JP3333035B2 - Polyimide resin and injection molded body with excellent fatigue properties - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyimide resin having good fatigue properties. More specifically, the present invention relates to a polyimide resin having good melt moldability and excellent fatigue resistance, a polyimide resin composition containing the polyimide resin and a fibrous reinforcing material, 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. It has good workability but low glass transition temperature, and it is soluble in halogenated hydrocarbon solvents, and is not satisfactory in terms of heat resistance and solvent resistance. Had pros and cons. For the purpose of solving these problems, the present inventors have previously developed melt-moldable polyimides and various copolyimides having excellent mechanical properties, thermal properties, electrical properties, and chemical resistance. Kaisho 61
No. 143478, 62-205124, and Japanese Patent Application No. 63-270778). 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. Generally, the fatigue properties of resin are entangled at the molecular level,
That is, it is said that when the crosslink density is increased, it is improved. However, in the case of a high heat-resistant resin as an injection molding material as used in the present application, when the molecular weight is increased for the purpose of increasing entanglement of molecules, there has been a problem that injection moldability is significantly inhibited.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors diligently seek a method of improving only the entangled state at the molecular level without increasing the molecular weight extremely, thereby improving the fatigue characteristics. As a result of the examination, the polyimide resin obtained by a specific method has excellent melt flow moldability,
In addition, the present inventors have found that an injection molded article having excellent fatigue properties can be obtained from this resin and a polyimide resin composition composed of this resin set and carbon fibers, and have reached the present invention. That is, the present invention relates to a compound of the formula (I)

[0005]

Embedded image means. ) To 1 mol of the diamine compound represented by the following formula (II):

[0006]

Embedded image And / or a tetraamino compound represented by the following formula (III):

[0007]

Embedded image Means )) Is 0.
005 to 0.11 mol of the amine compound represented by the following formula (I
V) [Chemical formula 8]

[0008]

Embedded image Means Melt molding with excellent fatigue properties characterized by being obtained by reacting the tetracarboxylic dianhydride component represented by the formula) in the presence or absence of a dicarboxylic anhydride or a monoamino compound. A polyimide resin, a polyimide resin composition comprising the polyimide resin and a fibrous reinforcing material, and an injection molded product thereof. Specifically, the diamine compound represented by the above formula (I) and the tetraamino compound represented by the above formula (II) are added to 1 mol of the tetracarboxylic dianhydride represented by the above formula (IV). And / or excellent in fatigue properties, wherein the total of the amino compounds having two or more amino groups consisting of the triamino compound represented by the above formula (III) is 0.8 to 1.20 mol. Melt moldable polyimide resin, and a polyimide resin composition comprising the polyimide resin and a fibrous reinforcing material and an injection molded body thereof,
More specifically, the amount of 0.001 to 0.001 to 1 mol of the total amount of the tetracarboxylic dianhydride represented by the above formula (IV).
Melt-moldable polyimide resin excellent in fatigue characteristics characterized by using 20 mol of dicarboxylic anhydride and / or monoamine, polyimide resin composition comprising the polyimide resin and fibrous reinforcing material, and injection molded article thereof It is.

In synthesizing the melt-moldable polyimide resin having excellent fatigue properties in the present invention, an amino compound having two or more amino groups is used as a raw material monomer. As the amino compound, a diamine compound represented by the above formula (I), a tetraamino compound represented by the above formula (II) and / or a triamino compound represented by the above formula (III) are used. It is essential that the total amount of the tetraamino compound and / or the triamino compound is used in an amount of 0.005 to 0.11 mol ratio to 1 mol of the diamine compound.

The diamine compound used in the present invention is a diamine compound represented by the above formula (I), that is, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4-
(3-Aminophenoxy) phenyl] -1,1,1,
Although 3,3,3-hexafluoropropane is used, there is no problem even if these diamine compounds are used alone or in combination of two or more. Other diamines may be mixed and used as long as the characteristics of the polyimide are not impaired. Examples of the diamine 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'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,
3′-diaminodiphenylsulfoxide, 3,4′-diaminodiphenylsulfoxide, 4,4′-diaminodiphenylsulfoxide, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone,
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,
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] -1,1,1,3,3,3-hexafluoropropane, , 3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy)
Benzene, 1,3-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-amino) Phenoxy) phenyl] sulfone,

Bis [4- (3-aminophenoxy) phenyl ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 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] sulfide, [4- (3-aminophenoxy) phenyl] [4- (3-amino Phenoxy) -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, and the like.

Further, the tetraamino compound and / or triamino compound used in the present invention include 3,3'-type compounds represented by the above formulas (II) and / or (III).
Diaminobenzidine, 3,3 ′, 4,4′-tetraaminobenzophenone, 3,3 ′, 4,4′-tetraaminodiphenyl ether, 3,3 ′, 4,4′-tetraaminodiphenylsulfone, 3,3 ′ , 4,4'-Tetraaminodiphenyl sulfide, 1,2,4-triaminobenzene, 2,4,6-triaminopyrimidine, 3,
3 ', 4, -triaminobenzophenone, 3,3',
4, -triaminobiphenyl, 3,3 ', 4, -triaminodiphenyl ether, 3,3', 4, -triaminodiphenylsulfone, 3,3 ', 4, -triaminodiphenylsulfide, 3,4,4 '-Triaminobenzophenone, 3,4,4'-triaminobiphenyl, 3,
4,4'-triaminodiphenyl ether, 3,4
4'-triaminodiphenyl sulfone, 3,4,4'-
Triaminodiphenyl sulfide, 1,3,5-tris (3-aminophenoxy) benzene, 1,3,5-tris (4-aminophenoxy) benzene, 1,3,5-tris (2-aminophenoxy) benzene However, basically, it is only necessary to form an entanglement point (crosslinking point) in the molecular chain, and 2,3′-diaminobenzidine, 2,2′-diaminobenzidine, 3,3 ′, 2,2 ′ -Triaminobiphenyl, 3,4 ', 2,2'-tetraaminobiphenyl, 3,3', 2,4'-tetraaminobiphenyl,
2,2 ′, 4,4′-tetraaminobenphenone, 2,
3 ', 4,4'-tetraaminobenphenone, 2,
2 ', 3,3'-tetraaminobenphenone, 2,
2 ', 3,4'-tetraaminobenphenone, 3,
3 ', 2,4'-tetraaminobenphenone, 2,
2 ', 4,4'-tetraaminodiphenyl ether,
2,3 ′, 4,4′-tetraaminodiphenyl ether, 2,2 ′, 3,3′-tetraaminodiphenyl ether, 2,2 ′, 3,4′-tetraaminodiphenyl ether, 3,3 ′, 2,4 '-Tetraaminodiphenyl ether, 2,2', 4,4'-tetraaminodiphenylsulfone, 2,3 ', 4,4'-tetraaminodiphenylsulfone, 2,2', 3,3'-tetra Aminodiphenylsulfone, 2,2 ′, 3,4′-tetraaminodiphenylsulfone, 3,3 ′, 2,4′-tetraaminodiphenylsulfone, 2,2 ′, 4,4′-tetraaminodiphenylsulfide, 2 , 3 ′, 4,4′-tetraaminodiphenyl sulfide, 2,2 ′, 3,3′-tetraaminodiphenyl sulfide, 2,2 ′, 3,4 ′
-Tetraaminodiphenyl sulfide, 3,3 ', 2
4'-tetraaminodiphenyl sulfide,

1,2,4,5-tetraaminobenzene,
1,2,3,4-tetraaminobenzene, 1,2,3
5-tetraaminobenzene, 1,3,4,5-tetraaminobenzene, 2,3,4,5-tetraaminobiphenyl, 2,4,5,6-tetraaminobiphenyl, 2,
3,5,6-tetraaminobiphenyl, 2,3,4,5
-Tetraaminobenzophenone, 2,4,5,6-tetraaminobenzophenone, 2,3,5,6-tetraaminobenzophenone, 2,3,4,5-tetraaminodiphenylsulfone, 2,4,5,6- Tetraaminodiphenylsulfone, 2,3,5,6-tetraaminodiphenylsulfone, 2,3,4,5-tetraaminodiphenylether, 2,4,5,6-tetraaminodiphenylether, 2,3,5,6- Tetraaminodiphenyl ether, 2,3,4,5-tetraaminodiphenyl sulfide, 2,4,5,6-tetraaminodiphenyl sulfide, 2,3,5,6-tetraaminodiphenyl sulfide, 1,2,4-tri Aminobenzene, 1,2,3-
Triaminobenzene, 1,3,5-triaminobenzene, 2,4,6-triaminopyridine, 2,3,4-triaminopyridine, 3,4,5-triaminopyridine,
2,3,5-triaminopyridine, triamterene,
3,4 ', 4, -triaminobenzophenone, 3,
2 ', 4-triaminobenzophenone, 3,2', 2-
Triaminobenzophenone, 3,3 ′, 2-triaminobenzophenone, 3,4 ′, 2-triaminobenzophenone, 2,3 ′, 4-triaminobenzophenone, 2,
2 ', 4-triaminobenzophenone, 2,4', 4-
Triaminobenzophenone,

3,4 ′, 4, -triaminobiphenyl,
3,2 ′, 4, -triaminobiphenyl, 3,2 ′,
2, -triaminobiphenyl, 3,3 ', 2, -triaminobiphenyl, 3,4', 2, -triaminobiphenyl, 2,3 ', 4, -triaminobiphenyl, 2,
2 ', 4, -triaminobiphenyl, 2,4', 4,-
Triaminobiphenyl, 3,4 ', 4, -triaminodiphenyl ether, 3,2', 4, -triaminodiphenyl ether, 3,2 ', 2, -triaminodiphenyl ether, 3,3', 2, -triamino Diphenyl ether, 3,4 ′, 2, -triaminodiphenyl ether, 2,3 ′, 4, -triaminodiphenyl ether,
2,2 ', 4, -triaminodiphenyl ether, 2,
4 ', 4, -triaminodiphenyl ether, 3,
4 ', 4, -triaminodiphenyl sulfone, 3,
2 ', 4, -triaminodiphenyl sulfone, 3,
2 ', 2, -triaminodiphenyl sulfone, 3,
3 ', 2, -triaminodiphenyl sulfone, 3,
4 ', 2, -triaminodiphenyl sulfone, 2,
3 ', 4, -triaminodiphenyl sulfone, 2,
2 ', 4, -triaminodiphenyl sulfone, 2,
4 ', 4, -triaminodiphenyl sulfone, 3,
4 ', 4, -triaminodiphenyl sulfide, 3,
2 ', 4, -triaminodiphenyl sulfide, 3,
2 ', 2, -triaminodiphenyl sulfide, 3,
3 ', 2, -triaminodiphenyl sulfide, 3,
4 ', 2, -triaminodiphenyl sulfide, 2,
3 ', 4, -triaminodiphenyl sulfide, 2,
2 ', 4, -triaminodiphenyl sulfide, 2,
4 ', 4, -triaminodiphenyl sulfide, 2,
3,4-triaminobenzophenone, 2,3,5-triaminobenzophenone, 2,4,5-triaminobenzophenone, 2,3,4-triaminobiphenyl, 2,
3,5-triaminobiphenyl, 2,4,5-triaminobiphenyl, 2,3,4-triaminodiphenyl ether, 2,3,5-triaminodiphenyl ether,
2,4,5-triaminodiphenyl ether,

2,3,4-triaminodiphenyl sulfone, 2,3,5-triaminodiphenyl sulfone, 2,
4,5-triaminodiphenyl sulfone, 2,3,4-
Triaminodiphenyl sulfide, 2,3,5-triaminodiphenyl sulfide, 2,4,5-triaminodiphenyl sulfide, 1,3-bis (3-aminophenoxy) -5- (2-aminophenoxy) benzene, ,
3-bis (3-aminophenoxy) -5- (4-aminophenoxy) benzene, 1,3-bis (2-aminophenoxy) -5- (3-aminophenoxy) benzene,
1,3-bis (2-aminophenoxy) -5- (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) -5- (3-aminophenoxy) benzene, 1,3-bis ( 4-aminophenoxy) -5- (2
-Aminophenoxy) benzene, 1- (3-aminophenoxy) -3- (4-aminophenoxy) -5- (2-
Any tetraamino and / or triamino compound such as (aminophenoxy) benzene can be used.

These tetraamino compounds and / or triamino compounds may be used alone or as a mixture of two or more, provided that the total sum is in the range of 0.005 to 0.11 per mole of diamine compound. . When the total amount of the tetraamino compound and / or the triamino compound is 0.005 mol or less per 1 mol of the diamine compound, the entanglement of molecules cannot be sufficiently formed, and the improvement of the fatigue property cannot be expected. On the other hand, if the amount is 0.11 mol or more, the number of entanglement points (crosslinking points) of the molecules becomes too large, and the melt fluidity is significantly inhibited. The amount of the tetraamino compound and / or the triamino compound to be used per 1 mol of the diamine compound is preferably 0.01 to 0.06 mol, particularly preferably 0.02 to 0.04 mol.

When synthesizing the polyimide of the present invention,
As the tetracarboxylic dianhydride component, a tetracarboxylic dianhydride represented by the formula (IV), that is, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride And 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride may be used, but these may be used alone or in combination of two or more.

Further, other tetracarboxylic dianhydrides may be mixed and used as long as the characteristics of the polyimide are not impaired. Examples of the tetracarboxylic dianhydride that can be used by mixing 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, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl)- 1,1,1,3,3,3-trifluoromethylpropane 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 Anhydride, 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.

In producing the polyimide resin of the present invention, a dicarboxylic anhydride or a monoamine is used for the purpose of sealing the terminal of the polymer molecule. Specific examples of these compounds include phthalic anhydride, 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,3-dicarboxyphenylphenyl 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 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. These can be used alone or in combination of two or more. Of these aromatic dicarboxylic anhydrides, phthalic anhydride is preferably used.

The following are examples of the monoamine. For example, aniline, o-toluidine, m
-Toluidine, p-toluidine, 2,3-xylysine,
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-amino Phenylphenyl ether, 3-aminophenylphenyl ether, 4-aminophenylphenyl ether, 2-aminobenzophenone, 3-aminobenzophenone,
Aminobenzophenone, 2-aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide, 4
-Aminophenylphenyl sulfide, 2-aminophenylphenylsulfone, 3-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. These aromatic monoamines and / or dicarboxylic anhydrides may be used alone or
There is no problem even if it mixes and uses more than seeds. The amount of these compounds used is 1 to 3 moles of monoamine (the difference between the total number of amino groups of the amine compound having two or more amino groups and the number of acid anhydride groups of tetracarboxylic dianhydride). The excess component may be a tetracarboxylic dianhydride) or a dicarboxylic anhydride (the excess component is an amine compound), but is generally used in an amount of at least about 0.01 mole of one component. The amount of the compound used as the polymer end capping agent may be the difference between the total number of amino groups of the amine compound having two or more amino groups and the number of acid anhydride groups of tetracarboxylic dianhydride. 1-2
It is preferably a double mole of monoamine (excess component is tetracarboxylic dianhydride) or dicarboxylic anhydride (excess component is amine compound), more preferably 1 to 2.
1.5 times mol.

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, an amine compound having two or more amino groups, a tetracarboxylic dianhydride, a dicarboxylic anhydride or an aromatic monoamine in an organic solvent is added and reacted as follows. (A) A method in which a tetracarboxylic dianhydride is reacted with an amine compound having two or more amino groups, and then a dicarboxylic anhydride or an aromatic monoamine is added to continue the reaction. (Ii) A dicarboxylic anhydride is added to an amine compound having two or more amino groups to cause a reaction, and then a tetracarboxylic dianhydride is added to continue the reaction, or an aromatic monoamine is added to the tetracarboxylic dianhydride. And then reacting by adding an amine compound. (C) A method in which a tetracarboxylic dianhydride, an amine compound having two or more amino groups and a dicarboxylic anhydride or an aromatic monoamine are simultaneously added to cause a reaction.
There is no problem using either method.

The amine compound may be added by adding the diamine compound and the tetraamino compound and / or the triamino compound separately, or by mixing the diamine compound and the tetraamino compound and / or the triamino compound in advance and then adding them at the same time. Then there is no problem. 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 is
Although it depends on the type of amine compound, the type of tetracarboxylic dianhydride, the type of solvent, the presence or absence of a catalyst, and the reaction temperature, usually 4 to 24 hours is sufficient. The polyimide resin of the present invention is obtained by the above method.

The polyimide resin composition of the present invention can be used as a reinforcing material in the above polyimide resin, for example, carbon fiber,
It is adjusted by adding a fibrous reinforcing material such as glass fiber, aromatic polyamide fiber and potassium titanate fiber. The amount of the reinforcing material is 5 to 100 parts by weight, preferably 10 to 5 parts by weight, based on 100 parts by weight of the polyimide resin.
0 parts by weight.

[0027] Carbon fiber is most preferred as the type of 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 without impairing 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. Injection molding is the most preferable from the viewpoint of work efficiency because it has a characteristic of excellent melt fluidity. 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.

[0030]

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 was heated and dissolved in 100 ml of a mixed solvent of p-chlorophenol and phenol (90:10 by weight), and then cooled to 35 ° C. and measured. 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: Measured using DTA-TG (Shimadzu DT-40 series, 40M) in air at a heating rate of 10 ° C / min. Melt viscosity: Using a Shimadzu high reduction type flow tester CFT-500, measured at a load of 100 k g.

[0031] Example 1 stirrer, reflux condenser, to a vessel equipped with a water separator and a nitrogen inlet tube, 4,4'-bis (3-aminophenoxy) biphenyl 3.606Kg (9.8 mol), 3 ,
21.4 g (0.1 mol) of 3'-diaminobenzidine,
Pyromellitic dianhydride 2.05 kg (9.40 mol), phthalic acid 177.6g (1.2 moles) anhydrous, .gamma.
Was charged with picolinic 138 g (1.5 mol) and m- cresol 21.8 k g, it was Atsushi Nobori with stirring to 145 ° C. in a nitrogen atmosphere. During this time, distillation of about 340 g of water was confirmed. Further, at 140 to 150 ° C., 4
A time reaction was performed. Then, cool to room temperature, 80
After discharging into kg of toluene, the mixture was filtered off. The polyimide powder was further washed with toluene, preliminarily dried at 50 ° C. for 24 hours under a nitrogen atmosphere, and then dried at 240 ° C. for 6 hours to obtain 5.33 kg (97% yield) of polyimide powder. The logarithmic viscosity of this polyimide is 0.44 dl /
g and Tg were 248 ° C and the 5% weight loss temperature was 560 ° C. The melt viscosity of the obtained polyimide at 420 ° C. was 5,600 poise.

[0032] Example 2 Example 1 4,4'-bis (3-aminophenoxy) biphenyl 3.606Kg (9.8 mol), 3,3'-diaminobenzidine 21.4 g (0.1 mol), pyromellitic dianhydride 2.05 kg (9.40 mol), and 177.6g of phthalic anhydride (1.2 mol), 4,4'-bis (3-aminophenoxy) biphenyl 3.496kg
(9.5 mol), 3,3'-diaminobenzidine
5 g (0.25 mol) of pyromellitic dianhydride 2.0
4 kg (9.35 mol), 192.4 g of phthalic anhydride
(1.3 mol), and 5.26 kg (97% yield) of polyimide powder was obtained in exactly the same manner, except that the amount was changed to (1.3 mol). The logarithmic viscosity of this polyimide is 0.50 dl / g, Tg is 250 ° C., 5
The% weight loss temperature was 560 ° C. The melt viscosity of the obtained polyimide at 420 ° C. was 9,000 poise.

[0033] The 4,4'-bis (3-aminophenoxy) biphenyl of Examples 3-7 Example 2 in the same manner except for changing the diamine compounds shown in Table 1 to obtain a polyimide powder. The basic physical properties are summarized together with the results of Example 2 in Table 1.

[0034] was obtained except that pyromellitic dianhydride was changed to tetracarboxylic dianhydride shown in Table 1 in the same manner as in Example 2 Polyimide powder of Example 8-9 Example 2. Look at the basic physical properties in Table 1
Shown collectively together with the results of the facilities Example 2

[0035]

[Table 1]

[0036] Example 10 stirrer, reflux condenser, to a vessel equipped with a water separator and a nitrogen inlet tube, 4,4'-bis (3-aminophenoxy) biphenyl 3.643Kg (9.9 mol), 1 ,
3,5-tris (4-aminophenoxy) benzene 5
9.9 g (0.15 mol), pyromellitic dianhydride 2.05 k g (9.40 mol) of phthalic anhydride 177.
6 g (1.2 mol), 138 g (1.5 mol) of γ-picoline and 21.8 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 toluene, and filtered. The polyimide powder was further washed with toluene, preliminarily dried at 50 ° C. for 24 hours under a nitrogen atmosphere, and then dried at 240 ° C. for 6 hours to obtain 5.33 kg (97% yield) of polyimide powder. The logarithmic viscosity of this polyimide was 0.49 dl / g, the Tg was 248 ° C., and the 5% weight loss temperature was 560 ° C. 4 of the obtained polyimide
The melt viscosity at 20 ° C. was 5,800 poise.

The change Example 11-1 3, 4,4'-bis in Comparative Example 1 Example 10 (3-aminophenoxy) biphenyl and 1,3,5-tris (4-aminophenoxy) molar ratio of benzene was synthesized logarithmic viscosity 0.50 dl / g before and after the polyimide powder according to the method of example 10 by. The molar ratio of 4,4'-bis (3-aminophenoxy) biphenyl to 1,3,5-tris (4-aminophenoxy) benzene and 42 of the resulting polyimide
The relationship between the melt viscosity at 0 ℃ together with the results of Example 10 are summarized in Table 2.

[0038] Example 1 4 to 1 6 1,3,5-tris in Synthesis Example 10 (4-aminophenoxy) Table 2 benzene 59.9 g (0.15 mol)
A polyimide powder was obtained in exactly the same manner as above except that the triamino compound (0.15 mol) was used. 4,4'-bis (3-aminophenoxy) relationship melt viscosity at 420 ° C. in a molar ratio between the obtained polyimide biphenyl and triamino compound together with the results of Example 10 are summarized in Table 2.

The logarithmic viscosity according to the method of Example 1 7-1 8 Example 4,4'-bis of 2 (3-aminophenoxy) biphenyl and 3,3' performed by changing the molar ratio of diaminobenzidine Example 2 0.5
A polyimide powder of about 0 dl / g was synthesized. 4,4'-
Bis (3-aminophenoxy) biphenyl and 3,3'-
The molar ratio of diaminobenzidine and the resulting polyimide 4
The relationship between the melt viscosity at 20 ° C. together with the results of Example 2 are summarized in Table 2.

[0040] Example 19 Example 2 in 3,3'-diaminobenzidine to 3,
A polyimide powder was synthesized in exactly the same manner except that 3 ', 4,4'-tetraaminodiphenyl ether was used.
4,4'-bis (3-aminophenoxy) biphenyl and 3,3 ', the result of the relationship of a second embodiment of the melt viscosity at 420 ° C. of the polyimide obtained with a molar ratio of 4,4'-tetra-diaminodiphenyl ether and Table 2 also shows the results.

[0041] 4,4'-bis (3-aminophenoxy) biphenyl 3.496Kg (9.5 mol) of Comparative Example 2 Example 2, 3,3'-diaminobenzidine 53.5 g (0.25 mol), pyromellitic dianhydride 2.04 kg (9.35 mol), 192.4G phthalic anhydride (1.3 mol) of 4,4'-bis (3-aminophenoxy) biphenyl 3.68 kg (1
0.0 mol), pyromellitic dianhydride 2.07kg
(9.55 mol), and a polyimide powder was synthesized in exactly the same manner except that phthalic anhydride was changed to 148 g (1.0 mol). Inherent viscosity and melt viscosity of the resulting polyimide shown soot in Table 2.

[0042] 4,4'-bis (3-aminophenoxy) biphenyl 3.496Kg (9.5 moles) of Example 2 0 Example 2, 3,3'-diaminobenzidine 53.5 g (0.25 mol) , pyromellitic dianhydride 2.04 kg (9.35 mol), 192.4G phthalic anhydride (1.3 mol) of 4,4'-bis (3-aminophenoxy) biphenyl 3.27 k g
(8.883 mol), 3,3′-diaminobenzidine 5
0.1 g (0.234 mol), pyromellitic dianhydride 2.18 k g (10. Mol), aniline 120.9g
(1.3 mol), except that the polyimide powder was synthesized. Inherent viscosity and melt viscosity of the resulting polyimide are shown in Table 2.

[0043]

[Table 2]

The addition of rayon carbon fiber (HTA-C6) 30 parts by Toho to polyimide powder 70 parts by weight obtained in Example 21 Example 2 was mixed with the drum blend Day mixer (manufactured by Kawata Seisakusho) Thereafter, the mixture was melt-kneaded at 400 ° C. by a single-screw extruder having a diameter of 30 mm, and the strand was air-cooled and cut to obtain a pellet. Using the obtained pellets, injection pressure 500 kg / cm ² , cylinder temperature 4
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 3 shows the relationship between the load and the number of times of repeated fatigue.

[0045] Using the polyimide powder obtained in Examples 22 to 39 Example 3-20 Example
A tensile test piece was prepared in the same manner as in Example 21, and the number of times of repeated fatigue was measured. The results are shown in Table 3.

Comparative Examples 3 and 4 Example 2 was repeated using the polyimide powders obtained in Comparative Examples 1 and 2.
A tensile test piece was prepared in exactly the same manner as in No. 1 and the number of times of repeated fatigue was measured. The results are shown in Table 3.

[0047]

[Table 3]

Example 40 To 70 parts by weight of the polyimide powder obtained in Example 1 , 30 parts by weight of glass fiber (RES-03) made by Nippon Sheet Glass was added, and mixed with a drive render mixer (manufactured by Kawada Seisakusho). 400 ° C by a single-screw extruder with a diameter of 30 mm
Then, the strand was air-cooled and cut to obtain pellets. Using the obtained pellets, injection molding was carried out using an Arburg injection molding machine under the conditions of an injection pressure of 500 kg / cm ² , a cylinder temperature of 410 ° C., and a mold temperature of 180 ° C.
A tensile test piece was obtained. JIS K7 using this test piece
The number of repeated fatigue was measured by the partial pulsating method in accordance with No. 118. When the maximum excitation stress was 4 kg / mm ² , the number of repeated fatigue was 2800 × 10 ⁵ times.

[0049]

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI // B29K 79:00 B29K 79:00 (72) Inventor Yoshihiro Sakata 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals, Inc. (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Pref.Mitsui Toatsu Chemicals Co., Ltd.Examiner, Tsutomu Onodera (56) References JP-A-1-113461 (JP, A) JP-A-1-121363 (JP, A) JP-A-58-180530 (JP, A) JP-A-3-109425 (JP, A) JP-A-4-88020 (JP, A) JP-A-5-254064 (JP, A) 40-40846 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 73/00-73/26 C08L 79/00-79/08 C08K 3/00-13/08

Claims (5)

(57) [Claims] (1) a compound represented by the formula (I): Means With respect to 1 mol of the diamine compound represented by the following formula (II): Means A) a tetraamino compound represented by the formula:
Or the following formula (III): Means )) Is 0.
005 to 0.11 mol of the amine compound represented by the following formula (I
V) [Chemical formula 4] [Chemical formula 4] Means a tetravalent group. A tetracarboxylic acid dianhydride component represented by), a dicarboxylic acid anhydride, or monoamino compound melt-moldable polyimide resins excellent in fatigue properties which is characterized in that it is obtained by reaction in the presence of . 2. A diamine compound represented by the above formula (I) and a tetracarboxylic acid dianhydride represented by the above formula (II) per 1 mol of the tetracarboxylic dianhydride represented by the above formula (IV) The total of the amino compound having two or more amino groups comprising the amino compound and / or the triamino compound represented by the formula (III) is 0.8 to 1.20 mol. 2. A melt-moldable polyimide resin having excellent fatigue properties according to 1. 3. The fatigue according to claim 1, wherein 0.001 to 0.20 mol of dicarboxylic anhydride and / or monoamine is used per 1 mol of the total amount of the tetracarboxylic dianhydride. Melt-moldable polyimide resin with excellent properties. 4. The polyimide resin 100 according to claim 1,
A polyimide resin composition containing 5 to 100 parts by weight of a fibrous reinforcing material with respect to parts by weight. 5. An injection molded article containing the polyimide resin according to claim 1.