JPH0853620A - Polyimide resin composition - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] Mixing a solvent-soluble and thermoplastic polyimide with a fibrous reinforcing material and applying it to the fibrous reinforcing material provides excellent resistance to water and moisture absorption. Provided are polyimide resin compositions and composites. [Configuration] The following equation (1) (In the formula, m and n are each independently an integer of 0 or 1, and R is independently a hydrogen atom, a halogen atom,
And a specific aromatic ring, an alkyl group, and the like, and Ar represents a specific aromatic group having 6 to 27 carbon atoms. ) Polyimide and fibrous reinforcing material such as carbon fiber. [Effect] Since it has a high degree of solvent solubility, it can be easily impregnated with a solution in a fibrous reinforcing material. In addition to the high heat resistance and other physical properties inherent in polyimide resin, its high resistance even under high temperature and high humidity. It retains mechanical properties and has thermoplasticity and adhesive strength.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a soluble and thermoplastic polyimide resin composition, and a method for producing the same.
Further, regarding the injection molded body, in detail, polyimide having good solubility in a general-purpose organic solvent and having thermoplasticity, carbon fiber, glass fiber, aromatic polyamide fiber and / or potassium titanate fiber, etc. The present invention relates to a polyimide resin composition containing the fibrous reinforcing material, a method for producing the same, and an injection-molded article obtained by using the resin composition. The present invention also relates to a polyimide-based composite, and more particularly, to a polyimide-based laminated composite obtained by molding the above-mentioned soluble and thermoplastic polyimide with a fibrous reinforcing material and a method for molding the same. Furthermore, the present invention relates to a fibrous reinforcing material whose surface is modified using the above polyimide. The surface modification of the fibrous reinforcing material using the polyimide used in the present invention improves the applicability as a fibrous reinforcing material. That is, the polyimide used in the present invention can be applied as a surface modifier of a fibrous reinforcing material, particularly in a solution dissolved in a solvent.

[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, so it is used for electrical and electronic equipment, aerospace equipment, and transportation. Widely used in the field of equipment. Conventionally,
Various polyimides showing excellent characteristics have been developed,
Even if it has excellent heat resistance, it does not have a clear glass transition temperature, so when it is used as a molding material, it must be processed using a special method such as sintering, but it has excellent processability. There are merits and demerits in terms of its performance, such as a low glass transition temperature and poor water and moisture absorption resistance compared to other engineering plastics. In particular, inferior water absorption / moisture absorption resistance may cause various problems such as not being able to be actively applied to applications requiring water absorption / moisture absorption resistance in addition to the excellent performance inherent in polyimide.
For example, in the field of aerospace equipment, it is considered to be used under severe conditions of high temperature and high humidity due to abrupt changes in weather conditions, cyclic conditions, etc., and resins that are inferior in water absorption and moisture absorption are
It is known that absorption of water dramatically reduces its mechanical strength and dimensional stability. The same applies to the field of electric / electronic devices, particularly in the field of semiconductor materials.
When used as an encapsulant for electronic circuit boards, it causes mechanical cracks, dimensional stability, microcracks, foaming, or deterioration of electrical insulation. Development is desired.

The present inventors have found that the formula (A)

Embedded image With respect to a polyimide having a basic skeleton, a polymer capable of being injected and extruded was found by sealing the polymer terminal to block the reactivity of the molecular terminal of the polymer and adjusting the polymer molecular weight (Japanese Patent Laid-Open No. H02-29242). -0184
19 publication). However, although this polyimide is also given thermoplasticity, it is difficult to impregnate it into a fibrous reinforcing material with a solution because it has poor solubility in general-purpose solvents, and it is more resistant to water and moisture absorption than conventional engineering plastics. Since it is inferior in sex, it has the above-mentioned problems.

One of the uses of polyimide, which takes advantage of its heat resistance and mechanical strength, is to use it in combination with glass fiber or carbon fiber. The polyimide used for this purpose is usually a non-thermoplastic polyimide, the fiber is impregnated with a solution of its precursor polyamic acid, and the solvent is removed by evaporation, followed by heating and pressing to cure simultaneously with imidization. It is generally performed (Japanese Patent Laid-Open No. 60-24).
0740 and 61-235437). However, in this method, it is necessary to perform imidization and molding at the same time, and water generated during imidization may cause various defects such as voids. On the other hand, it has been proposed to use a thermoplastic polyimide (Japanese Patent Laid-Open Nos. 01-113461 and 03-199234). However, in this case, even a polyimide having heat resistance and thermoplasticity is not sufficient in melt flowability, and like the method using the polyamic acid, it is possible to completely suppress the occurrence of defects such as voids. Was difficult.

As described above, in the already known polyimide, even if it is a non-thermoplastic polyimide, impregnation into the fiber is good if a solution of the polyamic acid as its precursor is used, but at the time of imidization There is a water problem that arises. On the other hand, if it is a thermoplastic polyimide, there is no problem that low molecules such as water are generated, but the fluidity is insufficient and the polyimide does not sufficiently impregnate the fiber, and it is difficult to obtain a molded product with excellent performance. Met. In addition, the fibrous reinforcing material used in various resin composites may have a different surface depending on the type of the resin to be reinforced in order to improve the compatibility with the resin and improve the performance of the obtained composite. A modified product is used. For example, among various fibrous reinforcing materials, carbon fiber is superior to glass fiber in terms of high elasticity and lightness, and particularly, it is a super resin such as polyimide resin, polyether ether ketone, polyether sulfone, polyether imide and polyphenylene sulfide. Suitable as a reinforcing material for heat-resistant resin,
Improves mechanical strength and other characteristics, making it an excellent material for automobile parts and machine parts. Conventionally, as a carbon fiber having a modified surface, one modified with an epoxy resin is widely known. However, the epoxy resin is effective as a surface modifier for a matrix of a thermosetting resin such as an epoxy resin, but for a matrix of a thermoplastic resin,
In many cases, the adhesiveness with the matrix is poor, and carbon fibers modified with an epoxy resin have not been able to sufficiently improve the properties such as mechanical strength of the molded product. Therefore, in JP-A-53-106752, it has been attempted to use a polyamide resin as a surface modifier of a fiber reinforcing material such as carbon fiber for a matrix of a thermoplastic resin.

However, when the super heat-resistant thermoplastic resin is used as the matrix, the molding temperature is higher than 300 ° C., so that the polyamide resin, which is the surface modifier, is thermally decomposed during the molding, forming voids and welding. A problem such as a decrease in part strength occurs, and a satisfactory surface modifier has not yet been obtained with a polyamide resin. On the other hand, in order to solve the above thermal decomposition problem, a polyetherimide resin (JP-A-62-299580) and a polyimide resin (JP-A-64-40569) having excellent heat resistance are used as the surface modifier. However, a modifier that leaves a problem with the adhesiveness with the thermoplastic resin that is the matrix, and that can still exert a sufficient modifying effect, and a surface-modified fibrous reinforcing material have not been found. It has not been issued. The present inventors have already found an organic solvent-soluble highly heat-resistant polyimide having a structure similar to that of the polyimide of the present application (Japanese Patent Application No. 05-11).
No. 8340, No. 05-203871), it has not been found that these polyimides have particularly excellent performance as surface modifiers for fibrous reinforcing materials such as carbon fibers.

[0007]

The object of the present invention is, in addition to excellent properties such as high heat resistance originally possessed by a polyimide resin, excellent water and moisture absorption resistance even under high temperature and high humidity conditions. It is intended to provide a polyimide resin composition that retains its excellent mechanical properties, a method for producing the same, and a molded product obtained by using this composition. Another object of the present invention is to provide a polyimide-based laminated composite having the above-mentioned characteristics and having no structural defects, and a method for producing the same. Yet another object is to provide a fibrous reinforcement having a surface improved with a polyimide having the above properties.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the following general formula (1) having excellent solvent solubility, which the present inventors have already found. ) Heat resistance, mechanical properties,
It was found that a polyimide-based resin composition having excellent resistance to water absorption and moisture absorption, a polyimide-based laminated composite, and a surface-modified fiber reinforcement can be produced, and by using the polyimide of the general formula (1) as a solution. , A polyimide composite without the occurrence of structural defects, capable of efficiently producing a polyimide resin composition, also capable of modifying the surface of the fibrous reinforcing material, further using a polyimide resin composition,
In particular, they have found that a polyimide molded product having excellent water absorption / moisture absorption resistance can be obtained and completed the present invention.

That is, the present invention relates to the general formula (1)

[Chemical 9] [In the formula, m and n are each independently an integer of 0 or 1, and R is

[Chemical 10] (Here, R ₁ , R ₂ , R ₃ , and R ₄ are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkenyl group, an aralkyl group, or 1 to 5 carbon atoms.
Represents an alkoxy group of R ₅ , R ₆ , R ₇ are hydrogen atoms,
C1-C8 alkyl, aryl, alkenyl, aralkyl or C1-C10 oxygen 1-3.
Of ω-alkyloxy oligo (alkyleneoxy) alkyl group), Ar has 6 to 27 carbon atoms,
And represents a tetravalent group which 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 bridging member] A polyimide containing at least one kind of repeating structural unit as an essential structural unit, and a polyimide resin composition containing a fibrous reinforcing material,

In this composition, the polyimide has an inherent viscosity of 0.3 dl / g or more, and the polyimide 100
A polyimide containing 0.5 to 65 parts by weight of a fibrous reinforcing material with respect to parts by weight and having a repeating structural unit represented by the general formula (1) has an aromatic dicarboxylic acid at the polymer molecular end. A compound which is sealed with an acid anhydride and / or an aromatic monoamine, that is, in the production of this polyimide, a compound represented by the formula (4)

[Chemical 11] (In the formula, Z ₁ has 6 to 15 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are directly or cross-linked to each other. An aromatic dicarboxylic acid anhydride represented by a divalent group which is an aromatic group) and / or general formula (5) Z ₂ —NH ₂ (5) (wherein Z ₂ has 6 carbon atoms). Is a monovalent 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 bridging member. A polymer resin obtained by reacting an aromatic monoamine represented by the formula (1) with the polymer molecule terminal blocked, or a polyimide resin composition containing the polymer molecule terminal blocked. It is a method of manufacturing them.

Further, according to the present invention, the fibrous reinforcing material is impregnated with a polyimide having a repeating structural unit represented by the general formula (1), which is soluble in a solvent and can be heated and melted under the conditions of impregnation. Then, a polyimide-based composite obtained by laminating and molding the prepreg, which is actually a laminated composite.

Further, the present invention is a fibrous reinforcing material having a surface modified by using a polyimide having a repeating structural unit represented by the general formula (1), that is, a solvent solution of this polyimide. Preferably, the polyimide of the repeating structural unit represented by the general formula (1) has the formula (6)

[Chemical 12] And / or formula (7)

[Chemical 13] A diamine compound represented by, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, bis (di Carboxyphenyl) sulfone dianhydride, bis [(dicarboxyphenyl) phenyl] propane dianhydride, bis (dicarboxyphenyl) propane dianhydride, bis (dicarboxyphenoxy) benzene dianhydride, bis (dicarboxyphenyl) A polyimide obtained by reacting at least one tetracarboxylic acid dianhydride selected from hexafluoropropane dianhydride with heating. The surface is modified with a surface modifier containing the polyimide. It is a carbon fiber made.

In these polyimide-based composites and surface-modified fibrous reinforcing materials, the polyimide heats the diamine compound and the tetracarboxylic acid dianhydride in the presence of the dicarboxylic acid anhydride and / or the monoamino compound. It is a polyimide obtained by reacting or contains this polyimide. The fiber surface modifier comprising the polyimide of the present invention can be put to practical use and sold in the form of powder or solution.

The polyimide used in the present invention has the general formula (1)

Embedded image Two or more kinds of polyimides having a repeating structural unit represented by the general formula (1) (wherein, m, n, R and Ar are as described above). Or a polyimide copolymer containing two or more kinds of repeating structural units represented by the general formula (1).

A particularly preferred polyimide copolymer has the general formula (2)

[Chemical 15] (Wherein, m, R and Ar are the same as in the case of the general formula (1)) and the general formula (3)

Embedded image (In the formula, m, R and Ar are the same as in the case of the general formula (1)), and it is a copolymer containing a structural unit.

The method for producing the polyimide used in the present invention is represented by the general formula (8).

[Chemical 17] (In the formula, m, n and R are the same as those in the general formula (1))
An aromatic diamine represented by, for example, a general formula (9) in which R is phenyl.

Embedded image (Wherein n and R _1-4 are the same as in the case of the general formula (1)) and a polyimide having a repeating structural unit represented by the general formula (10)

[Chemical 19] (In the formula, Ar has a carbon number of 6 to 27, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are connected to each other directly or by a crosslinking member. A tetravalent group, which is an aromatic group, is specifically shown by the formula (a)

Embedded image A monocyclic aromatic group represented by the formula (b)

[Chemical 21] Or a condensed polycyclic aromatic group represented by the formula (c)

[Chemical formula 22] [In the formula, X is a direct bond, -CO-, -O-, -S-,-
_{SO 2 -, - CH 2 -} , - C (CH 3) 2 -, - C (C
F ₃ ) ₂ − and formula (d), formula (e) or formula (f)

[Chemical formula 23]

[Chemical formula 24] (Where Y is a direct bond, -CO-, -O-, -S-,
_{-SO 2 -, - CH 2 -} , - C (CH 3) 2 -, - C
(CF _{3) 2} - shows a. ) Is a tetravalent group which is a non-condensed polycyclic aromatic group in which the aromatic group represented by) is directly or mutually linked by a crosslinking member. ) Is a polyimide obtained by polymerizing with an aromatic tetracarboxylic acid dianhydride.

The diamine compound used here is specifically 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5,5'-diphenoxybenzophenone, 3, 4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone,
3,4'-diamino-4-phenoxybenzophenone, 3,4 '
-Diamino-5-phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'-
Diamino-5,5'-dibiphenoxybenzophenone, 3,4 '
-Diamino-4,5'-dibiphenoxybenzophenone, 3,
3'-diamino-4-biphenoxybenzophenone, 4,4 '
-Diamino-5-biphenoxybenzophenone, 3,4'-
Diamino-4-biphenoxybenzophenone, 3,4'-diamino-5-biphenoxybenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 4,4'-diamino-5,5'-dimethoxybenzophenone , 3,4'-diamino-4,5'-dimethoxybenzophenone, 3,3'-diamino-
4-methoxybenzophenone, 4,4'-diamino-5-methoxybenzophenone, 3,4'-diamino-4-methoxybenzophenone, 3,4'-diamino-5-methoxybenzophenone,

1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxy) Benzoyl) benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino-4-)
Biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,
4-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,3-bis (3-amino-4-methoxybenzoyl) benzene, 1,4-bis (3-amino-4-methoxybenzoyl) benzene, 1,3-bis (4-amino-5-methoxybenzoyl)
Examples thereof include benzene and 1,4-bis (4-amino-5-methoxybenzoyl) benzene. You may use these aromatic diamine individually or in mixture of 2 or more types.

Although the above-mentioned aromatic diamine is used as an essential raw material monomer in the polyimide of the present invention, it is also possible to mix and use other aromatic diamine within a range not impairing good physical properties of this polyimide. Further, in the surface-modified fibrous reinforcing material of the present invention, when the fibrous reinforcing material is a carbon fiber, the formula (6) is used for modifying the fibrous reinforcing material.

[Chemical 25] 3,3'-diamino-4,4'-diphenoxybenzophenone represented by and / or formula (7)

[Chemical formula 26] 1,3-bis (3-amino-4-phenoxybenzoyl) benzene represented by is preferably used.

That is, it does not matter even if one or more other diamines are mixed and polymerized as long as the modification and physical properties of the polyimide are not impaired, but examples of diamines that can be mixed and used include: m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether , Bis (3-aminophenyl) sulfide, bis (4-
Aminophenyl) sulfide, (3-aminophenyl)
(4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, bis (4-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, (3-aminophenyl)
(4-aminophenyl) sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane,
4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [ 4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1, 2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] Propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-
Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy)
Phenyl] -1,1,1,3,3,3-hexafluoropropane,

1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4- Aminophenoxy) benzene, 1,3-bis (3-amino-α, α-
Dimethylbenzyl) benzene 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene 1,4-bis (4-amino- α, α-Dimethylbenzyl) benzene 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-
Bis (4-aminophenoxy) biphenyl, bis [4- (3-
Aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis 〔4- (3-
Aminophenoxy) phenyl] sulfoxide, bis [4-
(4-Aminophenoxy) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] Ether, bis [4- (4-aminophenoxy) phenyl] ether,

1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4'-bis [3- (4 -Aminophenoxy) benzoyl] diphenyl ether, 4,4'-
Bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4 -Amino-α, α-dimethylbenzyl) phenoxy] diphenyl sulfone, bis [4- [4- (4-aminophenoxy) phenoxy] phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) -α , Α-Dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy)-
α, α-Dimethylbenzyl] benzene, 3,3′-diamino
-4,4'-difluorobenzophenone, 3,3'-diamino-5,
5'-bis (trifluoromethyl) diphenyl ether,
4,4'-diamino-5,5'-bis (trifluoromethyl) diphenyl ether, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-fluorophenoxy) -α, α-dimethylbenzyl] benzene,
1,3-bis [4- (4-amino-6-methylphenoxy)-
α, α-Dimethylbenzyl] benzene, 1,3-bis [4-
(4-Amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene, 2,6-bis [4- (4-amino-α,
α-dimethylbenzyl) phenoxy] benzonitrile,
2,6-bis [4- (4-amino-α, α-bistrifluoromethylbenzyl) phenoxy] benzonitrile, 2,6-bis [4- (4-aminophenoxy) phenoxy] benzonitrile, 2,6- Bis [4- (4-aminobenzoyl) phenoxy]
Examples thereof include benzonitrile.

The tetracarboxylic dianhydride of the formula (10) used is specifically pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic 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,
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] sulfone dianhydride, bis [4- 〔3-
(1,2-Dicarboxy) phenoxy] phenyl] sulfone dianhydride, bis [4- [4- (1,2-dicarboxy) phenoxy] phenyl] sulfide dianhydride, bis [4- [3- (1 ,
2-dicarboxy) phenoxy] phenyl] sulfide dianhydride, 2,2-bis [4- [4- (1,2-dicarboxy) phenoxy] phenyl] -1,1,1,3,3,3- Hexafluoropropane dianhydride, 2,2-bis [4- [3- (1,2-dicarboxy) phenoxy] phenyl] -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,
2,3,4-naphthalenetetracarboxylic dianhydride, 3,4,9,10
-Perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride and the like. These may be used alone or in admixture of two or more.

In the surface modification of the fibrous reinforcing material of the present invention, particularly as the polyimide used for the surface modification of carbon fiber, 3,3'-diamino-4,4-diphenoxybenzophenone and / or 1,3 ' When -bis (3-amino-4-phenoxybenzoyl) benzene is used as the diamine component,
Pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride,
Diphenyl ether tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, bis (dicarboxyphenyl) sulfone dianhydride, bis (dicarboxyphenyl) propane dianhydride, bis [(dicarboxyphenoxy) phenyl] propane Tetracarboxylic acid dianhydrides of dianhydride, bis (dicarboxyphenyl) benzene dianhydride and / or bis (dicarboxyphenyl) hexafluoropropane dianhydride are preferably used. Among them, benzophenone tetracarboxylic dianhydride and biphenyl tetracarboxylic dianhydride are preferable. These tetracarboxylic dianhydrides may be used alone or in combination of two or more without any problem. Further, other tetracarboxylic acid dianhydride may be mixed and used within a range not impairing the characteristics of the surface treating agent for carbon fiber.

Polyimides obtained by using these aromatic diamine components and aromatic tetracarboxylic dianhydrides as monomer components are mainly represented by the general formula (1), (2) or (3).
A polyimide having a repeating structural unit of, a polyimide copolymer or a mixture, and also includes a polyimide in which the polymer molecular end of these polyimide is unsubstituted or substituted with a group having no reactivity with amine or dicarboxylic acid anhydride. . The polyimide having an aromatic ring having no substituent at this terminal or substituted with a group having no reactivity with amine or dicarboxylic acid anhydride is represented by the general formula (8) and / or (9). An aromatic diamine and a tetracarboxylic dianhydride mainly represented by the general formula (10) are represented by the aromatic dicarboxylic acid anhydride represented by the general formula (4) or the general formula (5). It is obtained by reacting in the presence of the aromatic monoamine described above, and thermally or chemically imidizing the resulting polyamic acid.

Here, the general formula (4) and the general formula (5)
The dicarboxylic acid anhydride represented by and the aromatic monoamine are conventionally known compounds. Specific dicarboxylic acid anhydrides, phthalic anhydride, 2,3-benzophenone dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4- Dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic acid anhydride, 3,4-biphenyl dicarboxylic acid anhydride, 2,3-dicarboxyphenyl phenyl sulfone anhydride, 3,4-dicarboxyphenyl phenyl sulfone anhydride Substance, 2,3-dicarboxyphenyl phenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalene dicarboxylic acid anhydride, 2,3-naphthalene dicarboxylic acid anhydride, 1,8- Naphthalene dicarboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, 1,9-anthracene dicarboxylic acid Anhydrous etc. are mentioned. These dicarboxylic acid anhydrides may be substituted with groups that are not reactive with amines or dicarboxylic acid anhydrides.

Among these dicarboxylic acid anhydrides, phthalic anhydride is most preferable from the viewpoint of properties and practical use of the polyimide. When phthalic anhydride is used, there is no problem in substituting a part of it with another dicarboxylic acid anhydride as long as the good physical properties of the polyimide are not impaired. The amount of the dicarboxylic acid anhydride used is 0.001 to 1.0 mol ratio per 1 mol of the aromatic diamine used, and the preferable amount is 0.01 to 0.5 mol.

When an aromatic monoamine is used,
Examples of aromatic monoamines include 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, m-nitroaniline, p-nitroaniline, o-aminophenol, m- Aminophenol, p-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenidine, m-phenidine, p-phenidine, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl,
4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether, 4-aminophenylphenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenylphenyl sulfide, 3- Aminophenylphenyl sulfide, 4-aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfone, 4-aminophenylphenyl sulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 2 -Amino-1-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol, 8-amino-
1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like can be mentioned. These aromatic monoamines may be substituted with groups that are not reactive with amines or dicarboxylic acid anhydrides. The amount of aromatic monoamine used is the amount of aromatic tetracarboxylic dianhydride 1 used.
The molar ratio is 0.001 to 1.0, and the preferable amount is 0.01 to 0.5 mol.

The method for producing the polyimide of the present invention includes:
Although any method including a known method that can produce a polyimide can be applied, it is particularly preferable to carry out the reaction in an organic solvent. The solvent used in such a reaction is preferably N, N-dimethylacetamide, but other usable solvents include, for example, N,
N-dimethylformamide, N, N-diethylacetamide,
N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1, 2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetra Examples thereof include methylurea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, m-cresylic acid, p-chlorophenol, anisole, benzene, toluene and xylene. These organic solvents may be used alone or in combination of two or more. Particularly, an amide solvent is preferable from the viewpoint of solution stability and utilization as workability.

Aromatic diamines, aromatic tetracarboxylic dianhydrides, aromatic dicarboxylic acid anhydrides or aromatic monoamines are added to an organic solvent by the method of the present invention, and the reaction is carried out as follows: After reacting a carboxylic acid dianhydride and an aromatic diamine, a method of continuing the reaction by adding an aromatic dicarboxylic acid anhydride or an aromatic monoamine, (b) adding an aromatic dicarboxylic acid anhydride to an aromatic diamine After the reaction, an aromatic tetracarboxylic acid dianhydride is added, and the reaction is further continued. (C) After the aromatic monoamine is added to the aromatic tetracarboxylic acid dianhydride and reacted, the aromatic diamine is added. Method of adding and continuing the reaction, (d) Simultaneous addition of aromatic tetracarboxylic dianhydride, aromatic diamine, aromatic dicarboxylic anhydride or aromatic monoamine It added, and a method of reacting the like, take no problem any addition method.

The reaction temperature is usually 250 ° C. or lower, preferably 50 ° C. or lower. The reaction pressure is not particularly limited and can be carried out at normal pressure. The reaction time varies depending on the type of raw material monomer such as aromatic tetracarboxylic dianhydride and aromatic diamine, the type of solvent and the reaction temperature, and 4 to 24 hours is usually sufficient. Further, the obtained polyamic acid is from 100 to
By heating to 400 ° C. for imidization or chemical imidization using an imidizing agent such as acetic anhydride, a polyimide having a repeating structural unit corresponding to a polyamic acid is obtained. Further, an aromatic diamine and an aromatic tetracarboxylic dianhydride, further, when the terminal of the polyimide is an aromatic ring, an aromatic dicarboxylic acid anhydride or an aromatic monoamine, was suspended or dissolved in an organic solvent. It is also possible to obtain the target polyimide by post-heating and performing imidization at the same time as the generation of the polyamic acid which is the precursor of the polyimide.

The polyimide used in the present invention by the above method (hereinafter, represented by the general formula (1) obtained by the above method,
A polyimide, a polyimide copolymer or a mixture having the repeating structural unit of (2) or (3), or a polymer molecule terminal of these polyimides which is unsubstituted or substituted with a group having no reactivity with an amine or a dicarboxylic acid anhydride. Polyimide used simply as "polyimide used in the present invention"
Can be obtained) is obtained. In the polyimide used in the present invention, the molecular weight is controlled by adjusting the molar ratio of the monomer components, as in the case of a normal polycondensation polymer,
A polyimide having the effects of the present invention is obtained. In the present invention, the molar ratio of the monomer component is 0.8 to 1.2 mol of the diamine compound based on 1 mol of the total amount of the tetracarboxylic dianhydride. This molar ratio is less than 0.8 or 1.
When it exceeds 2, a low molecular weight polyimide is obtained, which is not preferable as a polyimide for surface modification of a fibrous reinforcing material. The molar ratio of the diamine compound is preferably 0.9 to 1.1, and more preferably 0.95 to 1.05 with respect to 1 mol of the tetracarboxylic dianhydride.

The polyimide used in the present invention was heated and dissolved in a mixed solvent of 9 parts by weight of p-chlorophenol and 1 part by weight of phenol at a concentration of 0.5 g / dl, and then the logarithmic viscosity value measured at 35 ° C. Is preferably 0.30 dl / g or more, particularly 0.40 dl / g or more. If the logarithmic viscosity is less than 0.30 dl / g, the mechanical strength of the polyimide resin itself is insufficient, and even if such a polyimide is used in the composition of the present invention, the physical properties of the resin composition are also insufficient. .

The polyimide resin composition of the present invention contains the polyimide resin used in the present invention and 5 to 65 parts by weight, preferably 10 to 50 parts by weight, of the fibrous reinforcing material per 100 parts by weight of the resin. To do. If the content of the fibrous reinforcing material is less than 5 parts by weight, a sufficient reinforcing effect cannot be obtained. Further, if it exceeds 65 parts by weight, it is difficult to obtain a good molded product by melt molding such as injection molding. The polyimide resin composition of the present invention can be prepared by various methods. It can be prepared by adding a fibrous reinforcing material to a polyimide resin by various commonly known methods. For example, a mortar, a Henschel mixer, a drum blender, a tampler blender, a ball mill, a ribbon blender and the like of a polyimide resin powder and a fibrous reinforcing material are pre-kneaded, and then a melt mixer,
The most common method is to obtain a pellet or powder mixture using a hot roll or the like.

However, the production method of the present invention utilizing the solvent solubility characteristic of the polyimide used in the present invention is particularly preferable. That is, it can be manufactured through a pre-kneading state in which the solvent solubility, which is a characteristic of the polyimide used in the present invention, is utilized. In this method, a predetermined amount of the polyimide used in the present invention is dissolved in an organic solvent such as a halogenated hydrocarbon solvent, an amide solvent or a phenol solvent. A predetermined amount of fibrous reinforcing material is added to this solution and dispersed with stirring. After that, the fibrous reinforcing material is dispersed in this solution, the solution in which the polyimide is dissolved is discharged into the poor solvent under high-speed stirring to precipitate the polyimide, and the solvent is removed to remove the polyimide and the fibrous reinforcing material. A mixture is obtained in which the materials are uniformly mixed. The polyimide powder deposited by such an operation is in a pre-kneaded state in which the fibrous reinforcing material is uniformly dispersed. A melt-mixing machine, a hot roll, etc. can be used for this, and the polyimide resin composition of a pellet or a powder mixture can be obtained.

Specific examples of the solvent used in this method include dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, dibromomethane, tribromomethane, 1,2-dibromoethane, 1,2. 1,2-tribromoethane, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N -Methylcaprolactam, phenol, cresol, xylenol, halogenated phenol, halogenated cresol,
Examples thereof include dimethyl sulfoxide and dimethyl sulfone. In this method, the concentration of the polyimide solution is 5
˜50 wt%, and preferably 15 to 40 wt% from the viewpoint of mechanical viscosity in work. In addition, examples of the poor solvent for precipitating polyimide include methanol, ethanol, propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, and the like, and the amount used is 5 to 30 times the total composition weight, It is preferably 10 to 20 times.

The polyimide resin composition of the present invention thus obtained is molded by a known molding method such as an injection molding method, an extrusion molding method, a compression molding method or a rotational molding method, and put into practical use. Since the polyimide resin composition of the present invention has excellent fluidity, the injection molding method is most preferable from the viewpoint of work efficiency. The injection-molded article obtained from the polyimide resin composition of the present invention can be molded into any shape by changing the shape of the mold. In particular, it is expected to be applied to automobile parts that require excellent dynamic fatigue characteristics, such as valve lifters and impellers.

Further, when the polyimide resin composition of the present invention is subjected to melt molding, other thermoplastic resin resins such as polyethylene, polypropylene, polycarbonate, polyarylate and polyamide are used within a range not impairing the object of the present invention. , Polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyphenyl sulfide, polyamide imide, polyether imide, modified polyenylene oxide, polyimide other than the present invention, etc. in an appropriate amount according to the purpose of the present invention. You may mix. Further, the following fillers and the like used for ordinary resin compositions may be used within a range that does not impair the object of the present invention. That is, graphite, carborundum,
Wear resistance improver such as silica powder, molybdenum disulfide, fluorine resin, flame retardant improver such as antimony trioxide, magnesium carbonate, calcium carbonate, electrical property improver such as clay and mica, asbestos, silica, Cracking resistance improver such as graphite, barium sulfate, silica, acid resistance improver such as calcium metasilicate, iron powder,
Thermal conductivity improver such as zinc powder, aluminum powder, copper powder,
Other examples include glass beads, glass spheres, talc, diatomaceous earth, alumina, silasbaln, hydrated alumina, metal oxides, colorants and the like.

The polyimide-based composite of the present invention, particularly the laminated composite, is a composite composed of a base material composed of a fibrous reinforcing material and the polyimide used in the present invention. This polyimide-based composite of the present invention is obtained by impregnating a solution of the polyimide used in the present invention in an organic solvent into a fibrous reinforcing material, that is, a substrate composed of the fibrous reinforcing material, and then removing the solvent. It can be obtained by heating and pressing at a temperature above the temperature at which the polyimide flows, and molding. The fibrous base material impregnated with the polyimide used in the present invention may be a single layer or may be laminated in two or more layers.

Examples of the organic solvent that can be used to dissolve the polyimide include general-purpose halogen-based hydrocarbon solvents, amide-based solvents and phenol-based solvents. Specific examples include various solvents that can be used for producing the polyimide resin composition of the present invention. Among these solvents, N, N-dimethylformamide and N, N-dimethylacetamide are particularly preferable in terms of properties and practical use. Further, these solvents may be used alone or in combination of two or more. The concentration of the polyimide solution used is not particularly limited as long as it is within the range of the solubility of polyimide, but from the workability at the time of coating and impregnating the fibrous reinforcing material, 1 to 50 wt% is preferable. The mechanical viscosity of the polyimide solution at this time is 10 to 10
Although it is 10,000 centipoise, it is 500 from workability.
~ 50,000 centipoise is desirable. Further, the melting temperature is not particularly limited, and the pressure may be normal pressure.
As the fibrous reinforcing material used, any fibrous reinforcing material used as a base material such as a laminated plate can be applied.
Examples thereof include glass fiber, carbon fiber, aromatic polyamide fiber, silicon carbide fiber, boron fiber, and the like, woven cloth and nonwoven cloth thereof, and paper.

The method of impregnating these fibrous reinforcing materials with a polyimide solution is a method in which a base material composed of fibrous reinforcing materials is treated with a polyimide solution and a desired amount of polyimide is uniformly applied to the base material. I wish I had it. Usually, a method of impregnating a base material with a polyimide solution or applying a polyimide solution to the base material is often used. The amount of polyimide applied to the fibrous reinforcing material is 5 to 50% by weight, preferably 10 to 30% by weight, based on the fibrous reinforcing material. The polyimide solution may be applied to the fibrous reinforcing material by any method, for example, using a bar coater or a doctor blade.

In the present application, the state in which the polyimide solution is applied to the substrate is treated as substantially the same even in coating or impregnation, and "impregnation" means "coating or impregnation". Then, the solvent may be removed from the fibrous reinforcing material coated with the polyimide solution at a temperature not lower than the boiling point of the solvent used in a nitrogen stream or an air stream. The thus obtained polyimide-impregnated fibrous reinforcing material (prepreg sheet) is formed by stacking one or two or more sheets, and heating and pressing at a temperature above the temperature at which the polyimide flows to obtain a polyimide composite. You can
Molding temperature Temperature and pressure are 250 ° C-450 ° C, 1-
1000 kg / cm ² , preferably 300-40
It is 0 ° C. and 10 to 500 kg / cm ² .

In producing the polyimide composite of the present invention, other resins may be added within the range that does not impair the solubility, melt fluidity and adhesiveness of the polyimide used in the present invention. For example, there are various thermoplastic resins that can be blended in the composition of the present invention, thermosetting resins such as phenolic resins and bismaleimide.
Furthermore, various fillers and the like that can be used in the above-described polyimide resin composition of the present invention may be used within a range that does not impair the object of the invention.

Further, the fibrous reinforcing material of which the surface is modified with the polyimide used in the present invention of the present invention, the polyimide used in the present invention can effectively treat the surface of the fibrous reinforcing material. The obtained surface-modified fibrous reinforcing material,
It is based on the fact that it has excellent applicability as a fibrous reinforcing material for resins, particularly polyimide resins. Therefore, the polyimide used in the present invention can be applied to the surface modification of the fibrous reinforcing material as a powdery polyimide or an organic solvent thereof. It is also possible to obtain a fibrous reinforcing material which is imidized and surface-modified by applying it in the state of polyamic acid which is a precursor of polyimide or a mixture thereof with polyimide.

The surface-modified fibrous reinforcing material of the present invention is obtained by applying the organic solvent solution of the polyimide used in the present invention to the surface of the fibrous reinforcing material and removing the solvent. Preferably, 3,3'-diamino-4,4'-diphenoxybenzophenone and / or 1,3-bis (3-amino-4-
(Phenoxybenzoyl) benzene and pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, bis (dicarboxyphenyl) Sulfone dianhydride, bis [(dicarboxyphenyl) phenyl] propane dianhydride, bis (dicarboxyphenyl) propane dianhydride, bis (dicarboxyphenoxy) benzene dianhydride, bis (dicarboxyphenyl) hexafluoropropane 100-250 with at least one tetracarboxylic acid dianhydride selected from dianhydride in an organic solvent
A polyimide obtained by heating to ℃ is often used.

The fibrous reinforcing material used in the present invention includes glass fiber, carbon fiber, aromatic polyamide fiber, silicon carbide fiber, boron fiber and the like. Particularly preferably used carbon fiber is acrylic type, rayon type or lignin type. , Pitch-based, and the like. The form of the carbon fiber is not particularly limited, and any of chopped strand, tow (roving), woven fabric, and the like may be used. The method for obtaining the surface-modified fibrous reinforcing material of the present invention is as follows. (1) A method of modifying a surface of a fibrous reinforcing material by applying a modifier solution obtained by dissolving the polyimide used in the present invention and a precursor thereof in an organic solvent to the surface of the fibrous reinforcing material and performing thermal imidization and desolvation. ) A method of applying a polyamic acid, which is a precursor of a polyimide used in the present invention, to the surface of a fibrous reinforcing material, and modifying the surface by heat imidization on carbon fiber,
(3) A method of modifying the surface by applying a modifier solution in which the polyimide used in the present invention is dissolved in an organic solvent to the surface of the fibrous reinforcing material and removing the solvent, (4) the polyimide used in the present invention It is roughly classified into a method of heating and melting on the surface of the carbon fiber to modify the surface of the carbon fiber. Among these methods, the method (1) or (3) is the most general and useful method.

Generally, the coating amount of the polyimide used in the present invention as a surface modifier on the fibrous reinforcing material is preferably 0.5 to 10 parts by weight, and 0.5 part by weight with respect to 100 parts by weight of the fibrous reinforcing material. If it is less than 10 parts by weight, sufficient effects cannot be obtained, and if it exceeds 10 parts by weight, further improvement in physical properties cannot be obtained. It is particularly preferably 2 to 5 parts by weight. Incidentally, when surface-modifying the fibrous reinforcing material using the polyimide used in the present invention, another surface treatment of the fibrous reinforcing material in advance means that the polyimide and the fibrous reinforcing material used in the present invention are It is preferable because it enhances the adhesiveness. Other surface treatment methods are not particularly limited, and any general surface treatment method for fibrous reinforcing materials can be applied. For example, chemical oxidation (nitric acid, permanganic acid / sulfuric acid, etc.), liquid-phase oxidation such as electrolytic oxidation, heating in a gas phase (air, oxygen, ozone, etc.), plasma treatment, gas-phase oxidation such as corona discharge Etc.

After the surface of the fibrous reinforcing material is treated with the polyimide used in the present invention, it may be further heat treated. The heating temperature is 300 to 500 ° C., preferably 300 to 450 ° C. If the heating temperature is lower than 300 ° C., the effect of the heat treatment cannot be obtained, and if it exceeds 500 ° C., the surface modifier may be thermally decomposed. Therefore, it is not preferable.
The heating time is usually 0.1 to 30 hours. Surface-modified with the polyimide resin obtained as described above, for example, roving of carbon fiber is cut into a chopped strand by cutting to a length of 1 to 150 mm, and then a desired heat-resistant thermoplastic resin, for example, polyimide Pellets can be formed by dry blending with resin, polyether ether ketone, polyether sulfone, etc., extruding while melting and kneading in an extruder, and then cutting into a predetermined length. The pellet can be obtained by a known molding method, that is, compression molding, injection molding, and extrusion molding to obtain a desired molded body.

Further, the surface-modified carbon fibers may be aligned in one direction and then impregnated with a heat-resistant thermoplastic resin by a usual method to obtain a prepreg. To manufacture such a prepreg, for example, Japanese Patent Laid-Open No. 1-12
The melt impregnation method disclosed in Japanese Patent No. 1363 is exemplified. The prepreg thus obtained may then be cut into a certain length, laminated so that the fibers are oriented in a predetermined direction, and then a molded body may be obtained using a usual method such as hot pressing. it can. Further, the surface-modified fibrous reinforcing material of the present invention is not particularly limited to the thermoplastic resin,
It is applicable to all currently known thermoplastic resins. Specifically, polycarbonate resin, polyamide resin, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyether imide,
Examples include thermoplastic imide resins, polyether sulfones, polyether ether ketones, polyether ketones, and the like.

The present invention will be described in detail below with reference to synthesis examples, examples and comparative examples. The physical properties of polyimide were measured by the following methods. Tg, Tc, Tm: DSC (Shimadzu DE-40 series,
Measured by DSC-41M). 5% weight loss temperature: DTG in the air (Shimadzu DT-40
Series, DTG-40M). Logarithmic viscosity (ηinh): p-chlorophenol / phenol (weight ratio 9/1) 0.5g of polyimide powder in a mixed solvent /
Measured at 35 ° C after dissolution at a concentration of 100 ml. Injection molded product tensile test: Tensile test is ASTM D3039
It was measured based on. The measurement conditions are room temperature (18-25
℃) Moisture absorption rate 0.2% or less (RT / DRY) atmosphere and high temperature (177 ℃ and 204 ℃) moisture absorption rate 0.6 ± 0.1%
The atmosphere is (HOT / WET). Water absorption rate: Measured based on JIS K-7209. Mechanical viscosity: Measured at room temperature with an E-type viscometer manufactured by Toki Sangyo Co., Ltd. Melting start temperature: Shimadzu Koka type flow tester (CFT50
0A), load 100 kg, temperature rising rate 5 ° C / min
Measured by. Melt viscosity: Shimadzu Koka type flow tester (CFT500
Measured under A) with a load of 100 kg. Adhesion test (tensile shear adhesion): Each polyimide powder was suspended in ethanol to form a paste, and then two cold-rolled steel sheets (JIS G-3141 SPCC.SD. size 1.6 × 25 × 100 mm) were used. Apply and heat press 35
Bonding was performed at 0 ° C. and 300 psi. The tensile shear strength of the adhesive was measured according to JIS K-6848. Flexural strength, flexural modulus: AS at 25 ℃ and 200 ℃
Measured according to TM D-790.

Synthesis Example 1 396.5 g (1.0 mol) of 3,3'-diamino-4,4'-diphenoxybenzophenone and 3,3 'were placed in a container equipped with a stirrer, a reflux condenser, and a nitrogen introducing tube. 31,4'-benzophenone tetracarboxylic acid dianhydride 315.8 g (0.9
8 mol), phthalic anhydride 5.92 g (0.04 mo)
l), γ-picoline 14.0 g, m-cresol 284
9.2 g was charged and the temperature was raised to 150 ° C. with stirring under a nitrogen atmosphere. After that, when the reaction was carried out at 150 ° C. for 4 hours, it was confirmed that about 30 ml of water was distilled off. After completion of the reaction, the mixture was cooled to room temperature, discharged into about 20 l of methyl ethyl ketone, and then the polyimide powder was filtered off.
After washing this polyimide powder with methyl ethyl ketone,
It was dried in air at 50 ° C. for 24 hours and in nitrogen at 230 ° C. for 4 hours to obtain 670 g of polyimide powder (yield 98.2%).
The polyimide powder thus obtained has an inherent viscosity of 0.56 dl.
/ G. The glass transition temperature of this polyimide powder was 246 ° C, and the 5% weight loss temperature was 524 ° C.

Synthetic Examples 2 to 12 Using the aromatic diamine and aromatic tetracarboxylic dianhydride shown in Table 1, each polyimide powder was synthesized in the same manner as in Synthetic Example 1. Table 1 shows aromatic diamine, tetracarboxylic dianhydride, yield, logarithmic viscosity of polyimide powder, glass transition temperature and 5% weight loss temperature.

Synthesis Example 13 A polyimide powder was obtained in exactly the same manner as in Synthesis Example 1 except that phthalic anhydride was not used (yield 96.6%). In Table 1,
The yield, the logarithmic viscosity of the polyimide powder, the glass transition temperature and the 5% weight loss temperature are shown.

[0054]

[Table 1] * 1 3,3'-Diamino-4,4'-diphenoxybenzophenone * 2 3,3'-Diamino-4-phenoxybenzophenone * 3 3,4'-Diamino-4-phenoxybenzophenone * 4 3,3'- Diamino-4,4'-dibiphenoxybenzophenone * 5 3,3'-diamino-4-biphenoxybenzophenone * 6 3,4'-diamino-4-biphenoxybenzophenone * 7 1,3-bis (3-amino- 4-phenoxybenzoyl) benzene * 8 1,3-bis (3-amino-4-biphenoxybenzoyl)
Benzene * 9 3,3'-diaminobenzophenone * 10 1,3-bis (3-aminobenzoyl) benzene * 11 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride * 12 Pyromellitic dianhydride Stuff

Example 1 The polyimide obtained in Synthesis Example 1 was dissolved in N, N-dimethylformamide (DMF) at a concentration of about 30 wt%, and then 40 parts by weight of carbon fiber was added to 100 parts by weight of polyimide powder. (HTA-C6 manufactured by Toho Rayon Co., Ltd.) was dispersed under stirring. This polyimide resin composition solution was discharged into methyl ethyl ketone in an amount of about 15 times the weight of the polyimide powder under high speed stirring. The obtained resin composition was treated under a nitrogen stream to 200
The polyimide / carbon fiber mixture was dried at 4 ° C. for about 4 hours. The obtained resin mixture was melt-kneaded by a single-screw extruder having a diameter of 30 mm, and then the strand was air-cooled and cut to obtain pellets. Using the pellets obtained, an Aburg injection molding machine (injection pressure 500 kg / cm ² , cylinder temperature 4
A JIS No. 1 dumbbell test piece was obtained at 10 ° C. and a mold temperature of 180 ° C.). The water absorption of the resin composition obtained here was 0.73%. As described above, the tensile test of the test piece was performed at room temperature / drying (hereinafter referred to as RT / DRY) and high temperature (177 ° C, 204 ° C) / under moisture absorption (hereinafter referred to as HOT / WET). Table 2 shows the results. From this result, it is understood that the tensile strength in HOT / WET is maintained at about 80% of the tensile strength in RT / DRY.

Examples 2 to 11 Test pieces were prepared in the same manner as in Example 1 using the polyimide powders obtained in Synthesis Examples 2 to 10 and 13. The same tensile test as in Example 1 was performed using the obtained test piece.
The results are shown in Table 2 together with the results of water absorption. From this result, the tensile strength in HOT / WET is RT / DRY.
It can be seen that the tensile strength is maintained at about 80 to 90%.

Comparative Examples 1 and 2 The polyimide powders obtained in Synthesis Examples 11 and 12 were DMF.
Since it is insoluble in, a resin blend having the same ratio as in Example 1 was prepared by using a drum blender mixer (manufactured by Kawada Manufacturing Co., Ltd.).
Below, a test piece was prepared in the same manner as in Example 1, and the same tensile test was performed. The results are shown in Table 2 together with the results of water absorption.
Shown in From the results, the polyimides obtained in Examples 11 and 12 have a tensile strength in HOT · WET of RT.
-It can be seen that it is about 60% of the tensile strength in DRY.

Comparative Examples 3 and 4 With respect to the polyimide obtained in Synthesis Example 1, resin composition test pieces outside the composition range of the present invention were prepared, and the same tensile test as in the above Examples was conducted. The results are shown in Table 2. Compared to the case where the carbon fiber is used within the range of the present invention, the tensile strength is reduced when used outside the range of small use amount, and the injection molding is impossible when used outside the range of large use amount. It was

[0059]

[Table 2] * 1 RT / DRY: 18-25 ° C, moisture absorption rate 0.2%
Below 177 ℃ · WET: 177 ℃ · water absorption rate 0.6 ± 0.1
% 204 ℃ ・ WET: 204 ℃ ・ Moisture absorption rate 0.6 ± 0.1
%

Example 12 A polyimide in which the diamine component was 3,3'-diamino-5,5'-phenoxybenzophenone and the acid anhydride component was 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride ( ηinh =
0.45 dl / g, Tg = 245 ° C., flow starting temperature 325
° C., a melt viscosity 13500 poise 380 ° C., the tensile shear bond strength 332kg / mm ²⁾ 20g, was dissolved at room temperature under a stream of nitrogen in N, N- dimethylformamide 80 g. The mechanical viscosity of the obtained polyimide solution was 5000 centipoise. This polyimide solution was applied and impregnated on a carbon fiber woven cloth (Torayca T300 KPL). The carbon fiber woven cloth impregnated with the polyimide solution is about 2 at 170 ° C in nitrogen.
It was left for a time to remove the solvent. The polyimide impregnation rate in this polyimide impregnated carbon fiber woven fabric (prepreg sheet) was about 10 wt%. Eight prepreg sheets were laminated and thermocompressed at a temperature of 350 ° C. and a load of 50 kg / cm ² for 30 minutes to obtain a polyimide / carbon fiber composite having a thickness of about 2.5 mm. When the cut surface of the obtained composite was observed with an optical microscope, defects such as voids were not observed. In addition, the bending strength and bending elastic modulus of the composite were 89 kg / mm ² and 7400 kg / at the measurement temperature of 25 ° C.
mm ² , 81 kg / mm ² and 6600 at 200 ° C
It was kg / mm ² .

Examples 13 to 22 In the same manner as in Example 12, polyimide-impregnated carbon fiber composites were prepared using soluble polyimides obtained from diamine components and acid anhydride components as shown in Table 3. Table 3 shows diamine component, acid anhydride component, logarithmic viscosity of polyimide powder, glass transition temperature (Tg), flow starting temperature, 380
Melt viscosity at ℃, tensile shear adhesive strength, mechanical viscosity of polyimide solution, presence or absence of void defect of composite, flexural strength,
The flexural modulus is shown together with the results of Example 12.

Comparative Example 5 A polyimide having a diamine component of 3,3′-diaminobenzophenone and an acid anhydride of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (ηinh = 0.44 dl / g, The glass transition temperature of 240 ° C.) was tried to be dissolved in N, N-dimethylformamide at a concentration of 20 wt% as in Example 12, but it could not be dissolved at all, and therefore the solution impregnation into the fibrous reinforcing material was impossible. It was

Comparative Example 6 Polyimide powder (melting starting temperature 32
A carbon fiber woven fabric similar to that in Example 12 was heated and pressed (temperature: 350) with a melt viscosity of 12,000 poise at 5 ° C. and 380 ° C.
Melt impregnation was carried out at a temperature of 50 ° C. and a load of 50 kg / mm ² . Eight sheets of the obtained prepreg sheets were laminated in the same manner as in Example 12 to obtain a polyimide / carbon fiber composite having a thickness of about 2.5 mm. When the cut surface of the obtained composite was observed with an optical microscope, voids were observed. Also, the bending strength of the composite,
Flexural modulus is 63 kg / mm ² , 5000 k at 25 ° C
It was g / mm ² , and it was found that the mechanical properties were inferior to those of the polyimide / carbon fiber composites of the above examples.

Comparative Example 7 A polyimide having a diamine component of 1,3-bis (3-aminobenzoyl) benzene and an acid anhydride component of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (ηinh = 0.4
2 dl / g, glass transition temperature 228 ° C.) was tried to be dissolved in N, N-dimethylformamide at a concentration of 20 wt% as in Example 12, but it was completely insoluble and therefore the solution impregnation into the fibrous reinforcing material was impossible. It was impossible.

Comparative Example 8 Polyimide powder (melting starting temperature 31
A carbon fiber woven fabric similar to that used in Example 12 was heated and pressed at a melt viscosity of 8200 poise at 0 ° C. and 380 ° C. (temperature: 350).
Melt impregnation was carried out at a temperature of 50 ° C. and a load of 50 kg / mm ² . Eight sheets of the obtained prepreg sheets were laminated in the same manner as in Example 12 to obtain a polyimide / carbon fiber composite having a thickness of about 2.5 mm. When the cut surface of the obtained composite was observed with an optical microscope, voids were observed. Also, the bending strength of the composite,
Flexural modulus at 25 ° C is 57 kg / mm ² , 4800 k
It was g / mm ² , and it was found that the mechanical properties were inferior to those of the polyimide / carbon fiber composites of the above examples.

Comparative Example 9 Ultem 1000 (manufactured by General Electric Co., ηinh = 0.60 dl / g) which is a commercially available polyetherimide
In exactly the same manner as in Example 12, the carbon fiber woven fabric was solution-impregnated. However, it was found that this polyetherimide had a low glass transition temperature of 216 ° C. and was inferior in heat resistance to the polyimides of the previous examples. Also, the mechanical properties are inferior to those of the polyimides of the previous examples. The results of this comparative example are shown in Table 3 together with the above-mentioned examples.

[0067]

[Table 3] * 1 Flow start temperature * 2 Tensile shear adhesive strength (measured at 23 ° C, 50% humidity) * 3 3,3'-diamino-4,4'-diphenoxybenzophenone * 4 3,3 ', 4,4'- Benzophenone tetracarboxylic dianhydride * 5 3,3'-Diamino-4-phenoxybenzophenone * 6 3,4'-Diamino-4-phenoxybenzophenone * 7 3,3'-Diamino-4,4'-dibiphenoxybenzophenone * 8 3,3'-Diamino-4-biphenoxybenzophenone * 9 3,4'-Diamino-4-biphenoxybenzophenone * 10 3,3'-Diamino-4,4'-dimethoxybenzophenone * 11 3,3 ' -Diamino-4-methoxybenzophenone * 12 3,4'-Diamino-4-methoxybenzophenone * 13 1,3-bis (3-amino-4-phenoxy) benzene * 14 1,3-bis (3-amino-4 -Biphenoxy) benzene

Example 23 A container equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube was placed in a container.
3'-diamino-4,4'-diphenoxybenzophenone 39.
6 g (0.10 mol), N, N-dimethylacetamide 23
5 g was charged and, under a nitrogen atmosphere, 31.2 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (0.
(97 mol) was added in portions while paying attention to increase in solution temperature, and the mixture was stirred at room temperature for about 20 hours. The polyamic acid solution thus obtained was further treated with N, N-dimethylacetamide.
Diluted to wt%. Next, an acrylic carbon fiber bundle (trade name HTA, manufactured by Toho Rayon Co., Ltd., number of Ferment 12
000 pieces) is immersed in the above polyamic acid solution at a speed of 60 m / min, dried by heating at 130 ° C. for 60 minutes, and then heated in a nitrogen atmosphere at 260 ° C. for 1 hour for polyimidization, and the polyimide resin is 3% by weight. A carbon fiber having the surface of was obtained. Then, the obtained carbon fiber was cut into a length of 3 mm to form a chopped strand, and 30 wt% of the strand was dry-blended with a thermoplastic polyimide resin AURUM # 450 (Mitsui Toatsu Chemical Co., Inc .: trademark) 70 wt%,
A 40 mm diameter extruder was used to carry out extrusion while melting and kneading at an extrusion temperature of 400 ° C. to obtain a uniform blended pellet. Then, using the obtained compounded pellets, a dumbbell test piece was prepared with a usual injection molding machine under the conditions of a cylinder temperature of 400 ° C. and a mold temperature of 210 ° C., and a pulling speed of 5 m.
When the tensile strength was measured at m / min, it was 3350 kg / cm.
^{Was 2} .

Example 24 In addition to Example 23, 0.888 g of phthalic anhydride (0.
A dumbbell test piece was prepared in the same manner except that (006 mol) was added, and the tensile speed was measured to be 3400.
It was kg / cm ² .

Example 25 A container equipped with a stirrer, a reflux condenser, and a nitrogen introducing tube was placed in a container.
3'-diamino-4,4'-diphenoxybenzophenone 39.
6 g (0.10 mol), 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride 31.2 g (0.097 mol),
Phthalic anhydride 0.888 g (0.006 mol), γ-picoline 0.93 g, N-methyl-2-pyrrolidone 184
g and 36 g of xylene were added, the mixture was heated to 180 ° C. under an atmosphere, and stirring was continued at this temperature for 6 hours. During this period, it was confirmed that about 3 cc of water had been distilled off. The polyimide solution thus obtained was further treated with N-methyl-2-pyrrolidone
Diluted to wt%. Next, an acrylic carbon fiber bundle (trade name HTA, manufactured by Toho Rayon Co., Ltd., number of Ferment 12
000 pieces) were immersed in the above polyimide solution at a speed of 60 m / min, and dried by heating at 130 ° C. for 60 minutes and 200 ° C. for 60 minutes to obtain carbon fibers having 3% by weight of polyimide resin on the surface. Then, the obtained carbon fiber was cut into a length of 3 mm to form a chopped strand, and 30 wt% of the strand was dry-blended with a thermoplastic polyimide resin AURUM # 450 (Mitsui Toatsu Chemical Co., Inc .: trademark) 70 wt%,
A 40 mm diameter extruder was used to carry out extrusion while melting and kneading at an extrusion temperature of 400 ° C. to obtain a uniform blended pellet. Then, using the obtained compounded pellets, a dumbbell test piece was prepared with a usual injection molding machine under the conditions of a cylinder temperature of 400 ° C. and a mold temperature of 210 ° C., and a pulling speed of 5 m.
When the tensile strength was measured at m / min, it was 3330 kg / cm.
^{Was 2} .

Examples 26 to 32 Dumbbell test pieces were prepared using the carbon fiber surface modifiers in which the kind of tetracarboxylic dianhydride in Example 25 was changed, and the tensile strength was measured. The results are summarized in Table 4.

[0072]

[Table 4] * 1 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride * 2 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride * 3 3,3 ', 4,4'- Diphenyl sulfone tetracarboxylic dianhydride * 4 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride * 5 2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride Substance * 6 2,2-bis (3,4-dicarboxyphenoxy) phenyl
-1,1,1,3,3,3-Hexafluoropropane dianhydride * 7 Pyromellitic dianhydride

Comparative Example 10 Example except that acrylic carbon fiber surface-modified with epoxy resin (trade name HTA, manufactured by Toho Rayon Co., Ltd.) was used in place of the polyimide-modified carbon fiber used in the present invention. When treated in the same manner as in No. 23 and measured for tensile strength, it was 2300 kg / cm ² .

Comparative Example 11 Instead of the carbon fiber modified with polyimide used in the present invention, an acrylic carbon fiber surface-modified with polyetherimide (Ultem 1000 manufactured by Engineering Plastics Co., Ltd., manufactured by Toho Rayon Co., Ltd., The tensile strength was measured in the same manner as in Example 25 except that (trade name: HTA) was used, and the tensile strength was 2250 kg / cm ² .

[0075]

EFFECTS OF THE INVENTION The polyimide resin composition of the present invention, in addition to various physical properties such as high heat resistance inherent in the polyimide resin, maintains its high mechanical properties even under high temperature and high humidity, and also has hygroscopicity and water absorption. The sex is extremely small. In addition, various properties such as mechanical properties also have physical properties more than before. Also in the manufacturing method thereof, the polyimide / reinforcing material can be mixed in the solution by utilizing the solvent solubility of the present polyimide itself. Further, the polyimide composite of the present invention, compared with the solution impregnation method of the polyamic acid which is the precursor of the conventional non-thermoplastic polyimide, or the melt impregnation method of the thermoplastic polyimide, without the occurrence of structural defects such as voids. Since the polyimide used in the present invention is excellent in heat resistance and adhesive strength, the obtained polyimide composite is excellent in heat resistance and mechanical properties.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masaru Asanuma 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Masaji Tamai 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chem. Co., Ltd. (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (11)

[Claims] 1. A compound represented by the general formula (1): [Wherein, m and n are each independently an integer of 0 or 1, and R is (Here, R ₁ , R ₂ , R ₃ , and R ₄ are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkenyl group, an aralkyl group, or 1 to 5 carbon atoms.
Represents an alkoxy group of R ₅ , R ₆ , R ₇ are hydrogen atoms,
C1-C8 alkyl, aryl, alkenyl, aralkyl or C1-C10 oxygen 1-3.
Of ω-alkyloxy oligo (alkyleneoxy) alkyl group), Ar has 6 to 27 carbon atoms,
And a monovalent aromatic group, a condensed polycyclic aromatic group, or a tetravalent group that is a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member). A polyimide resin composition comprising a polyimide containing at least one of the repeating structural units as an essential structural unit, and a fibrous reinforcing material. 2. A polyimide is represented by the general formula (2): (In the formula, m and n are each independently an integer of 0 or 1, and R is (Here, R ₁ , R ₂ , R ₃ , and R ₄ are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkenyl group, an aralkyl group, or 1 to 5 carbon atoms.
Represents an alkoxy group of R ₅ , R ₆ , R ₇ are hydrogen atoms,
C1-C8 alkyl, aryl, alkenyl, aralkyl or C1-C10 oxygen 1-3.
Of ω-alkyloxy oligo (alkyleneoxy) alkyl group), Ar has 6 to 27 carbon atoms,
And a monovalent aromatic group, a condensed polycyclic aromatic group, or a tetravalent group that is a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member). Repeating structural unit and general formula (3): [Wherein, m and n are each independently an integer of 0 or 1, and R is (Here, R ₁ , R ₂ , R ₃ , and R ₄ are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkenyl group, an aralkyl group, or 1 to 5 carbon atoms.
Represents an alkoxy group of R ₅ , R ₆ , R ₇ are hydrogen atoms,
C1-C8 alkyl, aryl, alkenyl, aralkyl or C1-C10 oxygen 1-3.
Of ω-alkyloxy oligo (alkyleneoxy) alkyl group), Ar has 6 to 27 carbon atoms,
And a monovalent aromatic group, a condensed polycyclic aromatic group, or a tetravalent group that is a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member). The polyimide resin composition according to claim 1, which is a polyimide copolymer containing a repeating structural unit. 3. The polyimide according to claim 1, wherein the polyimide is a mixture of a polyimide having a structural unit represented by the general formula (2) and a polyimide having a structural unit represented by the general formula (3). -Based resin composition. 4. A polyimide represented by the following general formula (4): (In the formula, Z ₁ has 6 to 15 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are directly or cross-linked to each other. An aromatic dicarboxylic acid anhydride represented by a divalent group which is an aromatic group) and / or general formula (5) Z ₂ —NH ₂ (5) (wherein Z ₂ has 6 carbon atoms). Is a monovalent 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 bridging member. The polyimide according to claims 1 to 3, which is obtained by reacting in the coexistence of an aromatic monoamine represented by (4) and has a polymer molecule terminal blocked or a polymer molecule terminal blocked. Resin composition. 5. The polyimide resin composition according to claim 1, wherein the fibrous reinforcing material is carbon fiber, glass fiber, aromatic polyamide fiber and / or potassium titanate fiber. 6. The polyimide resin composition according to claim 1, wherein the fibrous reinforcing material is contained in an amount of 0.5 to 65 parts by weight based on 100 parts by weight of the polyimide represented by the general formula (1). 7. After dissolving the polyimide in an organic solvent,
The method for producing a polyimide resin composition according to claim 1, wherein the fibrous reinforcing material is mixed and then the solvent is removed. 8. The organic solvent is a halogenated hydrocarbon solvent,
The method for producing a polyimide resin composition according to claim 7, which is an amide solvent and / or a phenol solvent. 9. An injection-molded article obtained from the polyimide resin composition according to claim 1. 10. A solution obtained by dissolving the polyimide represented by the general formula (1) in an organic solvent is impregnated into a fibrous reinforcing material, and then the solvent is removed, followed by heating to a temperature at which the polyimide flows or higher, A polyimide-based laminated composite obtained by pressurizing and molding. 11. A fibrous reinforcing material whose surface is modified with a polyimide represented by the general formula (1).