JP2001131147A - Bisimide compounds, polyimide resin composition using the compounds and carbon fiber-reinforced polyimide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide-based resin composition which has melt flowability and an excellent KAOYUSEI in addition to the original heat resistance of the polyimide and is used for molding, to provide a polyimide O-based resin composition having more excellent mechanical strengths, and to provide a new bisimide compound useful as an aromatic bisimide compound in the resin compositions. SOLUTION: A polyimide resin composition obtained by including a polyimide resin in an aromatic bisimide compound, and a carbon fiber-reinforced polyimide- based resin composition obtained by coating the surfaces of carbon fibers with the aromatic bisimide compounds and then including the carbon fibers in the polyimide resin. Desired effects can be imparted to the compositions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a bisimide compound, a polyimide resin composition containing these compounds,
And a carbon fiber-reinforced polyimide resin composition containing a carbon fiber coated with these compounds on the surface.

[0002]

2. Description of the Related Art In recent years, in the fields of electronics, aerospace equipment, transportation equipment and the like, materials having better high-temperature characteristics have been demanded in order to improve the performance and reduce the weight of various industrial materials. Among these materials, polyimide has mechanical strength, dimensional stability, flame retardancy, electrical insulation, etc., in addition to its high heat resistance, and is used for electrical and electronic equipment, aerospace equipment, transportation equipment, etc. Although widely used as a material in the field, high molecular weight polyimide resins generally have a high softening temperature and are difficult to use because they are insoluble in most organic solvents.

[0003] A thermoplastic polyimide resin represented by Ultem (registered trademark of GE) is superior to general-purpose engineering plastics in heat resistance and mechanical strength. Widely studied for applications such as equipment, machinery, and automobiles. Recently, with the development of technology, development of a new thermoplastic polyimide resin having heat resistance and mechanical properties higher than Ultem has been required.

For example, a method for producing a polyimide resin obtained by reacting ether diamine with tetracarboxylic dianhydride is disclosed in US Pat. No. 4,847,349, and 3,3′-diaminobenzophenone is disclosed in US Pat. A method for producing a polyimide resin obtained by reacting with tetracarboxylic dianhydride has also been proposed by JP-A-2-018419 and the like. Each of them provides a novel polyimide resin having heat resistance and mechanical properties that have not been obtained in the past.

However, when compared with ordinary engineering plastics represented by polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polysulfone, polyphenylene sulfide, etc., the above-mentioned polyimides are far superior in heat resistance and other properties. On the other hand, when the molecular weight is large, the melt fluidity is reduced, and the moldability is still inferior to those resins.

[0006] In order to further enhance the properties of these polyimide resins, particularly the mechanical strength, a fibrous reinforcement, particularly carbon fibers, is generally blended. However, since carbon fibers are often used in carbon fiber reinforced plastics having an epoxy resin as a matrix, an epoxy resin is usually used as a sizing agent for carbon fibers. Therefore, when a thermosetting resin such as an epoxy resin is a matrix, an epoxy resin sizing agent is effective, but adhesion to polyimide resin is poor, and a resin composition having good mechanical strength cannot be obtained. .

Further, for example, Japanese Patent Application Laid-Open No. 53-106752
As disclosed in Japanese Patent Application Publication, there is also a method of using a polyamide resin as a sizing agent for carbon fibers, but generally a high temperature of at least 300 ° C. is required for molding of a polyimide resin. Pyrolysis to form voids,
There are problems such as a decrease in weld strength. further,
As disclosed in Japanese Patent Application Laid-Open No. 56-120730, there is a method using carbon fibers bundled with an aromatic polysulfone resin, but the improvement in mechanical strength is small, and the required characteristics have not been sufficiently satisfied. .

[0008]

An object of the present invention is to obtain a compound having excellent workability in addition to excellent heat resistance. Another object of the present invention is to provide a polyimide resin composition for molding which is extremely excellent in terms of fluidity during melting without impairing the inherent properties of polyimide.

Another object of the present invention is to provide a polyimide resin composition having excellent mechanical strength.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a polyimide resin composition containing an aromatic bisimide compound in a polyimide resin has a melt fluidity and a molding process. Polyimide resin compositions containing carbon fibers coated with these aromatic bisimide compounds on the surface have excellent mechanical strength and have excellent mechanical strength, and new bisimides extremely useful for these compositions have been found. The present inventors have found compounds and completed the present invention.

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

[0012]

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[Where A is

[0014]

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(Where X represents a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group or a sulfonyl group, and Y _{1 to} Y ₄ represent Each independently represents hydrogen, lower alkyl group, lower alkoxy group, chlorine or bromine atom),

[0016]

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R represents a monovalent 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 bridge member. A divalent group selected from the group consisting of cyclic aromatic groups]. Specifically, the following various bisimide compounds are included. That is, the general formula (2)

[0018]

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(Wherein X represents a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group or a sulfonyl group, and Y _{1 to} Y ₄ represent Each independently represents hydrogen, lower alkyl group, lower alkoxy group, chlorine or bromine atom,
R is a divalent group selected from the group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridge member. A bisimide compound represented by the general formula (3)

[0020]

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(Wherein R is a group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridging member. A bisimide compound represented by the following general formula (4):

[0022]

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(Wherein R is a group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridging member. A bisimide compound represented by the following general formula (5):

[0024]

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(Wherein R is a group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridging member. A bisimide compound represented by the following general formula (6):

[0026]

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(Wherein, R is a group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridging member. A bisimide compound represented by the following general formula (7):

[0028]

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(Wherein X represents a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group or a sulfonyl group, and Y _{1 to} Y ₄ represent Each independently represents hydrogen, lower alkyl group, lower alkoxy group, chlorine or bromine atom,
R is a divalent group selected from the group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridge member. Represents a bisimide compound represented by

Another aspect of the present invention is a polyimide resin composition containing an aromatic bisimide compound and polyimide. For example, as essential components (a) a bisimide compound represented by the general formula (1) and (b) a polyimide, particularly a general formula (8)

[0031]

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Wherein A 'is

[0033]

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(Where X is directly connected and has 1 to 10 carbon atoms)
Divalent hydrocarbon radical, hexafluorinated isopropylidene
Represents a group, carbonyl group, thio group or sulfonyl group
Then Y ₁~ Y₄Are each independently hydrogen, lower alkyl
Group, lower alkoxy group, chlorine or

Represents a bromine atom) or

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R ′ represents an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group directly or A tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups connected to each other by a cross-linking member].

Preferred examples of the combination of the aromatic bisimide compound and polyimide include the following. (1) Polyimide is represented by the general formula (9)

[0038]

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(Wherein R ′ is the same as in the case of the general formula (8)), and the aromatic bisimide compound is represented by the general formula (10)

[0040]

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Wherein B is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group,
Represents a group selected from a carbonyl group, a thio group, an ether group and a sulfonyl group, and the nitrogen atom independently occupies the para, ortho or meta position with respect to B. R is a divalent group selected from the group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridge member. And / or a bisimide compound represented by the general formula (2)

[0042]

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(Wherein X, Y _{1 to} Y ₄ and R are the same as described above), a polyimide resin composition which is a bisimide compound represented by the following formula (2):
1)

[0044]

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(Wherein X represents a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group or a sulfonyl group, and Y _{1 to} Y ₄ represent Each independently represents hydrogen, lower alkyl group, lower alkoxy group, chlorine or bromine atom,
R ′ is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, 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. Which represents a tetravalent group selected from the group consisting of cyclic aromatic groups), wherein the aromatic bisimide compound is a bisimide compound represented by the above general formula (10); / Or a polyimide resin composition which is a bisimide compound represented by the general formula (2),
(3) The polyimide has the general formula (9)

[0046]

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(Wherein R ′ is the same as defined above), which is a polyimide having a repeating structural unit represented by the general formula (3)

[0048]

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Wherein R is the same as defined above, and (4) a polyimide having the general formula (1)
1)

[0050]

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Wherein X, Y _{1 to} Y ₄ and R ′ are the same as those described above, wherein the aromatic bisimide compound is represented by the general formula (7):

[0052]

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Wherein X, Y _{1 to} Y ₄ and R are the same as those described above, and represented by the general formula (12)

[0054]

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(Wherein R is a group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridging member. Represents a selected divalent group, wherein the two isopropylidene groups occupy the para-position or the meta-position with respect to the central benzene nucleus);

[0056]

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(Wherein R is the same as described above), and general formula (13)

[0058]

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(Wherein R is a group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridging member. Represents a selected divalent group, wherein the two carbonyl groups occupy the meta or para position with respect to the central ether bond, and the adjacent two ether bonds occupy the meta or para position with respect to the carbonyl group. Represented by the general formula (14)

[0060]

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Wherein Z represents a group selected from the group consisting of a carbonyl group and a sulfonyl group, and R represents 2 carbon atoms.
From the above aliphatic groups, cycloaliphatic groups, monocyclic aromatic groups, fused polycyclic aromatic groups, and non-fused polycyclic aromatic groups in which the aromatic groups are connected to each other directly or by a crosslinking member A divalent group selected from the group consisting of:

[0062]

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(Wherein R is a group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridge member. Represents the selected divalent radical, and the two carbonyl groups occupy the para or meta positions with respect to the central benzene nucleus, and the two carbonyl groups occupy the para position with respect to the central benzene nucleus; The nitrogen atoms at both ends occupy the para or meta position with respect to the ether bond, and when the two carbonyl groups occupy the meta position with respect to the central benzene nucleus, the nitrogen atoms at both ends are para to each other with respect to the ether bond. Or occupying the meta position), or the general formula (16)

[0064]

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(Wherein R is a group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridging member. A polyimide resin composition which is a bisimide compound represented by a selected divalent group and two isopropylidene groups occupy para or meta positions with respect to a central benzene nucleus.

Further, (5) a polyimide represented by the general formula (1)
7)

[0067]

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(Wherein R ′ is an aliphatic group having 2 or more carbon atoms;
Cyclic aliphatic group, monocyclic aromatic group, fused polycyclic aromatic group,
Wherein the aromatic group is a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups directly or interconnected by a bridging member; The aromatic bisimide compound has the general formula (1)
0), (2), (7), (12), (4), (13),
(14) A polyimide resin composition represented by (15) or (16).

Further, the present invention relates to an aromatic bisimide compound, preferably, of the above general formula (2)

[0070]

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(Wherein X, Y _{1 to} Y ₄ and R are the same as those described above), and a carbon fiber coated on the surface with a bismaleimide compound represented by the following formula:

[0072]

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Wherein X, Y _{1 to} Y ₄ and R ′ are the same as described above, or a polyimide having a repeating structural unit represented by the general formula (9):

[0074]

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(Wherein R ′ is the same as defined above), a carbon fiber reinforced polyimide resin composition containing a polyimide having a repeating structural unit represented by the following general formula (10):

[0076]

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(Wherein B and R are as defined above)
A carbon fiber coated with a bisimide compound represented by the following general formula (11):

[0078]

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(Wherein X, Y _{1 to} Y ₄ and R ′ are the same as those described above), which is a carbon fiber-reinforced polyimide resin composition containing a polyimide having a repeating structural unit. Bisimide of the present invention, in order to impart good heat resistance and good workability when contained in polyimide, heat-resistant paint, heat-resistant adhesive, sizing agent such as carbon fiber or glass fiber, plasticizer of heat-resistant resin It is a compound useful as such.

Further, by adding a bisimide compound to the polyimide resin, the viscosity of the resin at the time of melting can be greatly reduced, and the moldability can be improved. In particular, the moldability of the polyimide resin composition containing the bisimide compound of the present invention is remarkably improved. The polyimide resin composition containing the carbon fiber coated with the bisimide compound of the present invention has excellent mechanical strength, and is suitable for all industries such as electric / electronic equipment, machinery, automobiles, aerospace equipment, and general industrial equipment. Its industrial value is great because it can be widely used as a material for parts in the market.

The bisimide compound of the present invention is a compound represented by the general formula (1), and specific compounds include the general formulas (2), (3), (4), (5) Bisimide compounds represented by the formula (6) and the general formula (7) are exemplified. These compounds have the general formula (1-a)

[0082]

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[Where A is

[0084]

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(Where X represents a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group or a sulfonyl group, and Y _{1 to} Y ₄ represent Each independently represents hydrogen, lower alkyl group, lower alkoxy group, chlorine or bromine atom),

[0086]

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And a divalent compound selected from the group consisting of:

[0088]

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(Wherein R is a group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridge member. (Representing a selected divalent group)). The diamine compound used to obtain the bisimide compound of the present invention includes a compound represented by the general formula (2-a)

[0090]

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[Wherein X and Y _{1 to} Y ₄ are the same as those in formula (2)], specific examples of which include bis [4- (3-aminophenoxy) ) Phenyl] methane, 1,1-bis [4-
(3-aminophenoxy) phenyl] ethane, 2,2-
Bis [4- (3-aminophenoxy) phenyl] propane, 2- [4- (3-aminophenoxy) phenyl]-
2- [4- (3-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (3-aminophenoxy) -3-methylphenyl] propane, 2- [4-
(3-aminophenoxy) phenyl] -2- [4- (3
-Aminophenoxy) -3,5-dimethylphenyl]
Propane, 2,2-bis [4- (3-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-
Bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4 '-Bis (3-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) -3
-Methylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3'-dimethylbiphenyl, 4,4'-
Bis (3-aminophenoxy) -3,5-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy)-
3,3 ′, 5,5′-tetramethylbiphenyl, 4,
4'-bis (3-aminophenoxy) -3,3'-dichlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,5-dichlorobiphenyl, 4,4'-bis (3-aminophenoxy ) -3,3 ′, 5,5′-Tetrachlorobiphenyl, 4,4′-bis (3-aminophenoxy) -3,3′-dibromobiphenyl, 4,4′-
Bis (3-aminophenoxy) -3,5-dibromobiphenyl, 4,4'-bis (3-aminophenoxy)-
3,3 ′, 5,5′-tetrabromobiphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-amino) Phenoxy) -3-methoxyphenyl] sulfide, [4- (3-aminophenoxy) phenyl] [4- (3-aminophenoxy) -3,
5-dimethoxyphenyl] sulfide, bis [4- (3
-Aminophenoxy) -3,5-dimethoxyphenyl]
Sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone and the like.

The formula (3-a)

[0093]

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3,3′-diaminobenzophenone of the formula
(4-a)

[0095]

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Bis- [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone of the formula (5-a)

[0097]

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1,3-bis- (4-amino-α, α-
Dimethylbenzyl) benzene, formula (6-a)

[0099]

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Bis- [3- {4- (4-aminophenoxy) benzoyl} phenyl] ether and a compound of the general formula (7-a)

[0101]

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[Wherein X is Y _{1 to} Y ₄ is a general formula (7)
The same is true for the diamine compound represented by the formula: 1,1-bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4-
(4-aminophenoxy) phenyl] ethane, 2,2-
Bis [4- (4-aminophenoxy) phenyl] propane, 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] butane,
2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4 '-Bis (4-aminophenoxy) -3-
Methylbiphenyl, 4,4'-bis (4-aminophenoxy) -3,3'-dimethylbiphenyl, 4,4'-bis (4-aminophenoxy) -3,5-dimethylbiphenyl, 4,4'-bis (4-aminophenoxy) -3,
3 ', 5,5'-tetramethylbiphenyl, 4,4'-
Bis (4-aminophenoxy) -3,3'-dichlorobiphenyl, 4,4'-bis (4-aminophenoxy)-
3,5-dichlorobiphenyl, 4,4'-bis (4-aminophenoxy) -3,3 ', 5,5'-tetrachlorobiphenyl, 4,4'-bis (4-aminophenoxy)
-3,3'-dibromobiphenyl, 4,4'-bis (4
-Aminophenoxy) -3,5-dibromobiphenyl,
4,4′-bis (4-aminophenoxy) -3,3 ′,
5,5'-tetrabromobiphenyl, bis [4- (4-
Aminophenoxy) phenyl] ketone, bis [4- (4
-Aminophenoxy) phenyl] sulfide, bis [4
-(4-aminophenoxy) -3-methoxyphenyl]
Sulfide, [4- (4-aminophenoxy) phenyl] [4- (4-aminophenoxy) -3,5-dimethoxyphenyl] sulfide, bis [4- (4-aminophenoxy) -3,5-dimethoxyphenyl] Sulfide, bis [4- (4-aminophenoxy) phenyl] sulfone and the like.

The diamine compounds listed above may be used alone or as a mixture of two or more. The aromatic dicarboxylic anhydride used to obtain the bisimide compound of the present invention is a dicarboxylic anhydride represented by the general formula (18), and specific compounds include phthalic anhydride and 3-methylphthalic anhydride. , 4-methylphthalic anhydride, 2,3
-Benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 3,4-biphenyl dicarboxylic acid Anhydride, 2,3-biphenyldicarboxylic anhydride, 2,3-dicarboxyphenylphenylsulfonic anhydride, 3,4-dicarboxyphenylphenylsulfonic anhydride, 2,3-dicarboxyphenylphenylsulfide anhydride 3,4-dicarboxyphenylphenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,
Examples thereof include 2-anthracene dicarboxylic anhydride, 2,3-anthracene dicarboxylic anhydride, and 1,9-anthracene dicarboxylic anhydride. These may be used alone or as a mixture of two or more.

The method of reacting the diamine with the dicarboxylic anhydride is not particularly limited, and any known method can be employed without any limitation, but it is particularly preferable to carry out the reaction in an organic solvent. Examples of the organic solvent used in this reaction include N, N
-Dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone,
1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-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, tetramethyl urea, hexamethyl phosphoramide, phenol, m-cresol, p-cresol, p-chlorophenol, anisole and the like. These organic solvents may be used alone or in combination of two or more.

The reaction temperature is generally 200 ° C. or lower, preferably 50 ° C. or lower. The reaction pressure is not particularly limited, and the reaction can be carried out at normal pressure. The reaction time varies depending on the type of the solvent and the reaction temperature, and the reaction is usually performed for a time sufficient to complete the generation of the bisamic acid, which is the precursor of the bisimide compound of the present invention. Usually, 10 minutes to 24 hours are sufficient. By such a reaction, a bisamic acid corresponding to the target bisimide compound is obtained.

The general formula (2-b) corresponding to the bisimide compound of the general formula (2)

[0107]

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Bisamic acid represented by the general formula (3)
Formula (3-b) corresponding to the bisimide compound of

[0109]

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A bisamic acid represented by the general formula (4)
Formula (4-b) corresponding to the bisimide compound of

[0111]

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A bisamic acid represented by the general formula (5):
Formula (5-b) corresponding to the bisimide compound of

[0113]

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A bisamic acid represented by the general formula (6):
General formula (6-b) corresponding to the bisimide compound of

[0115]

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A bisamic acid represented by the general formula (7):
Formula (7-b) corresponding to the bisimide compound of

[0117]

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And the like. Furthermore, these bisamidic acids obtained are heated to 80 to 400 ° C. to be imidized, or chemically dehydrated by using an imidizing agent such as acetic anhydride to obtain the general formulas (1) to (7). )) Can be obtained. In addition, after suspending or dissolving the diamine compound and the dicarboxylic acid anhydride in an organic solvent, the mixture is heated to 50 to 400 ° C., and the generation of bisamic acid and the dehydration and imidization are performed simultaneously. It is also possible to obtain bisimide compounds.

The bisimide compounds represented by the general formulas (2) and (7) obtained using the diamine compounds represented by the general formulas (2-a) and (7-a) are all 2
The bisimide compound represented by the general formula (3) obtained by using the diamine compound represented by the general formula (3-a) having a melting point of 90 ° C. or less has a melting point of 290 ° C. or less. The bisimide compound obtained in (1) has a lower melting point than that of high-molecular-weight polyimide, can be easily melt-molded, and is excellent in melt-moldability. It can be used as a solution by dissolving 5% by weight or more in halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride and dissolving in these solvents.

The polyimide resin composition of the present invention is a polyimide resin composition comprising, as essential components, an aromatic bisimide compound, for example, the bisimide compound represented by the general formula (1) of the present invention and a polyimide. . That is, the polyimide resin composition of the present invention is a novel polyimide resin composition containing an aromatic bisimide compound and a polyimide as essential components, and in particular, a novel aromatic bisimide compound represented by the general formula (1) of the present invention. A polyimide resin composition using a novel bisimide compound is preferred.

The polyimide in the polyimide resin composition of the present invention is not particularly limited, and various polyimides can be used. In particular, a polyimide frequently used is preferably represented by the general formula (8)

[0122]

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(Wherein A ′ and R ′ are the same as described above). Specifically, the general formula (9)

[0124]

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Wherein R ′ is the same as defined above, a polyimide having a repeating structural unit represented by the following general formula (11):

[0126]

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(Wherein X, Y _{1 to} Y ₄ and R ′ are the same as described above), a polyimide having a repeating structural unit represented by the following general formula (17):

[0128]

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(Wherein R ′ is the same as described above), and a polyimide resin having a repeating structural unit represented by the following formula: Accordingly, in the composition of the present invention, typical examples of the combination of the polyimide resin component and the bisimide compound component include the following.
That is, (1) polyimide is represented by the general formula (9)

[0130]

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Wherein R ′ is the same as defined above, and the bisimide compound is represented by the general formula (10):

[0132]

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(Wherein B and R are the same as described above)
And / or general formula (2)

[0134]

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Wherein X, Y _{1 to} Y ₄ and R are the same as defined above, and (2) polyimide is a compound represented by the general formula (11)

[0136]

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Wherein X, Y _{1 to} Y ₄ and R ′ are the same as those described above, wherein the bisimide compound is represented by the general formula (10)

[0138]

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(Wherein B and R are the same as described above)
And / or general formula (2)

[0140]

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(Wherein X, Y _{1 to} Y ₄ and R are the same as described above), and (3) a polyimide represented by the general formula (9)

[0142]

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Wherein R ′ is the same as defined above.

The bisimide compound has the general formula (3)

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(Wherein B and R are the same as described above)
A bisimide compound represented by the formula (4):
(17) Polyimide having the general formula (11) to (17)

[0146]

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[0147]

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Wherein R ′ is the same as defined above, and the bisimide compound is represented by the general formula (7):

[0149]

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(Wherein R is as defined above), and general formula (12)

[0151]

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(Wherein R is as defined above), and general formula (4)

[0153]

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(Wherein R is as defined above), and general formula (13)

[0155]

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(Wherein R is the same as described above).

[0157]

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(Wherein Z and R are the same as described above).

[0159]

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(Wherein R is as defined above) or
General formula (16)

[0161]

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(Wherein R is the same as described above). The polyimide used in the composition of the present invention is a diamine compound having the general formula (19)

[0163]

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(Wherein R ′ is an aliphatic group having 2 or more carbon atoms;
Cyclic aliphatic group, monocyclic aromatic group, fused polycyclic aromatic group,
A tetravalent dianhydride represented by a non-condensed polycyclic aromatic group in which the aromatic groups are interconnected directly or by a bridging member). The resulting polyamic acid can be synthesized by dehydration cyclization. Specifically, JP-A-2-022422,
133327, 2-229124, etc.

The diamine compound used as a raw material is
Various diamine compounds that provide the desired polyimide can be used. For example, the following diamine compounds are used. To obtain a polyimide having a repeating structural unit represented by the general formula (9), 3,3-diaminobenzophenone, and to obtain a polyimide resin having a repeating structural unit represented by the general formula (11), Bis [4- (3-aminophenoxy) phenyl] methane,
1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2- [4- (3-aminophenoxy) phenyl]- 2- [4- (3-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (3-aminophenoxy) -3-methylphenyl] propane, 2- [4- (3-amino Phenoxy) phenyl] -2- [4- (3-aminophenoxy) -3,
5-dimethylphenyl] propane, 2,2-bis [4-
(3-aminophenoxy))-3,5-dimethylphenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl ] -1,1,1,3,3,3
-Hexafluoropropane, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) -3-methylbiphenyl, 4,4'-bis (3-aminophenoxy)- 3,3'-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy)-
3,5-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl, 4,4'-bis (3-aminophenoxy)
-3,3'-dichlorobiphenyl, 4,4'-bis (3
-Aminophenoxy) -3,5-dichlorobiphenyl,
4,4′-bis (3-aminophenoxy) -3,3 ′,
5,5'-tetrachlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3'-dibromobiphenyl, 4,4'-bis (3-aminophenoxy) -3,
5-dibromobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetrabromobiphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) -3-methoxyphenyl] sulfide, [4- (3
-Aminophenoxy) phenyl] [4- (3-aminophenoxy) -3,5-dimethoxyphenyl] sulfide, bis [4- (3-aminophenoxy) -3,5-dimethoxyphenyl] sulfide, bis [4- ( Diamine compounds such as [3-aminophenoxy) phenyl] sulfone, and these may be used alone or in combination of two or more.

In order to obtain the polyimide represented by the general formula (17), bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone is used. On the other hand, the tetracarboxylic dianhydride represented by the general formula (19) used in this method includes, for example, ethylene tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride , Pyromellitic 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) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1 1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-
Benzophenonetetracarboxylic dianhydride, 3,3 '
4,4′-biphenyltetracarboxylic dianhydride, 2,
2 ', 3,3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3 4-dicarboxyphenyl) sulfone dianhydride, (4,4′-p-phenylenedioxy) diphthalic dianhydride, 4,4 ′-(m-phenylenedioxy) diphthalic 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, 3,4,9,1
0-perylenetetracarboxylic dianhydride, 2,3,6
7-anthracenetetracarboxylic dianhydride, 1,2,2
7,8-phenanthrene tetracarboxylic dianhydride and the like, and these tetracarboxylic dianhydrides are used alone or in combination of two or more.

In the production of these polyimides, a range that does not impair the good properties of the polyimide resin of the present invention,
For example, the other diamine can be used in place of the diamine in an amount of usually 50% by weight or less, preferably 30% by weight or less. In the production of a polyimide resin, performing the reaction in the presence of a dicarboxylic anhydride or a monoamine is a preferable method for improving the thermal stability.

Examples of the aromatic diamine that can be used as a partial substitute include, for example, m-phenylenediamine and o-diamine.
-Phenylenediamine, p-phenylenediamine, m-
Aminobenzylamine, p-aminobenzylamine, bis (3-aminophenyl) ether, (3-aminophenyl) (4-aminophenyl) ether, bis (4-aminophenyl) ether, bis (3-aminophenyl)
Sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3
-Aminophenyl) (4-aminophenyl) sulfoxide, bis (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) ) Sulfone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, bis [4-
(4-aminophenoxy) phenyl] methane, 1,1-
Bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-
Aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1
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, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4 -(4-aminophenoxy) phenyl] sulfide, bis [4- (4-
Aminophenoxy) phenyl] sulfoxide, bis [4
-(4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether,
Bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, Bis [4- (3-aminophenoxy) phenyl] methane, 1,1-bis [4
-(3-aminophenoxy) phenyl] ethane, 2,2
-Bis [4- (3-aminophenoxy) phenyl] propane, 2- [4- (3-aminophenoxy) phenyl]
-2- [4- (3-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (3-aminophenoxy) -3-methylphenyl] propane, 2- [4
-(3-aminophenoxy) phenyl] -2- [4-
(3-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (3-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2
-Bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4, 4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) -3-
Methylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3'-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,5'-dimethylbiphenyl, 4,4'- Bis (3-aminophenoxy)-
3,3 ′, 5,5′-tetramethylbiphenyl, 4,
4'-bis (3-aminophenoxy) -3,3'-dichlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,5'-dichlorobiphenyl, 4,4'-bis (3-amino Phenoxy) -3,3 ', 5,5'-tetrachlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3'-dibromobiphenyl, 4,4'-
Bis (3-aminophenoxy) -3,5-dibromobiphenyl, 4,4'-bis (3-aminophenoxy)-
3,3 ′, 5,5′-tetrabromobiphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-amino) Phenoxy) -3-methoxyphenyl] sulfide, [4- (3-aminophenoxy) phenyl] [4- (3-aminophenoxy) -3,
5-dimethoxyphenyl] sulfide, bis [4- (3
-Aminophenoxy) -3,5-dimethoxyphenyl]
Sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone and the like.

The logarithmic viscosity of the polyimide resin powder of the above formula (9) is usually in the range of 0.10 to 1.50 dl / g, preferably 0.30 to 1.22 dl / g. If it is less than 0.10, it is difficult to obtain desired mechanical properties, and if it is more than 1.50, the melt viscosity becomes high and the moldability becomes poor. The logarithmic viscosity of the polyimide resin powder of the above formula (11) is generally in the range of 0.10 to 1.50 dl / g, preferably 0.25 to 1.22 dl / g.
If it is less than 0.10, it is difficult to obtain desired mechanical properties, and if it is more than 1.50, the melt viscosity becomes high and the moldability becomes poor.

The logarithmic viscosity shown here was determined by heating and dissolving in a mixed solvent of parachlorophenol / phenol (weight ratio 90/10) with a solvent having a concentration of 0.5 g / 100 ml.
This is a value measured after cooling to 35 ° C. In the composition of the present invention, the aromatic bisimide compound used as a fluidization accelerator is represented by the general formula (1) of the present invention, general formulas (2), (3), and ( 4),
Including the bisimide compound represented by the general formula (5), (6) or (7), various aromatic bisimide compounds can be used.

Among the aromatic bisimide compounds used as one component of the composition of the present invention, the bisimide compound of the present invention can be produced by the above-mentioned production methods and the methods specifically described in Examples. The other bisimide compound used in the composition of the present invention, that is, the bisimide compound represented by the general formula (10), (13), (14), (15) or (17) is Can be manufactured as follows.

The bisimide compound represented by the general formula (10) and / or the general formula (2)
-A)

[0173]

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Wherein B is the same as in the case of the general formula (10), and / or a diamine represented by the formula (2-
The diamine represented by a) is reacted with the aromatic dicarboxylic anhydride represented by the general formula (19), and the resulting polyamic acid can be easily produced by dehydration cyclization. As the diamine represented by the general formula (10-a), for example, 3,3′-diaminodiphenyl ether,
3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,
3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 3,
4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane,
3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 1,1-bis (3-aminophenyl) ethane, 1,1-bis (4-aminophenyl) ethane, 1,1- (3-amino Phenyl) (4-aminophenyl) ethane, 2,2-bis (3-aminophenyl)
Propane, 2,2-bis (4-aminophenyl) propane, 2,2- (4-aminophenyl) (3-aminophenyl) propane, 2,2-bis (3-aminophenyl)
-1,1,1,3,3,3-hexafluoropropane,
2,2-bis (4-aminophenyl) -1,1,1,
3,3,3-hexafluoropropane, 2,2- (4-
Aminophenyl) (3-aminophenyl) -1,1,
Examples thereof include 1,3,3,3-hexafluoropropane, and these are used alone or in combination of two or more.

As the diamine represented by the formula (2-a), the compounds specifically mentioned above are used. These may be used alone or in combination of two or more.
Further, the diamine represented by the general formula (10-a) and the diamine represented by the general formula (2-a) may be mixed in advance at the time of producing a polyimide resin. The aromatic dicarboxylic anhydride used is represented by the general formula (1)
8), specifically, phthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 2,3-benzophenone dicarboxylic anhydride,
3,4-benzophenone dicarboxylic anhydride, 2,3-
Dicarboxyphenyl phenyl ether anhydride, 3,
4-dicarboxyphenyl phenyl ether anhydride,
3,4-biphenyldicarboxylic anhydride, 2,3-biphenyldicarboxylic anhydride, 2,3-dicarboxyphenylphenylsulfonic anhydride, 3,4-dicarboxyphenylphenylsulfonic anhydride, 2,3- Dicarboxyphenylphenyl sulfide anhydride, 3,4-dicarboxyphenylphenyl sulfide anhydride, 1,2
-Naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride,
Examples thereof include 2,3-anthracene dicarboxylic anhydride and 1,9-anthracene dicarboxylic anhydride, and these may be used alone or as a mixture of two or more.

The diamine compound used for producing the bisimide compound represented by the general formula (12), which is another bisimide compound, has a general formula (12-a)

[0177]

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Diamine compounds represented by the following formulas, specifically, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene And the like. Further, the diamine compound used for producing the bisimide compound represented by the general formula (13) is represented by the general formula (13-a)

[0179]

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Diamines represented by the following formulas, specifically, bis [3- {4- (4-aminophenoxy) benzoyl} phenyl] ether, bis [4- {4- (4-aminophenoxy) benzoyl} phenyl] ether, Screw [4-
{3- (4-aminophenoxy) benzoyl} phenyl] ether, bis [3- {3- (4-aminophenoxy) benzoyl} phenyl] ether and the like.

Further, the diamine compound used for producing the bisimide compound represented by the general formula (14) is
General formula (14-a)

[0182]

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Specifically, 4,4′-bis [4- (4-
Amino-α, α-dimethylbenzyl) phenoxy] benzophenone, bis [4- {4- (4-amino-α, α-
Dimethylbenzyl) phenoxydiphenyl] sulfone and the like. Furthermore, the diamine compound used for producing the bisimide compound represented by the general formula (15) is represented by the general formula (15-a)

[0184]

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Specifically, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [ 4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [3- (3-aminophenoxy) benzoyl] benzene and the like. Furthermore, the diamine compound used for producing the bisimide compound represented by the general formula (16) is represented by the general formula (1)
6-a)

[0186]

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Specifically, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy)-
α, α-dimethylbenzyl] benzene and the like.
The aromatic dicarboxylic acid is a compound represented by the above general formula (18), and any of the compounds specifically listed are used. The method for reacting the diamine and the dicarboxylic anhydride is not particularly limited, and any known method can be employed without any limitation, and the reaction can be carried out in the same manner as in the method for producing the bisimide compound of the present invention. For example, Japanese Patent Application No. 3-4
963, 3-25932, 3-218286, 3-23
1295, 231296, 3-282849 and the like can also be applied.

The resin composition for molding of the present invention is preferably used in an amount of 0.5 to 100 parts by weight of the aromatic bisimide compound based on 100 parts by weight of the polyimide. The effect of the aromatic bisimide compound as a fluidization accelerator is recognized even in a relatively small amount, and polyimide 100
Although 0.5 parts by weight is effective with respect to parts by weight, 1 part by weight or more is particularly effective. However, if the aromatic bisimide compound is used in an amount exceeding 100 parts by weight, the mechanical strength of the obtained polyimide resin composition tends to be slightly impaired. Therefore, it is preferable to use the aromatic bisimide compound in an amount of 100 parts by weight or less.

In preparing the polyimide resin composition according to the present invention, it can be produced by a generally known method. For example, the following methods are preferred. 1. The polyimide resin powder and the aromatic bisimide compound are pre-kneaded using a mortar, a Henschel mixer, a drum blender, a tumbler blender, a ball mill ribbon blender, or the like to make a powder. 2. After previously dissolving or suspending the polyimide resin powder in an organic solvent, adding an aromatic bisimide compound to this solution or suspension, and uniformly dispersing or dissolving,
The solvent is removed to make a powder.

3. An aromatic bisimide compound and / or an aromatic bisimide compound are added to an organic solvent solution of a polyamic acid as a polyimide precursor.
Or, after dissolving or suspending the aromatic bisamic acid as a precursor thereof, heat-treating to 100 to 400 ° C.,
Alternatively, after chemically imidizing using a commonly used imidizing agent, the solvent is removed to obtain a powder. The powdery resin composition thus obtained is used for various molding applications as it is, such as injection molding, compression molding, transfer molding, and extrusion molding, but it is more preferable to use it after melt blending. is there.

For the melt blending, an apparatus used for melt blending ordinary rubber or plastics, for example, a hot roll, a Banbury mixer, a Brabender, an extruder or the like can be used. The melting temperature is set to a temperature higher than the melting temperature of the compounding system and lower than the temperature at which the compounding system starts to thermally decompose.
° C, preferably 300-400 ° C.

The method for molding the resin composition of the present invention includes:
Extrusion molding or injection molding, which is a molding method that forms a homogeneous melt blend and has high productivity, is suitable, but other transfer molding, compression molding, sintering molding, and extruded film molding are also applicable. In the production of a prepreg for a composite material, the above-mentioned uniformly adjusted resin composition can be melt-impregnated into carbon fiber, glass fiber, or the like, or a polyimide resin or an aromatic bisimide compound can be uniformly dispersed or A method of impregnating various fibers with the dissolved liquid and then removing the solvent can also be adopted.

It is to be noted that one or more solid lubricants such as molybdenum disulfide, graphite, boron nitride, lead monoxide, and lead powder can be added to the resin composition of the present invention. Further, one or more reinforcing agents such as glass fiber, carbon fiber, aromatic polyamide, silicon carbide fiber, potassium titanate fiber, glass beads, and the like can be added.

In the resin composition of the present invention, an antioxidant, a heat stabilizer and a heat stabilizer are added as long as the object of the present invention is not impaired.
One or more ordinary additives such as an ultraviolet absorber, a flame retardant, a flame retardant auxiliary, an antistatic agent, a lubricant, and a colorant can be added. Still another aspect of the present invention is a polyimide resin composition comprising a polyimide resin and carbon fiber having an aromatic bisimide compound applied to the surface.

As a result of various studies on the carbon fiber reinforced polyimide resin composition, the present inventors found that a sizing agent represented by the general formula (10)

[0196]

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(Wherein B and R are as defined above)
A carbon fiber coated on the surface with a bisimide compound represented by the general formula (11)

[0198]

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Wherein X, Y _{1 to} Y ₄ and R ′ are the same as described above, or a polyimide resin composition containing a polyimide having a repeating structural unit represented by the general formula (2): Bisimide compound represented

[0200]

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(Wherein X, Y _{1 to} Y ₄ and R are the same as described above), and a carbon fiber coated on the surface with a bisimide compound represented by the general formula (11):

[0202]

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(Wherein X, Y _{1 to} Y ₄ and R ′ are the same as described above) or a polyimide having a repeating structural unit represented by the following general formula (9):

[0204]

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(Wherein R ′ is the same as described above), which is a polyimide resin composition containing a polyimide having a repeating structural unit represented by the following formula: In the present invention, the bisimide compound applied to the carbon fiber is a bisimide compound represented by the general formula (10) or a bisimide represented by the general formula (2) obtained by reacting a diamine and tetracarboxylic dianhydride as described above. Compound.

The polyimide resin used in the composition of the present invention has the general formula (11)

[0207]

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(Wherein X, Y _{1 to} Y ₄ and R ′ are the same as described above) or a polyimide having a repeating structural unit represented by the following general formula (9):

[0209]

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(Wherein R ′ is the same as described above). In particular, when the bisimide compound applied to the carbon fiber is a compound represented by the general formula (15), the polyimide resin may be a polyimide having a repeating structural unit represented by the general formula (11), or a bisimide applied to the carbon fiber. When the compound is a compound represented by the general formula (2), both a polyimide having a repeating structural unit represented by the general formula (11) and a polyimide having a repeating structural unit represented by the general formula (10) are preferably used. Is done.

The polyimide used in the composition of the present invention and the bisimide compound applied to the surface of the carbon fiber may have the same or different starting diamine components. Ie, X and _Y 1 to Y ₄ in the general formula (11), be the same as X and _Y 1 to Y ₄ in the general formula (2), may be different. Examples of the carbon fiber to which the bisimide compound is applied include acryl-based, rayon-based, lignin-based, and pitch-based carbon fibers, all of which can be used in the present invention. In the present invention, an acrylic resin having the highest fiber strength is most preferably used.

The form of the carbon fiber may be any of chopped strand, roving, woven fabric and the like. More preferably, the surface of these carbon fibers is previously oxidized by ozone or electrolytic oxidation. As a method for applying the bisimide compound to these carbon fibers, the bisimide compound is prepared by adding dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dimethyl sulfoxide, N, N-dimethylacetamide, -Methyl-pyrrolidone, methyl ethyl ketone, 1,1,2-
Trichloroethane, m-cresol, p-cresol,
Carbon fiber is immersed in a solution dissolved in a solvent such as o-cresol, p-chlorophenol, o-chlorophenol, m-chlorophenol, or phenol, and then dried, the solvent is removed, and the carbon coated with a bisimide compound is removed. Get the fiber.

Further, the carbon fiber is immersed in a solution of bisamic acid which is a precursor of bisimide, then dried and imidized to obtain a carbon fiber coated with a bisimide compound.
The bisimide compound represented by the general formula (2) used in the present invention has a melting point of about 290 ° C. or lower, and the bisimide compound represented by the general formula (15) has a melting point of about 35 ° C.
Since the temperature is 0 ° C. or lower and melt processing is possible, carbon fibers coated with a bisimide compound by a melt impregnation method can also be obtained.

The amount of the bisimide compound to be applied to the carbon fibers is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 9 parts by weight, and more preferably 1 to 8 parts by weight based on 100 parts by weight of the applied carbon fibers. . Various methods can be adopted as a method of mixing the carbon fiber coated and coated with the bisimide compound thus obtained and the polyimide resin. For example,
The coated carbon fiber can be cut to a length of 3 to 8 mm, and this and the polyimide resin can be individually supplied to the melt extruder and mixed, or can be mixed in advance with a mixer such as a Henschel mixer, a super mixer, or a ribbon blender. After pre-blending, it can be fed to a melt extruder.
Furthermore, the applied carbon fiber roving can be directly supplied to a melt extruder and mixed with a polyimide resin.

In the composition of the present invention, the mixing ratio of the carbon fiber coated with the bisimide compound and the polyimide resin as the matrix resin is 5 to 50 parts by weight of the carbon fiber,
Preferably 10 to 50 parts by weight, polyimide resin 95 to 5
0 parts by weight, preferably 90 to 50 parts by weight. When the amount of the carbon fiber is less than 5 parts by weight, the improvement in tensile strength of the obtained resin composition tends to be low. If the carbon fiber is added in an amount exceeding 50 parts by weight, it tends to be difficult to uniformly melt and mix the obtained resin composition.

In the composition of the present invention, a filler such as talc, calcium carbonate, mica, glass beads, a glass fiber, a potassium titanate fiber, an aramid fiber may be used, if necessary, in addition to the carbon fiber coated with the polyimide resin and the bisimide compound. , Fibrous reinforcing materials such as ceramic fibers, stabilizers,
A colorant may be mixed with the resin composition of the present invention as long as the quality and performance of the resin composition are not impaired.

As described above, the resin composition of the present invention comprising a carbon fiber coated with a bisimide compound and a polyimide resin can be prepared by known molding methods such as injection molding, extrusion molding, transfer molding, and compression molding. It can be molded into a predetermined molded product by the method. The resin composition of the present invention molded in this way has excellent mechanical strength, especially mechanical strength at high temperatures, so that mechanical parts requiring high mechanical strength at high temperatures, automobile parts, such as gears and cams, Used in pushers, pulleys, sleeves, etc., and as parts for internal combustion engines, exhaust system parts for silencers such as impellers and manifolds of integrated centrifugal compressors, valve guides, valve stems, piston skirts, oil pans, front covers, rockers Can be used for covers.

The carbon fiber reinforced polyimide resin composition of the present invention is usually made into a pellet-shaped molding material which is easy to handle, and a product is produced by injection molding. At this time, the pellets are formed by kneading and extruding the polyimide resin and the carbon fiber strand using a known single-screw or twin-screw extruder, and then cutting. Injection molding of the obtained pellets,
Using a normal injection molding machine, cylinder temperature 360-42
0 ° C, mold temperature 160 ~ 210 ° C, preferably 180 ~
The operation can be performed at 200 ° C., and a component having a complicated shape for an internal combustion engine, for example, an impeller for an integrated centrifugal compressor can be easily obtained.

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples. Example 1 368 g (1.0 mol) of 4,4′-bis (3-aminophenoxy) biphenyl, N, N-dimethylacetamide 5, and 4,4′-bis (3-aminophenoxy) biphenyl were placed in a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube. After charging 215 g, 311 g (2.1 mol) of phthalic anhydride was added at room temperature, and the mixture was stirred at room temperature for 2 hours.

Next, 404 g (4 mol) of triethylamine and 306 g (3 mol) of acetic anhydride were added dropwise to this solution. Stirring was continued at room temperature for 2 hours, and the resulting slurry was drained into methanol and filtered. Further, the operation of dispersing and washing in methanol and filtering was repeated twice,
For 2 hours to obtain 475 g of a white powder. The melting point of this powder was 286 ° C. (according to DSC; the same applies hereinafter).

The results of the elemental analysis are as follows. Elemental analysis _{(C 40 H 24 N 2 O} 6) C H N calc (%) 76.40 3.82 4.46 found (%) 76.27 3.80 4.49 In addition, the infrared of the powder FIG. 1 shows an absorption spectrum diagram. This spectrum diagram, around 1780 cm ^-1 and near 1720 cm ^-1 which is the characteristic absorption band of imide, and absorption at around 1240 cm ^-1 which is the characteristic absorption band of ether linkage was clearly observed.

From the production method, the results of elemental analysis and the infrared absorption spectrum, it was confirmed that the produced powder was a bisimide having a structure represented by the following formula (20).

[0223]

Embedded image The bisimide was dissolved in dichloromethane, chloroform and carbon tetrachloride in an amount of 5% by weight or more, and the workability was good.

Examples 2 to 4 Various operations were carried out in the same manner as in Example 1 except that the kind and amount of the diamine were changed as shown in Table 1, to obtain various bisimide powders. The melting point and elemental analysis value of the obtained bisimide powder are also shown in Table 1. All of these bisimide compounds were dissolved in dichloromethane, chloroform and carbon tetrachloride in an amount of 5% by weight or more, and the processability was good.

[0225]

[Table 1]

Comparative Example 1 368 g of 4,4′-bis (3-aminophenoxy) biphenyl in Example 1 was replaced with 195.6 g of aniline (2.
(1 mol), and 360 g of a pale yellow powder was obtained in the same manner as in Example 1 except that 311 g of phthalic anhydride was changed to 218.1 g (2.1 mol) of pyromellitic dianhydride. The results of elemental analysis of this powder are as follows.

Elemental analysis (C ₂₂ H ₁₂ N ₂ O ₄ ) Calculated value for CH N (%) 71.74 3.26 7.61 Measured value (%) 71.70 3.20 7.65 FIG. 2 shows the infrared absorption spectrum.
In this spectrum diagram, the characteristic absorption band of imide, 17
80cm and around 1720cm around ^{-1 -1,} and absorption at around 1240 cm ^-1 which is the characteristic absorption band of ether linkage was clearly observed.

From the production method, the results of elemental analysis and the infrared absorption spectrum, it was confirmed that the produced powder was a bisimide having a structure represented by the following formula (21).

[0229]

Embedded image This bisimide had a solubility of 0.01% by weight or less in halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride, and was poor in workability. Further, the melting point was extremely high at 442 ° C., and the melt processability was poor.

Example 5 A reaction vessel similar to that of Example 1 was charged with 212 g (1.0 mol) of 3,3'-diaminobenzophenone and 5,215 g of N, N-dimethylacetamide. 311 g (2.1 mol) of acid was added, and the mixture was stirred at room temperature for 2 hours.

Next, 404 g (4 mol) of triethylamine and 306 g (3 mol) of acetic anhydride were added dropwise to this solution. Stirring was continued at room temperature for 2 hours, and the reaction solution was discharged into methanol and filtered. Further, the operations of dispersing and washing in methanol and filtering were repeated twice, and dried at 150 ° C. for 2 hours to obtain 453 g of a white powder. This powder had a melting point of 240 ° C., and was melted at around 230 ° C., and had good melt processability.

The results of the elemental analysis are as follows. Elemental analysis _{(C 29 H 16 N 2 O} 5) C H N calc (%) 73.73 3.39 5.93 found (%) 73.61 3.30 5.96 In addition, the infrared of the powder FIG. 3 shows the absorption spectrum. This spectrum diagram, the absorption near 1780 cm ^-1 and near 1720 cm ^-1 which is the characteristic absorption band of imide were remarkably observed.

From the production method, the results of elemental analysis, and the infrared absorption spectrum, it was confirmed that the produced powder was a bisimide having a structure represented by the following formula (22).

[0234]

Embedded image The bisimide was dissolved in dichloromethane, chloroform and carbon tetrachloride in an amount of 5% by weight or more, and the workability was good.

Example 6 In the same reaction vessel as in Example 1, bis- [4- {4- (4
-Aminophenoxy) phenoxydiphenyl] sulfone 616.7 g (1.0 mol) and m-cresylic acid 18
505.6 g and phthalic anhydride 325.6 g at room temperature
(2.2 mol), and the mixture was heated to 140 ° C. and reacted for 2 hours.

Subsequently, the reaction solution was discharged into methanol,
The precipitate was filtered. After the filter cake was washed three times with methanol, it was dried at 150 ° C. for 2 hours to obtain 873.7 g (yield 96.4%) of white powder. The melting point of the powder was 217 ° C. The results of the elemental analysis are as follows.

[0237] Elemental analysis _{(C 52 H 32 N 2 S} 1 O 10) C H N S Calculated (%) 71.2 3.6 3.2 3.6 measured value (%) 70.8 3.7 3 3.3 3.6 The infrared absorption spectrum of this powder is shown in FIG.

[0238] In the infrared absorption spectrum, absorption at around 1780 cm ^-1 and near 1720 cm ^-1 imide characteristic absorption bands were remarkably observed. From the production method, elemental analysis results, and infrared absorption spectrum diagram, it was confirmed that the produced powder was a bisimide having a structure represented by the following formula (23).

[0239]

Embedded image The bisimide was dissolved in dichloromethane, chloroform and carbon tetrachloride in an amount of 5% by weight or more, and the workability was good.

Example 7 325.6 g (2.2 mol) of phthalic anhydride in Example 6 was replaced with 436 g of 2,3-naphthalenedicarboxylic anhydride.
(2.2 mol) in the same manner as in Example 6 except for changing to 93 mol.
8 g (96% yield) of a white powder was obtained.

The melting point of the powder was 218 ° C. The results of the elemental analysis are as follows. Elemental analysis _{(C 60 H 36 N 2 S} 1 O 10) C H N S Calculated (%) 73.8 3.7 2.9 3.3 measured value (%) 73.6 3.5 3.0 3 .3 In the infrared absorption spectrum, imide characteristic absorption band 1
Absorption around 780 cm ^-1 and around 1720 cm ^-1 was remarkably observed.

From the production method, the results of elemental analysis and the infrared absorption spectrum, it was confirmed that the produced powder was a bisimide having a structure represented by the following formula (24).

[0243]

Embedded image The bisimide was dissolved in dichloromethane, chloroform and carbon tetrachloride in an amount of 5% by weight or more, and the workability was good.

Example 8 In the same reaction vessel as in Example 1, 1,3-bis- (4-amino-α, α-dimethylbenzyl) benzene 344.5 was added.
g (1.0 mol) and 3426 g of m-cresylic acid were charged, and 325.6 g (2.2 mol) of phthalic anhydride were added at room temperature.
Was added, and the temperature was raised to 140 ° C., and the reaction was performed for 2 hours.

Next, the reaction solution was charged into methanol,
The precipitate was separated by filtration, washed several times with methanol, and dried at 100 ° C. under reduced pressure for 16 hours.
6 g (yield 97.7%) of a white powder was obtained. The melting point of the powder was 240 ° C. The results of the elemental analysis are as follows.

Elemental analysis (C ₄₀ H ₃₂ N ₂ O ₄ ) Calculated value for CH N (%) 79.47 5.30 4.64 Measured value (%) 79.73 5.43 4.60 Also, this powder was used. FIG. 5 shows the infrared absorption spectrum of the sample.

In the infrared absorption spectrum, the imide characteristic absorption bands around 1780 cm ⁻¹ and 1720 cm ^{−1 were} observed.
^-1 is remarkably recognized, while the absorption around 1550 cm ^-1 which is the amic acid characteristic absorption band,
No absorption of diamine around 3400 cm ^-1 and no absorption near 1850 cm ^-1 which is an acid anhydride characteristic absorption band was observed.

From the production method, the results of elemental analysis and the infrared absorption spectrum, it was confirmed that the produced powder was a bisimide having a structure represented by the following formula (25).

[0249]

Embedded image The bisimide was dissolved in dichloromethane, chloroform and carbon tetrachloride in an amount of 5% by weight or more, and the workability was good.

Example 9 325.6 g (2.2 mol) of phthalic anhydride in Example 8 was replaced with 436 g of 2,3-naphthalenedicarboxylic anhydride.
(2.2 mol), except that 6 mol was used in the same manner as in Example 8.
87 g (97% yield) of a white powder was obtained.

The melting point of the powder was 241 ° C. The results of the elemental analysis are as follows. The elemental analysis _{(C 48 H 40 N 2 O} 4) C H N calc (%) 81.36 5.65 3.95 found (%) 81.05 5.58 3.94 IR absorption spectrum, Imide characteristic absorption band 1
Absorption around 780 cm ^-1 and around 1720 cm ^-1 is remarkably observed, while 1 which is an amic acid characteristic absorption band.
Absorption around 550cm ^-1 , 3200-3400cm
The absorption of diamine around ^-1 and the absorption around 1850 cm ^-1 which is an acid anhydride characteristic absorption band were not recognized.

From the production method, the results of elemental analysis, and the infrared absorption spectrum, it was confirmed that the produced powder was a bisimide having a structure represented by the following formula (26).

[0253]

Embedded image The bisimide was dissolved in dichloromethane, chloroform and carbon tetrachloride in an amount of 5% by weight or more, and the workability was good.

Example 10 In the same reaction vessel as in Example 1, bis- [3- {4- (4
-Aminophenoxy) benzoyl @ phenyl] ether (592.7 g, 1.0 mol) and m-cresylic acid 48
325.6 g of phthalic anhydride were added at room temperature.
(2.2 mol), and the mixture was heated to 140 ° C. and reacted for 2 hours.

Next, the reaction solution was charged into methanol,
The precipitate was separated by filtration, washed several times with methanol, and dried at 100 ° C. under reduced pressure for 16 hours.
3 g (yield 96.2%) of a yellow powder was obtained. The melting point of the powder was 202 ° C. The results of the elemental analysis are as follows.

Elemental analysis (C ₅₄ H ₃₂ N ₂ O ₉ ) Calculated value for CH N (%) 76.06 3.76 3.29 Measured value (%) 76.18 3.85 3.42 FIG. 6 shows the infrared absorption spectrum of the sample.

In the infrared absorption spectrum, the imide characteristic absorption bands around 1780 cm ⁻¹ and 1720 cm ^{−1 were} observed.
^-1 is remarkably recognized, while the absorption around 1550 cm ^-1 which is the amic acid characteristic absorption band,
No absorption of diamine around 3400 cm ^-1 and no absorption near 1850 cm ^-1 which is an acid anhydride characteristic absorption band was observed.

From the production method, the results of elemental analysis and the infrared absorption spectrum, it was confirmed that the produced powder was a bisimide having a structure represented by the following formula (27).

[0259]

Embedded image The bisimide was dissolved in dichloromethane, chloroform and carbon tetrachloride in an amount of 5% by weight or more, and the workability was good.

Example 11 325.6 g of phthalic anhydride in Example 10 (2.2
Mol) is converted to 2,3-naphthalenedicarboxylic anhydride 436
909 g (yield 95%) of a yellow powder was obtained in the same manner as in Example 10 except that the amount was changed to 2.2 g.

The melting point of the powder was 176 ° C. The results of the elemental analysis are as follows. The elemental analysis _{(C 62 H 32 N 2 O} 9) C H N calc (%) 77.82 3.35 2.93 found (%) 77.68 3.45 3.02 IR absorption spectrum, Imide characteristic absorption band 1
Absorption around 780 cm ^-1 and around 1720 cm ^-1 is remarkably observed, while 1 which is an amic acid characteristic absorption band.
Absorption around 550cm ^-1 , 3200-3400cm
The absorption of diamine around ^-1 and the absorption around 1850 cm ^-1 which is an acid anhydride characteristic absorption band were not recognized.

From the production method, the results of elemental analysis and the infrared absorption spectrum, it was confirmed that the produced powder was a bisimide having a structure represented by the following formula (28).

[0263]

Embedded image The bisimide was dissolved in dichloromethane, chloroform and carbon tetrachloride in an amount of 5% by weight or more, and the workability was good.

Example 12 In the same reaction vessel as in Example 1, 4,4'-bis- (4-
Aminophenoxy) biphenyl (368.4 g, 1.0 mol) and m-cresol (3561 g) were charged, and at room temperature, 325.6 g (2.2 mol) of phthalic anhydride were added.
And the reaction was carried out for 2 hours. Next, methanol was charged to the reaction solution, the precipitate was separated by filtration, washed with methanol several times, and dried under reduced pressure at 100 ° C. for 16 hours to obtain 600.1 g (yield 95.5%). ) Was obtained as a pale yellow powder.

The melting point of the powder was 292 ° C. The results of elemental analysis were as follows. Elemental analysis _{(C 40 H 24 N 2 O} 6) C H N calc (%) 76.40 3.82 4.46 found (%) 76.72 3.92 4.51 In addition, the infrared of the powder FIG. 7 shows an absorption spectrum diagram.

In the infrared absorption spectrum, the characteristic absorption bands of imide, around 1780 cm ⁻¹ and 1720 cm ⁻¹ , were observed.
Absorption around ^-1 was remarkably observed. On the other hand, the absorption around 1550 cm ⁻¹ which is the amic acid characteristic absorption band, 3200
No absorption of diamine around ３3400 cm ⁻¹ and no absorption near 1850 cm ⁻¹ which is an acid anhydride characteristic absorption band was observed.

From the results of the production method, the results of elemental analysis, and the infrared absorption spectrum, it was confirmed that the produced powder was a bisimide having a structure represented by the following formula (29).

[0268]

Embedded image The bisimide was dissolved in dichloromethane, chloroform and carbon tetrachloride in an amount of 5% by weight or more, and the workability was good.

Example 13 325.6 g of phthalic anhydride in Example 12 was added to 2,2 g of phthalic anhydride.
696 g in the same manner as in Example 12 except that 436 g (2.2 mol) of 3-naphthalenedicarboxylic anhydride was used.
(95% yield) was obtained. The melting point of the powder was 293 ° C. The results of elemental analysis were as follows.

Elemental analysis (C ₄₈ H ₃₂ N ₂ O ₆ ) Calculated for CH N (%) 78.69 4.37 3.83 Measured value (%) 78.70 4.28 3.61 Infrared absorption spectrum in the figure, the absorption around 1780 cm ^-1 and around 1720 cm ^-1 which is the characteristic absorption band of imide were remarkably observed. On the other hand, the absorption around 1550 cm ⁻¹ which is the amic acid characteristic absorption band, 3200 to 3400 c
No absorption of diamine near m ^-1 and no absorption near 1850 cm ^-1 which is an acid anhydride characteristic absorption band was observed.

From the production method, the results of elemental analysis and the infrared absorption spectrum, it was confirmed that the produced powder was a bisimide having a structure represented by the following formula (30).

[0272]

Embedded image The bisimide was dissolved in dichloromethane, chloroform and carbon tetrachloride in an amount of 5% by weight or more, and the workability was good.

Example 14 The same reaction vessel as in Example 1 was charged with 2,2-bis- {4-
(4-aminophenoxy) phenyl @ propane
5 g (1.0 mol) and 3800 g of m-cresol were charged and, at room temperature, 325.6 g (2.2 mol) of phthalic anhydride.
Was added, and the temperature was raised to 140 ° C., and the reaction was performed for 2 hours. Next, methanol was charged into the reaction solution, the precipitate was separated by filtration, and further washed with methanol several times.
After drying at 00 ° C. for 16 hours, 612.8 g (yield 9) was obtained.
(1.4%). The melting point of the powder was 218 ° C (by DSC). The results of elemental analysis were as follows.

Elemental analysis (C ₄₃ H ₃₀ N ₂ O ₆ ) Calculated value for CH N (%) 77.01 4.48 4.18 Measured value (%) 76.84 4.55 4.26 FIG. 8 shows an infrared absorption spectrum of the sample.

In the infrared absorption spectrum, the characteristic absorption bands of imide, around 1780 cm ⁻¹ and 1720 cm ⁻¹ , were observed.
Absorption around ^-1 was remarkably observed. On the other hand, the absorption around 1550 cm ⁻¹ which is the amic acid characteristic absorption band, 3200
No absorption of diamine around ３3400 cm ⁻¹ and no absorption near 1850 cm ⁻¹ which is an acid anhydride characteristic absorption band was observed.

From the production method, the results of elemental analysis, and the infrared absorption spectrum, it was confirmed that the produced powder was a bisimide having a structure represented by the following formula (31).

[0277]

Embedded image The bisimide was dissolved in dichloromethane, chloroform and carbon tetrachloride in an amount of 5% by weight or more, and the workability was good.

Example 15 325.6 g of phthalic anhydride in Example 14 was added to 2,2 g of phthalic anhydride.
697 g in the same manner as in Example 14 except that 436 g (2.2 mol) of 3-naphthalenedicarboxylic anhydride was used.
A white powder (yield 90%) was obtained. The melting point of the powder was 219 ° C. The results of elemental analysis were as follows.

[0279] Elemental analysis _{(C 51 H 38 N 2 O} 6) C H N calc (%) 79.07 4.91 3.62 found (%) 78.72 5.05 3.54 IR spectrum in the figure, the absorption around 1780 cm ^-1 and around 1720 cm ^-1 which is the characteristic absorption band of imide were remarkably observed. On the other hand, the absorption around 1550 cm ⁻¹ which is the amic acid characteristic absorption band, 3200 to 3400 c
No absorption of diamine near m ^-1 and no absorption near 1850 cm ^-1 which is an acid anhydride characteristic absorption band was observed.

From the production method, the results of elemental analysis and the infrared absorption spectrum, it was confirmed that the powder produced was a bisimide having a structure represented by the following formula (32).

[0281]

Embedded image The bisimide was dissolved in dichloromethane, chloroform and carbon tetrachloride in an amount of 5% by weight or more, and the workability was good.

Example 16 400.5 g of bis- {4- (4-aminophenoxy) phenyl} sulfide was placed in a reaction vessel similar to that of Example 1.
(1.0 mol) and 3743 g of m-cresol,
At room temperature, 325.6 g (2.2 mol) of phthalic anhydride was added, the temperature was raised to 140 ° C., and the reaction was carried out for 2 hours. Next, methanol was charged to the reaction solution, and the precipitate was separated by filtration.
Further, after washing with methanol several times, 100
Drying at 16 ° C. for 16 hours gave 612.9 g (yield 92.8).
%) Of a white powder. Melting point of powder is 252 ℃
(By DSC). The results of elemental analysis were as follows.

Elemental analysis (C ₄₀ H ₂₄ N ₂ O ₆ S) Calculated value for CH NS (%) 72.70 3.64 4.24 4.85 Measured value (%) 72.66 3.73 4. 26 4.99 FIG. 9 shows an infrared absorption spectrum of this powder.

In the infrared absorption spectrum, the characteristic absorption bands of imide, around 1780 cm ⁻¹ and 1720 cm ⁻¹ , were observed.
Absorption around ^-1 was remarkably observed. On the other hand, the absorption around 1550 cm ⁻¹ which is the amic acid characteristic absorption band, 3200
No absorption of diamine around ３3400 cm ⁻¹ and no absorption near 1850 cm ⁻¹ which is an acid anhydride characteristic absorption band was observed.

From the production method, the results of elemental analysis, and the infrared absorption spectrum, it was confirmed that the produced powder was a bisimide having a structure represented by the following formula (33).

[0286]

Embedded image The bisimide was dissolved in dichloromethane, chloroform and carbon tetrachloride in an amount of 5% by weight or more, and the workability was good.

Example 17 In Example 16, 325.6 g of phthalic anhydride was added to 2,2 g of phthalic anhydride.
703 g in the same manner as in Example 16 except that 436 g (2.2 mol) of 3-naphthalenedicarboxylic anhydride was used.
A white powder (yield 92%) was obtained. The melting point of the powder was 253 ° C. The results of elemental analysis were as follows.

Elemental analysis (C ₄₈ H ₃₂ N ₂ O ₆ S) Calculated value for CH NS (%) 75.39 4.19 3.66 4.19 Measured value (%) 75.52 4.26 3. 42 in 3.88 IR absorption spectrum, absorption at around 1780 cm ^-1 and around 1720 cm ^-1 which is the characteristic absorption band of imide were remarkably observed. On the other hand, the absorption around 1550 cm ⁻¹ which is the amic acid characteristic absorption band, 3200 to 3400 c
No absorption of diamine near m ^-1 and no absorption near 1850 cm ^-1 which is an acid anhydride characteristic absorption band was observed.

From the production method, the results of elemental analysis and the infrared absorption spectrum, it was confirmed that the produced powder was a bisimide having a structure represented by the following formula (34).

[0290]

Embedded image The bisimide was dissolved in dichloromethane, chloroform and carbon tetrachloride in an amount of 5% by weight or more, and the workability was good.

Synthesis Example Synthesis of Polyimide-1 According to the examples described in JP-A-2-18419, 3,3 ′
Diaminobenzophenone and 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride are reacted in the presence of phthalic anhydride to give a logarithmic viscosity of 0.52 dl / g (where the logarithmic viscosity is parachlorophenol: 0.5 g / 100 ml using a mixed solvent of phenol (weight ratio 90:10)
This is a value measured after heating and dissolving at a concentration and cooling to 35 ° C.
The same applies hereinafter), glass transition temperature 250 ° C, melting point 298 ° C
A polyimide powder (according to DSC; the same applies hereinafter) was obtained.

Synthesis of Polyimide-2 As in the synthesis of polyimide-1, except that the ratio of diamine, tetracarboxylic dianhydride and phthalic anhydride was changed, the logarithmic viscosity was 0.85 dl / g, and the glass transition temperature was 262 ° C. A polyimide powder having a melting point of 298 ° C. was obtained.

Synthesis of Polyimide-3 According to JP-A-1-110530, 4,4′-bis (3
-Aminophenoxy) biphenyl, pyromellitic anhydride and phthalic acid gave a polyimide powder having an logarithmic viscosity of 0.53 dl / g. The glass transition temperature of this polyimide is 25
The melting point was 0 ° C. and the melting point was 390 ° C. (according to DSC).

Synthesis of Polyimide-4 As in the synthesis of Polyimide-3, except that the amount ratio of diamine, tetracarboxylic dianhydride and phthalic anhydride was changed, the logarithmic viscosity was 0.78 dl / g, and the glass transition temperature was 254 ° C. Thus, a polyimide powder having a melting point of 390 ° C. was obtained.

Synthesis of Polyimide-5 Similarly to the synthesis of Polyimide-3, bis [4- (3-aminophenoxy) phenyl] sulfide was combined with pyromellitic dianhydride and phthalic anhydride to have a logarithmic viscosity of 0.49 dl /.
g, a polyimide having a glass transition temperature of 235 ° C. was obtained.

Synthesis of Polyimide-6 Similarly to the synthesis of Polyimide-3, bis [4- (3-aminophenoxy) phenyl] ketone and bis (3,4-dicarboxyphenyl) ether dianhydride and phthalic anhydride were used. Logarithmic viscosity 0.51 dl / g, glass transition temperature 201
The polyimide of ° C was obtained.

Synthesis of Polyimide-7 Bis [4- @ 4-
(4-Aminophenoxy) phenoxydiphenyl] sulfone and pyromellitic anhydride and phthalic acid gave a polyimide powder having a logarithmic viscosity of 0.57 dl / g. This polyimide has a glass transition temperature of 285 ° C and a melting point of 420 ° C (D
SC).

Synthesis of Polyimides 8 to 12 Various polyimide powders were obtained in the same manner as in the synthesis of Polyimide-7, except that the type of tetracarboxylic dianhydride was changed. Table 2 summarizes the physical properties of the raw materials and the resulting polyimide. Table 2 also shows the results of polyimide-7.

[0299]

[Table 2]

Synthesis of Bisimide Compound-1 By the method of Example 1, bisimide having a melting point of 286 ° C. was obtained from 4,4′-bis (3-aminophenoxy) biphenyl and phthalic anhydride. Synthesis of Bisimide Compound-2 Similarly to the synthesis of bisimide compound-1, bis [4-
Bisimide having a melting point of 230 ° C. was obtained from (3-aminophenoxy) phenyl] sulfide and phthalic anhydride.

Synthesis of Bisimide Compound-3 A reaction vessel equipped with a stirrer, reflux condenser and nitrogen inlet tube was charged with 4,4'-diaminodiphenyl ether 200
g (1.0 mol) and 4000 g of m-cresol, 311 g (2.1 mol) of phthalic anhydride were added at room temperature, and the temperature was raised from room temperature to 200 ° C.
Continued stirring for hours. The reaction was then drained into methanol and filtered. Further, operations of dispersing and washing in methanol and filtering were repeated, and dried at 150 ° C. for 2 hours to obtain 450 g of a white powder. This powder had a melting point of 295 ° C. and melted at around 290 ° C., and had good melt processability. The results of the elemental analysis are as follows.

Elemental analysis (C ₂₈ H ₁₆ N ₂ O ₄ ) Calculated value of CH N (%) 73.36 3.06 6.11 Measured value (%) 73.30 3.10 6.16 This powder was also used. Is shown in FIG. This spectrum diagram, around 1780 cm ^-1 and near 1720 cm ^-1 which is the characteristic absorption band of imide, and absorption at around 1240 cm ^-1 which is the characteristic absorption band of ether linkage markedly observed.

From the production method, elemental analysis and infrared absorption spectrum, it was confirmed that the produced powder was bisimide represented by the following formula (35).

[0304]

Embedded image

Synthesis of bisimide compound-4 By the method of Example 5, bisimide having a melting point of 240 ° C. was obtained from 3,3′-diaminobenzophenone and phthalic anhydride. Synthesis of Bisimide Compound-5 By the method of Example 12, bisimide having a melting point of 292 ° C. was obtained from 4,4′-bis (4-aminophenoxy) biphenyl and phthalic anhydride. Synthesis of Bisimide Compounds-6 to 12 Various bisimides were obtained in the same manner as in the synthesis of bisimide compound-5, except that the type of diamine was changed. Table 3 summarizes the physical properties of the starting materials and the resulting bisimide. Table 3 also shows the results of the aromatic bisimide compound-5.

[0306]

[Table 3]

Examples 18 to 20, Comparative Example 2 Polyimide-1 and bisimide compound-1 were dry-blended in the proportions shown in Table 4. The obtained resin composition was maintained at a temperature of 380 ° C. for 5 minutes using an orifice having a diameter of 0.1 cm and a length of 1 cm with a Koka type flow tester (Shimadzu Corporation) and then extruded with a load of 100 kg, and the melt viscosity was measured. did. Table 4 shows the results. As the ratio of the bisimide compound increases, the melt viscosity sharply decreases, indicating that the processability has improved.

Examples 21 to 23, Comparative Example 3 Polyimide-2 and bisimide compound-2 were dry-blended in the proportions shown in Table 4. After maintaining the temperature at 400 ° C. for 5 minutes in the same manner as in Examples 18 to 20, the melt viscosity was measured, and the results shown in Table 4 were obtained.

Examples 24 to 26 In the same manner as in Examples 18 to 20, except that bisimide was replaced with bisimide compound-3, dry blending was performed at the ratio shown in Table 4, and the mixture was held at 380 ° C. for 5 minutes and then extruded with a load of 100 kg. The results shown in Table 4 were obtained.

[0310]

[Table 4]

Examples 27 to 32, Comparative Example 4 Polyimide-3 and bisimide compound-1 or bisimide compound-3 were dry blended in the proportions shown in Table 5. The resulting resin composition was maintained at a temperature of 400 ° C. for 5 minutes using an orifice having a diameter of 0.1 cm and a length of 1 cm with a Koka type flow tester (Shimadzu Corporation) and then extruded with a load of 100 kg, and the melt viscosity was measured. did. Table 5 shows the results. As the ratio of the bisimide compound increases, a sharp decrease in the melt viscosity is observed, indicating that the processability is improved.

Examples 33 to 35, Comparative Example 5 Polyimide-5 and bisimide compound-1 were dry-blended in the proportions shown in Table 5. The melt viscosity was measured in the same manner as in Examples 27 to 32 except that the temperature was maintained at 360 ° C. for 5 minutes, and the results shown in Table 5 were obtained.

Examples 36 to 38, Comparative Example 6 Polyimide-6 and bisimide compound-1 were dry-blended in the proportions shown in Table 5 and held at 340 ° C. for 5 minutes.
Extrusion was performed with a load of 00 kg, and the results shown in Table 5 were obtained.

[0314]

[Table 5]

Examples 39 to 42, Comparative Example 7 Polyimide-1 and bisimide compound-4 were dry blended in the proportions shown in Table 6. The obtained resin composition was maintained at a temperature of 380 ° C. for 5 minutes using an orifice having a diameter of 0.1 cm and a length of 1 cm with a Koka type flow tester (Shimadzu Corporation) and then extruded with a load of 100 kg, and the melt viscosity was measured. did. Table 6 shows the results. As the ratio of the bisimide compound increases, the melt viscosity sharply decreases, indicating that the processability has improved.

Examples 43 to 45, Comparative Example 8 Polyimide-2 and bisimide compound-4 were dry-blended in the proportions shown in Table 6. As in Examples 39-42,
However, after keeping at a temperature of 400 ° C. for 5 minutes, the melt viscosity was measured, and the results shown in Table 6 were obtained.

[0317]

[Table 6]

Examples 46 to 51, Comparative Example 9 Polyimide-3 and bisimide compound-5 or bisimide compound-7 were dry-blended in the proportions shown in Table 7. The obtained resin composition was measured with a Koka type flow tester (CFT-500, manufactured by Shimadzu Corporation) to have a diameter of 0.1 cm and a length of 1.
After maintaining the temperature at 400 ° C. for 5 minutes using an orifice having a diameter of 5 cm, the melt viscosity was measured by extruding with a load of 100 kg.

The results are shown in Table 7. As the ratio of the bisimide compound increases, the melt viscosity sharply decreases, indicating that the processability has improved.

Examples 52 to 57 and Comparative Example 10 Polyimide-4 and bisimide compound-5 or bisimide compound-11 were dry-blended at the ratios shown in Table 7. The melt viscosity was measured in the same manner as in Examples 46 to 51 and Comparative Example 9, and the results shown in Table 7 were obtained.

Examples 58 to 63 and Comparative Example 11 Polyimide-5 and bisimide compound-6 or bisimide compound-8 were dry blended in the proportions shown in Table 7,
After holding at a temperature of 360 ° C. for 5 minutes, it was extruded with a load of 100 kg, and the results shown in Table 7 were obtained.

Examples 63-71, Comparative Example 12 Polyimide-6 and bisimide compound-9, -10 or -12 were dry blended in the proportions shown in Table 7 to obtain 340
After holding at a temperature of 5 ° C. for 5 minutes, it was extruded with a load of 100 kg, and the results shown in Table 7 were obtained.

[0323]

[Table 7]

Examples 72 to 77 and Comparative Example 13 Polyimide-7 and bisimide compound-1 or bisimide compound-3 were dry blended in the proportions shown in Table 8. The obtained resin composition was measured with a Koka type flow tester (CFT-500, manufactured by Shimadzu Corporation) to have a diameter of 0.1 cm and a length of 1.
After maintaining the temperature at 420 ° C. for 5 minutes using an orifice having a diameter of 5 cm, the melt viscosity was measured by extrusion with a load of 100 kg. Table 8 shows the results. As the proportion of the bisimide compound increased, the melt viscosity sharply decreased, indicating that the processability was improved.

Examples 78 to 83, Comparative Example 14 Polyimide-8 and bisimide compound-5 or bisimide compound-7 were dry blended in the proportions shown in Table 8. The melt viscosity was measured in the same manner as in Examples 72 to 77 and Comparative Example 13, and the results shown in Table 8 were obtained.

Examples 84 to 89, Comparative Example 15 Polyimide-9 and bisimide compound-1 or bisimide compound-8 were dry-blended in the proportions shown in Table 8,
After holding at a temperature of 380 ° C. for 5 minutes, it was extruded with a load of 100 kg, and the results shown in Table 8 were obtained.

Examples 90 to 93, Comparative Example 16 Polyimide-10 and bisimide compound-9 or bisimide compound-11 were dry-blended in the proportions shown in Table 8 and held at a temperature of 360 ° C. for 5 minutes. Extrusion was performed under load, and the results shown in Table 8 were obtained.

Examples 94 to 96 and Comparative Example 17 Polyimide-11 and bisimide compound-12 were dry-blended in the proportions shown in Table 8, held at a temperature of 370 ° C. for 5 minutes, and extruded with a load of 100 kg. The results shown in Table 8 were obtained.

Examples 97 to 99, Comparative Example 18 Polyimide-12 and bisimide compound-10 were dry-blended in the proportions shown in Table 8, kept at 340 ° C. for 5 minutes, and extruded with a load of 100 kg. The results shown in Table 8 were obtained.

By adding the bisimide, the viscosity of the resin at the time of melting was greatly reduced, and the moldability was improved.

[0331]

[Table 8] Table 8 (**) Melt viscosity is below the lower limit of measurable 100 poise

Examples 100 to 102 Bisimide compounds obtained according to Example 1 using 4,4-bis (3-aminophenoxy) biphenyl and phthalic anhydride as raw materials (logarithmic viscosity 0.52 dl / g, glass transition temperature 250 20% by weight, dichloromethane 40% by weight,
A bisimide solution consisting of 40% by weight of 1,2-trichloroethane was prepared. A roving of acrylic carbon fiber (product name: HTA, manufactured by Toho Rayon Co., Ltd., manufactured by Toho Rayon Co., Ltd., in the following Examples and Comparative Examples, except that carbon fiber was used unless otherwise specified) was applied to the bisimide solution for 60 rovings.
After continuous immersion at a speed of m / Hr, drying and desolvation, it was cut into a length of 3 mm to obtain a chopped strand. At this time, the adhesion amount of the bisimide compound to the carbon fibers was 5% by weight.

The carbon fiber chopped strands thus obtained and the polyimide-4 were dry-blended in the proportions shown in Table 9 and then extruded at an extrusion temperature of 40 mm with a 40 mm diameter extruder.
Extrusion operation was performed while melt-kneading at 00 ° C. to obtain a uniformly blended pellet. Next, the uniform pellets were subjected to a cylinder temperature of 410 ° C. and a mold temperature of 2 using an ordinary injection molding machine.
A dumbbell specimen was prepared at a temperature of 00 ° C.
The tensile strength was measured at 3 ° C. at a tensile speed of 5 mm / min. The results are shown in Table 9.

Comparative Examples 19 to 20 The same procedures as in Examples 100 to 102 were conducted except that acrylic carbon fibers bundled with an epoxy resin were used instead of the carbon fiber chopped strands coated with a bisimide compound in Examples 100 to 102. A dumbbell test piece of a carbon fiber-containing polyimide resin was prepared by the operation, and the tensile strength was measured in the same manner. The results are shown in Table 9 together with the values of Examples 100 to 102.

[0335]

[Table 9]

Examples 103 to 105 Bisimide compounds obtained according to Example 3 using bis [4- (3-aminophenoxy) phenyl] sulfide and phthalic anhydride (melting point: 230 ° C., hereinafter simply referred to as bisimide-B Say). Next, a roving of carbon fiber whose surface has been oxidized is continuously melt-impregnated at a rate of 30 m / Hr into the bisimide melted at 240 ° C.
It was cut into mm length to obtain chopped strands. At this time, the adhesion amount of the bisimide compound to the carbon fibers was 7% by weight.

The carbon fiber chopped strands thus obtained and the polyimide-5 were dry-blended at the ratios shown in Table 10, and then extruded while being melt-kneaded at an extrusion temperature of 360 ° C. with a 40 mm diameter extruder. To obtain a uniformly blended pellet. Next, a dumbbell test piece was prepared from the above uniform blended pellet using a normal injection molding machine under the conditions of a cylinder temperature of 360 ° C and a mold temperature of 180 ° C, and the tensile strength was measured at a temperature of 23 ° C and a tensile speed of 5 mm / min. The measurement was performed, and the results are shown in Table 10.

Comparative Examples 22 to 23 The same procedures as in Examples 102 to 104 were carried out except that the mixing ratio of the carbon fibers coated with the polyimide and the bisimide compound was changed, and the results shown in Table 10 were obtained. The pellet containing 60% by weight of carbon fiber had poor melt fluidity, and a dumbbell specimen could not be prepared by injection molding.

[0339]

[Table 10]

Examples 106 to 108 In the same manner as in Examples 100 to 102, except that the polyimide resin was changed to polyimide-6 instead of polyimide-4, and the extrusion temperature was set to 320 ° C., to obtain uniformly mixed pellets. next,
Using a conventional injection molding machine, a dumbbell test piece was prepared from the above uniform blended pellet under the conditions of a cylinder temperature of 330 ° C. and a mold temperature of 160 ° C., at a temperature of 23 ° C. and a tensile speed of 5 m.
The tensile strength was measured at m / min, and the results are shown in Table 11.

Comparative Example 24 A dumbbell test piece was prepared in the same manner as in Examples 106 to 108 except that the polyimide resin was used alone without mixing with the carbon fiber, and the values shown in Table 11 were obtained.

[0342]

[Table 11]

Examples 109 to 111 In the same manner as in Examples 106 to 108, except that the polyimide resin was changed to polyimide-1 instead of polyimide-4, and the extrusion temperature was set to 360 ° C., to obtain uniformly blended pellets. next,
A dumbbell test piece was prepared from the uniform blended pellet using a normal injection molding machine under the conditions of a cylinder temperature of 380 ° C. and a mold temperature of 180 ° C.
/ Min was measured for tensile strength, and the results are shown in Table 12.

Comparative Examples 25 to 27 The same as Examples 109 to 111 except that acrylic carbon fibers converged with an epoxy resin were used instead of the carbon fiber chopped strands coated with the bisimide compound in Examples 109 to 111. A dumbbell test piece of a carbon fiber-containing polyimide resin was prepared by the operation, and the tensile strength was measured in the same manner. The results are shown in Table 12.

[0345]

[Table 12]

Examples 112 to 114 Dichloromethane 40% by weight, 1,1,2-trichloroethane 40% by weight, Bisimide compound obtained in Synthesis Example
A bisimide solution comprising 3% (hereinafter simply referred to as bisimide C) of 20% by weight was prepared. A roving of acrylic carbon fiber (trade name: HTA, manufactured by Toho Rayon Co., Ltd., manufactured by Toho Rayon Co., Ltd., in the following examples and comparative examples, except that carbon fiber was used unless otherwise specified) was applied to the bisimide solution for 60 m. / Hr, immersed continuously, dried and desolvated, and cut into 3 mm lengths to obtain chopped strands. At this time, the amount of the attached bisimide to the carbon fibers was 5% by weight.

The thus obtained carbon fiber chopped strands and polyimide-4 were dry-blended in the proportions shown in Table 13 and then extruded while being melt-kneaded at an extrusion temperature of 400 ° C. by a 40 mm diameter extruder. To obtain a uniformly blended pellet. Next, a dumbbell test piece was prepared from the uniform pellet under a temperature condition of cylinder temperature 400 ° C. and mold temperature 200 ° C. using a normal injection molding machine,
The tensile strength was measured at a temperature of 23 ° C. and a tensile speed of 5 mm / min,
Table 13 shows the results.

Comparative Examples 28 to 30 The same procedures as in Examples 112 to 114 were carried out except that acrylic carbon fibers bundled with an epoxy resin were used instead of the carbon fiber chopped strands coated with the bisimide compound in Examples 112 to 114. A dumbbell test piece of a carbon fiber-containing polyimide resin was prepared by the above operation, and the tensile strength was measured in the same manner. The results are shown in Table 13 in Examples 112 to 11.
4 are shown together with the results.

[0349]

[Table 13]

Examples 115 to 117 Bisimide C, whose roving of carbon fiber whose surface was oxidized was melted at 300 ° C., was continuously melt-impregnated at a rate of 30 m / Hr, cut into 3 mm lengths, and chopped. Strand. At this time, the adhesion amount of the bisimide compound to the carbon fibers was 7% by weight.

The thus obtained carbon fiber chopped strands and polyimide-5 were dry-blended at the ratios shown in Table 14 and then extruded while being melt-kneaded at an extrusion temperature of 360 ° C. by a 40 mm diameter extruder. To obtain a uniformly blended pellet. Next, a dumbbell test piece was prepared from the above uniform blended pellet using a normal injection molding machine under the conditions of a cylinder temperature of 360 ° C and a mold temperature of 180 ° C, and the tensile strength was measured at a temperature of 23 ° C and a tensile speed of 5 mm / min. The measurement was performed, and the results are shown in Table 14.

Comparative Examples 31-32 The same procedures as in Examples 115-117 were carried out except that the mixing ratio of the carbon fibers coated with polyimide and bisimide was changed, and the results shown in Table 14 were obtained. The pellet containing 60% by weight of carbon fiber had poor melt fluidity, and a dumbbell specimen could not be produced by injection molding.

[0353]

[Table 14]

Examples 118 to 120 In the same manner as in Examples 112 to 114 except that polyimide was changed to polyimide-6 instead of polyimide-4, and the extrusion temperature was set to 320 ° C., to obtain uniformly blended pellets. Next, a dumbbell specimen was prepared from the uniform blended pellet using a normal injection molding machine under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 160 ° C., and a tensile strength of 23 ° C. at a tensile speed of 5 mm / min. The measurement was performed, and the results shown in Table 15 were obtained.

Comparative Example 33 A dumbbell test piece was prepared in the same manner as in Examples 118 to 120 except that the polyimide resin was used alone without mixing with carbon fiber, and the results shown in Table 15 were obtained.

[0356]

[Table 15]

[0357]

Industrial Applicability The polyimide resin composition of the present invention is a composition comprising an aromatic bisimide compound in a polyimide, and has improved moldability and processability, and the improved carbon fiber and polyimide resin of the present invention. Can be formed into a desired molded product by a known molding method such as an injection molding method, an extrusion molding method, a transfer molding method, and a compression molding method.

The resin composition of the present invention thus formed is excellent in mechanical strength, particularly mechanical strength at high temperatures. Therefore, mechanical parts requiring high mechanical strength at high temperatures, automobile parts, such as gears , Cams, bushings, pulleys, sleeves, etc., and exhaust system parts for silencers such as impellers and manifolds for integrated centrifugal compressors, valve guides, valve stems, piston skirts, oil pans, front parts for internal combustion engines Can be used for covers and rocker covers.

The carbon fiber reinforced polyimide resin composition according to the present invention is usually made into a pellet-shaped molding material which is easy to handle, and a product is produced by injection molding. At this time, the pellets are formed by kneading and extruding the polyimide resin and the carbon fiber strand using a known single-screw or twin-screw extruder, and then cutting. The injection molding of the obtained pellet r was performed using a normal injection molding machine, and the cylinder temperature was 360 to 360.
420 ° C, mold temperature 160-210 ° C, preferably 18
It can be performed at 0 to 200 ° C., and a molded article having a complicated shape can be easily obtained.

The carbon fiber reinforced polyimide resin composition according to the present invention has excellent mechanical strength, and is used as a material for parts in various industries such as electric and electronic equipment, machinery, automobiles, aviation and space equipment, and general industrial equipment. Its industrial value is great because it can be widely used. further,
The bisimide compound of the present invention is an extremely useful compound for a composition having a polyimide resin having such excellent performance.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of the bisimide obtained in Example 1.

FIG. 2 is an infrared absorption spectrum of the bisimide obtained in Comparative Example 1.

FIG. 3 is an infrared absorption spectrum of the bisimide obtained in Example 5.

FIG. 4 is an infrared absorption spectrum of the bisimide obtained in Example 6.

FIG. 5 is an infrared absorption spectrum of the bisimide obtained in Example 8.

FIG. 6 is an infrared absorption spectrum of the bisimide obtained in Example 10.

FIG. 7 is an infrared absorption spectrum of the bisimide obtained in Example 12.

FIG. 8 is an infrared absorption spectrum of the bisimide obtained in Example 14.

FIG. 9 is an infrared absorption spectrum of the bisimide obtained in Example 16.

FIG. 10 is an infrared absorption spectrum of bisimide-3 obtained in a synthesis example.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 79/08 C07D 209 / 48Z (31) Priority claim number Japanese Patent Application No. 3-61685 (32) Priority date March 26, 1991 (1991. 3.26) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-86558 (32) Priority date April 18, 1991 (1991.4.3.18) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-156792 (32) Priority date June 27, 1991 (June 27, 1991) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-160211 (32) Priority date July 1, 1991 (1991.7.1) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-218286 (32) Priority date August 29, 1991 (1991.29.29) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-231295 (32) Priority date September 11, 1991 (1991.11.11) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-231296 (32) Priority date September 11, 1991 (1991.11.11) (33) Priority claiming country Japan (JP) (31) Priority claim number 32) Priority date October 29, 1991 (Oct. 29, 1991) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-287660 (32) Priority date 1991 November 1, 1991 (11.1.1) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-287661 (32) Priority date November 1, 1991 (1991. 11.1) (33) Priority Country Japan (JP) (72) Inventor Fumiaki Kuwano 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Chemicals, Inc. (72) Inventor Eiji Segami Asamuta-cho, Omuta-shi, Fukuoka 30 Mitsui Chemicals, Inc. (72) Inventor Osamu Yasui 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Chemicals, Inc. (72) Inventor Ikuki Yoshida 30 Asamuta-cho, Omuta-shi, Fukuoka Prefecture Mitsui Chemicals Co., Ltd. Mitsui Chemicals, Inc. 30 Asamuta-cho, Omuta-shi, Fukuoka

Claims (15)

[Claims] 1. A compound of the general formula (1) [Wherein A is (Where B represents a direct bond, a group selected from a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a thio group, an ether group and a sulfonyl group,
The nitrogen atoms independently occupy the para, ortho, or meta positions relative to B. ), Embedded image (Where Z represents a carbonyl group or a sulfonyl group), (Here, the two carbonyl groups occupy the para or meta position with respect to the central benzene nucleus, and when the two carbonyl groups occupy the para position with respect to the central benzene nucleus, the nitrogen atoms at both ends are ether-bonded. When two carbonyl groups occupy the meta position with respect to the central benzene nucleus, the nitrogen atoms at both ends occupy the para or meta position with respect to the ether bond.) Embedded image (Wherein the two isopropylidene groups occupy the para-position or the meta-position with respect to the central benzene nucleus). R represents a monocyclic aromatic group or a condensed polycyclic group. A cyclic aromatic group, or a divalent group selected from the group consisting of a non-fused polycyclic aromatic group in which the aromatic groups are directly or mutually linked by a bridge member. 2. A compound of the general formula (10) [In the formula, B represents a group selected from a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a thio group, an ether group and a sulfonyl group. Independently occupies the para, ortho or meta positions. R is a divalent group selected from the group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridge member. Represents a group. The bisimide compound according to claim 1, which is represented by the formula: 3. A compound of the general formula (14) (In the formula, Z represents a carbonyl group or a sulfonyl group, and R represents a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic ring in which aromatic groups are connected to each other directly or by a bridge member. A bisimide compound according to claim 1, which represents a divalent group selected from the group consisting of aromatic groups. 4. A compound of the general formula (15) Wherein R is selected from the group consisting of a monocyclic aromatic group, a fused polycyclic aromatic group, and a non-fused polycyclic aromatic group in which the aromatic groups are interconnected directly or by a bridging member. The two carbonyl groups occupy the para or meta positions with respect to the central benzene nucleus, and when the two carbonyl groups occupy the para position with respect to the central benzene nucleus, When the nitrogen atoms occupy the para or meta positions with respect to the ether bond and the two carbonyl groups occupy the meta position with respect to the central benzene nucleus, the nitrogen atoms at both ends are para or meta with respect to the ether bond. The bisimide compound according to claim 1, which is represented by the following formula: 5. A compound of the general formula (16) Wherein R is selected from the group consisting of a monocyclic aromatic group, a fused polycyclic aromatic group, and a non-fused polycyclic aromatic group in which the aromatic groups are interconnected directly or by a bridging member. 2. The bisimide compound according to claim 1, wherein the bisimide compound is a divalent group, and the two isopropylidene groups occupy para or meta positions with respect to a central benzene nucleus. 6. Polyimide and a compound represented by the general formula (10): [In the formula, B represents a group selected from a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a thio group, an ether group and a sulfonyl group. Independently occupies the para, ortho or meta positions. R is a divalent group selected from the group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridge member. A bisimide compound represented by the formula:
General formula (14) [In the formula, Z represents a carbonyl group or a sulfonyl group,
R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic ring in which aromatic groups are connected to each other directly or by a crosslinking member. A divalent group selected from the group consisting of aromatic groups of the formula: Wherein R is selected from the group consisting of a monocyclic aromatic group, a fused polycyclic aromatic group, and a non-fused polycyclic aromatic group in which the aromatic groups are interconnected directly or by a bridging member. The two carbonyl groups occupy the para or meta positions with respect to the central benzene nucleus, and when the two carbonyl groups occupy the para position with respect to the central benzene nucleus, When the nitrogen atoms occupy the para or meta positions with respect to the ether bond and the two carbonyl groups occupy the meta position with respect to the central benzene nucleus, the nitrogen atoms at both ends are para or meta with respect to the ether bond. A bisimide compound represented by the general formula (16): Wherein R is selected from the group consisting of a monocyclic aromatic group, a fused polycyclic aromatic group, and a non-fused polycyclic aromatic group in which the aromatic groups are interconnected directly or by a bridging member. A polyimide resin composition containing an aromatic bisimide compound selected from bisimide compounds represented by a divalent group, wherein two isopropylidene groups occupy para or meta positions with respect to a central benzene nucleus. 7. The polyimide is represented by the following general formula (9): (In the formula, R ′ is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group connected directly or by a crosslinking member. The polyimide resin composition according to claim 6, which is a polyimide having a repeating structural unit represented by a non-condensed polycyclic aromatic group. 8. The polyimide is represented by the general formula (11): (In the formula, X represents a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group or a sulfonyl group, and Y1 to Y4 each independently represent hydrogen, Represents a lower alkyl group, a lower alkoxy group, a chlorine or bromine atom, and R ′ is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group. Wherein the group represents a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups which are connected to each other directly or by a cross-linking member). Polyimide resin composition. 9. The polyimide is represented by the following general formula (17): (In the formula, R ′ is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group connected directly or by a crosslinking member. The polyimide resin composition according to claim 6, which is a polyimide having a repeating structural unit represented by the following formula (4) which represents a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups. 10. The polyimide resin composition according to claim 6, wherein 0.5 to 100 parts by weight of the aromatic bisimide compound is blended with respect to 100 parts by weight of the polyimide. 11. Polyimide and a compound represented by the general formula (10) [In the formula, B represents a group selected from a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a thio group, an ether group and a sulfonyl group. Independently occupies the para, ortho or meta positions. R is a divalent group selected from the group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridge member. A bisimide compound represented by the formula:
General formula (14) [In the formula, Z represents a carbonyl group or a sulfonyl group,
R represents an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic ring in which aromatic groups are connected to each other directly or by a bridge member. A divalent group selected from the group consisting of an aromatic group represented by the general formula (15): Wherein R is selected from the group consisting of a monocyclic aromatic group, a fused polycyclic aromatic group, and a non-fused polycyclic aromatic group in which the aromatic groups are interconnected directly or by a bridging member. It represents a divalent group, and the two carbonyl groups occupy the para or meta positions with respect to the central benzene nucleus, and when the two carbonyl groups occupy the para position with respect to the central benzene nucleus, When the nitrogen atoms occupy the para or meta positions with respect to the ether bond and the two carbonyl groups occupy the meta position with respect to the central benzene nucleus, the nitrogen atoms at both ends are para or meta with respect to the ether bond. A bisimide compound represented by the general formula (16): Wherein R is selected from the group consisting of a monocyclic aromatic group, a fused polycyclic aromatic group, and a non-fused polycyclic aromatic group in which the aromatic groups are interconnected directly or by a bridging member. Represents a divalent group, and the two isopropylidene groups occupy the para position or the meta position with respect to the central benzene nucleus). A carbon fiber reinforced polyimide resin composition comprising: 12. The polyimide is represented by the following general formula (9): (In the formula, R ′ is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group connected directly or by a crosslinking member. And a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups). 13. A polyimide represented by the following general formula (11): (Wherein, X represents a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group or a sulfonyl group, and Y _{1 to} Y ₄ each independently represent Hydrogen, a lower alkyl group, a lower alkoxy group, a chlorine or bromine atom, and R ′ is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, Wherein the aromatic group represents a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups which are interconnected directly or by a bridging member). The carbon fiber reinforced polyimide resin composition according to the above. 14. A polyimide represented by the general formula (17): (In the formula, R ′ is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group connected directly or by a crosslinking member. The carbon fiber-reinforced polyimide resin composition according to claim 11, which is a polyimide having a repeating structural unit represented by the following formula: (a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups). 15. An aromatic bisimide compound having a surface coated with 5 to 50 parts by weight of a carbon fiber and 95 to 50 parts by weight of a polyimide.
15. The carbon fiber reinforced polyimide resin composition according to claim 11, comprising parts by weight.