JPH06179816A - Polyimide resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition improved in melt moldability by mixing the thermoplastic resin with a liquid crystal aromatic polyimide. CONSTITUTION:The resin composition comprises 99.9-50 pts.wt. at least one thermoplastic resin (a) and 0.1-50 pts.wt. at least one liquid crystal aromatic polyimide (b). A preferred example of the polyimide (b) has a backbone made up of repeating units represented by the formula. In the formula, R1 to R5 may be the same or different and each is hydrogen, fluorine, trifluoromethyl, methyl, ethyl, or cyano, and R is a 2-27C tetravalent group selected from a monocyclic aromatic group, a fused aromatic group, and a nonfused aromatic group consisting of aromatic groups bonded together directly or through a cross-linking member. The resin (a) is one selected from an aromatic polyimide, an aromatic polyetherimide, an aromatic polyamideimide, an aromatic polyethersulfone, and an aromatic polyetherketone.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition having improved melt moldability. Melt-moldable aromatic polyimide resin composition, melt-moldable aromatic polysulfone resin composition, aromatic polyetherimide resin composition, aromatic polyamideimide resin composition and aromatic polyetherketone resin composition Regarding things.
More specifically, aromatic polyimide having excellent heat resistance, chemical resistance, and mechanical strength, aromatic polysulfone having excellent mechanical strength, aromatic polyether imide having excellent heat resistance, excellent heat resistance, and mechanical strength. The present invention relates to a thermoplastic resin composition having improved melt moldability, which is obtained by mixing an aromatic polyamide imide excellent in heat resistance or an aromatic polyether ketone excellent in heat resistance and mechanical strength with a liquid crystalline aromatic polyimide.

[0002]

2. Description of the Related Art Conventionally, various thermoplastic resins having excellent heat resistance have been developed. Among them, polyimide has not only high heat resistance but also excellent mechanical strength, dimensional stability, flame retardancy, electrical insulation, etc., and therefore electrical and electronic equipment, aerospace equipment, and transportation equipment. It is used in the fields such as above, and is expected to be widely used in the fields where heat resistance is required in the future. Heretofore, various polyimides having excellent characteristics have been developed.

For example, the formula (A)

[Chemical 29] The polyimide represented by is already found by Proger et al. (USP 4,065,345). This polyimide has excellent mechanical properties, thermal properties, electrical properties, solvent resistance, and heat resistance,
Moreover, it was known as polyimide showing melt fluidity. However, this polyimide also has a high melt viscosity as compared with engineering plastics other than the usual polyimides that can be extrusion-molded and injection-molded, and it has been difficult to perform extrusion-molding and injection-molding.

The inventors of the present invention have also previously described the general formula (B) as a polyimide having excellent mechanical properties, thermal properties, electrical properties, solvent resistance, and heat resistance.

[Chemical 30] (In the formula, X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms,
Hexafluorinated isopropylidene group, carbonyl group,
Represents a group selected from the group consisting of a thio group and a sulfonyl group, and R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group , A tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by a cross-linking member), and a polyimide having a repeating structural unit represented by (JP-A-61-143478, 62-677717, 62-86021, 62-2353
81, 63-128025).

The above-mentioned polyimide is a novel heat-resistant resin having many good physical properties peculiar to polyimide. For example, the formula (6) included in the polyimide represented by this formula

[Chemical 31] A polyimide having a repeating structural unit represented by has a glass transition temperature (hereinafter abbreviated as Tg) of 260 ° C and a crystallization temperature.
(Hereinafter abbreviated as Tc) is 310 to 340 ° C., and crystal melting temperature (hereinafter abbreviated as Tm) is 367 to 385 ° C., which is a melt-moldable crystalline polyimide excellent in chemical resistance. But,
Since the Tm is as high as 367 to 385 ℃, the temperature during molding had to be a high temperature near 400 ℃.

[0006] As described above, polyimide has heat resistance and other properties as compared with ordinary engineering plastics typified by polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polysulfone, polyphenylene sulfide, polyether ether ketone, and polyetherimide. Although far superior in properties, moldability still falls short of those resins.

Other known polyimides also have excellent heat resistance, but since they do not have a clear glass transition temperature, they must be processed by a method such as sintering when used as a molding material. Although it has excellent workability, it has a low glass transition temperature and is soluble in a halogenated hydrocarbon solvent, and is not satisfactory in terms of heat resistance and solvent resistance. Further, conventionally, aromatic polysulfones, aromatic ether imides, aromatic polyamide imides, aromatic polyether ketones, and the like have excellent mechanical strength and dimensional stability in addition to their high heat resistance, flame resistance, and electrical insulation. It is used in the fields of electric / electronic equipment, spacecraft equipment, transportation equipment, etc. to have such properties, and is expected to be widely used in the fields where heat resistance is required in the future.

Although aromatic polysulfone is an engineering plastic having good moldability, it has a problem of moldability in aromatic ether imides, aromatic polyamide imides and aromatic polyether ketones called super engineering plastics. Therefore, it has been desired that the molding processability be good while maintaining the heat resistance. On the other hand, liquid crystalline polymers can be classified into thermotropic liquid crystals and lyotropic liquid crystals due to their properties. Conventionally known liquid crystalline polymers include polyester, polyesteramide, polyazomethine (above, thermotropic liquid crystal), polyamide, polybenzothiazole (above, lyotropic liquid crystal), etc. No polyimide is known. Therefore, a resin composition obtained from liquid crystalline polyimide and other thermoplastic resin including polyimide is not known at all.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition having improved moldability without impairing the excellent properties inherent in thermoplastic resins.
Specifically, the first purpose is to add a liquid crystalline aromatic polyimide having good fluidity to a conventional aromatic polyimide while maintaining its molding processability without deteriorating the excellent heat resistance originally possessed by the aromatic polyimide. To provide an improved aromatic polyimide-based thermoplastic resin composition.
The second purpose is to improve the molding processability of the aromatic polysulfone by adding a liquid crystalline aromatic polyimide having good fluidity to a conventional aromatic polysulfone without deteriorating the excellent heat resistance of the aromatic polysulfone. An object is to provide an aromatic polysulfone-based thermoplastic resin composition.

A third object of the present invention is to obtain a liquid crystalline aromatic polyimide having good moldability and fluidity from the conventional aromatic polyetherimide without impairing the excellent heat resistance inherent in the aromatic polyetherimide. To provide an improved aromatic polyetherimide-based thermoplastic resin composition. The fourth purpose is to improve the processability of a liquid crystalline aromatic polyimide having good fluidity to a conventional aromatic polyamideimide without deteriorating the excellent heat resistance and mechanical properties originally possessed by the aromatic polyamideimide. An object of the present invention is to provide an improved aromatic polyamideimide-based thermoplastic resin composition by adding it. The fifth purpose is to improve the molding processability of aromatic polyether ketone without impairing the excellent heat resistance and mechanical properties originally possessed by aromatic polyether ketone.
It is an object of the present invention to provide an improved aromatic polyetherketone-based thermoplastic resin composition by adding a liquid crystalline aromatic polyimide having good fluidity to a conventional aromatic polyetherketone.

[0011]

Means for Solving the Problems As a result of intensive studies to achieve these objects, the present inventors have found that liquid crystalline aromatic polyimides can be used as aromatic polyimides, aromatic polysulfones, aromatic polyether imides, It has been found that a thermoplastic resin composition obtained by mixing with an aromatic polyamideimide or an aromatic polyether ketone has improved moldability without impairing the inherent performance of each resin. Was completed.

That is, the present inventors have found that the equation (4)

[Chemical 32] We have developed an aromatic polyimide having a repeating structural unit represented by. (Japanese Patent Laid-Open No. 03-160024). Then, it was found that this aromatic polyimide exhibits liquid crystallinity in a temperature range of about 270 to 300 ° C. That is, the liquid crystallinity of this aromatic polyimide could be confirmed by observation with a polarizing microscope. Polarizing microscope (OLYMPU)
Heated on a hot stage equipped with Company S, BHS-751P (1
0 ° C./min), polarization is observed in the temperature range of about 270 to 300 ° C.

Further, the above-mentioned aromatic polyimide is used as DSC (Di
fferential scanning calorimetry) measurement (Shimadzu, DT-4
0 series, DSC-41M) (10 ℃ / min), approx. 2
Two endothermic peaks are observed at 75 ° C and about 295 ° C, and it can be confirmed that liquid crystallinity is exhibited in the temperature range between these two endothermic peaks. Further, this aromatic polyimide is an aromatic polyimide which not only exhibits liquid crystallinity between two endothermic peaks, but also has a very low melt viscosity in a molten state and is excellent in moldability.

The inventors of the present invention have used the aromatic polyimide exhibiting liquid crystallinity by mixing it with an aromatic polyimide and other thermoplastic resins for which workability is desired to be improved. The inventors have found that the workability is improved and completed the present invention. That is, the present invention is a melt-moldable thermoplastic resin composition in which a liquid crystalline aromatic polyimide is contained in another aromatic polyimide or another thermoplastic resin.

The present invention includes the following inventions. 1. A thermoplastic resin composition containing 99.9 to 50 parts by weight of at least one thermoplastic resin and 0.1 to 50 parts by weight of at least one liquid crystalline aromatic polyimide, and having good moldability.

2. At least one thermoplastic resin 99.9-
50 parts by weight and formula (1)

[Chemical 33] (In the formula, R _{1 to} R ₅ are hydrogen, fluorine, trifluoromethyl,
A methyl, ethyl or cyano group, which may be the same or different, and R has 6 to 27 carbon atoms,
A tetravalent 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 linked to each other directly or by a bridging member. A thermoplastic resin composition having good moldability, containing 0.1 to 50 parts by weight of a liquid crystalline aromatic polyimide having at least one repeating structural unit represented by

3. In the thermoplastic resin composition of the above 2,
The liquid crystalline aromatic polyimide has the formula (4)

[Chemical 34] A thermoplastic resin composition which is a liquid crystalline aromatic polyimide having a repeating structural unit represented by the following as a basic skeleton.

4. In the thermoplastic resin composition of the above 1,
The liquid crystalline aromatic polyimide has the formula (4)

[Chemical 35] Basic skeleton which is a repeating structural unit represented by 1 to 99 mol%
And equation (1)

[Chemical 36] (In the formula, R _{1 to} R ₅ are hydrogen, fluorine, trifluoromethyl,
A methyl, ethyl or cyano group, which may be the same or different, and R has 6 to 27 carbon atoms,
A tetravalent 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 linked to each other directly or by a bridging member. A liquid crystalline aromatic polyimide copolymer containing 1 to 99 mol% of a basic skeleton which is a repeating structural unit represented by the formula (excluding the same repeating structural unit as the formula (4)). Plastic resin composition.

5. In the thermoplastic resin composition of the above 1,
Thermoplastic resin composition in which the thermoplastic resin is at least one thermoplastic resin selected from the group consisting of aromatic polyimide, aromatic polyetherimide, aromatic polyamideimide, aromatic polyether sulfone and aromatic polyether ketone. .

6. In the thermoplastic resin composition of the above 5,
Aromatic polyimide has formula (5)

[Chemical 37] (In the formula, X represents a divalent group selected from the group consisting of a direct bond, an isopropylidene group, a hexafluorinated isopropylidene group, a carbonyl group, a thio group and a sulfonyl group,
In addition, R has 6 to 27 carbon atoms, and is selected from 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 thermoplastic resin composition, which is an aromatic polyimide having a repeating structural unit represented by the formula (4) selected from the group consisting of

7. In the thermoplastic resin composition of the above 5,
The aromatic polyimide has the formula (6)

[Chemical 38] A thermoplastic resin composition which is an aromatic polyimide having a repeating structural unit represented by the following as a basic skeleton.

8. In the thermoplastic resin composition of the above 5,
Aromatic polyimide has formula (7)

[Chemical Formula 39] A thermoplastic resin composition which is an aromatic polyimide having a repeating structural unit represented by the following as a basic skeleton.

9. In the thermoplastic resin composition of the above 5,
The aromatic polyimide has the formula (6)

[Chemical 40] Basic skeleton having a repeating structural unit represented by 99 to 1 mol
% And expression (8)

[Chemical 41] Where R is

[Chemical 42] Where n is an integer of 0,1,2,3, Q is directly connected, -O-, -S-, -CO
-, -SO _2- , -CH ₂ , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- , and when there are a plurality of bonding groups Q connecting the aromatic rings, they are bonded to each other. The groups may be the same or different combinations, and R "is

[0024]

[Chemical 43] (Where M is

[0025]

[Chemical 44] A repeating structural unit represented by at least one divalent group selected from the group consisting of (representing at least one tetravalent group selected from the group consisting of
(Excluding the same structural unit as)
A thermoplastic resin composition which is an aromatic polyimide copolymer containing, in particular, a basic skeleton which is a repeating structural unit of the formula (8) is

[0026]

[Chemical formula 45] A thermoplastic resin composition which is a repeating structural unit represented by the formula (wherein R is as described above) (excluding the same structural unit as in the formula (6)).

10. In the thermoplastic resin composition of the above 5, the aromatic polysulfone has the formula (11)

[Chemical formula 46] (Where X is a direct connection,

[Chemical 47] The thermoplastic resin composition is an aromatic polysulfone having as a basic skeleton at least one repeating structural unit represented by

11. In the thermoplastic resin composition of the above 5, the aromatic polyetherimide is represented by the formula (12)

[Chemical 48] (Where X is

[Chemical 49] And Y is

[Chemical 50] The thermoplastic resin composition is an aromatic polyetherimide having at least one repeating structural unit represented by

12. In the thermoplastic resin composition of the above 5, the aromatic polyamideimide has the formula (D)

[Chemical 51] (In the formula, Y represents a divalent organic group having 6 to 27 carbon atoms) and at least one repeating structural unit represented by the basic skeleton,
Especially. Formula (13)

[Chemical 52] A repeating structural unit represented by and / or formula (14)

[Chemical 53] A thermoplastic resin composition which is an aromatic polyamideimide having at least one of the repeating structural units represented by as a basic skeleton.

13. In the thermoplastic resin composition of the above 5, the aromatic polyether ketone is represented by the formula (15)

[Chemical 54] A repeating structural unit represented by and / or formula (16)

[Chemical 55] A thermoplastic resin composition which is an aromatic polyether ketone having a repeating structural unit represented by the following as a basic skeleton.

14. Further, the aromatic polyimide and / or the liquid crystalline aromatic polyimide used in the thermoplastic composition of the above 1 to 9 has the polymer molecule terminal represented by the formula (2).

[Chemical 56] (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group and a divalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are directly or linked to each other by a bridge member) Dicarboxylic acid anhydride and / or general formula (3) V-NH ₂ (3) (In the formula, V has 6 to 15 carbon atoms, and a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group, a monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by a crosslinking member) A thermoplastic resin composition which is an aromatic polyimide or a liquid crystalline aromatic polyimide obtained by sealing with a monoamine, preferably phthalic anhydride and / or aniline.

According to the present invention, there is provided a thermoplastic resin composition which is excellent in molding processability and excellent in thermal stability in addition to the excellent properties inherent in each resin.

The liquid crystalline aromatic polyimide used in the present invention is an aromatic polyimide showing liquid crystallinity such as thermotropic liquid crystal and lyotropic liquid crystal. For example, the expression
(1)

[Chemical 57] (In the formula, R _{1 to} R ₅ are hydrogen, fluorine, trifluoromethyl,
A methyl, ethyl or cyano group, which may be the same or different, and R has 2 to 27 carbon atoms,
Represents a tetravalent 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 aromatic groups are connected to each other directly or by a bridging member. ) A wholly aromatic polyimide showing liquid crystallinity,

Preferably, the formula (4)

[Chemical 58] Liquid crystalline aromatic polyimide represented by

Or equation (4)

[Chemical 59] A basic skeleton having a repeating structural unit represented by the formula (1)

[Chemical 60] (In the formula, R _{1 to} R ₅ are hydrogen, fluorine, trifluoromethyl,
A methyl, ethyl or cyano group, which may be the same or different, and R has 6 to 27 carbon atoms,
Represents a tetravalent 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 aromatic groups are connected to each other directly or by a bridging member. And a liquid crystal aromatic polyimide copolymer containing 1 to 99 mol% of a basic skeleton having a repeating structural unit represented by the formula (excluding the same structural unit as the formula (4)).

Alternatively, the terminal of the polymer molecule of the liquid crystalline aromatic polyimide or the liquid crystalline aromatic polyimide copolymer has the formula (2).

[Chemical formula 61] (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group and a divalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are directly or linked to each other by a bridge member) Dicarboxylic acid anhydride and / or formula (3) V-NH ₂ (3) (In the formula, V has 6 to 15 carbon atoms, and a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group, a monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by a crosslinking member) A liquid crystalline aromatic polyimide or a liquid crystalline aromatic polyimide copolymer obtained by sealing with a monoamine may be mentioned.

Such a liquid crystalline aromatic polyimide comprises at least one aromatic diamine represented by the following formula (17) and at least one aromatic tetracarboxylic dianhydride represented by the following formula (18). And the resulting polyamic acid is thermally or chemically imidized to obtain.

The aromatic diamine used in this method has the formula (17)

[Chemical formula 62] (In the formula, R _{1 to} R ₅ and R are the same as in the case of the formula (1)), specifically, 1,3- or 1,4-bis [4- ( 4-aminophenoxy) -α, α
-Dimethylbenzyl] benzene, 1,3- or 1,4
-Bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3- or 1,4-bis [4- (4-amino-6-methylphenoxy) -α, α
-Dimethylbenzyl] benzene, 1,3- or 1,4
-Bis [4- (4-amino-6-fluorophenoxy)
-Α, α-dimethylbenzyl] benzene, 1,3- or 1,4-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-or 1,4-bis [4- (4-aminophenoxy) -3-methyl-α, α-dimethylbenzyl] benzene, 1,3- or 1,4-bis [4- (4
-Amino-6-methylphenoxy) -3-methyl-α,
α-dimethylbenzyl] benzene, 1,3- or 1,
4-bis [4- (3-aminophenoxy) -3-dimethyl-α, α-dimethylbenzyl] benzene, 1,3- or 1,4-bis [4- (3-amino-6-methylphenoxy)- 3-Dimethyl-α, α-dimethylbenzyl]
Benzene, 1,3- or 1,4-bis [4- (4-amino-6-trifluoromethylphenoxy) -3,5-
Dimethyl-α, α-dimethylbenzyl] benzene, 1,
3- or 1,4-bis [4- (4-amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene and the like can be mentioned. These may be used alone or in admixture of two or more.

Above all, the formula (18)

[Chemical formula 63] 1,3-bis [4- (4-aminophenoxy) -α,
α-Dimethylbenzyl] benzene is preferred. When two or more kinds of diamines are mixed and used, the above liquid crystalline aromatic polyimide copolymer can be obtained by using the diamine of the formula (18) and other diamines. These aromatic diamines can be produced by subjecting a corresponding nitro compound to a conventional reduction reaction in the presence of a base in an aprotic polar solvent.

The aromatic tetracarboxylic dianhydride used is represented by the formula (19)

[Chemical 64] (In the formula, R has 6 to 27 carbon atoms, a monocyclic aromatic group,
And a condensed polycyclic aromatic group, and a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which the aromatic groups are connected to each other directly or by a bridging member) And specifically, pyromellitic dianhydride, 3,3 ′,
4,4'-benzophenone tetracarboxylic dianhydride,
2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid Dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride,
2,2-bis (3,4-dicarboxyphenyl) -1,
1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl)-
1,1,1,3,3,3-hexafluoropropane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl)
Sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride,
1,2-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride 1,3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride,

2,2-bis [4- (4- (1,2-dicarboxy) phenoxy) phenyl] propane dianhydride,
2,2-bis [4- (3- (1,2-dicarboxy) phenoxy) phenyl] propane dianhydride, bis [4-
(4- (1,2-dicarboxy) phenoxy) phenyl] ketone dianhydride, bis [4- (3- (1,2-dicarboxy) phenoxy) phenyl] ketone dianhydride, bis [4- (4 -(1,2-dicarboxy) phenoxy)
Phenyl] sulfone dianhydride, bis [4- (3- (1,
2-dicarboxy) phenoxy) phenyl] sulfone dianhydride, 4,4-bis [4- (1,2-dicarboxy)
Phenoxy] biphenyl dianhydride, 4,4-bis [3-
(1,2-Dicarboxy) phenoxy] biphenyl dianhydride, 2,2-bis [4- (4- (1,2-dicarboxy) phenoxy) phenyl] sulfide dianhydride, 2,
2-bis [4- (3- (1,2-dicarboxy) phenoxy) phenyl] sulfide dianhydride, 2,2-bis [4- (4- (1,2-dicarboxy) phenoxy) phenyl]- 1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis [4- (3- (1,2-
Dicarboxy) phenoxy) phenyl] -1,1,1,
3,3,3-hexafluoropropane dianhydride, 1,3
-Bis [4- (1,2-dicarboxy) phenoxy] benzene dianhydride, 1,3-bis [3- (1,2-dicarboxy) phenoxy] benzene dianhydride, 1,4-bis [4 -(1,2-Dicarboxy) phenoxy] benzene dianhydride, 1,4-bis [3- (1,2-dicarboxy) phenoxy] benzene dianhydride, 1,3-bis [4
-((1,2-Dicarboxy) -α, α-dimethyl) benzyl] benzene dianhydride, 1,3-bis [3-
((1,2-Dicarboxy) -α, α-dimethyl) benzyl] benzene dianhydride, 1,4-bis [4-((1,
2-dicarboxy) -α, α-dimethyl) benzyl] benzene dianhydride, or 1,4-bis [3-((1,2
-Dicarboxy) -α, α-dimethyl) benzyl] benzene dianhydride and the like, and these aromatic tetracarboxylic dianhydrides may be used alone or in combination of two or more.
Of these, pyromellitic dianhydride is preferable.

The liquid crystalline aromatic polyimide used in the present invention is obtained by using an aromatic diamine represented by the formula (17) as a diamine component. The liquid crystalline aromatic polyimide of the obtained liquid crystalline aromatic polyimide is used. There is no problem even if one or more other diamines are further mixed and polymerized within a range that does not impair the properties and physical performance. Examples of the diamine that can be used in combination include m-phenylenediamine,
o-phenylenediamine, p-phenylenediamine, m
-Aminobenzylamine, o-aminobenzylamine,
3-chloro-1,2-phenylenediamine, 4-chloro-1,2-phenylenediamine, 2,3-diaminetoluene, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 3,5-diaminotoluene, 2-methoxy-
1,4-phenylenediamine, 4-methoxy-1,2-
Phenylenediamine, 4-methoxy-1,3-phenylenediamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 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'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,
4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminobenzophenone, 3,4'-
Diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, 2
-(3-aminophenyl) -2- (4-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- (3-aminophenyl) -2- (4-aminophenyl) -1,1,
1,3,3,3-hexafluoropropane,

1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene,
1,4-bis (4-aminophenoxy) benzene, 1,
3-bis (3-aminobenzoyl) benzene, 1,4-
Bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (4
-Aminobenzoyl) benzene, 1,3-bis (3-amino-α, α-dimethylbenzoyl) benzene, 1,4
-Bis (3-amino-α, α-dimethylbenzoyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzoyl) benzene, 1,4-bis (4-amino-)
α, α-dimethylbenzoyl) benzene, bis [4-
(3-Aminophenoxy) phenyl] methane, bis [4
-(4-aminophenoxy) phenyl] methane, 1,1
-Bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4
-(3-aminophenoxy) phenyl] propane, 1,
1-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [4- (3-aminophenoxy)
Phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4-
(3-Aminophenoxy) phenyl] propane, 1,3
-Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane , 1,1-bis [4-
(3-Aminophenoxy) phenyl] butane, 1,1-
Bis [4- (4-aminophenoxy) phenyl] butane, 1,2-bis [4- (3-aminophenoxy) phenyl] butane, 1,2-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (3-aminophenoxy) phenyl] butane, 1,3-bis [4
-(4-Aminophenoxy) phenyl] butane, 1,4
-Bis [4- (3-aminophenoxy) phenyl] butane, 1,4-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4
-(3-Aminophenoxy) phenyl] butane, 2,3
-Bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2, 2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 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] sulfone, bis [4- (4-aminophenoxy) phenyl] ], Such as sulfone,
These may be used alone or in combination of two or more.

The liquid crystalline aromatic polyimide used in the present invention has the repeating structural unit of the formula (1) obtained by using the aromatic diamine component and the aromatic tetracarboxylic dianhydride as the monomer components as described above. Having a repeating structural unit of formula (4), and formula (1) and formula
A polyimide having an aromatic ring, which is a copolymer having both of the repeating structural units of (4), and whose polymer molecular end is unsubstituted or substituted with a group having no reactivity with amine or dicarboxylic acid anhydride. included.

The liquid crystalline aromatic polyimide having an aromatic ring which is unsubstituted or substituted with a group having no reactivity with amine or dicarboxylic acid anhydride at the terminal of the polymer is represented by the formula (18):

[Chemical 65] (In the formula, R _{1 to} R ₅ and R are as described above), for example, 1,3-bis [4- (4-
Aminophenoxy) -α, α-dimethylbenzyl] benzene and a compound of formula (19)

[Chemical formula 66] (In the formula, R is as described above), an aromatic tetracarboxylic dianhydride,

For example, pyromellitic dianhydride is represented by the formula (2)

[Chemical formula 67] (In the formula, R is as described above) and / or the aromatic dicarboxylic acid anhydride represented by the general formula (3) V—NH ₂ (3) (wherein V is as described above). It can be obtained by reacting in the presence of an aromatic monoamine represented by Examples of the aromatic dicarboxylic acid anhydride represented by the formula (2) used include:
Phthalic anhydride, 2,3-benzophenone dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride,
2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic acid anhydride, 3,4
-Dicarboxyphenyl phenyl sulfone anhydride, 2,
3-dicarboxyphenyl phenyl sulfide anhydride,
3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic acid anhydride, 2,3-
Naphthalene dicarboxylic acid anhydride, 1,8-naphthalene dicarboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride,
1,9-anthracene dicarboxylic acid anhydride etc. are mentioned. These dicarboxylic acid anhydrides may be substituted with a group having no reactivity with the amine or the dicarboxylic acid anhydride, and may be used alone or in combination of two or more kinds. Among these dicarboxylic acid anhydrides, phthalic anhydride is most preferable from the viewpoints of performance and practical use of the resulting polyimide and liquid crystalline polyimide. The amount of the dicarboxylic acid anhydride used is 0.001 to 1.0 mol ratio per mol of the diamine of the formula (18). If it is less than 0.001 mol, the viscosity is increased during high temperature molding, which causes deterioration of moldability. Further, if it exceeds 1.0 mol, mechanical properties are deteriorated. The preferred amount used is 0.01 to 0.5 mol.

Examples of the aromatic monoamine represented by the general formula (3) include aniline, o-toluidine,
m-toluidine, p-toluidine, 2,3-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5
-Xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, p-nitroaniline, m-nitroaniline, o- Aminophenol, m-aminophenol, p-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenidine, m-phenidine, p-phenidine, o-aminobenzaldehyde, m-aminobenzaldehyde, p-amino Benzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether, 4 -Amino E alkenyl phenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenyl phenyl sulfide, 3-aminophenyl phenyl sulfide, 4
Aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfone, 4-aminophenylphenyl sulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 2-amino-1-naphthol, 4-amino-
1-naphthol, 5-amino-1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol,
8-amino-1-aphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like can be mentioned. These aromatic monoamines may be substituted with a group having no reactivity with the amine or the dicarboxylic acid anhydride, and may be used alone or in combination of two or more kinds.

The amount of the aromatic monoamine is 1 mol of the aromatic tetracarboxylic dianhydride represented by the above formula (19).
The molar ratio is 0.001 to 1.0. If it is less than 0.001 mol, the viscosity is increased during high temperature molding, which causes deterioration of moldability. Further, if it exceeds 1.0 mol, mechanical properties are deteriorated.
The preferable amount is 0.01 to 0.5 mol.

The liquid crystalline aromatic polyimide used in the present invention can be produced by any known method. For example, the following method is exemplified. 1) After synthesizing an aromatic polyamic acid in an organic solvent and removing the solvent by decompression or the like, or after isolating the aromatic polyamic acid from the resulting aromatic polyamic acid solution by using a poor solvent or the like , A method of obtaining a liquid crystalline aromatic polyimide by heating the same to obtain a liquid crystalline aromatic polyimide, 2) obtaining an aromatic polyamic acid solution in the same manner as 1), further adding a dehydrating agent typified by acetic anhydride, and if necessary. A method in which a catalyst is appropriately added to chemically imidize the aromatic polyimide, and then the aromatic polyimide is isolated by a known method, and washed and dried if necessary, 3) An aromatic polyamic acid similar to 1) After the solution is obtained, the solvent is removed under reduced pressure or heating to simultaneously perform the thermal imidization. 4) After charging the raw materials in an organic solvent, heating is performed to synthesize the aromatic polyamic acid and perform the imidization reaction. Done at the same time, Catalyst and azeotropic agent in accordance with the requirements, a method of coexisting dehydrating agent, and the like.

In producing the liquid crystalline aromatic polyimide by these methods, it is particularly preferable to carry out the reaction in an organic solvent. Examples of the organic solvent used include N, N
-Dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-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, tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, m-cresylic acid, p- Examples include chlorophenol, xylenols, and anisole. These organic solvents may be used alone or in combination of two or more.

When a liquid crystalline aromatic polyimide is produced in the presence of a dicarboxylic acid anhydride or an aromatic monoamine to seal the polymer molecule ends, an aromatic diamine or an aromatic tetracarboxylic acid diamine is added to an organic solvent. As a method for adding and reacting an anhydride and a dicarboxylic acid anhydride or an aromatic monoamine, (a) an aromatic tetracarboxylic acid dianhydride and an aromatic diamine are reacted and then the dicarboxylic acid anhydride or the aromatic monoamine is reacted. (B) Aromatic dicarboxylic acid anhydrides are added to the aromatic diamines to cause a reaction, and then aromatic tetracarboxylic acid dianhydrides are added to continue the reaction, or A method of reacting an aromatic monoamine with tetracarboxylic dianhydride and then adding an aromatic diamine to continue the reaction. Tetracarboxylic dianhydride, a method of reacting by adding aromatic diamines and dicarboxylic anhydride or aromatic monoamine simultaneously, etc., take no problem any addition-reaction method.

In these methods, the polymerization / imidization reaction temperature is 300 ° C. or lower. The polymerization / imidization reaction pressure is not particularly limited and can be sufficiently carried out at normal pressure. The polymerization / imidation reaction time varies depending on the type of aromatic diamine, the type of aromatic tetracarboxylic dianhydride, the type of solvent and the reaction time, and usually 4 to 24 hours are sufficient. Aromatic tetracarboxylic dianhydrides and aromatic diamines are reacted by the above method in the presence of a dicarboxylic acid anhydride such as phthalic anhydride or aniline or an aromatic monoamine,
In addition, the end of the polymer molecule

[Chemical 68] It is possible to produce a liquid crystalline aromatic polyimide which is unsubstituted or substituted with an aromatic ring substituted with a group having no reactivity with amine or dicarboxylic acid anhydride.

Next, the thermoplastic resin used in the present invention will be described. First, the aromatic polyimide used in the present invention has the formula (5)

[Chemical 69] (In the formula, X represents a group selected from the group consisting of a direct bond, an isopropylidene group, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, or a sulfonyl group, and R represents a carbon number of 2 to 27. And a tetravalent 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 bridging member. Represents an aromatic polyimide having a repeating structural unit represented by a basic skeleton,

Among those expressed by the equation (5),
Expression (6) in which X is directly connected in Expression (5)

[Chemical 70] An aromatic polyimide having a repeating structural unit represented by the following formula, or a formula (20) wherein X is SO ₂ in the formula (5)

[Chemical 71] An aromatic polyimide having a repeating structural unit represented by is often used.

Further, the equation (7)

[Chemical 72] An aromatic polyimide having a repeating structural unit represented by is also frequently used.

Further, it is also effective for the following aromatic polyimide copolymers developed by the present inventors as having improved moldability of the aromatic polyimide of the formula (B). The aromatic polyimide represented by the formula (B) has Tg of 260 ° C. and Tc
Has a Tm of 310-340 ° C and a Tm of 367-385 ° C. It is a crystalline polyimide with excellent chemical resistance that can be melt-molded.
Since it is as high as 367 to 385 ℃, the temperature during molding had to be a high temperature near 400 ℃. In high heat resistant engineering plastics, comparing Tg at the same level with high crystallinity crystalline resin and low crystallinity amorphous resin,
It is generally known that crystalline materials are superior in terms of mechanical properties such as chemical resistance and elastic modulus, and amorphous materials are superior in terms of moldability. Each resin has its advantages and disadvantages. Therefore, it is more preferable that the crystalline polyimide having the repeating structural unit represented by the formula (B) maintains the essentially excellent heat resistance and the molding processability is improved.

The present inventors have studied the improvement of such a polyimide, and have a basic skeleton of 1 to 99 mol% which is a repeating structural unit represented by the above formula (B) and which has crystallinity.
(8)

[Chemical formula 73] Where R is

[Chemical 74] Where n is an integer of 0,1,2,3, Q is directly connected, -O-, -S-, -CO
-, -SO _2- , -CH ₂ , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- , and when there are a plurality of bonding groups Q connecting aromatic rings, they are bonded to each other. The groups may be the same or different combinations,

In addition, R "is

[Chemical 75] (Where M is

[Chemical 76] (Representing at least one tetravalent group selected from the group consisting of at least one divalent group selected from the group consisting of An aromatic polyimide copolymer containing a basic skeleton of 1 to 99 mol%

Among them, the repeating structural unit represented by the formula (8) is

[Chemical 77] The aromatic polyimide copolymer, which is a repeating structural unit represented by the formula (wherein R is as described above) (excluding the same structural unit as the formula (B)), is , The moldability is improved in the amorphous state during molding,
When used after molding, a crystalline state is formed to obtain a polyimide having excellent heat resistance, and the molding processability is improved in the amorphous state from the molding process to the molding state, and in the amorphous state. It was found that a high heat-resistant engineering plastic having good molding processability, excellent chemical resistance such as high heat resistance, and high elastic modulus can be obtained, and provided it. This aromatic polyimide copolymer can also be preferably used as the aromatic polyimide used in the resin composition having improved melt moldability of the present invention.

The terminal of the polymer molecule of these aromatic polyimide and aromatic polyimide copolymer has the formula (2)

[Chemical 78] (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group and a divalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are directly or linked to each other by a bridge member) Dicarboxylic acid anhydride and / or formula (3) V-NH ₂ (3) (In the formula, V has 6 to 15 carbon atoms, and a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group, a monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by a crosslinking member) An aromatic polyimide or an aromatic polyimide copolymer obtained by sealing with a monoamine may be mentioned.

Such an aromatic polyimide or an aromatic polyimide copolymer is prepared by reacting at least one aromatic diamine with at least one aromatic tetracarboxylic acid dianhydride to form a polyamic acid thermally or chemically. It is obtained by imidization. That is, the aromatic polyimide represented by the formula (5) can be represented by, for example, the formula (21)

[Chemical 79] (In the formula, X represents a group selected from the group consisting of a direct bond, an isopropylidene group, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, and a sulfonyl group). ,

Or equation (22)

[Chemical 80] It is obtained by reacting an aromatic diamine represented by and at least one aromatic tetracarboxylic dianhydride.

Aromatic diamines that can be used here include bis [4- (3-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane and 1,2-bis. [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (3-
Aminophenoxy) phenyl] propane, 1,2-bis [4- (3-aminophenoxy) phenyl] propane,
1,3-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 1,1-bis [4- (3-
Aminophenoxy) phenyl] butane, 1,2-bis [4- (3-aminophenoxy) phenyl] butane,
1,3-bis [4- (3-aminophenoxy) phenyl] butane, 1,4-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) Phenyl] butane, 2,3-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, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide or bis [4- (3-aminophenoxy) Examples thereof include phenyl] sulfone, and these may be used alone or in admixture of two or more. Among these,
In the formula (21), X is a direct bond or a sulfone group,
4,4'-bis (3-aminophenoxy) biphenyl or bis [4- (3-aminophenoxy) phenyl] sulfone is preferably used. Furthermore, 3,3'- in equation (22)
Diaminobenzophenone may be mentioned.

On the other hand, the aromatic tetracarboxylic dianhydride used is represented by the formula (19)

[Chemical 81] (In the formula, R has 6 to 27 carbon atoms, and is a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group, a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by a crosslinking member) It is a tetracarboxylic dianhydride. That is, as the aromatic tetracarboxylic dianhydride, there may be mentioned the aromatic tetracarboxylic dianhydrides that can be used for producing a liquid crystalline aromatic polyimide, and those listed above as specific examples. These tetracarboxylic dianhydrides may be used alone or in admixture of two or more. Preferred is pyromellitic dianhydride.

An aromatic polyimide copolymer composed of a basic skeleton which is a repeating structural unit represented by the formula (6) and a basic skeleton which is a repeating structural unit represented by the formula (8) has the formula: (twenty three)

[Chemical formula 82] 4,4-bis (3-aminophenoxy) biphenyl represented by the formula (24) H ₂ N—R—NH ₂ (24)
(In the formula, R is

[Chemical 83] Where n is an integer of 0,1,2,3, Q is directly connected, -O-, -S-, -CO
-, -SO _2- , -CH ₂ , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- , and when there are a plurality of bonding groups Q connecting aromatic rings, they are bonded to each other. (Groups may be the same or different combinations) in the presence of at least one aromatic diamine represented by the formula (25)

[Chemical 84] (In the formula, R "is

[Chemical 85]

(Where M is

[Chemical 86] Is a divalent group selected from the group consisting of) and represents a tetravalent group selected from the group consisting of), and is obtained by reacting with at least one aromatic tetracarboxylic dianhydride represented by .

The aromatic diamine used here has the formula (26)

[Chemical 87] M-phenylenediamine, which is a diamine represented by
o-phenylenediamine, p-phenylenediamine,

Formula (27)

[Chemical 88] Benzidine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3, which is a diamine represented by
4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3 '
-Diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,
3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane,
2,2-bis (3-aminophenyl) propane, 2-
(3-Aminophenyl) -2- (4-aminophenyl)
Propane, 2,2-bis (3-aminophenyl) -1,
1,1,3,3,3-hexafluoropropane, 2,2
-Bis (3-aminophenyl) -1,1,1,3,3,3
3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3
3,3-hexafluoropropane,

Formula (28)

[Chemical 89] 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4 which are diamines represented by -Bis (4-aminophenoxy)
Benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene,
1,4-bis (4-aminobenzoyl) benzene,

Formula (29)

[Chemical 90] 4,4'-bis (4-aminophenoxy) biphenyl, 3,3'-bis (4-aminophenoxy) biphenyl, 3,4'-bis (3-aminophenoxy) biphenyl, which are diamines represented by Bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] ketone, bis [3- (4-aminophenoxy) phenyl] ketone, bis [3- (3-aminophenoxy) ) Phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4-
(3-Aminophenoxy) phenyl] sulfide, bis [3- (4-aminophenoxy) phenyl] sulfide, bis [3- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, bis [3- (3-aminophenoxy) phenyl] sulfone, bis [4- (3 -Aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, bis [3- (3
-Aminophenoxy) phenyl] ether, bis [3-
(4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane,
Bis [3- (3-aminophenoxy) phenyl] methane, bis [3- (4-aminophenoxy) phenyl] methane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2- Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-
(3-Aminophenoxy) phenyl] propane, 2,2
-Bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2, 2-bis [4- (4-aminophenoxy)
Phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Examples include propane and 2,2-bis [3- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane. These may be used alone or in combination of two or more.

Examples of the tetracarboxylic dianhydride used as one of the monomers include, for example, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 3,3. ', 4,4'-Benzophenonetetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride,
2,2-bis (3,4-dicarboxyphenyl) -1,
1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis [4- (1,2-dicarboxy) phenoxy] benzene dianhydride, 1,4-bis [4- (1 ，
2-dicarboxy) phenoxy] benzene dianhydride,
4,4'-bis [4- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, 4,4'-bis [4-
(1,2-Dicarboxy) phenoxy] benzophenone dianhydride, bis [4- (4- (1,2-dicarboxy)]
Phenoxy) phenyl] sulfone dianhydride, 2,2-bis [4- (4- (1,2-dicarboxy) phenoxy)
Phenyl] propane dianhydride, 2,2-bis [4- (4
-(1,2-Dicarboxy) phenoxy) phenyl]-
1,1,1,3,3,3-hexafluoropropane dianhydride and the like can be mentioned.

The aromatic polyimide or the formula represented by the formula (5), the formula (6), the formula (20) or the formula (7)
Basic skeleton 9 having a repeating structural unit represented by (6)
The aromatic polyimide copolymer containing 9 to 1 mol% and 1 to 99 mol% of the basic skeleton having the repeating structural unit represented by the formula (8) is prepared by using the above-mentioned raw material monomers corresponding to the respective polymers as raw materials. Although produced, in addition to the aromatic diamine and the aromatic tetracarboxylic dianhydride, which are the essential raw materials for producing each aromatic polyimide, the obtained aromatic polyimide or aromatic polyimide copolymer is good. Other aromatic diamines or aromatic tetracarboxylic dianhydrides may be mixed and used as long as the physical properties are not impaired.

Examples of the aromatic diamine that can be mixed and used include those exemplified as the aromatic diamine that may be used together in the production of the liquid crystalline aromatic polyimide. These may be selected and used in combination according to the purpose. The aromatic tetracarboxylic dianhydride that can be mixed and used can be appropriately selected and used in combination from those exemplified as the aromatic tetracarboxylic dianhydride represented by the formula (19). . An aromatic polyimide or an aromatic polyimide copolymer obtained by using at least one aromatic diamine component and at least one aromatic tetracarboxylic dianhydride as a monomer component, has an end of the polymer molecule not substituted or an amine or Also included are aromatic polyimide copolymers having aromatic rings substituted with groups that are not reactive with dicarboxylic acid anhydrides.

An aromatic polyimide having an aromatic ring which is unsubstituted or substituted with a group having no reactivity with amine or dicarboxylic acid anhydride at the terminal of the polymer is represented by the above formula (21), (22), Equation (23), Equation (24), Equation (26)
, An aromatic diamine such as formula (27), formula (28) or formula (29) and a tetracarboxylic dianhydride such as formula (19) or formula (25)

[Chemical Formula 91] (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group and a divalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are directly or linked to each other by a bridge member) Dicarboxylic acid anhydride and / or formula (3) V-NH ₂ (3) (In the formula, V has 6 to 15 carbon atoms, and a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group, a monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by a crosslinking member) It can be obtained by reacting in the presence of a monoamine. The aromatic monoamine or aromatic dicarboxylic acid anhydride used in this method is
The above-mentioned ones can be mentioned as those used for producing the liquid crystalline aromatic polyimide or the polyimide copolymer.

The aromatic polyimide, the aromatic polyimide copolymer or the aromatic polymer having an aromatic ring whose terminal of the polymer molecule is unsubstituted or substituted with a group having no reactivity with amine or dicarboxylic acid anhydride The polyimide copolymer can be produced by any known method. For example, specifically, the same method as the above-mentioned method for producing a liquid crystalline aromatic polyimide can be applied. By these methods, an aromatic tetracarboxylic dianhydride or an aromatic diamine is reacted in the presence of a dicarboxylic acid anhydride such as phthalic anhydride or aniline or an aromatic monoamine, and the end of the polymer molecule is an amine. Or a group having no reactivity with a dicarboxylic acid anhydride, for example, at the terminal

[Chemical Formula 92] A polyimide having an aromatic ring substituted with groups such as can be produced.

When the melt-moldable resin composition of the present invention contains a liquid crystalline aromatic polyimide or an aromatic polyimide, a liquid crystalline aromatic polyimide in which the ends of such polymer molecules are blocked or The aromatic polyimide may be sealed at any one of either one side or the other side. In particular, a liquid crystalline aromatic polyimide and / or aromatic polyimide whose polymer end is sealed with a group derived from the above-mentioned phthalic anhydride or aniline is preferable.

Next, the aromatic polyether sulfone used in the present invention has the formula (11)

[Chemical formula 93] (Where X is a direct connection,

[Chemical 94] Represents an aromatic polysulfone having as a basic skeleton at least one repeating structural unit.

Specifically,

[Chemical 95]

[Chemical 96]

[Chemical 97] As other aromatic polysulfones, specifically,

[Chemical 98]

[Chemical 99]

[Chemical 100]

[Chemical 101]

[Chemical 102]

[Chemical 103]

[Chemical 104]

[Chemical 105]

[Chemical formula 106]

[Chemical formula 107] It is an aromatic polysulfone having repeating structural units such as

A particularly typical aromatic polysulfone and formula
(30)

[Chemical 108] It is represented by "ICT eye company in the United Kingdom""VICTREX PES
, And / or formula (31)

[Chemical 109] It is represented by the "DUEL POL
A polysulfone marketed under the trademark "YSLFONE" and / or formula (32)

[Chemical 110] "RADEL PO from Union Carbide Company, USA
The polyallyl sulfone marketed under the trademark "LYSLFONE" may be mentioned. As these aromatic polysulfones, those having various degrees of polymerization can be freely selected, and those giving suitable melt viscosity characteristics to the intended composition can be arbitrarily selected.

Then, the aromatic polyetherimide used in the present invention has the formula (12)

[Chemical 111] (Where X is

[Chemical 112] And Y is

[Chemical 113] Aromatic polyether imide having at least one repeating structural unit represented by the formula) as a basic skeleton, and specific examples thereof include the following.

[Chemical 114]

[Chemical 115]

[Chemical formula 116]

[Chemical 117]

[Chemical 118]

[Chemical formula 119] Aromatic polyether imides having repeating units such as, and these aromatic polyether imides are commercially available from GE, Inc. as "Ultem-1000, Ultem-4000, Ultem-6000.
Etc. ”are commercially available.

Next, the aromatic polyamide-imide used in the present invention has the formula (D)

[Chemical 120] (In the formula, Y represents a divalent organic group having 6 to 27 carbon atoms) is an aromatic polyamideimide having at least one repeating structural unit represented by a basic skeleton, particularly preferably the formula (13)

[Chemical 121] Repeating structural unit represented by and formula (14)

[Chemical formula 122] Is an aromatic polyamideimide having at least one kind of repeating structural unit represented by as a basic skeleton. These aromatic polyamide imides are commercially available, for example, from Acomo, Inc., USA under the trademark TORLON. As these aromatic polyamideimides, those having various degrees of polymerization can be freely selected, and those having appropriate melt viscosity characteristics for the intended blended product can be arbitrarily selected.

Further, the aromatic polyether ketone used in the present invention has the formula (15)

[Chemical 123] A repeating structural unit represented by the formula (16)

[Chemical formula 124] Is an aromatic polyether ketone having at least one repeating structural unit represented by as a basic skeleton.

The melt-processable thermoplastic resin composition of the present invention comprises a liquid crystalline aromatic polyimide having a repeating structural unit represented by the above formula (1) and a repeating structure represented by the formula (4). A liquid crystalline aromatic polyimide having units,
A liquid crystalline polyimide containing 1 to 99 mol% of a basic skeleton having a repeating structural unit represented by the formula (1) and 99 to 1 mol% of a basic skeleton having a repeating structural unit represented by the formula (4). At least one selected from the group consisting of a copolymer and a liquid crystalline aromatic polyimide having an aromatic ring whose terminals of these polymer molecules are unsubstituted or substituted with a group having no reactivity with an amine or a dicarboxylic acid anhydride. One liquid crystalline aromatic polyimide, and at least one thermoplastic resin selected from the group consisting of another aromatic polyimide, aromatic polysulfone, aromatic polyetherimide, aromatic polyamideimide and aromatic polyetherketone. It contains and.

This thermoplastic resin composition is adjusted in the range of 0.1 to 50% by weight of liquid crystalline aromatic polyimide and 99.9 to 50% by weight of thermoplastic resin. The thermoplastic resin composition of the present invention exhibits remarkably low melt viscosity in a high temperature range of 300 ° C or higher. The effect of good melt fluidization of the liquid crystalline aromatic polyimide of the present invention is recognized even in a small amount, and the lower limit of the composition ratio is
It is 0.1% by weight, but preferably 0.5% by weight. Further, although the liquid crystal aromatic polyimide belongs to a very excellent class among the heat resistant resins in chemical resistance, flame retardancy and mechanical strength, it has drawbacks such as strong anisotropy in mechanical properties. Therefore, increasing the amount of the liquid crystalline aromatic polyimide in the composition is not preferable because the original properties of the polyimide cannot be maintained. The composition ratio of the liquid crystalline aromatic polyimide has an upper limit, and is usually 50% by weight or less, preferably 30% by weight or less, more preferably 10% by weight or less.

In preparing the thermoplastic resin composition according to the present invention, a thermoplastic resin and a liquid crystalline aromatic polyimide can be contained and the product can be produced by a generally known method.
For example, the following method is preferable. The thermoplastic resin and the liquid crystalline aromatic polyimide are pre-kneaded by using a mortar, a Henschel mixer, a drum blender, a tumbler blender, a ball mill, a ribbon blender and the like. The thermoplastic resin is previously dissolved or suspended in an organic solvent, the liquid crystalline aromatic polyimide is added to this solution or suspension, and the solvent is removed after being uniformly dispersed or dissolved. When the thermoplastic resin is an aromatic polyimide, in a solution of a polyamic acid, which is a precursor of polyimide, in an organic solvent,
After suspending or dissolving the liquid crystalline aromatic polyimide 100
After heat treatment at ˜400 ° C. or chemical imidization using a commonly used imidizing agent, the solvent is removed by a known method. Similarly, when the thermoplastic resin is an aromatic polyimide, after mixing an organic solvent solution of a polyamic acid that is a polyimide precursor and an organic solvent solution of a polyamic acid that is a precursor of a liquid crystalline aromatic polyimide, 100 to 400 After heat treatment at 0 ° C. or chemical imidization using a commonly used imidizing agent, the solvent is removed by a known method.

The mixture of the liquid crystalline aromatic polyimide and the thermoplastic resin thus obtained is directly used in various molding methods such as injection molding, compression molding, transfer molding and extrusion molding. It is a more preferable method to use it again. Particularly, in mixing and preparing the composition, it is a simple and effective method to mix powders, mix pellets, or mix powders and pellets. For melt blending, the equipment used to melt blend ordinary rubbers or plastics,
For example, a hot roll, a Banbury mixer, a Brabender, an extruder, etc. can be used. The melting temperature is
The temperature is set to a temperature above the melting temperature of the compounding system and below the temperature at which the compounding system begins to thermally decompose.
The temperature is 420 ° C, preferably 300 to 400 ° C.

As a method of molding the resin composition capable of being melt-molded according to the present invention, a uniform melt blend is formed,
In addition, injection molding or extrusion molding, which is a molding method having high productivity, is suitable, but other compression molding, transfer molding, sintering molding or the like may be used. Other thermoplastic resins within the range that does not impair the object of the present invention, for example,
Polystyrene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, polyether sulfone, polyether ketone, polyphenylene sulfide, polyamide imide, polyether imide, modified polyphenylene oxide, other polyimide and thermosetting resin in appropriate amounts according to the purpose It is also possible to mix. Further, one or more solid lubricants such as molybdenum disulfide, graphite, boron nitride, lead monoxide, and lead powder can be added to the polyimide resin composition of the present invention.

Further, a reinforcing material such as glass fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber,
One or more glass beads can be added. Furthermore, to the extent that the object of the present invention is not impaired with respect to the resin composition of the present invention, antioxidants, heat stabilizers, ultraviolet absorbers, flame retardants, flame retardant aids, antistatic agents, coloring agents, etc. One or more of the above additives can be added.

[0089]

The present invention will be described in detail below with reference to Synthesis Examples, Examples and Comparative Examples. In the examples, various physical properties were measured by the following methods. Logarithmic viscosity: A value measured by dissolving 0.50 g of polyimide powder in 100 ml of a mixed solvent of p-chlorophenol and phenol (90:10 weight ratio) by heating and then cooling to 35 ° C. Glass transition temperature (Tg); measured by DSC (Shimadzu DT-40 series, DSC-41M). 5% weight loss temperature: DTA-Tg (Shimadzu DT-
40 series, DSC-40M).

Synthesis Example-1 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene 5.29 was placed in a container equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube. kg
(10.0 mol), pyromellitic dianhydride 2.094 kg (9.
6 mol), γ-picoline 138 g (1.5 mol) and m-
Cresol (23.0 kg) was charged, and the temperature was raised to 145 ° C. with stirring under a nitrogen atmosphere. During this time, about 340g
Distillation of water was confirmed. Furthermore, the reaction was carried out at 140 to 150 ° C. for 4 hours. Then, the mixture was cooled to room temperature, discharged into 81.2 kg of methyl ethyl ketone, and then filtered. This polyimide powder was further washed with methyl ethyl ketone and pre-dried under a nitrogen atmosphere at 50 ° C for 24 hours, then at 200 ° C.
After drying for 6 hours, 6.85 kg (yield 97.3%) of polyimide powder was obtained. The logarithmic viscosity of this polyimide powder is 0.
At 49 dl / g, two endothermic peaks were observed at 274 ° C. and 294 ° C. by DSC measurement. Also, 5% in air
The weight loss temperature was 525 ° C.

Synthetic Examples-2 to 6 Various diamines and various tetracarboxylic dianhydrides were combined and reacted in the same manner as in Synthetic Example-1 to obtain various polyimide powders. Table 1 shows the polyimide synthesis conditions and the logarithmic viscosity, glass transition temperature and 5% weight loss temperature of the produced polyimide powder.

[0092]

[Table 1] Note 1) m-BP: 4,4'-bis (3-aminophenoxy) biphenyl m-BS: bis [4- (3-aminophenoxy) phenyl]
Sulfone mBAPP: 2,2-bis [4- (3-aminophenoxy) phenyl] propane m-APS: Bis [4- (3-aminophenoxy) phenyl] sulfide Note 2) PMDA: Pyromellitic dianhydride BTDA: 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride ODPA: bis (3,4-dicarboxyphenyl) ether dianhydride

Synthesis Example-7 In carrying out the reaction, 118.49 g (0.8%) of phthalic anhydride was used.
The reaction was performed in the same manner as in Synthesis Example-1 except that 0 mol) was added, and 6.93 kg of polyimide powder (yield 97.0%)
Got The logarithmic viscosity of this polyimide powder is 0.49 dl /
g, two endothermic peaks were observed at 274 ° C. and 295 ° C. by DSC measurement. The 5% weight loss temperature in air was 536 ° C.

Synthetic Example-8 Polyimide powder was prepared by the same method as in Synthetic Example-1 except that 158.54 g (0.80 mol) of 1,8-naphthalenedicarboxylic anhydride was added during the reaction. 7.02
kg (yield 97.0%) was obtained. The logarithmic viscosity of this polyimide powder is 0.50 dl / g, and it is 275 by DSC measurement.
Two endothermic peaks were observed at ° C and 297 ° C. Also,
The 5% weight loss temperature in air was 538 ° C.

Synthesis Example-9 In carrying out the reaction, 148.11 g of phthalic anhydride (1.0
A polyimide powder was obtained by performing the reaction in the same manner as in Synthesis Example-2 except that 0 mol) was added. Table 2 shows the polyimide synthesis conditions and the logarithmic viscosity, glass transition temperature and 5% weight loss temperature of the produced polyimide powder.

Synthesis Example-10 In carrying out the reaction, 118.49 g (0.8%) of phthalic anhydride was used.
(0 mol) was added and the reaction was performed in the same manner as in Synthesis Example-3 to obtain a polyimide powder. Table 2 shows the polyimide synthesis conditions and the logarithmic viscosity, glass transition temperature and 5% weight loss temperature of the produced polyimide powder.

Synthesis Example-11 When carrying out the reaction, 88.87 g (0.60) of phthalic anhydride was used.
A polyimide powder was obtained by performing the reaction in the same manner as in Synthesis Example-4 except that (Mole) was added. Table 2 shows the polyimide synthesis conditions and the logarithmic viscosity of the produced polyimide powder, the glass transition temperature and 5
The% weight loss temperature is shown.

Synthesis Example-12 Polyimide powder was prepared by the same procedure as in Synthesis Example-2 except that 198.18 g (1.00 mol) of 1,8-naphthalenedicarboxylic anhydride was added during the reaction. Got
Table 2 shows the polyimide synthesis conditions and the logarithmic viscosity, glass transition temperature and 5% weight loss temperature of the produced polyimide powder.

[Table 2] Note 1) m-BP: 4,4'-bis (3-aminophenoxy) biphenyl m-BS: bis [4- (3-aminophenoxy) phenyl]
Sulfone mBAPP: 2,2-bis [4- (3-aminophenoxy) phenyl] propane Note 2) PMDA: Pyromellitic dianhydride

Synthesis Example-13 In a container equipped with a stirrer, a reflux condenser, a water separator and a nitrogen introducing tube, 3.50 kg (9.5 mol) of 4,4'-bis (3-aminophenoxy) biphenyl and pyro 2.18 kg (10.0 mol) of mellitic dianhydride, 140 g (1.5 mol) of γ-picoline, 93.0 g (1.0 of aniline)
Mol) and 23.0 kg of m-cresol were charged, and the mixture was heated to 145 ° C. while stirring under a nitrogen atmosphere. During this period, distillation of about 360 g of water was confirmed. Furthermore, the reaction was carried out at 140 to 150 ° C. for 4 hours. afterwards,
After cooling to room temperature and discharging into 81.2 kg of methyl ethyl ketone, it was filtered. This polyimide powder was further washed with methyl ethyl ketone and then at 50 ° C under a nitrogen atmosphere.
4. Pre-dry for 24 hours, then dry at 200 ° C. for 6 hours.
25 kg (yield 97.0%) of polyimide powder was obtained. The logarithmic viscosity of this polyimide powder is 0.46 dl / g, the glass transition temperature is 247 ° C., and the 5% weight loss temperature in air is
It was 555 ° C.

Synthesis Example-14 In Synthesis Example-13, 107.15 g of p-toluidine (1.
(0 mol) was used and carried out in the same manner as in Synthesis Example-13 to obtain 52.6 kg (yield 97.0%) of polyimide powder. The polyimide powder has an inherent viscosity of 0.47 dl / g, a glass transition temperature of 245 ° C., and a 5% weight loss temperature in air of 552 ° C.
Met.

Synthetic Example-15 In Synthetic Example-13, 1,3-bis [4- (4: 4,4'-bis (3-aminophenoxy) biphenyl was used instead of 3.50 kg (9.5 mol). -Aminophenoxy] -α, α-dimethylbenzyl] benzene 5.07k
The same procedure as in Synthesis Example 13 was carried out using g (9.6 mol) to obtain 6.76 kg of polyimide powder (yield 97.0%).
The logarithmic viscosity of this polyimide powder is 0.47 dl / g, DS
By C measurement, two endothermic peaks were observed at 274 ° C and 295 ° C. The 5% weight loss temperature in air is 532
It was ℃.

Synthesis Example-16 In Synthesis Example-15, 85.72 g (0.8 mol) of p-toluidine was used instead of 74.4 g (0.8 mol) of aniline.
Was used in the same manner as in Synthesis Example-15 to obtain 6.77 kg (yield 97.0%) of polyimide powder. The logarithmic viscosity of this polyimide powder was 0.48 dl / g, and two endothermic peaks were observed at 274 ° C. and 297 ° C. by DSC measurement. The 5% weight loss temperature in air was 535 ° C.

Synthetic Example-17 In Synthetic Example-13, instead of 3.5,4 kg (9.5 mol) of 4,4'-bis (3-aminophenoxy) biphenyl, 2,2-bis [4- (3 -Aminophenoxy) phenyl] propane (3.98 kg, 9.7 mol) was used and the same procedure as in Synthesis Example-13 was performed to obtain polyimide powder 5.7.
0 kg (yield 97.3%) was obtained. The polyimide powder has an inherent viscosity of 0.54 dl / g and a glass transition temperature of 217.
C., 5% weight loss temperature in air was 534.degree.

Synthesis Example-18 3,3'-diaminebenzophenone 2.12 was placed in a container equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube.
3 kg (10.0 mol), 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride 3.093 kg
(9.6 mol), γ-picoline 138 g (1.5 mol)
Then, 20.9 kg of m-cresol were charged, and the temperature was raised to 145 ° C. with stirring under a nitrogen atmosphere.
During this time, about 340 g of water was confirmed to be distilled. 140 more
The reaction was carried out at ℃ to 150 ℃ for 4 hours. Then, the mixture was cooled to room temperature, discharged into 81.2 kg of methyl ethyl ketone, and then filtered. This polyimide powder was washed with methyl ethyl ketone, pre-dried under a nitrogen atmosphere at 50 ° C. for 24 hours, then dried at 200 ° C. for 6 hours, and 4.74 kg.
(Yield 97.3%) of polyimide powder was obtained. The logarithmic viscosity of this polyimide powder was 0.49 dl / g. The glass transition temperature of this polyimide powder was 240 ° C., and the 5% weight loss temperature in air was 532 ° C.

Synthesis Example-19 In carrying out the reaction, 118.49 g of phthalic anhydride (0.8
The reaction was performed in the same manner as in Synthesis Example-18 except that 0 mol) was added, and 4.88 kg (yield 98.0%) of polyimide powder was obtained.
Got The logarithmic viscosity of this polyimide powder is 0.48 dl /
g, glass transition temperature was 245 ° C, and 5% weight loss temperature in air was 550 ° C.

Synthesis Example-20 Polyimide powder was prepared by the same procedure as in Synthesis Example-18 except that 158.54 g (0.80 mol) of 1,8-naphthalenedicarboxylic anhydride was added during the reaction. 4.8
6 kg (yield 97.0%) was obtained. The polyimide powder has an inherent viscosity of 0.49 dl / g and a glass transition temperature of 247.
C., 5% weight loss temperature in air was 538.degree.

Synthesis Example-21 3,3'-diaminebenzophenone 2.03 was placed in a container equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube.
8 kg (9.6 mol), 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride 3.222 kg (1
0.0 mol), 138 g (1.5 mol) of γ-picoline,
74.50 g (0.8 mol) of aniline and 20.9 kg of m-cresol were charged, and the temperature was raised to 145 ° C. with stirring under a nitrogen atmosphere. 340g during this period
Distillation of water was confirmed. 4 at 140 ℃ ~ 150 ℃
The reaction was carried out over time. Then, cool to room temperature,
It was discharged into kg of methyl ethyl ketone and then filtered off. The polyimide powder was further washed with methyl ethyl ketone, pre-dried at 50 ° C. for 24 hours in a nitrogen atmosphere, and then dried at 200 ° C. for 6 hours to obtain 4.74 kg (yield 9
7.3%) of polyimide powder was obtained. The logarithmic viscosity of this polyimide powder was 0.48 dl / g. The glass transition temperature of this polyimide powder is 240 ° C, 5% in air.
The weight loss temperature was 548 ° C.

Synthesis Example-22 In Synthesis Example-21, 74.50 g (0.8
0 mol) instead of p-toluidine 85.72 g
(0.8 mol) was used in the same manner as in Synthesis Example-21 to obtain 4.85 kg of polyimide powder (yield 97.5%). The polyimide powder had an inherent viscosity of 0.49 dl / g, a glass transition temperature of 244 ° C., and a 5% weight loss temperature in air of 545 ° C.

Synthesis Example-23 In a container equipped with stirring, a reflux condenser, a water separator and a nitrogen introducing tube, 4,4'-bis (3-aminophenoxy) biphenyl 3.316 kg (9.00 mol), 4,4 ''-Diaminodiphenyl ether 0.200 kg (1.00 mol), pyromellitic dianhydride 2.072 kg (9.50 mol), γ-picoline 140 g
(1.5 mol) and 22.4 kg of m-cresol were charged,
The temperature was raised to 145 ° C. with stirring under a nitrogen atmosphere. During this time, it was confirmed that about 340 g of water was distilled. Furthermore, the reaction was carried out at 140 to 150 ° C. for 4 hours. Then, the mixture was cooled to room temperature, discharged into 56.1 kg of methyl ethyl ketone, and then filtered. The polyimide powder was further washed with methyl ethyl ketone, pre-dried at 50 ° C. for 24 hours in a nitrogen atmosphere, and then dried at 200 ° C. for 6 hours to obtain 5.09 kg (yield 97.0%) of polyimide powder. The polyimide powder had an inherent viscosity of 0.50 dl / g, a glass transition temperature of 258 ° C., and Tc and Tm were not observed. The 5% weight loss temperature in air was 542 ° C.

Synthesis Example-24 In Synthesis Example 23, 4,4'-bis (3-aminophenoxy) biphenyl 3.316 kg (9.00 mol), 4,4'-diaminodiphenyl ether 0.200 kg (1.00 mol), pyromellitic dianhydride 4, instead of 2.072 kg (9.50 mol)
4'-bis (3-aminophenoxy) biphenyl 2.579 k
g (7.00 mol), bis [4- (3-aminophenoxy)
Phenyl] sulfone 1.297 kg (3.00 mol) and pyromellitic dianhydride 2.094 kg (9.60 mol) were used, and the reaction was performed in the same manner as in Synthesis Example-23 to prepare polyimide powder 5.51.
Polyimide powder (yield 98.0%) was obtained. The polyimide powder had an inherent viscosity of 0.51 dl / g, a glass transition temperature of 253 ° C., and Tc and Tm were not observed. The 5% weight loss temperature in air was 539 ° C.

Synthesis Example-25 In Synthesis Example-23, phthalic anhydride was used when carrying out the reaction.
The reaction was performed in the same manner as in Synthesis Example-23 except that 148.11 g (1.00 mol) was added, and 5.26 g of polyimide powder (yield 97.8
%) Was obtained. The logarithmic viscosity of this polyimide powder is 0.50 dl /
g, glass transition temperature was 254 ° C., and Tc and Tm were not observed. Also, the 5% weight loss temperature in air is 54
It was 6 ° C.

Synthesis Example-26 Polyimide powder was prepared by the same procedure as in Synthesis Example-23 except that 195.68 g (1.00 mol) of 1.8-naphthalenedicarboxylic acid anhydride was added in the reaction. 5.31 g (yield 98.0%) was obtained. The logarithmic viscosity of this polyimide powder was 0.49 dl / g, the glass transition temperature was 250 ° C., and Tc and Tm were not observed. The 5% weight loss temperature in air was 543 ° C.

Synthesis Example-27 In a container equipped with stirring, a reflux condenser, a water separator and a nitrogen inlet tube, 4,4'-bis (3-aminophenoxy) biphenyl 3.150 kg (8.55 mol), 4,4 '-Diaminodiphenyl ether 0.190 kg (0.95 mol), pyromellitic dianhydride 2.18 kg (10.0 mol), γ-picoline 140 g
(1.5 mol), 93.12 g (1.0 mol) of aniline and 23.0 kg of m-cresol were charged, and the mixture was heated to 145 ° C. with stirring under a nitrogen atmosphere. During this time, about
Distillation of 360 g of water was confirmed. Furthermore, the reaction was carried out at 140 to 150 ° C. for 4 hours. After that, cool to room temperature, 81.2k
After discharging into g of methyl ethyl ketone, it was filtered off. This polyimide powder was further washed with methyl ethyl ketone and pre-dried at 50 ° C. for 24 hours in a nitrogen atmosphere, then 20
After drying at 0 ° C. for 6 hours, 5.16 kg (yield 98.2%) of polyimide powder was obtained. The logarithmic viscosity of this polyimide powder is 0.49dl
/ G, the glass transition temperature was 256 ° C, and the 5% weight loss temperature in air was 549 ° C.

Synthesis Example 28 In the same manner as in Synthesis Example 27 except that 107.15 g (1.0 mol) of p-toluidine was used in place of 93.12 g (1.0 mol) of aniline in Synthesis Example 27, 5.16 kg of polyimide powder
(Yield 98.0%) was obtained. The logarithmic viscosity of this polyimide powder is
0.49 dl / g, glass transition temperature 255 ℃, 5% in air
The weight loss temperature was 547 ° C.

Synthesis Example 29 In Synthesis Example 27, 4,4'-bis (3-aminophenoxy) biphenyl 3.150 kg (8.55 mol), 4,4'-diaminodiphenyl ether 0.190 kg (0.95 mol), aniline 93.12 g (1.0 4,4'-bis (3-aminophenoxy) biphenyl 2.476 kg (6.72 mol) instead of (mol),
Bis [4- (3-aminophenoxy) phenyl] sulfone 1.246 kg (2.88 mol) and aniline 74.50 g (0.80 mol) were used to carry out the same reaction as in Synthesis Example 27 to obtain polyimide powder 5.49 (yield 97.8%). ) Got. This polyimide powder has an inherent viscosity of 0.50 dl / g and a glass transition temperature of 251.
C., 5% weight loss temperature in air was 544.degree.

Synthesis Example-30 In Synthesis Example-29, 74.50 g (0.80 mol) of aniline was used.
Instead of using 85.72 g (0.80 mol) of p-toluidine, the same reaction was carried out as in Synthesis Example-29 to obtain 5.52 kg of polyimide powder (yield 98.0%). The logarithmic viscosity of this polyimide powder is 0.50 dl / g, the glass transition temperature is 252 ° C,
The 5% weight loss temperature in air was 540 ° C.

Synthesis Example-31 In a container equipped with a thermometer, a reflux condenser and a stirrer, 200 g of N, N-dimethylformamide (DMF), 65 g (0.409 mol) of 3,4-difluoronitrobenzene and 1,3-bis (Four-
Hydroxycumyl) benzene 69.1 g (0.199 mo
1) and 33.1 g (0.239 mol) of potassium carbonate were charged, the mixture was heated to 80 ° C. under stirring, and then aged at 80 ° C. for 6 hours.

After the reaction was completed, the inorganic temperature was removed by filtration. 50 ml of water was added to the filtrate and cooled to room temperature to crystallize the desired product. The precipitated crystals were separated by filtration and further sludged with isopropyl alcohol to obtain 1,3-bis [4- (4-nitro-6-fluorophenyloxy) -α, α-dimethylbenzyl] benzene. Melting point 150.7-151.8 [deg.] C., yield 129.4.
g, yield 97% Then, the 1,3-bis [4- (4-nitro-6-fluorophenyloxy) -α obtained above was placed in a reducing apparatus equipped with a thermometer, a reflux condenser and a stirrer. , Α-Dimethylbenzyl]
115 g of benzene (0.184 mol), 250 g of isopropyl alcohol and 4.8 g of 5% -Pd / C (50%)
(Hydrated product) was charged and the reaction was carried out at 70 to 80 ° C. for 4 hours under a hydrogen atmosphere. After completion of the reaction, the catalyst was filtered and the filtrate was concentrated under reduced pressure to obtain pale yellow crystals of 1,3-bis [4- (4-amino-6-fluorophenyloxy) -α, α-dimethylbenzyl] benzene. It was Melting point 130.4-132.9 [deg.] C., yield 84.2 g,
Yield 81% Elemental analysis (C ₃₆ H ₃₄ N ₂ O ₂ F ₂ ) C H N F Calculated value (%) 76.52 6.07 5.96 6.73 Measured value (%) 76.55 6.11 5.91 6.77

Furthermore, 1,3-bis [4- (4-amino-6-fluorophenoxy) -α, α-dimethylbenzyl] was added to a container equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube. Benzene 56.47 g (0.1 mol), pyromellitic dianhydride 21.38 g (0.098 mol), phthalic anhydride 0.592 g
(0.004 mol), γ-picoline 1.40 g, m-cresol
Charge 311.4 g with stirring under a nitrogen atmosphere.
The temperature was raised to 150 ° C. Then, the reaction was carried out at 150 ° C. for 4 hours. During this period, it was confirmed that about 3.6 ml of water was distilled.
After completion of the reaction, the mixture was cooled to room temperature, discharged into about 2.0 L of methyl ethyl ketone, and then the polyimide powder was filtered off. After washing this polyimide powder with methyl ethyl ketone, it was dried in air at 50 ° C for 24 hours and under reduced pressure at 180 ° C for 4 hours to 72.56.
g (yield 97.0%) of polyimide powder was obtained. The polyimide powder thus obtained had an inherent viscosity of 0.50 dl / g, a glass transition temperature of 186 ° C. and a melting point of 350 ° C.

Further, this polyimide powder is a commercially available polyether sulfone (manufactured by ICI, trade name: VICTR).
(EX PES 4100P) (weight ratio: polyether sulfone / main polyimide = 7/3) and melt viscosity at 370 ° C. was measured (residence time 5 minutes). The results are shown below. (Melt viscosity: Poise) Polyether sulfone: 5700 Polyether sulfone / main polyimide: 3350 That is, by mixing the present polyimide with polyether sulfone, the melt viscosity is significantly reduced, and the obtained strand is extruded in the extrusion direction. The properties peculiar to the liquid crystalline polymer such as the orientation of fibrous fibrils were observed.

Synthesis Example-32 200 g of N, N-dimethylformamide (DMF) and 10 parts of toluene were placed in a container equipped with a thermometer, a reflux condenser and a stirrer.
g, 2-chloro-5-nitrotoluene 80g (0.466mo
l), 1,3-bis (4-hydroxycumyl) benzene 78.
8 g (0.227 mol), potassium carbonate 37.7 g (0.27 mol)
(3 mol) was charged, the mixture was heated to 150 ° C. with stirring, and then aged at 150 ° C. for 7 hours. After completion of the reaction, 9
The inorganic temperature was removed by cooling to 0 ° C. and filtering. 56 ml of water was added to the filtrate and cooled to room temperature to crystallize the desired product. The precipitated crystals were separated by filtration and further sludged with isopropyl alcohol to obtain 1,3-bis [4- (4-nitro-6-methylphenoxy) -α, α-dimethylbenzyl] benzene. Melting point 116.3-117.6 [deg.] C., yield 133.9.
g, 96% yield 96% in a reducing device equipped with a thermometer, a reflux condenser and a stirrer,
1,3-bis [4- (4-nitro-6-methylphenoxy) above
-Α, α-Dimethylbenzyl] benzene 120 g (0.19
5 mol), 400 g of isopropyl alcohol and 5
% -Pd / C (5% hydrous product) was charged, and the reaction was carried out at 70 to 80 ° C. for 4 hours under a hydrogen atmosphere. After the reaction was completed, the catalyst was filtered off and the filtrate was concentrated under reduced pressure to obtain pale yellow crystals of 1,3-bis [4- (4-amine-6-methylphenoxy) -α, α-dimethylbenzyl] benzene. . Melting point 118.1 to 118.2 ° C, Yield 89.0
g, yield 82%

The obtained 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl] benzene
Using 55.68 g (0.1 mol) of the same procedure as in Synthesis Example 30, 71.29 g of polyimide powder (yield 96.3%) was obtained. The polyimide powder thus obtained had an inherent viscosity of 0.51 dl / g and a glass transition temperature of 185 ° C. Further, this polyimide powder was mixed with a commercially available polyether sulfone (manufactured by ICI, trade name: VICTREX PES 4100P) (weight ratio: polyether sulfone / main polyimide = 7 /
3) The melt viscosity at 370 ° C. was measured (residence time 5 minutes). The results are shown below. (Melt viscosity: Poise) Polyethersulfone; 5700 Polyethersulfone / main polyimide; 3230 That is, by mixing the present polyimide with polyethersulfone, the melt viscosity is significantly reduced, and the obtained strand is extruded. The properties peculiar to the liquid crystalline polymer such as the orientation of fibrous fibrils were observed.

Synthesis Example-33 In a container equipped with a thermometer, a reflux condenser and a stirrer, 700 ml of N, N-dimethylformamide (DMF) and 30 m of toluene were added.
1, 2-chloro-5-nitrobenzotrifluoride 87g
(0.386 mol), 1,3-bis (4-hydroxycumyl) benzene 63.6 g (0.184 mol), potassium carbonate 5
3.3 g (0.386 mol) of each was charged, the temperature was raised to 110 ° C. with stirring, and then the mixture was aged at 110 ° C. for 4 hours.

After completion of the reaction, the inorganic temperature was removed by cooling to 80 ° C. and filtering. 30 ml of water was added to the filtrate and cooled to room temperature to crystallize the desired product. The precipitated crystals were separated by filtration and sludged with isopropyl alcohol to give the desired product, 1,3-bis [4- (4-nitro-6-trifluoromethylphenyloxy) -α, α-
Dimethylbenzyl] benzene was obtained. Melting point 127.4 to 128.4 ° C., yield 120 g, yield 90% A reducing device equipped with a thermometer, a reflux condenser, and a stirrer,
1,3-bis [4- (4-nitro-6-trifluoromethylphenyloxy) -α, α-dimethylbenzyl] benzene 90
g (0.124 mol), methyl cellosolve 500 ml and 5% -Pd / C 5 g (50% water-containing product) were charged, and the reaction was carried out at 70 to 80 ° C. for 4 hours under a hydrogen atmosphere. After the reaction was completed, the catalyst was filtered off and the filtrate was concentrated under reduced pressure to give pale yellow crystals.
1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene was obtained. Melting point 118.5-119.2 [deg.] C., yield 73.4 g,
Yield 89% Elemental analysis (C ₃₈ H ₃₄ N ₂₀ O ₂ F ₆ ) C H N F Calculated value (%) 68.67 5.16 4.21 17.15 Measured value (%) 68.78 5.22 4.15 17.01

Furthermore, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethyl was placed in a container equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube. Benzyl] benzene 66.47 g (0.1 mol), pyromellitic dianhydride 21.38 g (0.098 mol), phthalic anhydride 0.592 g (0.004 mol), γ-picoline 1.40 g, m-
Cresol (351.4 g) was charged, and the mixture was heated to 150 ° C. with stirring under a nitrogen atmosphere. Then, the mixture was reacted at 150 ° C for 4 hours. During this period, distillation of about 3.6 ml of water was confirmed.

After completion of the reaction, the mixture was cooled to room temperature, discharged into about 2.0 L of methyl ethyl ketone, and then the polyimide powder was filtered off. This polyimide powder was washed with methyl ethyl ketone and then dried in air at 50 ° C. for 24 hours and under reduced pressure at 180 ° C. for 4 hours to obtain 83.22 g (yield 98.1%) of polyimide powder. The polyimide powder thus obtained has an inherent viscosity of 0.45 dl /
g, glass transition temperature was 186 ° C, and melting point was 196 ° C.
The elemental analysis values of the polyimide powder were as follows. Elemental analysis value C H N F calculated value (%) 68.08 3.82 3.31 13.46 Measured value (%) 67.86 3.75 3.40 13.02 Pressure of the polyimide powder obtained here About 50 by pressing and heating under the conditions of 300 psi and temperature of 350 ℃.
It was a polyimide film of μm. When the dielectric constant was measured using this polyimide film, it was 3.
It was 2.99 at 02, 3 KHz and 2.96 at 1 MHz.

Further, this polyimide powder is a commercially available polyether sulfone (manufactured by ICI, trade name: VICTR).
(EX PES 4100P) (weight ratio: polyether sulfone / main polyimide = 7/3), and melt viscosities at 350 ° C. and 370 ° C. were measured (residence time 5
Minutes). The results are shown below. (Measurement Value of Melt Viscosity: Unit Poise) 350 ° C. 370 ° C. Polyethersulfone 12000 5700 Polyethersulfone / Main Polyimide 5250 3350 That is, by mixing the present polyimide with polyethersulfone, the melt viscosity is significantly reduced and obtained. The resulting strands were oriented in the extrusion direction and fibrous fibrils were observed, and the properties peculiar to the liquid crystalline polymer were observed.

Examples-1 to 8 After the polyimide powders obtained in Synthesis Examples-2 and 3 and the liquid crystalline polyimide powder obtained in Synthesis Example-1 were dry blended with various compositions as shown in Table 3, , Koka type flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1
cm, length 1 cm, pressure 100 kg / cm ² ) to measure melt viscosity. Table 3 shows the measured results.

Comparative Examples-1 to 8 Table 3 shows the results of measurement of melt viscosity using the compositions outside the scope of the present invention and in the same manner as in Examples-1 to 8.

[0130]

[Table 3]

Examples-9 to 16 After dry blending the polyimide powders obtained in Synthesis Examples 4,5 and the liquid crystalline polyimide powder obtained in Synthesis Example-1 with various compositions as shown in Table 4, , Koka type flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1
cm, length 1 cm, pressure 100 kg / cm ² ) to measure melt viscosity. Table 4 shows the measurement results.

Comparative Examples-9 to 16 Table 4 shows the results of measurement of melt viscosity by the same operation as in Examples-9 to 16 using the composition outside the range of the present invention.

[0133]

[Table 4]

Examples-17 to 20 The polyimide powder obtained in Synthesis Example-6 and the liquid crystalline polyimide powder obtained in Synthesis Example-1 were dry blended with various compositions as shown in Table 5, and Chemical Flow Tester (Shimadzu, CFT-500, orifice diameter 0.1c
The melt viscosity was measured at m, length 1 cm, and pressure 100 kg / cm ² ). Table 5 shows the measured results.

Comparative Examples -17 to 20 Table 5 shows the results of melt viscosity measurement using the compositions outside the scope of the present invention and the same operation as in Examples -17 to 20.

[0136]

[Table 5]

Examples 21 to 28 Polyimide powders obtained in Synthesis Examples 9 and 10 and Synthesis Example-7
The liquid crystalline polyimide powder obtained in 1. was dry blended with various compositions as shown in Table 6, and then a Koka type flow tester (CFT-500, Shimadzu Corporation, orifice diameter 0.
The melt viscosity was measured at 1 cm, length 1 cm, and pressure 100 kg / cm ² . Table 6 shows the measured results.

Comparative Examples-21 to 28 Table 6 shows the results of melt viscosity measurement using a composition outside the scope of the present invention and in the same manner as in Examples-21 to 28.

[0139]

[Table 6]

Examples 29 to 32 The polyimide powders obtained in Synthesis Example-11 and the liquid crystalline polyimide powders obtained in Synthesis Example-7 were dry blended with various compositions as shown in Table 7, and then the levels were increased. Flow tester (Shimadzu, CFT-500, orifice diameter 0.1)
cm, length 1 cm, pressure 100 kg / cm ² ) to measure melt viscosity. The measured results are shown in Table 7.

Comparative Examples-29 to 32 Table 7 shows the results of measurement of melt viscosity using the compositions outside the scope of the present invention and in the same manner as in Examples-29 to 32.

[0142]

[Table 7]

Examples-33 to 36 The polyimide powder obtained in Synthesis Example-12 and the liquid crystalline polyimide powder obtained in Synthesis Example-8 were dry blended with various compositions as shown in Table 8 and Chemical Flow Tester (Shimadzu, CFT-500, orifice diameter 0.1)
cm, length 1 cm, pressure 100 kg / cm ² ) to measure melt viscosity. Table 8 shows the measurement results.

Comparative Examples-33 to 36 Table 8 shows the results of measurement of melt viscosity using the compositions outside the scope of the present invention and in the same manner as in Examples-33 to 36.

[0145]

[Table 8]

Examples-37 to 44 Synthesis Examples-13 and 17 and the polyimide powders obtained in Synthesis Examples
The liquid crystalline polyimide powder obtained in No. 15 was dry blended with various compositions as shown in Table 9, and then a Koka type flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1 cm, length 1 cm, pressure) The melt viscosity was measured at 100 kg / cm ² ). The measured results are shown in Table 9.

Comparative Examples-37 to 44 Table 9 shows the results of melt viscosity measurement using the compositions outside the scope of the present invention and the same operation as in Examples-37 to 44.

[0148]

[Table 9]

Examples-45 to 48 The polyimide powder obtained in Synthesis Example-14 and the liquid crystalline polyimide powder obtained in Synthesis Example-16 were dry-blended with various compositions as shown in Table 10, and Chemical flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.
The melt viscosity was measured at 1 cm, length 1 cm, and pressure 100 kg / cm ² . Table 10 shows the measured results.

Comparative Examples-45 to 48 Table 10 shows the results of melt viscosity measurement using a composition outside the scope of the present invention and in the same manner as in Examples-45 to 48.

[0151]

[Table 10]

Examples-49 to 56 The polyimide powders obtained in Synthetic Examples-9, 10, 11, and 12 and the liquid crystalline polyimide powders obtained in Synthetic Examples-7 and 8 were mixed in various amounts as shown in Table 11. After dry blending with composition,
Extruding was performed while melt-kneading with an extruder (with a screw having a diameter of 40 mm and a compression ratio of 3.0 / 1.0) to obtain uniform blended pellets. Next, the pellets obtained as described above were molded by an ordinary injection molding machine, and the minimum injection pressure of the molded product was measured. The results are shown in Table 11 as Examples-49 to 56.

Comparative Examples-49 to 56 Table 11 shows the results of melt viscosity measurement using a composition outside the scope of the present invention and in the same manner as in Examples-49 to 56.

[0154]

[Table 11]

Examples-57 to 60 The polyimide powder obtained in Synthesis Example-18 and the liquid crystalline polyimide powder obtained in Synthesis Example-1 were dry blended with various compositions as shown in Table 12, and Chemical Flow Tester (Shimadzu, CFT-500, orifice diameter 0.1c
The melt viscosity was measured at m, length 1 cm, and pressure 100 kg / cm ² ). Table 12 shows the measurement results.

Comparative Examples-57 to 60 Table 12 shows the results of measuring the melt viscosity by the same operation as in Examples-57 to 60 using the compositions outside the scope of the present invention.

[0157]

[Table 12]

Examples-61 to 64 The polyimide powder obtained in Synthesis Example-19 and the liquid crystalline polyimide powder obtained in Synthesis Example-7 were dry blended with various compositions as shown in Table 13, and Chemical Flow Tester (Shimadzu, CFT-500, orifice diameter 0.1c
The melt viscosity was measured at m, length 1 cm, and pressure 100 kg / cm ² ). Table 13 shows the measurement results.

Comparative Examples-61-64 Table 13 shows the results of measurement of melt viscosity by the same operation as in Examples-61-64 using compositions outside the scope of the present invention.

[0160]

[Table 13]

Examples-65 to 68 The polyimide powder obtained in Synthesis Example-20 and the liquid crystalline polyimide powder obtained in Synthesis Example-8 were dry blended with various compositions as shown in Table 14, and Chemical Flow Tester (Shimadzu, CFT-500, orifice diameter 0.1c
The melt viscosity was measured at m, length 1 cm, and pressure 100 kg / cm ² ). Table 14 shows the measurement results.

Comparative Examples-65 to 68 Table 14 shows the results of measurement of melt viscosity by the same operation as in Examples-65 to 68 using the compositions outside the scope of the present invention.

[0163]

[Table 14]

Examples-69 to 72 The polyimide powder obtained in Synthesis Example-21 and the liquid crystalline polyimide powder obtained in Synthesis Example-15 were dry blended with various compositions as shown in Table 15, and Chemical Flow Tester (Shimadzu, CFT-500, orifice diameter 0.1c
The melt viscosity was measured at m, length 1 cm, and pressure 100 kg / cm ² ). Table 15 shows the measured results.

Comparative Examples-69 to 72 Table 15 shows the results of melt viscosity measurement by the same operation as in Examples-69 to 72 using the compositions outside the scope of the present invention.

[0166]

[Table 15]

Examples-73 to 76 The polyimide powder obtained in Synthesis Example-22 and the liquid crystalline polyimide powder obtained in Synthesis Example-16 were dry blended with various compositions as shown in Table 16, and Chemical Flow Tester (Shimadzu, CFT-500, orifice diameter 0.1c
The melt viscosity was measured at m, length 1 cm, and pressure 100 kg / cm ² ). Table 16 shows the measured results.

Comparative Examples-73 to 76 Table 16 shows the results of melt viscosity measurement using a composition outside the scope of the present invention and in the same manner as in Examples-73 to 76.

[0169]

[Table 16]

Examples-77 to 80 Polyimide powders obtained in Synthesis Examples-19 and 21 and Synthesis Examples-7 and
The liquid crystalline polyimide powder obtained in 15 was dry blended with various compositions as shown in Tables 17 and 18, and then melted with an extruder (with a screw diameter of 40 mm and a compression ratio of 3.0 / 1.0). It was extruded while kneading to obtain uniform blended pellets. Next, the pellets obtained as described above were molded by an ordinary injection molding machine, and the minimum injection pressure of the molded product was measured. The results are shown in Tables 17 and 18 as Examples-77 to 80.

Comparative Examples-77 to 80 Tables 17 and 18 show the results of melt viscosity measurement by the same operation as in Examples-77 to 80 using the compositions outside the scope of the present invention.

[0172]

[Table 17]

[0173]

[Table 18]

Examples-81 to 88 The polyimide powders obtained in Synthesis Examples-23 and 24 and the liquid crystalline polyimide powder obtained in Synthesis Example-1 were dry blended in various compositions as shown in Tables 19 and 20. After that, the melt viscosity was measured using a Koka type flow tester (CFT-500, Shimadzu Corporation, orifice diameter 0.1 cm, length 1 cm, pressure 100 kg / cm ² ). The measured results are shown in Tables 19 and 20. Table 1 also shows the results of DSC measurement of the transition temperature (Tg) of the strands obtained by the flow tester.
Shown in 9 and 20. A mixture of the aromatic polyimide copolymer and the liquid crystalline aromatic polyimide in the proportion of this example has a lower melt viscosity than the aromatic polyimide copolymer alone, and has a Tg which is not different from that of the aromatic polyimide copolymer. Had.

Comparative Examples-81 to 88 Tables 19 and 20 show the results of measuring the melt viscosity by the same operation as in Examples-81 to 88 using the compositions outside the scope of the present invention.

[0176]

[Table 19]

[0177]

[Table 20]

Examples-89 to 96 The polyimide powders obtained in Synthesis Examples-25 and 29 and the liquid crystalline polyimide powder obtained in Synthesis Example-7 were dry blended in various compositions as shown in Tables 21 and 22. After that, the melt viscosity was measured using a Koka type flow tester (CFT-500, Shimadzu Corporation, orifice diameter 0.1 cm, length 1 cm, pressure 100 kg / cm ² ). The measured results are shown in Tables 21 and 22. Table 2 also shows the results of DSC measurement of the transition temperature (Tg) of the strands obtained by the flow tester.
Shown in 1 and 22. A mixture of the aromatic polyimide copolymer and the liquid crystalline aromatic polyimide in the proportion of this example has a lower melt viscosity than the aromatic polyimide copolymer alone, and has a Tg which is not different from that of the aromatic polyimide copolymer. Had.

Comparative Examples-89 to 96 Tables 21 and 22 show the results of measurement of melt viscosity by the same operation as in Examples-89 to 96 using the compositions outside the scope of the present invention.

[0180]

[Table 21]

[0181]

[Table 22]

Examples-97 to 100 The polyimide powder obtained in Synthesis Example-26 and the liquid crystalline polyimide powder obtained in Synthesis Example-8 were dry-blended with various compositions as shown in Table 23, and Chemical Flow Tester (Shimadzu, CFT-500, orifice diameter 0.1c
The melt viscosity was measured at m, length 1 cm, and pressure 100 kg / cm ² ). The measured results are shown in Table 23. Also, the transition temperature (T
Table 23 also shows the results of measurement of g) by DSC. A mixture of the aromatic polyimide copolymer and the liquid crystalline aromatic polyimide in the proportion of this example has a lower melt viscosity than the aromatic polyimide copolymer alone, and has a Tg which is not different from that of the aromatic polyimide copolymer. Had.

Comparative Examples-97 to 100 Table 23 shows the results of melt viscosity measurement using a composition outside the range of the present invention and the same operation as in Examples-97 to 100.

[0184]

[Table 23]

Examples 101 to 108 The polyimide powders obtained in Synthesis Examples 27 and 30 and the liquid crystalline polyimide powders obtained in Synthesis Example-15 were dry blended with various compositions as shown in Tables 24 and 25. Then, the melt viscosity was measured with a Koka type flow tester (CFT-500 manufactured by Shimadzu Corporation, orifice diameter 0.1 cm, length 1 cm, pressure 100 kg / cm ² ). The measured results are shown in Tables 24 and 25.
Also, the transition temperature (Tg) of the strand obtained by the flow tester was measured by DSC.
Shown in. A mixture of the aromatic polyimide copolymer and the liquid crystalline aromatic polyimide in the proportion of this example has a lower melt viscosity than the aromatic polyimide copolymer alone, and has a Tg which is not different from that of the aromatic polyimide copolymer. Had.

Comparative Examples-101 to 108 Tables 24 and 25 show the results of measurement of melt viscosity using a composition outside the scope of the present invention and in the same manner as in Examples-101 to 108.

[0187]

[Table 24]

[0188]

[Table 25]

Examples 109 to 112 The polyimide powder obtained in Synthesis Example-28 and the liquid crystalline polyimide powder obtained in Synthesis Example-16 were dry blended with various compositions as shown in Table 26, and then, Flow tester (Shimadzu, CFT-500, orifice diameter 0.1c
The melt viscosity was measured at m, length 1 cm, and pressure 100 kg / cm ² ). Table 26 shows the measurement results. In addition, the transition temperature (Tg) of the strand obtained by the flow tester
Table 26 also shows the results of measurement by DSC. A mixture of the aromatic polyimide copolymer and the liquid crystalline aromatic polyimide in the proportion of this example has a lower melt viscosity than the aromatic polyimide copolymer alone, and has a Tg which is not different from that of the aromatic polyimide copolymer. Had.

Comparative Examples-109 to 112 Table 26 shows the results of melt viscosity measurement using a composition outside the scope of the present invention and in the same manner as in Examples-109 to 112.

[0191]

[Table 26]

Examples-113 to 120 The polyimide powders obtained in Synthesis Examples-25, 27, 29 and 30 and the liquid crystalline polyimide powders obtained in Synthesis Examples-7 and 15 are shown in Tables 27 and 28.
After dry-blending with various compositions as shown in (1), the mixture was extruded while being melt-kneaded with an extruder (with a screw having a diameter of 40 mm and a compression ratio of 3.0 / 1.0) to obtain uniform blended pellets. Next, the pellets obtained as described above were molded by an ordinary injection molding machine, and the minimum injection pressure of the molded product was measured. The results are shown in Tables 27 and 28 as Examples-113 to 120. It can be seen that the mixture of the aromatic polyimide copolymer and the liquid crystalline aromatic polyimide in the ratio of this example has a lower minimum injection pressure than that of the aromatic polyimide copolymer alone and has good moldability.

Comparative Examples-113 to 120 [0193] Tables 27 and 28 in which the minimum injection pressure was measured by performing the same operations as in Examples-113 to 120 using the compositions outside the range of the present invention are shown. Those that do not contain liquid crystalline aromatic polyimide have a high minimum injection pressure, and if the liquid crystalline aromatic polyimide exceeds 50 parts by weight with respect to 50 parts by weight of the aromatic polyimide copolymer, the melt viscosity becomes too low and the minimum injection occurs. The pressure could not be measured. That is, the melt viscosity is too high, which makes injection molding difficult.

[0194]

[Table 27]

[0195]

[Table 28]

Examples 121 and 122 Pellets obtained by blending the aromatic polyimide copolymer and the liquid crystalline aromatic polyimide of Examples 113 and 115 at a mixing ratio of 90:10 were subjected to a conventional injection molding machine, Injection molding was performed at a molding temperature of 360 to 400 ° C. and a mold temperature of 150 ° C., and the mechanical substance of the molded product was measured. The results are shown in Table-29 as Examples 121 and 122. The tensile strength, tensile modulus, and tensile elongation in the table are based on ASTM D-638. The mixture of the aromatic polyimide copolymer and the liquid crystalline aromatic polyimide in the ratio of this example has the same mechanical properties as those of the aromatic polyimide copolymers of Comparative Examples 121 and 122 alone. Even if the liquid crystalline aromatic polyimide is mixed within the range, the mechanical properties are not deteriorated.

Comparative Examples 121, 122 Pellets obtained in Comparative Examples 113 and 115 were treated with
A molded product was prepared in the same manner as 122, and the mechanical properties of the molded product were measured. The results are shown in Table 29 as Comparative Examples 121 and 122.

[0198]

[Table 29]

Examples 123 to 126 Aromatic polysulfone resin powders (VIC, V
(ICTREX PES4100P) and the liquid crystal aromatic polyimide obtained in Synthesis Example 1 were dry-blended with various compositions as shown in Table 30, and then the high chemical flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1c).
The melt viscosity was measured at m, length 1 cm and pressure 100 kg / cm ² ). Table 30 shows the measurement results.

Comparative Examples-123 to 126 Table 30 shows the results obtained by measuring the melt viscosity by the same operation as in Examples-123 to 126 using the compositions outside the scope of the present invention.

[0201]

[Table 30]

Example-127 to 130 Aromatic polysulfone resin powder (ICI Co., Ltd.,
VICTREX PES 4100P) and the liquid crystalline aromatic polyimide obtained in Synthesis Example 7 were dry-blended with various compositions as shown in Table 31, and then a chemical conversion flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.
The melt viscosity was measured at 1 cm, length 1 cm and pressure 100 kg / cm ² ). Table 31 shows the measured results.

Comparative Examples-123, 125, 127, 128 Table 31 shows the results of measurement of melt viscosity by the same operation as in Examples-127 to 130 using compositions outside the scope of the present invention.

[0204]

[Table 31]

Examples 131 to 134 Aromatic polysulfone resin powder (manufactured by ICC Co., Ltd.,
VICTREX PES 4100P) and the liquid crystalline aromatic polyimide obtained in Synthesis Example 15 were dry blended with various compositions as shown in Table 32, and then a high chemical flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1) was used.
The melt viscosity was measured at cm, length 1 cm, and pressure 100 kg / cm ² ). Table 32 shows the measurement results.

Comparative Examples-123, 125, 129, 130 Table 32 shows the results of measurement of melt viscosity by the same operation as in Examples-131 to 134, using a composition outside the scope of the present invention.

[0207]

[Table 32]

Examples-135 to 138 Aromatic polysulfone resin powder (trademark of Union Carbide, UDEL POLYSULFONE P-170)
0) and the liquid crystalline aromatic polyimide obtained in Synthesis Example 7 are shown.
As shown in 33, after dry blending with various compositions, high chemical flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1 cm, length 1 cm, pressure 100 kg
Melt viscosity was measured in / cm ² ). Table 33 shows the measurement results.
Shown in.

Comparative Examples-131 to 134 Table 33 shows the results of measurement of melt viscosity by the same operation as in Examples-135 to 138 using compositions outside the scope of the present invention.

[0210]

[Table 33]

Examples -139 to 142 Aromatic polysulfone resin powder (trademark of Union Carbide, UDEL POLYSULFONE P-170)
0) and the liquid crystalline aromatic polyimide obtained in Synthesis Example 8 are shown.
As shown in 34, after dry blending with various compositions, a high chemical flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1 cm, length 1 cm, pressure 100 kg
Melt viscosity was measured in / cm ² ). Table 34 shows the measurement results.
Shown in.

Comparative Examples-131, 133, 135 and 136 Table 34 shows the results of measurement of melt viscosity by the same operation as in Examples-139 to 142 using compositions outside the scope of the present invention.

[0213]

[Table 34]

Examples -143 to 146 Aromatic polysulfone resin powder (trademark of Union Carbide, UDEL POLYSULFONE P-170)
0) and the liquid crystalline aromatic polyimide obtained in Synthesis Example 15 are shown.
As shown in 35, after dry blending with various compositions, high chemical flow tester (CFT-500, Shimadzu, orifice diameter 0.1 cm, length 1 cm, pressure 100 kg
Melt viscosity was measured in / cm ² ). Table 35 shows the measurement results.
Shown in.

Comparative Examples-131, 133, 137, 138 Table 35 shows the results of measurement of melt viscosity using the compositions outside the scope of the present invention and in the same manner as in Examples-143 to 146.

[0216]

[Table 35]

Example 147 to 150 Aromatic polysulfone resin powder (trademark of Union Carbide, RADEL POLYSULFONE A-40)
0) and the liquid crystalline aromatic polyimide obtained in Synthesis Example 7 are shown.
As shown in 36, after dry blending with various compositions, a high chemical flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1 cm, length 1 cm, pressure 100 kg
Melt viscosity was measured in / cm ² ). Table 36 shows the measurement results.
Shown in.

Comparative Examples-139 to 142 Table 36 shows the results of measurement of melt viscosity using a composition outside the scope of the present invention and in the same manner as in Examples-147 to 150.

[0219]

[Table 36]

Examples -151 to 154 Aromatic polysulfone resin powder (trade name, RADEL POLYSULFONE A-40, trade name of Union Carbide Co., Ltd.)
0) and the liquid crystalline aromatic polyimide obtained in Synthesis Example 15 are shown.
As shown in 37, after dry blending with various compositions, high chemical flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1 cm, length 1 cm, pressure 100 kg
Melt viscosity was measured in / cm ² ). Table 37 shows the measurement results.
Shown in.

Comparative Examples-139, 141, 143 and 144 Table 37 shows the results of measurement of melt viscosity by the same operation as in Examples-151 to 154 using compositions outside the scope of the present invention.

[0222]

[Table 37]

Examples -155 to 159 Aromatic polysulfone resin powder (trademark of Union Carbide Co., UDEL POLYSULFONE A-400)
And the liquid crystalline aromatic polyimide obtained in Synthesis Example 16 were dry blended with various compositions as shown in Table 38, and then a high chemical flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1 cm, length 1 cm) was used. , Pressure 100kg / c
Melt viscosity was measured in m ² ). Table 38 shows the measurement results.

Comparative Examples-139, 141, 145, 146 Table 38 shows the results of measurement of melt viscosity using the compositions outside the scope of the present invention and in the same manner as in Examples-155 to 159.

[0225]

[Table 38]

Example-159 to 164 Aromatic polysulfone sun resin powder "VICTREX PES 4100P
(Trademark of ICI Corporation), "UDEL POLYSULFONE
P-1700 "(trademark of Union Carbide Corporation) and" RADEL
POLYSULFONE A-400 "(trademark of Union Carbide Corporation)
And the crystalline polyimide powders obtained in Synthetic Examples-7 and 15, Table 3
After dry blending with various compositions as shown in 9, 40 and 41, extruder (caliber 40 mm, compression ratio = 3.0 /
It was extruded while being melt-kneaded with a 1.0 screw) to obtain uniform blended pellets. Next, the pellets obtained as described above were molded by an ordinary injection molding machine, and the minimum injection pressure of the molded product was measured. The results are shown in Tables 39, 40 and 41 as Example-1.
Shown as 59-164.

Comparative Example-147-152 The results of measuring the minimum injection pressure by performing the same operation as in Example-159-164 using the composition outside the range of the present invention are also shown in Tables 39, 40 and 41. .

[0228]

[Table 39]

[0229]

[Table 40]

[0230]

[Table 41]

Examples-165 to 184 The aromatic polyether imides (trade name Ultem 1000 manufactured by GE, USA) and the liquid crystal aromatic polyimides obtained in Synthesis Examples 1, 7, 8, 15 and 16 are shown in Tables 42 to 46. After dry-blending with various compositions as shown in Fig. 1, a Koka type flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.
The melt viscosity was measured at 1 cm, length 1 cm, and pressure 100 kg / cm ² . The measured results are shown in Tables 42 to 46. The results of measuring the glass transition temperature (Tg) of the strands obtained by the flow tester by DSC are also shown in Table 42-
Shown in 46. The mixture of the aromatic polyetherimide and the liquid crystalline aromatic polyimide in the proportion of this example has a lower melt viscosity than that of the aromatic polyetherimide alone, and has a Tg that does not replace the aromatic polyetherimide. It was Also, the strands obtained by the flow tester were as tough as the aromatic polyetherimide alone.

Comparative Examples-153 to 172 Tables 42 to 46 show the results of measuring the melt viscosity by the same operation as in Examples 165 to 184 using the compositions outside the scope of the present invention. Those which do not contain liquid crystalline aromatic polyimide at all have a high melt viscosity, and when the amount of liquid crystalline aromatic polyimide mixed with 50 parts by weight of aromatic polyetherimide is more than 50 parts by weight, the melt viscosity becomes low, but a flow tester. The Tetland obtained at was brittle.

[0233]

[Table 42]

[0234]

[Table 43]

[0235]

[Table 44]

[0236]

[Table 45]

[0237]

[Table 46]

Examples 185 to 188 Aromatic polyether imide (trade name Ultem 1000 manufactured by GE, USA) and the polyimide powders obtained in Synthesis Examples 7 and 15 were dried in various compositions as shown in Table 47. After blending, extruder (caliber 40 mm, compression ratio = 3.0 /
Extrude while melting and kneading with a 1.0 screw),
A uniform blended pellet was obtained. Next, the pellets obtained as described above were molded by an ordinary injection molding machine, and the minimum injection pressure of the molded product was measured. The results are shown in Table 47 as Examples -185 to 188. It can be seen that the mixture of the aromatic polyetherimide and the liquid crystalline aromatic polyimide in the proportion of this example has a lower minimum injection pressure than that of the aromatic polyetherimide alone and has good moldability.

Comparative Example-173 to 176 The same procedure as in Examples-185 to 188 was carried out using a composition outside the range of the present invention, and the minimum injection pressure was measured.
Those that do not contain liquid crystalline aromatic polyimide have a high minimum injection pressure, and if the liquid crystalline aromatic polyimide exceeds 50 parts by weight with respect to 50 parts by weight of the aromatic polyetherimide, the melt viscosity becomes too low and the minimum injection occurs. The pressure could not be measured. That is, the melt viscosity is too low to make injection molding difficult.

[0240]

[Table 47]

Examples -189 to 208 Aromatic polyamide imide (trade name TORLON manufactured by Amoco, USA)
4203L) and the liquid crystalline aromatic polyimides obtained in Synthetic Examples 1, 7, 8, 15, 16 were dry blended with various compositions as shown in Tables 48 to 52, and then a Koka type flow tester (Shimadzu Corporation,
CFT-500, orifice diameter 0.1 cm, length 1c
The melt viscosity was measured at m and a pressure of 100 kg / cm ² ).
The measured results are shown in Tables 48 to 52. Further, the glass transition temperature (T
The results of measuring g) by DSC are also shown in the same Tables 48 to 52. The mixture of the aromatic polyamide-imide and the liquid crystalline aromatic polyimide in the proportion of this example had a lower melt viscosity than the aromatic polyamide-imide alone, and had Tg which was not different from that of the aromatic polyamide-imide.

Comparative Examples-177 to 196 Tables 48 to 52 show the results of measurement of melt viscosity using the compositions outside the scope of the present invention and in the same manner as in Examples -189 to 208.

[0243]

[Table 48]

[0244]

[Table 49]

[0245]

[Table 50]

[0246]

[Table 51]

[0247]

[Table 52]

Examples -209 to 212 Aromatic polyamide imide (trade name TORLON manufactured by Amoco, USA)
4203L) and the polyimide powders obtained in Synthesis Examples-7 and 15
As shown in 53, after dry blending with various compositions, extrusion was performed while melt-kneading with an extruder (with a screw having a diameter of 40 mm and a compression ratio of 3.0 / 1.0) to obtain uniform blended pellets. Next, the pellets obtained as described above were molded by an ordinary injection molding machine, and the minimum injection pressure of the molded product was measured. The results are shown in Table 53 as Examples -209 to 212. It can be seen that the mixture of the aromatic polyamideimide and the liquid crystalline aromatic polyimide in the proportion of this example has a lower minimum injection pressure than that of the aromatic polyamideimide alone and has good moldability.

Comparative Example-197 to 200 [0249] Table 53 shows the results of measuring the minimum injection pressure by performing the same operation as in Examples-209 to 212 using the composition outside the range of the present invention. Those containing no liquid crystalline aromatic polyimide have a high minimum injection pressure, and when the liquid crystalline aromatic polyimide exceeds 50 parts by weight with respect to 50 parts by weight of the aromatic polyamideimide, the melt viscosity becomes too low and the minimum injection pressure is reduced. I couldn't measure. That is, the melt viscosity is too low, which makes injection molding difficult.

[0250]

[Table 53]

Example-213 Pellets obtained by dry blending the aromatic polyamide-imide of Example-209 and the liquid crystalline aromatic polyimide at a mixing ratio of 90/10 were subjected to a conventional injection molding machine, and the molding temperature was 360 to 400. Injection molding at a mold temperature of 160 ° C. and the mechanical properties of the molded product were measured. The results are shown in Table 54 as Example 213.
Show as. In the table, tensile strength, tensile modulus, and tensile elongation are A
According to STM D-638. The mixture of the aromatic polyamideimide and the liquid crystalline aromatic polyimide in the ratio of this Example has the same mechanical properties as the aromatic polyamideimide of Comparative Example-201 alone. The mechanical properties are not deteriorated even when the aromatic aromatic polyimide is mixed.

Comparative Example-201 The pellet obtained in Comparative Example-197 was made into a molded product by the same operation as in Example-213, and the mechanical properties of the molded product were measured.
The results are shown in Table 54 as Comparative Example-201.

[0253]

[Table 54]

Examples -214 to 233 The aromatic polyether ketone (trade name: VICTREX PEEK 450P manufactured by ICI Co.) and the liquid crystalline aromatic polyimides obtained in Synthesis Examples 1, 7, 8, 15, and 16 were used. After dry blending with various compositions as shown in Tables 55 to 59, the melt viscosity was measured with a Koka type flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1 cm, length 1 cm, pressure 100 kg / cm ² ). It was measured. The measured results are shown in Tables 55-59. Further, the results of measuring the glass transition temperature (Tg) of the strand obtained by the flow tester by DSC are also shown in Tables 55 to 59. The mixture of the aromatic polyether ketone and the liquid crystalline aromatic polyimide in the proportion of this example is
Lower melt viscosity than aromatic polyether ketone alone,
Moreover, it had Tg which was not different from that of the aromatic polyether ketone.

Comparative Examples-202 to 221 Tables 55 to 59 show the results of measurement of melt viscosity by the same operation as in Examples 214 to 233 using the compositions outside the scope of the present invention.

Examples -234 to 245 Aromatic polyether ketone (trademark of ICI Co., Ltd.)
(VICTREX PEEK 220G) and Synthetic Examples-1, 7, 15
Liquid crystalline aromatic polyimides are available in various types as shown in Tables 60-62.
After dry blending with composition, Koka type flow tester
(Shimadzu, CFT-500, orifice diameter 0.1
cm, length 1 cm, pressure 100 kg / cm ²) With melt viscosity
The degree was measured. The measurement results are shown in Tables 60 to 62. Well
Stranded glass obtained by flow tester
The results of measuring the transition temperature (Tg) by DSC are also shown in Table 60.
~ 62. Aromatic polyether keto in proportions of this example
Mixture of liquid crystalline aromatic polyimide and aromatic
Lower melt viscosity than polyetherketone alone,
Has Tg similar to aromatic polyetherketone
I was there.

Comparative Examples-222 to 233 Tables 60 to 62 show the results of measurement of melt viscosity in the same manner as in Examples 234 to 245 using compositions outside the scope of the present invention.

[0258]

[Table 55]

[0259]

[Table 56]

[0260]

[Table 57]

[0261]

[Table 58]

[0262]

[Table 59]

[0263]

[Table 60]

[0264]

[Table 61]

[0265]

[Table 62]

Examples -246 to 253 Obtained in Aromatic Polyether Ketones (trade name VICTREX PEEK 450P manufactured by ICI and VICTREX PEK 220G manufactured by IC) and Synthesis Examples-7 and 15. After dry blending the obtained polyimide powder with various compositions as shown in Tables 63 to 64, an extruder (diameter 40 mm, compression ratio = 3.0
/1.0 screw) and extruded while melt-kneading to obtain uniform blended pellets. Next, the pellets obtained as described above were molded by an ordinary injection molding machine, and the minimum injection pressure of the molded product was measured. The results are shown in Tables 63 and 64 as Example-247.
Shown as ~ 254. The mixture of the aromatic polyether ketone and the liquid crystalline aromatic polyimide in the proportion of this example is
It can be seen that the minimum injection pressure is lower than that of the aromatic polyether ketone alone, and the moldability is good.

Comparative Examples-234 to 241 The same operation as in Examples 246 to 253 was performed using the compositions outside the scope of the present invention, and the results of measuring the minimum injection pressure are shown in Table 63.
Shown in 64. Those that do not contain liquid crystalline aromatic polyimide have a high minimum injection pressure.
When the amount of the liquid crystalline aromatic polyimide was more than 50 parts by weight with respect to parts by weight, the melting year was low and the minimum injection pressure could not be measured. That is, the melt viscosity is too low, which makes injection molding difficult.

[0268]

[Table 63]

[0269]

[Table 64]

Examples 254 and 255 Pellets obtained by dry blending the aromatic polyether ketone and the liquid crystalline aromatic polyimide of Examples 246 and 250 at a mixing ratio of 90/10 were subjected to a conventional injection molding machine. Then, injection molding was performed at a molding temperature of 360 to 400 ° C. and a mold temperature of 160 ° C., and the mechanical properties of the molded product were measured. The results are shown in Table-65.
Examples-255 and 256. The tensile strength, tensile modulus, and tensile elongation in the table are based on ASTM D-638. The mixture of the aromatic polyether ketone and the liquid crystalline aromatic polyimide in the ratio of this Example has the same mechanical properties as those of Comparative Examples 242 and 243, which have only the aromatic polyether ketone. Even if the liquid crystalline aromatic polyimide is mixed within the range, the mechanical properties are not deteriorated.

Comparative Examples 242 and 243 The pellets obtained in Comparative Examples 234 and 238 were used in Example 254.
, 255 to obtain a molded product, and the mechanical properties of the molded product were measured. The results are shown in Table 65 together with Comparative Examples 242 and 243.
Show as.

[0272]

[Table 65]

[0273]

EFFECTS OF THE INVENTION According to the present invention, there is provided a thermoplastic resin composition which is excellent in molding processability and is excellent in thermal stability, in addition to the excellent characteristics inherent in the thermoplastic resin.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese Patent Application No. 4-160807 (32) Priority date Hei 4 (1992) June 19 (33) Country of priority claim Japan (JP) (31) Priority Claim Number Japanese Patent Application No. 4-275916 (32) Priority Day 4 (1992) October 14 (33) Country of priority claim Japan (JP) (72) Inventor Masaru Asanuma 1190 Kasamacho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals Co., Ltd. (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals Co., Ltd.

Claims (16)

[Claims] 1. At least one thermoplastic resin 99.9-
50 parts by weight and at least one liquid crystalline aromatic polyimide 0.
A thermoplastic resin composition containing 1 to 50 parts by weight and having good moldability. 2. A liquid crystalline aromatic polyimide has the following (1),
The thermoplastic resin composition according to claim 1, which is at least one liquid crystalline aromatic polyimide selected from the group consisting of (2) and (3). (1) Formula (1) [Chemical formula 1] (In the formula, R _{1 to} R ₅ are hydrogen, fluorine, trifluoromethyl,
A methyl, ethyl or cyano group, which may be the same or different, and R has 2 to 27 carbon atoms,
Represents a tetravalent 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 aromatic groups are connected to each other directly or by a bridging member. ) A liquid crystalline aromatic polyimide having a repeating structural unit represented by the formula (2) as a basic skeleton, (2) Having a repeating structural unit represented by the above formula (1) as a basic skeleton, and the polymer molecule having a terminal of the formula (2) ) [Chemical 2] (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group and a divalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are directly or linked to each other by a bridge member) A liquid crystalline aromatic polyimide obtained by sealing with a dicarboxylic acid anhydride, (3) having a repeating structural unit represented by the above formula (1) as a basic skeleton, and the end of the polymer molecule thereof is represented by the formula (3) V —NH ₂ (3) (In the formula, V has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group, a monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by a crosslinking member) A liquid crystalline aromatic polyimide obtained by sealing with a monoamine. 3. A liquid crystalline aromatic polyimide is prepared from the following (4),
The thermoplastic resin composition according to claim 1, which is at least one liquid crystalline aromatic polyimide selected from the group consisting of (5) and (6). Formula (4) [Formula 3] A liquid crystalline aromatic polyimide having a repeating skeleton represented by formula (4) as a basic skeleton, (5) having a repeating skeleton represented by the above formula (4) as a skeleton, and the polymer molecule having a terminal of the formula (2) [Chemical 4] (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group and a divalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are directly or linked to each other by a bridge member) Liquid crystalline aromatic polyimide obtained by sealing with dicarboxylic acid anhydride (6) Having a repeating structural unit represented by the above formula (4) as a basic skeleton, and the end of the polymer molecule is represented by the formula (3) V- NH ₂ (3) (In the formula, V has 6 to 15 carbon atoms, a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group, a monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by a crosslinking member) A liquid crystalline aromatic polyimide obtained by sealing with a monoamine. 4. A liquid crystalline aromatic polyimide is prepared by
The thermoplastic resin composition according to claim 1, which is at least one liquid crystalline aromatic polyimide selected from the group consisting of (8) and (9). (7) Formula (4) 1 to 99 mol% of a basic skeleton having a repeating structural unit represented by the formula (1) (In the formula, R _{1 to} R ₅ are hydrogen, fluorine, trifluoromethyl,
A methyl, ethyl or cyano group, which may be the same or different, and R has 2 to 27 carbon atoms,
Represents a tetravalent 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 aromatic groups are connected to each other directly or by a bridging member. A liquid crystalline aromatic polyimide copolymer comprising a repeating skeleton represented by the formula (excluding the same repeating structural unit as the formula (4)) in an amount of 99 to 1 mol%, (8) The end of the polymer molecule of the above liquid crystalline aromatic polyimide copolymer is represented by the formula (2): (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group and a divalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are directly or linked to each other by a bridge member) A liquid crystalline aromatic polyimide copolymer obtained by sealing with a dicarboxylic acid anhydride, (9) wherein the terminal of the polymer molecule of the above liquid crystalline aromatic polyimide copolymer has the formula (3) V-NH ₂ (3) (In the formula, V has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group, a monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by a crosslinking member) The thermoplastic resin composition according to claim 1, which is a liquid crystalline aromatic polyimide copolymer obtained by sealing with a monoamine. 5. The thermoplastic resin is at least one thermoplastic resin selected from the group consisting of aromatic polyimide, aromatic polyetherimide, aromatic polyamideimide, aromatic polyethersulfone and aromatic polyetherketone. The thermoplastic resin composition according to claim 1. 6. The thermoplastic resin composition according to claim 5, wherein the aromatic polyimide is at least one aromatic polyimide selected from the group consisting of the following (10), (11) and (12). Equation (10) Equation (5) (In the formula, X represents a group selected from the group consisting of a direct bond, an isopropylidene group, a hexafluorinated isopropylidene group, a carbonyl group, a thio group and a sulfonyl group, and R
Is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member. An aromatic polyimide having a repeating skeleton represented by a selected tetravalent group as a basic skeleton, (11) a polymer having a repeating skeleton represented by the above formula (5) as a basic skeleton, The terminal of the molecule is represented by the formula (2): (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group and a divalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are directly or linked to each other by a bridge member) Aromatic polyimide obtained by sealing with dicarboxylic acid anhydride, (1
2) It has a repeating structural unit represented by the above formula (5) as a basic skeleton, and the end of the polymer molecule is represented by the formula (3) V—NH ₂ (3) (wherein V has 6 to 15 carbon atoms). Yes, monocyclic aromatic groups,
An aromatic group represented by a condensed polycyclic aromatic group, a monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by a crosslinking member) An aromatic polyimide obtained by sealing with a monoamine. 7. The repeating structural unit of an aromatic polyimide has the formula (6): The thermoplastic resin composition according to claim 6, which is a repeating structural unit represented by: 8. The thermoplastic resin composition according to claim 5, wherein the aromatic polyimide is at least one aromatic polyimide selected from the group consisting of the following (13), (14) and (15). (1
3) Formula (7) An aromatic polyimide having a repeating structural unit represented by the following as a basic skeleton, (14) having a repeating structural unit represented by the above formula (7) as a basic skeleton, and the end of the polymer molecule is represented by the following formula (2): 12] (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group and a divalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are directly or linked to each other by a bridge member) Aromatic polyimide obtained by sealing with dicarboxylic acid anhydride, (1
5) It has a repeating structural unit represented by the above formula (7) as a basic skeleton, and the end of the polymer molecule is represented by the formula (3) V—NH ₂ (3) (wherein V has 6 to 15 carbon atoms). Yes, monocyclic aromatic groups,
An aromatic group represented by a condensed polycyclic aromatic group, a monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by a crosslinking member) An aromatic polyimide obtained by sealing with a monoamine. 9. The thermoplastic resin composition according to claim 5, wherein the aromatic polyimide is at least one aromatic polyimide selected from the group consisting of the following (16), (17) and (18). (1
6) Formula (6) The basic skeleton, which is a repeating structural unit represented by 99 to 1 mol%
And equation (8) In the formula, R is Where n is an integer of 0,1,2,3, Q is directly connected, -O-, -S-, -CO
-, -SO _2- , -CH ₂ , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- , and when there are a plurality of bonding groups Q connecting aromatic rings, they are bonded to each other. The groups may be the same or different combinations, and R "is (Where M is Which is at least one divalent group selected from the group consisting of) and represents at least one tetravalent group selected from the group consisting of) (provided that it is the same as the formula (6)). An aromatic polyimide copolymer containing a basic skeleton of 1 to 99 mol% (excluding structural units), (17) wherein the terminal of the polymer molecule of the aromatic polyimide copolymer is represented by the formula (2): (In the formula, Z is a monocyclic aromatic group having 6 to 15 carbon atoms, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are directly or cross-linked to each other. An aromatic polyimide copolymer obtained by sealing with an aromatic dicarboxylic acid anhydride represented by a divalent group selected from the group consisting of:
(18) The terminal of the polymer molecule of the aromatic polyimide copolymer is represented by the formula (3) V-NH ₂ (3) (wherein, V has 6 to 15 carbon atoms, a monocyclic aromatic group,
An aromatic group represented by a condensed polycyclic aromatic group, a monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by a crosslinking member) An aromatic polyimide copolymer obtained by sealing with a monoamine. 10. The repeating structural unit represented by the formula (9) has the formula (10): The thermoplastic resin composition according to claim 9, which is a repeating structural unit represented by the formula (wherein R is as described above) (however, the same structural unit as in the formula (6) is excluded). 11. An aromatic polysulfone has the formula (11): (In the formula, X is directly connected, and The thermoplastic resin composition according to claim 5, which is an aromatic polysulfone having at least one repeating structural unit represented by the formula (1) as a basic skeleton. 12. The aromatic polyetherimide has the formula (1
2) [Chemical 22] (In the formula, X is And Y is The thermoplastic resin composition according to claim 5, which is an aromatic polyetherimide having at least one repeating structural unit represented by the formula (1) as a basic skeleton. 13. The aromatic polyamideimide has the formula (13): Or formula (14) The thermoplastic resin composition according to claim 5, which is an aromatic polyamideimide having a repeating structural unit represented by the following as a basic skeleton. 14. The aromatic polyether ketone has the formula (1
5) [Chemical 27] The repeating structural unit represented by and / or the formula (16): The thermoplastic resin composition according to claim 5, which is an aromatic polyether ketone having a repeating structural unit represented by the following as a basic skeleton. 15. The thermoplastic resin composition according to claim 2, wherein the aromatic dicarboxylic acid anhydride is phthalic anhydride. 16. The thermoplastic resin composition according to claim 2, wherein the aromatic monoamine is aniline.