianhydride (9.55
Mol), 133.2 g (0.9 mol) of phthalic anhydride, γ
138 g (1.5 mol) of picoline and 21.8 kg of m-cresol were charged, and heated to 145 ° C. while stirring under a nitrogen atmosphere. During this time, about 340g
Distillation of water was confirmed. Further, the reaction was performed at 140 to 150 ° C. for 4 hours. Then, cool to room temperature,
After discharging into 0 kg of methyl ethyl ketone, the mixture was separated by filtration.
The polyimide powder was further washed with methyl ethyl ketone, preliminarily dried at 50 ° C. for 24 hours under a nitrogen atmosphere, and then dried at 200 ° C. for 6 hours to obtain 5.45 kg (yield 98.5%) of polyimide powder. . The logarithmic viscosity of this polyimide was 0.49 dl / g, the Tg was 249 ° C., and the 5% weight loss temperature was 550 ° C.

Synthesis Example 2 2.08 kg (9.55 mol) of pyromellitic dianhydride of Synthesis Example 1 was added to 3,3 ′, 4,4
4'-biphenyltetracarboxylic dianhydride 2.81K
g (9.55 mol), and 6.14 kg of polyimide powder (98% yield) was obtained in exactly the same manner. This polyimide has a logarithmic viscosity of 0.51 dl / g and a Tg of 221.
° C, 5% weight loss temperature was 542 ° C.

(Synthesis Example 3) 3.68 kg (4,4'-bis (3-aminophenoxy) biphenyl of Synthesis Example 1)
0.04 mol), and 4.32 Kg of 4,4'-bis [4- (3-aminophenoxy) phenyl] sulfone (10.0 mol)
Mol), to obtain 6.08 kg of a polyimide powder (yield 98.5%) in exactly the same manner as in Synthesis Example 1. The polyimide has a logarithmic viscosity of 0.54 dl / g and a Tg of 24.
The 5 ° C, 5% weight loss temperature was 545 ° C.

(Synthesis Example 4) 3.68 kg (4,4′-bis (3-aminophenoxy) biphenyl of Synthesis Example 1)
5.89 kg of polyimide powder in exactly the same manner as in Example 1 except that (0.0 mol) was changed to 4.10 kg (10.0 mol) of 2,2-bis [4- (3-aminophenoxy) phenyl] propane. (99% yield). This polyimide has a logarithmic viscosity of 0.52 dl / g and a Tg of 21.
7 ° C.

(Synthesis Example 5) 3.68 kg (1,4′-bis (3-aminophenoxy) biphenyl of Synthesis Example 1)
0.0 mol) was changed to 5.18 kg (10.0 mol) of 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane. Except for the above, the polyimide powder was 6.9 exactly as in Example 1.
6 Kg (99% yield) was obtained. The logarithmic viscosity of this polyimide was 0.52 dl / g, and Tg was 230 ° C.

Synthesis Example 6 3.68 kg of 4,4′-bis (3-aminophenoxy) biphenyl of Synthesis Example 1
0.0 mol) was changed to 3.96 Kg (10.0 mol) of bis [4- (3-aminophenoxy) phenyl] ketone in the same manner as in Example 1 except that the polyimide powder 5.7 was used.
6 Kg (99% yield) was obtained. The logarithmic viscosity of this polyimide was 0.51 dl / g, and the Tg was 227 ° C.

(Synthesis Example 7) 3.68 kg (1,4′-bis (3-aminophenoxy) biphenyl of Synthesis Example 1)
5.77 Kg of polyimide powder (yield 98) in exactly the same manner as in Example 1 except that 0.0 mol) was changed to 4.00 Kg (10.0 mol) of bis [4- (3-aminophenoxy) phenyl] sulfide. 0.5%). The logarithmic viscosity of this polyimide is 0.48 dl / g, and the Tg is 208
° C.

(Synthesis Example 8) 2.08 kg (9.55 mol) of pyromellitic dianhydride of Synthesis Example 1, 2,2-bis [4
-(3,4-dicarboxyphenoxy) phenyl] propane dianhydride 4.97 Kg (9.55 mol), except that the polyimide powder was 8.25 in the same manner as in Example 1.
Kg (98% yield) was obtained. The logarithmic viscosity of this polyimide was 0.48 dl / g, and the Tg was 172 ° C.

Synthesis Example 9 2.08 kg (9.55 mol) of pyromellitic dianhydride of Synthesis Example 1 and phthalic anhydride 1
33.2 g (0.9 mol) of pyromellitic dianhydride 2.28 Kg (1.05 mol), aniline 79.7 g
(0.9 mol), and 5.58 kg of a polyimide powder (98.5% yield) was obtained in the same manner as in Example 1. The logarithmic viscosity of this polyimide is 0.49 dl / g,
g was 248 ° C and the 5% weight loss temperature was 550 ° C.

(Synthesis Example A) Pyromellitic dianhydride 2.08 Kg (9.55 mol) of Synthesis Example 1, phthalic anhydride 1
33.2 g (0.9 mol) of pyromellitic dianhydride 2.16 kg (9.90 mol), phthalic anhydride 29.6
5.46 kg (yield 99%) of polyimide powder was obtained in exactly the same manner as in Example 1 except that the amount was changed to g (0.2 mol). The logarithmic viscosity of this polyimide is 0.79 dl / g,
g was 256 ° C and the 5% weight loss temperature was 565 ° C.

(Synthesis Example B) 1.84 kg of 4,4'-bis (3-aminophenoxy) biphenyl was placed in a vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube.
(5.0 mol), 1.84 kg (5.0 mol) of 4,4'-bis (4-aminophenoxy) biphenyl, 2.16 kg (9.90 mol) of pyromellitic dianhydride, phthalic anhydride 29 0.6 g (0.2 mol), γ-picoline 138
g (1.5 mol) and 26.8 kg of m-cresol were charged and heated to 145 ° C. while stirring under a nitrogen atmosphere. During this time, distillation of about 340 g of water was confirmed. Further, the reaction was performed at 140 to 150 ° C. for 4 hours. Thereafter, the mixture was cooled to room temperature, discharged into 80 kg of methyl ethyl ketone, and filtered. This polyimide powder was further washed with methyl ethyl ketone, preliminarily dried at 50 ° C. for 24 hours under a nitrogen atmosphere, and then dried at 200 ° C. for 6 hours to obtain 5.46 kg (99% yield) of polyimide powder. The logarithmic viscosity of this polyimide is 0.85 dl
/ G, 5% weight loss temperature was 550 ° C.

(Examples 1 to 3) 25 parts by weight of the polyimide powder having an logarithmic viscosity of 0.79 dl / g obtained in Synthesis Example A based on 100 parts by weight of the polyimide powder obtained in Synthesis Example 1, carbon fiber manufactured by Toho Rayon After adding 40 parts by weight of (HTA-C6) and mixing with a drum blender mixer (manufactured by Kawada Seisakusho), the mixture was melt-kneaded at 400 ° C. by a single-screw extruder having a diameter of 30 mm, and then the strand was air-cooled and cut. I got Pelleto. Using the obtained pellets, an injection pressure of 500 Kg / cm ² and a cylinder temperature of 4 were obtained using an Arburg injection molding machine.
Injection molding was performed at 10 ° C. and a mold temperature of 180 ° C. to obtain a tensile test piece. JIS K7 using this test piece
The number of repeated fatigue was measured by the partial pulsating method in accordance with No. 118. Table 1 shows the relationship between the load and the number of times of repeated fatigue.

(Examples 4 to 11) Using the polyimide powders obtained in Synthesis Examples 2 to 8, tensile test pieces were prepared in the same manner as in Example 1, and the number of times of fatigue was repeatedly measured. The results are shown in Table 1. (Comparative Examples 1 to 9) Using the polyimide powders obtained in Synthesis Examples 1 to 9, the tensile test pieces were prepared in exactly the same manner as in Example 1 except that the polyimide powder of Example A was not added. It was measured. The results are shown in Table 1. (Examples 12 to 15) With respect to 100 parts by weight of the polyimide powder obtained in Synthesis Example 2, the logarithmic viscosity obtained in Synthesis Example B was 0.8.
5 dl / g of polyimide powder and 40 parts by weight of carbon fiber (HTA-C6) manufactured by Toho Rayon were added, and a test piece in which the amount of the polyimide powder of Synthesis Example B was changed by the method of Example 1 was prepared. The relationship between the number of times of repeated fatigue was measured. Table 2 shows the results.

(Comparative Example 10) A tensile test piece was prepared in the same manner as in Examples 12 to 15 except that the polyimide powder of Example B was not added using the polyimide powder obtained in Synthesis Example 2, and the number of times of fatigue was repeated. Was measured. Table 2 shows the results.
Are shown together. (Examples 16 to 15) With respect to 100 parts by weight of the polyimide powder obtained in Synthesis Example 3, the logarithmic viscosity obtained in Synthesis Example A was 0.7.
Carbon fiber (HTA-C6) manufactured by Toho Rayon Co., Ltd. was added to 25 parts by weight of 9 dl / g polyimide powder, and a test piece in which the amount of carbon fiber was changed was prepared by the method of Example 1, and the load and the number of times of fatigue were repeated. Was measured. Table 3 shows the results.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

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

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Examiner, Mitsui Toatsu Chemicals Co., Ltd. Hiroki Amano (56) References JP-A-3-7763 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 79/00-79/08 C08K 3/00-13/08

Claims (4)

(57) [Claims] 1. A compound of the general formula (I) (Wherein X represents a group selected from the group consisting of a direct bond, an isopropylidene group, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, and a sulfonyl group;
[Chemical 2] is Means a tetravalent group represented by Have a repeating structural unit represented by), the polyimide 100 parts by weight having a logarithmic viscosity of degrees 0.48~0.54dl / g, the following formula (II) [Formula 3] ## STR3 ## Logarithmic viscosity having a repeating structural unit represented by 0.7
dl / g or more of 3-45 parts by weight of polyimide;
At least one selected from carbon fiber, glass fiber, aromatic polyamide fiber and potassium titanate fiber by weight.
Polyimide resin composition with excellent fatigue properties consisting of seeds. 2. A polyimide having a repeating structural unit represented by the above general formula (I), when producing the polyimide, the polyimide represented by the general formula (III): And / or V-NH ₂ (IV) (wherein Z and V each have 6 to 15 carbon atoms, a monocyclic aromatic group, a condensed polycyclic Aromatic group, and at least one divalent or monovalent group selected from the group consisting of non-fused polycyclic aromatic groups in which the aromatic groups are directly or mutually linked by a bridge member.) The fatigue according to claim 1, characterized in that the polymer obtained by coexisting an aromatic dicarboxylic anhydride and / or an aromatic monoamine to be used is a polymer obtained by sealing a molecular terminal and / or a polyimide containing the polyimide. Polyimide resin composition with excellent properties. 3. A compound of the above formula (II) When a polyimide having a repeating structural unit represented by the following formula is produced, the polyimide has the general formula (V): And / or general formula (VI) [Chemical formula 8] W—NH ₂ (VI) (wherein Y and W each have 6 to 15 carbon atoms, a monocyclic aromatic group, a condensed polycyclic Aromatic group, and at least one divalent or monovalent group selected from the group consisting of non-fused polycyclic aromatic groups in which the aromatic groups are directly or mutually linked by a bridge member.) 2. A polymer obtained by coexisting an aromatic dicarboxylic anhydride and / or an aromatic monoamine to be used, wherein the polymer has a sealed molecular end and / or the polyimide, and has excellent fatigue properties. Polyimide resin composition. 4. An injection molded article obtained from the polyimide resin composition according to claim 1.