JPH09188812A - Crystallization accelerator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crystallization accelerator for a crystalline polyimide by mixing at least one compd. having a bisimide structure represented by a specific formula with a carbon powder. SOLUTION: A bisimide compd. represented by formula l or III (wherein R1 is a 630C divalent arom. group; X is a group represented by formula II; X1 is a direct bond, an ether bond, etc.; R2 is Cn H2n+1 or a 6-30C monovalent arom. group; Y is a group represented by formula IV; and Y1 is a direct bond, an ether bond, etc.) is obtd. by imidizing 1 equivalent of a diamine (e.g. diaminodiphenyl ether) with about 2-2.5 equivalents of a dicarboxylic anhydride (e.g. phthalic anhydride) in an org. solvent at about 25 deg.C or lower. A crystallization accelerator for a crystalline polyimide is obtd. by mixing the bisimide compd. with a carbon powder (e.g. carbon black) in a wt. ratio of (1:9)-(9:1). A polyimide resin compsn. is prepd. by mixing and melt kneading 100 pts.wt. crystalline polyimide with 1-50 pts.wt. above accelerator and, if necessary, up to 70 pts.wt. reinforcement (e.g. carbon fibers) with an extruder, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a crystallization accelerator for crystalline polyimide. More specifically, it relates to a crystallization accelerator for crystalline polyimide, a method for producing them, and a polyimide resin composition comprising a crystalline polyimide and a crystallization accelerator.

[0002]

2. Description of the Related Art In addition to its excellent heat resistance, polyimide has excellent properties such as mechanical properties, chemical resistance and flame resistance, and electrical properties. Therefore, it is used in the fields of molding materials, composite materials, electric / electronic parts, etc. Widely used. Molding materials and polyimides for composite materials are trade name Vespel (made by DuPont) or trade name Upimol (made by Ube Industries)
However, since all polyimides are insoluble and infusible, they must be molded using a special method such as sintering molding via the precursor polyamic acid, which makes molding processability difficult. There is. Further, this method is difficult to obtain a processed product having a complicated shape, and in order to obtain a satisfactory molded product, a finishing process such as cutting must be further performed, which poses a serious problem in the process and cost. An injection-moldable thermoplastic polyetherimide having improved molding processability is represented by the formula (A)

[0003]

[Chemical 6] A polyimide having a repeating structural unit represented by (General Electric Co .; trade name Ultem) is known (US Pat. No. 3,730,946, 3,84).
7,867,3,847,869). However, since this polyimide is completely amorphous and has a glass transition temperature (Tg) of 215 ° C., it cannot be said that it has sufficient heat resistance. That is, taking the deflection temperature under load (DTUL), which is the practical limit temperature, as an example,
When the carbon fiber reinforcing material is not used, Ultem is 200 ° C., and when the carbon fiber content is 30 wt%, Ultem is as low as 212 ° C., which is not satisfactory heat resistance for super engineering plastics. On the other hand, an injection-moldable thermoplastic polyimide having excellent moldability and heat resistance is represented by the formula (3)

[0004]

Embedded image A polyimide having a repeating structural unit represented by the formula (manufactured by Mitsui Toatsu Chemical Co., Inc .; trade name AURUM) has been developed (Japanese Patent Laid-Open No. Sho-6).
2-68817). Since this polyimide has a glass transition temperature of 250 ° C, DTUL has no reinforcement.
AURUM has a heat resistance of 238 ° C, and AURUM containing 30 wt% of carbon fiber (hereinafter referred to as CF30-AURUM) has a heat resistance of 248 ° C, which is higher than that of the polyimide / Ultem described above.

Furthermore, the polyimide of formula (3) is crystalline in nature. When the polyimide of the formula (3) is cooled from the molten state, it remains in an amorphous state at a cooling rate of 10 ° C./min or more, but crystallization proceeds at less than 10 ° C./min. Further, it can be crystallized by a specific heat treatment (annealing treatment). D when crystallized
UTL is AURUM at 260 ℃ without reinforcement, CF30-AU
RUM has a very high heat resistance of 349 ° C. Therefore, various methods for controlling the crystallization or the crystallization rate have been studied. For example, as a method for reducing the crystallization rate, there is a method in which a predetermined amount of the third component monomer is copolymerized and introduced into the polyimide of the formula (3) (Japanese Patent Laid-Open No. 03-47837). However, this technique aims at delaying crystallization, and there is a method for keeping the amorphous state for a long time.

On the other hand, a method for speeding up crystallization has not been found yet. If the crystallization rate becomes extremely high, the molded product can be crystallized in the mold during injection molding, and no special treatment such as the above-mentioned annealing treatment is required. From such a viewpoint, in the field of crystalline polyimide capable of melt injection molding (for example, AURUM described above), development of a crystallization accelerator for increasing the crystallization rate is desired.

[0007]

SUMMARY OF THE INVENTION The present invention provides a mixed crystallization accelerator of bisimide and carbon powder for increasing the crystallization rate of crystalline polyimide.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the inventors have found that a mixture of bisimide and carbon powder having a specific structure remarkably accelerates the crystallization rate of crystalline polyimide. We have found this and completed the present invention.

That is, the present invention provides [1] general formula (1)

[0010]

Embedded image (In the formula, R 1 represents a divalent aromatic group having 6 to 30 carbon atoms,
Is Represents at least one divalent group selected from Here, X1 is a direct bond, an ether bond, a sulfide bond, a hydrocarbon group having 1 to 10 carbon atoms, a carbonyl group, a sulfonyl group, a hexafluorinated isopropylidene group, or an aromatic group having 6 to 18 carbon atoms. It represents at least one or more divalent groups from the group consisting of ) And / or general formula (2)
(Chemical formula 9)

[0011]

Embedded image (In the formula, R 2 is —C _n H _{2n + 1} (n = 0 to 3) or a monovalent aromatic group having 6 to 30 carbon atoms, and Y is Is a tetravalent group consisting of Here, Y1 is composed of a direct bond, an ether bond, a sulfide bond, a hydrocarbon group having 1 to 10 carbon atoms, a carbonyl group, a sulfonyl group, a hexafluorinated isopropylidene group, and an aromatic group having 6 to 18 carbon atoms. It represents at least one divalent group from the group. ) A crystallization accelerator for crystalline polyimide, comprising a mixture of at least one compound having a bisimide structure represented by the formula (1) and carbon powder. [2] In the general formula (1), X is a diphenyl ether group and R1 is a benzene ring.
0)

[0012]

Embedded image The crystallization accelerator for crystalline polyimide according to [1], which comprises a bisimide represented by the following as a main component. [3] and in the general formula (2), Y is a biphenyl group, and R2 is a benzene ring or a benzene ring substituted at the para position.

[0013]

Embedded image (In the formula, R ′ is —C _n H _{2n + 1} (n = 0 to 3), The crystallization accelerator for crystalline polyimide according to [1], which comprises a bisimide represented by the following as a main component. [4] The main component of carbon powder is carbon black [1]
A crystallization accelerator for the crystalline polyimide described. [5] A mixture of the bisimide compound represented by the general formula (1) and / or the general formula (2) and carbon powder,
The crystallization accelerator for crystalline polyimide according to [1], wherein the weight ratio of the bisimide mixture and the carbon powder is 1/9 to 9/1. [6] Formula (3) (Formula 12)

[0014]

Embedded image For a crystalline polyimide comprising a mixture of a bisimide compound represented by the general formula (1) and / or the general formula (2) and a carbon powder with respect to 100 parts by weight of the crystalline polyimide having a repeating structural unit represented by Crystallization accelerator 1-5
A polyimide resin composition containing 0 part by weight. [7] 100 parts by weight of the polyimide resin composition described in [6] and a fibrous reinforcing material 0 to 7 selected from carbon fiber, glass fiber, aromatic polyamide fiber and potassium titanate fiber.
A polyimide resin composition containing 0 part by weight. [8] An injection molded product obtained from the polyimide resin composition according to [6] and / or the polyimide resin composition according to [7].

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The diamine used in the bisimide represented by the above general formula (1-1) is diaminodiphenyl ether, and specifically, 3,3'-diaminodiphenyl ether and 3,4 '. -Diaminodiphenyl ether, 4,
4'-diaminodiphenyl ether. More preferably, 3,4'-diaminodiphenyl ether.

In the present invention, the bisimide represented by the above general formula (1-1) having the ability to promote crystallization has the diaminodiphenyl ethers as essential diamines, but other diamines may be used within the range not impairing the object of the present invention. The bisimide consisting of may be included. Specific examples of other diamines include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-aminophenyl) sulfide, bis (4- Aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, bis (4-
Aminophenyl) sulfoxide, (3-aminophenyl)
(4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, 3,3′-diaminobenzophenone, 4, 4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-
Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, 2- (3- Aminophenyl) -2- (4-aminophenyl) propane, 2,2-bis (4-aminophenyl)
-1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-
Aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3- Hexafluoropropane, bis [4-
(3-Aminophenoxy) phenyl] methane, bis [4- (4
-Aminophenoxy) phenyl] methane, 1,1-bis [4-
(3-Aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-
Bis [4- (4-aminophenoxy) phenyl] ethane, 2,
2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] Butane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3,3
-Hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-
Bis (4-aminophenoxy) benzene, 4,4'-bis (3-
Aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4 -(3-Aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] ] Sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- ( 4-Aminophenoxy) phenyl] ether, 1,4-bis [4- (3-
Aminophenoxy) benzoyl] benzene,

1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3-
(3-Aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4- (4
-Amino-α, α-dimethylbenzyl) phenoxy] diphenyl sulfone, bis [4- [4- (4-aminophenoxy)
Phenoxy] phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α -Dimethylbenzyl] benzene, 1,3-
Bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4
-(4-Amino-6-fluorophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl] benzene, 1 , 3-bis [4- (4-amino-6-cyanophenoxy) -α,
α-Dimethylbenzyl] benzene, 3,3'-diamino-4,
4'-diphenoxybenzophenone, 4,4'-diamino-5,5 '
-Diphenoxybenzophenone, 3,4'-diamino-4,5'-
Diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5'- Phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibiphenoxybenzophenone , 3,3'-diamino-4-biphenoxybenzophenone,
4,4'-diamino-5-biphenoxybenzophenone, 3,4'-
Diamino-4-biphenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone, 1,3-bis (3-
Amino-4-phenoxybenzoyl) benzene, 1,4-bis
(3-Amino-4-phenoxybenzoyl) benzene, 1,3-
Bis (4-amino-5-phenoxybenzoyl) benzene,
1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino-4-biphenoxybenzoyl)
Benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5- Biphenoxybenzoyl) benzene, 2,6-bis [4- (4-amino
-α, α-dimethylbenzyl) phenoxy] benzonitrile, 2,6-bis [4- (4-amino-α, α-bistrifluoromethylbenzyl) phenoxy] benzonitrile, 2,
Examples thereof include 6-bis [4- (4-aminophenoxy) phenoxy] benzonitrile and 2,6-bis [4- (4-aminobenzoyl) phenoxy] benzonitrile.

Further, in the present invention, the bisimide represented by the above general formula (1-1) having the ability to promote crystallization uses phthalic anhydride as an essential dicarboxylic acid anhydride,
Bisimides composed of other dicarboxylic acid anhydrides may be included as long as the object of the present invention is not impaired. As other dicarboxylic acid anhydrides, for example, 2,3-benzophenone dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl Phenyl ether anhydride, 2,3-biphenyldicarboxylic acid anhydride, 3,4-biphenyldicarboxylic acid anhydride, 2,3-dicarboxyphenylphenyl sulfone anhydride, 3,4-dicarboxyphenylphenyl sulfone anhydride, 2 , 3-Dicarboxyphenyl phenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic acid anhydride, 2,3-naphthalenedicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid Anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, 1,
9-anthracene dicarboxylic acid anhydride and the like can be mentioned. Any conventionally known imidization reaction can be applied to the method for producing the bisimide of the general formula (1-1) in the present invention.
The amount of phthalic anhydride used may be at least twice the equivalent amount of the diaminodiphenyl ethers, but considering the complexity of post-treatment, cost, etc., it is preferable to use it in the range of 2 to 2.5 times equivalent amount. desirable. It is particularly preferable to carry out the reaction in an organic solvent. The solvent used here is preferably N,
Although it is N-dimethylacetamide, other usable solvents are N, N-dimethylformamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl.
-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone,
N-methylcaprolactam, 1,2-dimethoxyethane, bis
(2-Methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyrroline , Picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, m-cresylic acid,
Examples thereof include p-chlorophenol, anisole, benzene, toluene and xylene. These organic solvents may be used alone or as a mixture of two or more.

The reaction temperature is usually 250 ° C. or lower, preferably 150 ° C. or lower. The reaction pressure is not particularly limited, and the reaction can be sufficiently performed at normal pressure. The reaction time varies depending on the type of diaminodiphenyl ethers, the type of solvent and the reaction temperature, and usually 4 to 24 hours is sufficient. Further, as a method of imidization, the precursor bisamic acid is added to 100 to 30
By heating at 0 ° C. for imidization or chemical imidization using an imidizing agent such as acetic anhydride, a bisimide having a structure in which two molecules of water are dehydrated from bisamic acid can be obtained.

The monoamine used in the bisimide represented by the general formula (2-1) is specifically aniline,
p-toluidine, 4-n-ethylaniline, 4-n-propylaniline, 4-aminobiphenyl, 4-amino-p-terphenyl. More desirable is p-toluidine. The monoamine used here may be one kind or two or more kinds.

In the present invention, the bisimide represented by the general formula (2-1), which has the ability to promote crystallization, is
Although 3 ′, 4,4′-biphenyltetracarboxylic dianhydride is used as an essential acid anhydride, a bisimide composed of another acid anhydride may be included as long as the object of the present invention is not impaired.
Other acid anhydrides include, for example, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, and 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride. Anhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) Ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane Dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,
1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-
Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetra Carboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7, -anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic Examples thereof include acid dianhydrides, but the above acid anhydrides may be used alone or in combination of two or more.

Further, in the present invention, the bisimide represented by the above general formula (2-1) having the ability to promote crystallization has the above monoamines as essential monoamines, but other than the above-mentioned range as long as the object of the present invention is not impaired. The bisimide consisting of the monoamine may be contained. Other monoamines include:
Specifically, o-toluidine, m-toluidine, 2,3
-Xylidine, 2,4-xylidine, 2,5-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5
-Xylidine, 2-ethylaniline, 3-ethylaniline, 2,3,4-trimethylaniline, 2,3,6-trimethylaniline, 2-n-propylaniline, 3-n
-Propylaniline, 2-ethyl-3-methylaniline, 2-ethyl-4-methylaniline, 2-ethyl-5
-Methylaniline, 2-ethyl-6-methylaniline,
3-ethyl-4-methylaniline, 3-ethyl-5-methylaniline, 4-ethyl-2-methylaniline, 4-
Ethyl-3-methylaniline, o-chloroaniline, m
-Chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o
-Nitroaniline, p-nitroaniline, m-nitroaniline, o-aminophenol, m-aminophenol, p-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, p-phenetidine, m -Phenetidine, o-aminobenzaldehyde, m-aminobenzaldehyde,

P-Aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 2-amino-p-terphenyl, 3-amino.
-p- terphenyl, 2-amino-o- terphenyl, 3-
Amino-o-terphenyl, 4-amino-o-terphenyl, 2-amino-m-terphenyl, 3-amino-m-terphenyl, 4-amino-m-terphenyl, 2-aminophenylphenyl ether, 3-aminophenyl phenyl ether, 4-aminophenyl phenyl ether, 2-
Aminobenzophenone, 3-aminobenzophenone, 4
-Aminobenzophenone, 2-aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide,
4-aminophenyl phenyl sulfide, 2-aminophenyl phenyl sulfone, 3-aminophenyl phenyl sulfone, 4-aminophenyl phenyl sulfone, α-
Naphthylamine, β-naphthylamine, 1-amino-2
-Naphthol, 2-amino-1-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 5
-Amino-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like can be mentioned. The above monoamines may be used alone or in combination of two or more.

Any conventionally known imidization reaction can be applied to the method for producing the bisimide of the general formula (2-1) in the present invention. The amount of monoamines used may be 2 times equivalent moles or more with respect to the acid anhydride, but in consideration of complexity of post-treatment, cost, etc., it is used within a range of 2 to 2.5 times equivalent moles. Is desirable. It is particularly preferable to carry out the reaction in an organic solvent. The solvent used here is preferably N, N-dimethylacetamide, but other usable solvents are N, N-dimethylformamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl. -2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane,
Bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, Pyroline, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, m-cresylic acid, p-chlorophenol, anisole, benzene, toluene, Xylene etc. are mentioned. These organic solvents may be used alone or as a mixture of two or more.

The reaction temperature is usually 250 ° C. or lower, preferably 150 ° C. or lower. The reaction pressure is not particularly limited, and the reaction can be sufficiently performed at normal pressure. The reaction time varies depending on the type of monoamine, the type of solvent and the reaction temperature, and is usually 4 to 24.
Time is enough. Further, as a method of imidization, a bisamidic acid as a precursor is heated to 100 to 300 ° C. to imidize it, or chemically imidized with an imidizing agent such as acetic anhydride to convert the bisamidic acid into 2 A bisimide having a structure in which water of the molecule is dehydrated is obtained.

In the present invention, claim 1 and claim 4
The average primary particle size of the described carbon black is 1 to 100 n
m is appropriate. It is preferably 1 to 70 nm, more preferably 1 to 50 nm. As the carbon black used in the present invention, general commercially available ordinary carbon black can be used without any problem. Commercially available carbon blacks include Mitsubishi Carbon Black (Mitsubishi Kasei), Seast, Toka Black (Tokai Carbon), Denka Black (Denka), Ketchen Black (Akzo), and RAVEN (Colombian Carbon). Toka black (Tokai Carbon) is preferable. These carbon blacks may be used alone or in combination of two or more.

In the crystallization accelerator of the present invention comprising a mixture of bisimides represented by the general formulas (1) and (2), the weight ratio of the mixture is 0/10 to 1
It is 0/0. Preferably, in the crystallization accelerator, which comprises a mixture of bisimides represented by the general formulas (1) and (2), the weight ratio of the mixture is 3 /.
It is 7 to 7/3. More preferably, in the crystallization accelerator, which is composed of a mixture of bisimides represented by the general formulas (1) and (2), the weight ratio of the mixture is 4/6 to 6/4.

In the crystallization promoter of the present invention, which comprises a mixture of at least one or more of the general formula (1) and / or the general formula (2) and carbon powder, the general formula (1)
And / or the mixing ratio of at least one or more of the general formula (2) and the carbon powder is 1/9 to 9/1. Preferably, the mixing ratio of at least one or more of the general formula (1) and / or the general formula (2) and the carbon powder is 3/7 to 7/3.

The crystallization accelerator of the present invention can be applied to any crystalline polyimide, but in particular the above formula (3)
It is effective as a crystallization accelerator for the crystalline polyimide represented by (Mitsui Toatsu Chemical Co., Ltd .; trade name AURUM). The mixing ratio of the polyimide and the crystallization accelerator of the present invention is such that at least one or more of the general formula (1) and / or the general formula (2) and carbon powder are used with respect to 100 parts by weight of the polyimide of the above formula (3). 1 to 50 parts by weight of the crystallization accelerator characterized in that it consists of a mixture. If the content of the crystallization accelerator is less than 1 part by weight, sufficient crystallization will not proceed, and if it exceeds 50 parts by weight, the mechanical strength of the obtained injection-molded product will be insufficient. More preferably, the mixing ratio of the polyimide and the crystallization accelerator of the present invention is such that the polyimide 1 of the formula (3) is
The amount of the crystallization accelerator represented by the mixture of the bisimides represented by the general formulas (1) and (2) is 5 to 30 parts by weight with respect to 00 parts by weight.

A commonly known method can be used as a method for adding the crystallization accelerator. The polyimide powder and the crystallization accelerator can be added using a mortar, a Henschel mixer, a drum blender, a tumbler blender, a ball mill, a ribbon blender or the like. The most common method is to obtain pellets or a powdery mixture by using a melt mixer, a hot roll or the like after pre-kneading, and this method can be carried out also in this patent.

Further, in the present invention, when it is subjected to melt molding,
Other thermoplastic resins within the range not impairing the object of the present invention, for example, polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, polyether sulfone, polyether ketone, polyphenyl sulfide, polyamide imide, polyether imide,
The modified polyphenylene oxide and the polyimide other than the formula (3) may be blended in appropriate amounts according to the purpose.
Further, the following fillers and the like used in ordinary resin compositions may be used as long as the object of the invention is not impaired.
That is, graphite, carborundum, silica powder,
Abrasion resistance improver such as molybdenum disulfide and fluorocarbon resin, reinforcing agent such as glass fiber and carbon fiber, flame retardant improver such as antimony trioxide, magnesium carbonate and calcium carbonate, electrical characteristics such as clay and mica Improver, tracking resistance improver such as asbestos, silica, graphite, acid resistance improver such as barium sulfate, silica, calcium metasilicate, thermal conductivity improver such as iron powder, zinc powder, aluminum powder, copper powder, etc. Examples thereof include glass beads, glass spheres, talc, diatom degree, alumina, silasbaln, hydrated alumina, metal oxides, colorants and the like.

[0032]

EXAMPLES The present invention will be described in detail below with reference to examples. The physical properties of the bisimide and the polyimide resin composition in the examples were measured by the following methods. Melting point (Tm); DSC (Mac Science DSC-
3100 series). Crystallization Behavior; DSC (Mac Science DSC-3
Crystallization temperature (Tc) and crystal energy (ΔHc) were measured by 100 series). The pattern of DSC is as follows: room temperature → (heating rate 20 ° C./min)→420° C. 420 ° C. → (cooling rate 20 ° C./min)→200° C. 200 ° C. → (heating rate 20 ° C./min)→420° C. Step by step. 5% weight loss temperature; DTA-TG (Mac
Measured by Science DTA-TG2000 series). Izod impact strength; measured according to ASTM D-256. Deflection temperature under load (DTUL); measured according to ASTM D-648.

(Synthesis Example 1) 3,4'-diaminodiphenyl ether (20.03 g, 0.1 mol) and phthalic anhydride (3) were placed in a container equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube.
2.58 g (0.22 mol), γ-picoline 1.39
g, m-cresol 80.08 g were charged, and the temperature was raised to 150 ° C. with stirring under a nitrogen atmosphere. Then one
When the reaction was carried out at 50 ° C. for 3 hours, the distillation of 3.6 ml of water was confirmed during that time.

After completion of the reaction, the mixture was cooled to room temperature, charged with about 20 ml of methanol, and the bisimide powder was filtered off. After washing this bisimide powder with methanol, it is heated to 50 ° C in nitrogen.
12 hours, dried at 180 ℃ 6 hours, bisimide powder 4
4.48 g (yield 96.5%) was obtained. FIG. 1 shows the infrared absorption spectrum of this bisimide powder. 1720c
Characteristic absorptions of the imide ring were observed at m ^-1 and 1780 cm ^-1 . The purity in HPLC was 99.9%, and the elemental analysis values were as follows. C H N calculated value (%) 73.03 3.51 6.09 measured value (%) 72.72 3.69 5.87 Further, the melting point (Tm) of bisimide is 209 ° C., and 5
The% weight loss temperature (Td5) was 400 ° C.

(Synthesis Example 2) 29.42 g (0.1 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was placed in a container equipped with a stirrer, a reflux condenser, and a nitrogen introducing tube. ), P
-Toluidine (23.58 g, 0.22 mol), γ-picoline (5.60 g) and m-cresol (110.80 g) were charged, and the mixture was heated to 150 ° C. with stirring under a nitrogen atmosphere. After that, the reaction was carried out at 150 ° C. for 3 hours, during which 3.6 ml of water was confirmed to be distilled.

After completion of the reaction, the mixture was cooled to room temperature, charged with about 20 ml of methanol, and the bisimide powder was filtered off. After washing this bisimide powder with methanol, it is heated to 50 ° C in nitrogen.
Dry for 12 hours at 250 ° C for 2 hours to obtain bisimide powder 9
1.80 g (yield 90.3%) was obtained. The infrared absorption spectrum of this bisimide powder is shown in FIG. 1720c
Characteristic absorptions of the imide ring were observed at m ^-1 and 1780 cm ^-1 . The elemental analysis values were as follows. C H N calculated value (%) 76.26 4.27 5.93 measured value (%) 75.88 4.16 5.64 Further, the melting point (Tm) of bisimide is 333.6 ° C., 38.
0.1 ° C., 5% weight loss temperature (Td5) is 40
It was 6.6 ° C.

100 parts by weight of crystalline polyimide AURUM # 450 (manufactured by Mitsui Toatsu Chemicals, Inc.) and a bisimide compound and carbon in which the mixing weight ratio of the bisimide of Synthesis Example 1 and the bisimide of Synthesis Example 2 is 5/5. Black mixing ratio is 1
After adding and mixing 5 parts by weight of a crystallization accelerator of 1/1,
The mixture was melt-kneaded with a single-screw extruder having a diameter of 30 mm, and the strand was air-cooled and cut into pellets. DSC of this pellet
When measured, the crystallization temperature (Tc) was 330 ° C. and the crystal energy was 32.degree. C. in the process of cooling rate 20 ° C./min.
3 J / g was observed. That is, by adding the two kinds of bisimides of this example and carbon black, the crystalline polyimide AURUM became much easier to crystallize.

Further, the obtained pellets are used to arve
Rug injection molding machine (injection pressure 500kg / cm ^Two, Cylinder temperature 4
Injection molding at 10 ℃, cooling rate 20 ℃ in the mold
/ Min to 180 ° C, JIS standard Izo
A test piece for impact strength (with a notch) was obtained. This test piece
Izod impact strength value (IZ) is 8.5 kg · cm /
cm, deflection temperature under load (DTUL) is 257 ° C
Was.

(Examples 2 to 5) The same as Example 1 except that the mixing weight ratio of the bisimide of Synthesis Example 1 and the bisimide of Synthesis Example 2 and the mixing weight ratio of the bisimide compound and Toca Black in Example 1 were changed. And various measurements were performed. Table 1 shows the mixing weight ratio of the bisimide, the mixing weight ratio of the bisimide compound and Toka Black, and the addition amount of the crystallization accelerator, the crystallization temperature, the crystal energy, and the injection molding when mixed with the crystalline polyimide AURUM. The Izod impact strength value and the deflection temperature under load (DTUL) of the body are shown together with the results of Example 1.

Comparative Example 1 When DSC was measured only for the polyimide AURUM which is essentially crystalline, no crystallization temperature was observed during the cooling rate of 20 ° C./min. That is, it is understood that this polyimide does not crystallize under rapid cooling. Therefore DTUL is 236 ℃
Therefore, the result is obviously inferior to the result of Example 1. Table 1 shows the results.
Are shown together.

(Comparative Examples 2 to 3) Regarding the bisimide of Synthesis Example 1 and the bisimide of Synthesis Example 2 obtained in Example 1,
A resin composition test piece was prepared in which the mixing weight ratio of the bisimide compound and Toka Black was out of the composition range of the present invention, and the same Izod impact strength test and load deflection temperature measurement as those in the above-mentioned Examples were performed. The results are shown in Table 1. When the mixing ratio of the bisimide is outside the composition range of the present invention, the crystallization is clearly inferior in the cooling process as compared with the case where it is within the composition range.

[0042]

[Table 1]

[0043]

The crystallization accelerator according to the present invention markedly increases the crystallization rate without impairing the physical properties of the crystalline polyimide. Therefore, if the present crystallization accelerator is added to crystalline polyimide and melt injection molding is performed, the polyimide can be crystallized in the mold during cooling.

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[Procedure amendment]

[Submission date] April 18, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Brief description of drawings

[Correction method] Added

[Correction contents]

[Brief description of the drawings]

FIG. 1 shows a diagram of an infrared absorption spectrum of the bisimide powder obtained in Synthesis Example 1 above.

FIG. 2 shows a diagram of an infrared absorption spectrum of the bisimide powder obtained in Synthesis Example 2 described above.

Claims (8)

[Claims] 1. A compound of the general formula (1) (In the formula, R 1 represents a divalent aromatic group having 6 to 30 carbon atoms,
Is Represents at least one divalent group selected from Here, X1 is a direct bond, an ether bond, a sulfide bond, a hydrocarbon group having 1 to 10 carbon atoms, a carbonyl group, a sulfonyl group, a hexafluorinated isopropylidene group, or an aromatic group having 6 to 18 carbon atoms. At least 1 consisting of
Represents two or more divalent groups. ) And / or general formula (2) (Chemical Formula 2) (In the formula, R 2 is —C _n H _{2n + 1} (n = 0 to 3) or a monovalent aromatic group having 6 to 30 carbon atoms, and Y is Is a tetravalent group consisting of Here, Y1 is composed of a direct bond, an ether bond, a sulfide bond, a hydrocarbon group having 1 to 10 carbon atoms, a carbonyl group, a sulfonyl group, a hexafluorinated isopropylidene group, and an aromatic group having 6 to 18 carbon atoms. It represents at least one divalent group from the group. ) A crystallization accelerator for crystalline polyimide comprising a mixture of at least one compound having a bisimide structure represented by the formula (1) and carbon powder. 2. In the general formula (1), X is a diphenyl ether group and R1 is a benzene ring. The crystallization accelerator for crystalline polyimide according to claim 1, which comprises a bisimide represented by the following as a main component. 3. In the general formula (2), Y is a biphenyl group, R2 is a benzene ring or a para-substituted benzene ring, and the general formula (2-1) (chemical formula 4): (In the formula, R ′ is —C _n H _{2n + 1} (n = 0 to 3), The crystallization accelerator for crystalline polyimide according to claim 1, which comprises a bisimide represented by the following as a main component. 4. The crystallization accelerator for crystallimide according to claim 1, wherein the main component of the carbon powder is carbon black. 5. A mixture of a bisimide compound represented by general formula (1) and / or a general formula (2) and carbon powder, wherein the weight ratio of the bisimide compound to the carbon powder is 1/9 to 9 /.
1. The crystallization accelerator for crystalline polyimide according to claim 1, which is 1. 6. Formula (3) (Chemical Formula 5) [Chemical Formula 5] For a crystalline polyimide comprising a mixture of a bisimide compound represented by the general formula (1) and / or the general formula (2) and a carbon powder with respect to 100 parts by weight of the crystalline polyimide having a repeating structural unit represented by Crystallization accelerator 1-5
A polyimide resin composition containing 0 part by weight. 7. The polyimide resin composition 1 according to claim 6.
A polyimide resin composition comprising 00 parts by weight and 0 to 70 parts by weight of a fibrous reinforcing material selected from carbon fiber, glass fiber, aromatic polyamide fiber and potassium titanate fiber. 8. An injection-molded article obtained from the polyimide resin composition according to claim 6 and / or the polyimide resin composition according to claim 7.