JPH11263839A - Polyimide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having an improved processability in melt molding. SOLUTION: A composition comprises 99.9-50 pts.wt. at least one thermoplastic resin selected from an aromatic polyimide and an aromatic polyetherimide and 0.1-50 pts.wt. at least one compound selected from a first liquid crystalline aromatic polyimide having a repeating structural unit represented by the formula (wherein R<1> , R<2> , R<3> , R<4> and R<5> , which may be the same or different, are each hydrogen atom, fluorine atom, trifluoromethyl, methyl, ethyl or cyano, and the Rs have 2 to 27 carbon atoms and represent a tetravalent group selected form the group consisting of a monocyclic aromatic group, a fused polycyclic aromatic group, and a non-fused polycyclic aromatic group in which aromatic groups are linked directly or through a crosslinking member) as a base skeleton or a second liquid crystalline aromatic polyimide obtained by blocking the terminal of a polymer molecule of the first liquid crystalline aromatic polyimide with an aromatic carboxylic acid or/and an aromatic monoamine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having improved melt moldability. The present invention relates to an aromatic polyimide resin composition that can be melt-molded and an aromatic polyetherimide resin composition that can be easily melt-molded.
More specifically, heat-resistant, chemical-resistant, aromatic polyimide having excellent mechanical strength, improved melt-molding processability obtained by mixing aromatic polyetherimide and liquid-crystalline aromatic polyimide having excellent heat resistance. The present invention relates to a thermoplastic resin composition.

[0002]

2. Description of the Related Art Conventionally, various thermoplastic resins having excellent heat resistance have been developed. Among them, in addition to its high heat resistance, polyimide has excellent mechanical strength and dimensional stability, flame retardancy, electric insulation, etc. It is expected to be widely used in fields requiring heat resistance in the future. Conventionally, various polyimides exhibiting excellent characteristics have been developed.

For example, the formula (A)

Embedded image Has already been found by Proger et al. (US Pat. No. 4,065,345). This polyimide has been known as a polyimide having excellent mechanical properties, thermal properties, electrical properties, solvent resistance and heat resistance, and exhibiting melt fluidity. However, this polyimide also has a higher melt viscosity than engineering plastics other than polyimide which can be usually extruded and injection-molded, so that extrusion molding and injection molding are difficult.

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

Embedded image (Where X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms,
Hexafluorinated isopropylidene group, carbonyl group,
R 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). (JP-A-61-143478, 62-677717,
62-86021, 62-235381, 63-128
025).

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

Embedded image The polyimide having a repeating structural unit represented by the following has a glass transition temperature (hereinafter abbreviated as Tg) of 260 ° C., a crystallization temperature (hereinafter abbreviated as Tc) of 310 to 340 ° C., and a crystal melting temperature (hereinafter abbreviated as Tm). ) Is 367 to 385 ° C., and is a crystalline polyimide which can be melt-molded and has excellent chemical resistance. However, since the Tm is as high as 367 to 385 ° C., the molding temperature needs to be as high as about 400 ° C.

As described above, polyimide has heat resistance and other properties as compared with ordinary engineering plastics represented by polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polysulfone, polyphenylene sulfide, polyether ether ketone, polyetherimide and the like. Although much better in properties, the moldability is still inferior to those resins.

[0007] Even if other known polyimides have excellent heat resistance, they do not have a clear glass transition temperature, so when they are used as a molding material, they must be processed by a technique such as sintering molding. Although it has excellent processability, it has a low glass transition temperature and is soluble in halogenated hydrocarbon solvents, and it is not satisfactory in terms of heat resistance and solvent resistance. Further, conventionally, aromatic polysulfone, aromatic ether imide, aromatic polyamide imide, aromatic polyether ketone, and the like have excellent mechanical strength and dimensional stability in addition to their high heat resistance, flame retardancy, and electrical insulation properties. In addition, they are used in the fields of electric / electronic equipment, spacecraft equipment, transportation equipment, etc., and are expected to be widely used in fields requiring heat resistance in the future.

On the other hand, liquid crystalline polymers can be classified into thermotropic liquid crystals and lyotropic liquid crystals in view of their properties. Conventionally known liquid crystalline polymers are:
There are polyester, polyesteramide, polyazomethine (above, thermotropic liquid crystal), polyamide, polybenzothiazole (above, lyotropic liquid crystal) and the like, but no polyimide showing liquid crystal properties has been known at all. Therefore, a resin composition obtained from a liquid crystalline polyimide and other thermoplastic resins such as polyimide and aromatic polyetherimide 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 object is to add a liquid crystalline aromatic polyimide having good flowability to a conventional aromatic polyimide without deteriorating the excellent heat resistance inherent in the aromatic polyimide, without deteriorating its moldability. An object of the present invention is to provide an aromatic polyimide-based thermoplastic resin composition which has been improved by the above method.

A second object of the present invention is to improve the processability of the aromatic polyetherimide without deteriorating its inherent excellent heat resistance by changing the liquid crystalline aromatic polyimide having good flowability to the conventional aromatic polyetherimide. To provide an aromatic polyetherimide-based thermoplastic resin composition which is improved by adding the same.

[0011]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve these objects, and as a result, a liquid crystalline aromatic polyimide is mixed with an aromatic polyimide or an aromatic polyetherimide. The present inventors have found that the thermoplastic resin composition has improved moldability without impairing the inherent properties of each resin, and have completed the present invention.

That is, the present inventors have obtained the formula (4)

Embedded image An aromatic polyimide having a repeating structural unit represented by (Japanese Patent Application Laid-Open No. 03-460024). afterwards,
This aromatic polyimide was found to exhibit 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. When the aromatic polyimide is heated (10 ° C./min) on a hot stage equipped with a polarizing microscope (OLYMPUS, BHS-751P type), polarized light is observed in a temperature range of about 270 to 300 ° C.

Further, the above aromatic polyimide is converted to a DSC (D
differential scanning calor
measurement (Shimadzu Corporation, DT-40 series, D
SC-41M) (10 ° C / min), two endothermic peaks are observed at about 275 ° C and about 295 ° C,
It can be confirmed that liquid crystallinity is exhibited in a temperature range between these two endothermic peaks. Also, this aromatic polyimide has 2
It 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 this aromatic polyimide exhibiting liquid crystallinity by mixing it with a thermoplastic resin of an aromatic polyimide and an aromatic polyetherimide which are required to be improved in workability. It was found that the moldability of the resin was improved, and the present invention was completed. That is, the invention of the present application is a thermoplastic resin composition which can be melt-molded and processed by adding a liquid crystalline aromatic polyimide to another aromatic polyimide or aromatic polyetherimide thermoplastic resin.

The present invention includes the following inventions. 1. A thermoplastic resin of an aromatic polyimide or an aromatic polyetherimide is converted into at least one thermoplastic resin,
9.9 to 50 parts by weight and the formula (1)

Embedded image (Wherein, R _{1 to} R ₅ are hydrogen, fluorine, trifluoromethyl, methyl, ethyl or a cyano group, which may be the same or different from each other; R has 6 to 27 carbon atoms; Which represents a tetravalent group selected from the group consisting of a formula 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 having good moldability, comprising 0.1 to 50 parts by weight of a liquid crystalline aromatic polyimide having at least one kind of repeating structural unit represented by the formula:

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

Embedded image A thermoplastic resin composition which is a liquid crystalline aromatic polyimide having a repeating structural unit represented by the following formula as a basic skeleton.

3. In the above thermoplastic resin composition, the liquid crystalline aromatic polyimide is represented by the formula (4):

Embedded image 1 to 99 mol% of a basic skeleton which is a repeating structural unit represented by the formula (1)

Embedded image (Wherein, R _{1 to} R ₅ are hydrogen, fluorine, trifluoromethyl, methyl, ethyl or an ano group, which may be the same or different from each other, 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 connected to each other directly or by a bridging member; Which is a liquid crystalline aromatic polyimide copolymer containing 1 to 99 mol% of a basic skeleton which is a repeating structural unit represented by the following formula (excluding the same repeating structural unit as the formula (4)): Plastic resin composition.

4. In the thermoplastic resin composition of the above item 1, the aromatic polyimide has the formula (5)

Embedded image (Wherein 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;
R has 6 to 27 carbon atoms, and includes a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridge member. A thermoplastic resin composition which is an aromatic polyimide having a repeating structural unit represented by the following formula:

5. In the thermoplastic resin composition of the above item 4, the aromatic polyimide has the formula (6)

Embedded image A thermoplastic resin composition which is an aromatic polyimide having a repeating structural unit represented by the following as a basic skeleton.

6. In the thermoplastic resin composition of the above item 1, the aromatic polyimide has the formula (7)

Embedded image Is an aromatic polyimide having a repeating structural unit represented by

7. In the above thermoplastic resin composition, the aromatic polyimide is represented by the formula (6):

Embedded image Basic skeleton 99-1 having a repeating structural unit represented by
Mole% and formula (8)

Embedded image Where R is

Embedded imageAnd n is an integer of 0, 1, 2, and 3, Q is directly connected, -O-,-
S-, -CO-, -SO ₂-, -CH₂-, -C (CH
₃)₂-Or -C (CF₃)₂-Represents an aromatic ring
When there are a plurality of linking groups Q connecting
May be the same or different, and R ″ is

[0022]

Embedded image (Where M is

Embedded image Which is at least one kind of divalent group selected from the group consisting of), which represents at least one kind of tetravalent group selected from the group consisting of

A thermoplastic resin composition which is an aromatic polyimide copolymer containing 1 to 99 mol% of the basic skeleton (excluding the same structural unit as (6)), particularly a repeating structural unit of the formula (8) The basic skeleton is

Embedded image (Wherein R is as defined above), a thermoplastic resin composition which is a repeating structural unit (excluding the same structural unit as in formula (6)).

8. In the thermoplastic resin composition of the above item 1, the aromatic polyetherimide is represented by the formula (22)

Embedded image (Where X is

Embedded image And Y is

Embedded image A thermoplastic resin composition which is an aromatic polyetherimide having at least one kind of repeating structural unit represented by the following formula:

9. In addition, the aromatic polyimide and / or the liquid crystalline aromatic polyimide used in the thermoplastic compositions 1 to 7 described above have the polymer molecule terminal represented by the formula (2)

Embedded image (Wherein, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group,
Represented by a condensed polycyclic aromatic group, or a divalent 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 bridge member) Dicarboxylic anhydride and / or general formula (3) V—NH ₂ (3) (wherein, V has 6 to 15 carbon atoms and is a monocyclic aromatic group;
Represented by a condensed polycyclic aromatic group or a monovalent 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) A thermoplastic resin composition which is an aromatic polyimide or a liquid crystalline aromatic polyimide obtained by being sealed with a monoamine, preferably phthalic anhydride and / or aniline. ADVANTAGE OF THE INVENTION According to this invention, in addition to the outstanding characteristic which each resin has originally, the moldability is remarkably favorable, and the thermoplastic resin composition excellent in thermal stability is provided.

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

Embedded image (Wherein, R _{1 to} R ₅ are hydrogen, fluorine, trifluoromethyl, methyl, ethyl or a cyano group, which may be the same or different from each other; R has 2 to 27 carbon atoms; A tetravalent group selected from the group consisting of a formula 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 wholly aromatic polyimide exhibiting liquid crystallinity expressed,

Preferably, the formula (4)

Embedded image A liquid crystalline aromatic polyimide represented by

Or (4)

Embedded image A basic skeleton having a repeating structural unit represented by
9 mol% and the formula (1)

Embedded image (Wherein, R _{1 to} R ₅ are hydrogen, fluorine, trifluoromethyl, methyl, ethyl or a cyano group, which may be the same or different from each other; R has 6 to 27 carbon atoms; A tetravalent group selected from the group consisting of a formula 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) And a liquid crystalline aromatic polyimide copolymer containing 1 to 99 mol% of a basic skeleton having a repeating structural unit represented by the formula (4).

Alternatively, the terminal of the polymer molecule of the liquid crystalline aromatic polyimide or the liquid crystalline aromatic polyimide copolymer is represented by the formula (2)

Embedded image (Wherein, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group,
Represented by a condensed polycyclic aromatic group, or a divalent 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 bridge member) Dicarboxylic anhydride and / or formula (3) V—NH ₂ (3) (wherein V has 6 to 15 carbon atoms, and is a monocyclic aromatic group;
Represented by a condensed polycyclic aromatic group or a monovalent 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) A liquid crystalline aromatic polyimide or a liquid crystalline aromatic polyimide copolymer obtained by being sealed with a monoamine is exemplified.

Such a liquid crystalline aromatic polyimide comprises at least one kind of aromatic diamine represented by the following formula (10) and at least one kind of aromatic tetracarboxylic dianhydride represented by the following formula (12): And the resulting polyamic acid is thermally or chemically imidized.

The aromatic diamine used in this method has the formula (10)

Embedded image (Wherein R _{1 to} R ₅ and R are the same as those in 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-methyl-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. These may be used alone or in combination of two or more.

In particular, equation (11)

Embedded image 1,3-bis [4- (4-aminophenoxy) -α,
[α-dimethylbenzyl] benzene is preferred. When a mixture of two or more kinds is used, the liquid crystalline aromatic polyimide copolymer can be obtained by using a diamine of the formula (11) and another diamine. These aromatic diamines can be produced by subjecting the corresponding nitro compound to a normal reduction reaction in the presence of a base in an aprotic polar solvent.

The aromatic tetracarboxylic dianhydride used is represented by the formula (12)

Embedded image (Wherein, R has 6 to 27 carbon atoms, a monocyclic aromatic group,
A condensed polycyclic aromatic group and a tetravalent group selected from the group consisting of a non-condensed polycyclic aromatic group in which the aromatic groups are directly or mutually connected by a bridge member) Specifically, pyromellitic dianhydride, 3,3 ′,
4,4′-benzophenonetetracarboxylic dianhydride,
2,2 ′, 3,3′-benzophenonetetracarboxylic 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 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 and 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. These aromatic tetracarboxylic dianhydrides may be used alone or as a mixture of two or more.
Among them, pyromellitic dianhydride is preferred.

The liquid crystalline aromatic polyimide used in the present invention is obtained by using an aromatic diamine represented by the formula (10) as a diamine component. As long as the properties and physical performance are not impaired, other diamines may be further mixed and polymerized. Examples of the diamine that can be used in combination include, for example, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, o-aminobenzylamine, 3-chloro-1,2-phenylenediamine, 4-
Chloro-1,2-phenylenediamine, 2,3-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-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) pheny ], 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 a repeating structural unit of the formula (1) obtained by using an aromatic diamine component and an aromatic tetracarboxylic dianhydride as monomer components as described above. , Those having a repeating structural unit of formula (4), and formula (1) and formula
(4) Copolymers having both repeating structural units, and polyimides having an aromatic ring in which the polymer molecular terminal is unsubstituted or substituted with a group having no reactivity with amine or dicarboxylic anhydride. included.

The liquid crystalline aromatic polyimide having an aromatic ring which is unsubstituted or substituted with a group having no reactivity with an amine or dicarboxylic anhydride at the terminal of the polymer molecule is represented by the formula (10)

Embedded image (Wherein R _{1 to} R ₅ and R are as defined above), for example, 1,3-bis [4-
(4-aminophenoxy) -α, α-dimethylbenzyl] benzene and a compound of the formula (12)

Embedded image (Wherein R is as defined above), an aromatic tetracarboxylic dianhydride represented by the formula:

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

Embedded image (Wherein R is as defined above) and / or a general formula (3) V—NH ₂ (3) (where V is as defined above) In the presence of an aromatic monoamine represented by the formula: The aromatic dicarboxylic anhydride represented by the formula (2) used includes:
Phthalic anhydride, 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride,
2,3-dicarboxyphenylphenyl ether anhydride, 3,4-dicarboxyphenylphenyl ether anhydride, 2,3-biphenyldicarboxylic anhydride, 3,4
-Dicarboxyphenylphenylsulfone anhydride, 2,
3-dicarboxyphenylphenyl sulfide anhydride,
3,4-dicarboxyphenylphenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-
Naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride, 2,3-anthracenedicarboxylic anhydride,
1,9-anthracene dicarboxylic anhydride and the like. These dicarboxylic anhydrides may be substituted with a group having no reactivity with an amine or dicarboxylic anhydride, and may be used alone or in combination of two or more. Of these dicarboxylic 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 anhydride used is 0.001 to 1.0 mole ratio per mole of the diamine of the above formula (10). 0.
If the amount is less than 001 mol, an increase in viscosity is observed during high-temperature molding, which causes a reduction in molding workability. On the other hand, if it exceeds 1.0 mol, the mechanical properties are deteriorated. The preferred amount is 0.0
It is a ratio of 1 to 0.5 mol.

The aromatic monoamine represented by the general formula (3) includes, for example, 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-phenezine, m-phenezine, p-phenezine, 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-aminophenylphenylsulfone, 3-aminophenylphenylsulfone, 4-aminophenylphenylsulfone, 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,
Examples thereof include 8-amino-1-aptol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, and 9-aminoanthracene. These aromatic monoamines may be substituted with a group having no reactivity with an amine or dicarboxylic anhydride, or may be used alone or as a mixture of two or more.

The amount of the aromatic monoamine is determined per mole of the aromatic tetracarboxylic dianhydride represented by the formula (12).
The molar ratio is 0.001 to 1.0. If it is less than 0.001 mol, an increase in viscosity is observed during high-temperature molding, which causes a reduction in molding processability. On the other hand, if it exceeds 1.0 mol, the mechanical properties are deteriorated. The preferred amount is 0.01 to 0.5 mol.

The method for producing the liquid crystalline aromatic polyimide used in the present invention is 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 under reduced pressure or the like, or isolating the aromatic polyamic acid from the obtained aromatic polyamic acid solution by using a poor solvent or the like, A method for obtaining a liquid crystalline aromatic polyimide by heating the resultant to imidization, 2) obtaining an aromatic polyamic acid solution in the same manner as in 1), further adding a dehydrating agent represented by acetic anhydride, and A method in which a catalyst is added and chemically imidized according to the method, and then the aromatic polyimide is isolated by a known method, followed by washing and drying if necessary. 3) Aromatic polyamic acid in the same manner as 1) After obtaining the solution, the solvent is removed under reduced pressure or heating, and at the same time thermal imidization is carried out. 4) The raw materials are charged into an organic solvent, and then heated to carry out the synthesis of the aromatic polyamic acid and the imidization reaction. Done at the same time, Catalyst and azeotropic agent in accordance with necessity, and a method of coexisting a dehydrating agent, and the like.

In the production of the liquid crystalline aromatic polyimide by these methods, it is particularly preferable to carry out the reaction in an organic solvent. As the organic solvent used, for example, 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-cresolic acid, p- Chlorophenol, xylenols, anisole and the like can be mentioned. These organic solvents may be used alone or in combination of two or more.

In producing a liquid crystalline aromatic polyimide in the presence of a dicarboxylic anhydride or an aromatic monoamine in order to seal the terminal of the polymer molecule, an aromatic diamine or an aromatic tetracarboxylic acid dicarboxylic acid is contained in an organic solvent. As a method of adding and reacting an anhydride and a dicarboxylic anhydride or an aromatic monoamine, (a) reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine and then reacting the dicarboxylic anhydride or an aromatic monoamine , The reaction is continued by adding (b) an aromatic dicarboxylic acid anhydride to an aromatic diamine, and then adding an aromatic tetracarboxylic dianhydride to continue the reaction; or A method of reacting an aromatic monoamine with a 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 less. The polymerization / imidization reaction pressure is not particularly limited, and the reaction can be sufficiently performed at normal pressure. The polymerization / imidization 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 is sufficient. Aromatic tetracarboxylic dianhydride or aromatic diamines are reacted in the above manner in the presence of dicarboxylic anhydride or aromatic monoamine such as phthalic anhydride or aniline, and the terminal of the polymer molecule is changed.

Embedded image And a liquid crystalline aromatic polyimide sealed with an aromatic ring substituted with an unsubstituted or non-reactive group with an amine or a dicarboxylic 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)

Embedded image (Wherein, 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 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 crosslinking member Is an aromatic polyimide having a repeating structural unit represented by the following as a basic skeleton,

Of the formula (5),
Equation (6) where X is directly connected in equation (5)

Embedded image Or an aromatic polyimide having a repeating structural unit represented by the formula (5), wherein X is SO ₂ in the formula (5).
3)

Embedded image An aromatic polyimide having a repeating structural unit represented by the following formula is frequently used.

The equation (7)

Embedded image An aromatic polyimide having a repeating structural unit represented by the following formula is also frequently used.

Further, the present invention is also effective for the following aromatic polyimide copolymers which have been developed as improved moldability of the aromatic polyimide of the formula (B). The aromatic polyimide represented by the formula (B) has a Tg of 260
° C, Tc is 310-340 ° C, Tm is 367-385 ° C
It is a crystalline polyimide excellent in chemical resistance that can be melt-molded, but because Tm is as high as 367 to 385 ° C,
The molding temperature had to be as high as about 400 ° C. When comparing high crystalline resin with high crystallinity and amorphous resin with low crystallinity having the same level of Tg in engineered plastics with high heat resistance, crystalline plastics generally show mechanical properties such as chemical resistance and elastic modulus. It is known that amorphous resins are superior in terms of mechanical properties and in terms of moldability, and crystalline resins and amorphous resins each have advantages and disadvantages. Therefore, it is more desirable that the crystalline polyimide having the repeating structural unit represented by the formula (B) maintain the essentially excellent heat resistance as it is and improve the moldability.

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

Embedded image Where R is

Embedded imageAnd n is an integer of 0, 1, 2, and 3, Q is directly connected, -O-,-
S-, -CO-, -SO ₂-, -CH₂-, -C (CH
₃)₂-Or -C (CF₃)₂-Represents an aromatic ring
When there are a plurality of linking groups Q connecting
May be the same or different,

R ″ is

Embedded image (Where M is

Embedded image (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 1 to 99 mol% of a basic skeleton which is the same as

In particular, the repeating structural unit represented by the formula (8) is represented by the following formula:

Embedded image (Wherein R is as defined above), the aromatic polyimide copolymer which is a repeating structural unit represented by the formula (B) except for the same structural unit as the formula (B), , Formability is improved in the amorphous state during molding,
When used after molding, a crystalline state is formed and a polyimide with excellent heat resistance is obtained, and the molding processability is improved in the amorphous state from the molding process to after the molding process, and in the amorphous state. The present inventors have found that a high heat-resistant engineering plastic having a high elastic modulus and a good elasticity can be obtained. As the aromatic polyimide used in the resin composition having improved melt moldability of the present invention, this aromatic polyimide copolymer can also be preferably used.

The terminal of the polymer molecule of the aromatic polyimide and the aromatic polyimide copolymer is represented by the formula (2)

Embedded image (Wherein, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group,
Represented by a condensed polycyclic aromatic group, or a divalent 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 bridge member) Dicarboxylic anhydride and / or formula (3) V—NH ₂ (3) (wherein V has 6 to 15 carbon atoms, and is a monocyclic aromatic group;
Represented by a condensed polycyclic aromatic group or a monovalent 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) An aromatic polyimide or an aromatic polyimide copolymer obtained by being sealed with a monoamine is exemplified.

Such an aromatic polyimide or an aromatic polyimide copolymer is obtained by reacting at least one kind of aromatic diamine with at least one kind of aromatic tetracarboxylic dianhydride, and thermally or chemically converting the resulting polyamic acid. It is obtained by imidization. That is, equation (5),
The aromatic polyimide represented by (6) or (7) is, for example, a compound represented by the formula (14)

Embedded image (Wherein, 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 (15)

Embedded image Is obtained by reacting the aromatic diamine represented by the formula with at least one kind of aromatic tetracarboxylic dianhydride.

Examples of the aromatic diamine usable 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) Phenyl] sulfone, etc., and these may be used alone or in combination of two or more. Among these,
In the formula (14), 4,4′-bis (3-aminophenoxy) biphenyl or bis [4- (3-aminophenoxy) phenyl] sulfone in which X is a direct bond or a sulfone group is preferably used. Furthermore, equation (1)
5) 3,3-diaminobenzophenone.

On the other hand, the aromatic tetracarboxylic dianhydride used is represented by the formula (12)

Embedded image (Wherein, R has 6 to 27 carbon atoms, a monocyclic aromatic group,
A condensed polycyclic aromatic group, or 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) Tetracarboxylic dianhydride. That is, examples of the aromatic tetracarboxylic dianhydride include aromatic tetracarboxylic dianhydrides which can be used for producing a liquid crystalline aromatic polyimide, and specific examples thereof include those already listed. These tetracarboxylic dianhydrides are used alone or in combination of two or more. Preferably, pyromellitic dianhydride is used.

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) is represented by the following formula: (16)

Embedded image And 4,4-bis (3-aminophenoxy) biphenyl represented by the formula (21) H ₂ N—R—NH ₂ (21) (where R is

Embedded imageAnd n is an integer of 0, 1, 2, and 3, Q is directly connected, -O-,-
S-, -CO-, -SO ₂-, -CH₂-, -C (CH
₃)₂-Or -C (CF₃)₂-Represents an aromatic ring
When there are a plurality of linking groups Q connecting
May be the same or different.)
In the presence of at least one kind of aromatic diamine,

Equation (17)

Embedded image (Where R "is

Embedded image (Where M is

Embedded image Is a divalent group selected from the group consisting of: represents a tetravalent group selected from the group consisting of :) and is obtained by reacting at least one aromatic tetracarboxylic dianhydride represented by .

The aromatic diamine used here is represented by the formula (18)

Embedded image M-phenylenediamine, which is a diamine represented by
o-phenylenediamine, p-phenylenediamine,

Equation (19)

Embedded image (Wherein Q is as defined above), benzidine, 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 '
-Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 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-hexafluoropropane, -(3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane,

Equation (20)

Embedded image (Wherein Q is as defined above), 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,

Equation (21)

Embedded image (Wherein Q is as defined above), 4,4′-bis (4-aminophenoxy) biphenyl, 3,3′-bis (4-aminophenoxy) biphenyl, 4'-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl]
Ketone, bis [4- (3-aminopheno) 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-amino) Phenoxy) 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
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-hexafluoropropane,
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.

The tetracarboxylic dianhydride used as one monomer includes, for example, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic 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] bensophenone 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]-
Examples thereof include 1,1,1,3,3,3-hexafluoropropane dianhydride.

These equations (5), (6) and (13)
Alternatively, 99 to 1 mol% of an aromatic polyimide represented by the formula (7) or a basic skeleton having a repeating structural unit represented by the formula (6) and a basic skeleton 1 having a repeating structural unit represented by the formula (8) Aromatic polyimide copolymers containing up to 99 mol% are produced using the above-mentioned raw material monomers corresponding to the respective polymers as raw materials. The aromatic polyimide which is an essential raw material for producing each aromatic polyimide is used. In addition to diamines and aromatic tetracarboxylic dianhydrides, other aromatic diamines or aromatic tetracarboxylic dianhydrides are mixed within a range that does not impair the good physical properties of the obtained aromatic polyimide or aromatic polyimide copolymer. You can use it.

As the aromatic diamines which can be used by mixing, those exemplified as the aromatic diamines which may be used in combination in the production of the liquid crystalline aromatic polyimide are exemplified. These may be selected and used together according to the purpose. The aromatic tetracarboxylic dianhydride that can be used by mixing is selected from those exemplified as the aromatic tetracarboxylic dianhydride represented by the above formula (12).
They can be appropriately selected and used together. Aromatic polyimide or aromatic polyimide copolymer obtained by using at least one kind of aromatic diamine component and at least one kind of aromatic tetracarboxylic dianhydride as a monomer component,
An aromatic polyimide copolymer having an aromatic ring in which the polymer molecular terminal is unsubstituted or substituted by a group having no reactivity with an amine or a dicarboxylic anhydride is also included.

The aromatic polyimide having an aromatic ring at the polymer molecule terminal which is unsubstituted or substituted with a group having no reactivity with an amine or a dicarboxylic anhydride can be obtained by the above-mentioned formula (14), formula (15), Equation (16), Equation (1)
8), an aromatic diamine such as Formula (19), Formula (20), or Formula (21) and a tetracarboxylic dianhydride such as Formula (12) or Formula (17) are combined with Formula (2).

Embedded image (Wherein, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group,
Represented by a condensed polycyclic aromatic group, or a divalent 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 bridge member) Dicarboxylic anhydride and / or formula (3) V—NH ₂ (3) (wherein V has 6 to 15 carbon atoms, and is a monocyclic aromatic group;
Represented by a condensed polycyclic aromatic group, or a monovalent group selected from the group consisting of non-fused polycyclic aromatic groups in which the aromatic groups are connected to each other directly or by a bridge member) It can be obtained by reacting in the presence of a monoamine. The aromatic monoamine or aromatic dicarboxylic anhydride used in this method is
The above-mentioned compounds are used for producing the liquid crystalline aromatic polyimide or the polyimide copolymer.

The aromatic polyimide having an aromatic ring in which the terminal of the aromatic polyimide, the aromatic polyimide copolymer or the polymer molecule thereof is unsubstituted or substituted with a group having no reactivity with amine or dicarboxylic anhydride. The polyimide copolymer can be produced by any known method. For example, a method similar to the above-described method for producing a liquid crystalline aromatic polyimide can be specifically applied. An aromatic tetracarboxylic dianhydride or an aromatic diamine is reacted by these methods in the coexistence of a dicarboxylic anhydride such as phthalic anhydride or aniline or an aromatic monoamine. Or a group having no reactivity with dicarboxylic anhydride, for example, at the terminal

Embedded image A polyimide having an aromatic ring substituted with such a group can be produced.

When the melt-moldable resin composition of the present invention contains a liquid crystalline aromatic polyimide or an aromatic polyimide, the liquid crystal aromatic polyimide or the liquid crystal aromatic polyimide in which the terminal of such a polymer molecule is sealed is used. The aromatic polyimide may be one in which any or one of them is sealed. In particular, a liquid crystalline aromatic polyimide and / or an aromatic polyimide having a polymer terminal sealed with a group derived from phthalic anhydride or aniline is preferable.

Next, the aromatic polyetherimide used in the present invention has the formula (22)

Embedded image (Where X is

Embedded image And Y is

Embedded image Is an aromatic polyetherimide having at least one of the repeating structural units represented by the following as a basic skeleton, and specific examples thereof include the following.

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image Aromatic polyetherimide having a repeating unit such as these, these aromatic polyetherimide, from U.S.A.G.E.Ultem-1000, Ultem-4000, Ultem-6000
Etc. under the trademark. It is.

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 following formula (4): Liquid crystalline aromatic polyimide having units,
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 in which the terminal of these polymer molecules is unsubstituted or substituted with a group having no reactivity with an amine or dicarboxylic anhydride. It contains one kind of liquid crystalline aromatic polyimide and at least one kind of thermoplastic resin selected from the group consisting of another kind of aromatic polyimide and aromatic polyetherimide.

This thermoplastic resin composition contains 0.1 to 50% by weight of a liquid crystalline aromatic polyimide and 99.
It is adjusted in the range of 9 to 50% by weight. The thermoplastic resin composition of the present invention exhibits a 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 0.1% by weight, preferably 0.1% by weight.
5% by weight. Further, the chemical resistance, flame retardancy, and mechanical strength of the liquid crystalline aromatic polyimide belong to a very excellent class among heat-resistant resins, but have disadvantages such as strong mechanical property anisotropy. Therefore, when the amount of the liquid crystalline aromatic polyimide in the composition is increased, the inherent characteristics of the polyimide cannot be maintained, which is not preferable. 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, and more preferably 10% by weight.
It is as follows.

In preparing the thermoplastic resin composition according to the present invention, a thermoplastic resin and a liquid crystalline aromatic polyimide are contained, and can be produced by a generally known method.
For example, the following method is preferred. The thermoplastic resin and the liquid crystalline aromatic polyimide are pre-kneaded using a mortar, Henschel mixer, drum blender, tumbler blender, ball mill, ribbon blender and the like.
A thermoplastic resin is dissolved or suspended in an organic solvent in advance, and a liquid crystalline aromatic polyimide is added to the solution or suspension to uniformly disperse or dissolve, and then the solvent is removed. When the thermoplastic resin is an aromatic polyimide, in a solution of a polyamic acid as a polyimide precursor in an organic solvent, after suspending or dissolving the liquid crystalline aromatic polyimide, heat-treating to 100 to 400 ° C., or After 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 which is a precursor of the polyimide and an organic solvent solution of a polyamic acid which is a precursor of the liquid crystalline aromatic polyimide, 100 to 400 ° C or after chemically imidizing 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 used as it is in various molding methods, such as injection molding, compression molding, transfer molding, and extrusion molding. It is a more preferable method to use after that. In particular, in mixing and preparing the composition, it is also a simple and effective method to mix powders and pellets or to mix powder and pellets. For melt blending, equipment used to melt blend ordinary rubber or plastics,
For example, a hot roll, a Banbury mixer, a Brabender, an extruder, or the like can be used. The melting temperature is
The temperature is set above the temperature at which the blending system can be melted and below the temperature at which the blending system begins to thermally decompose.
420 ° C, preferably 300-400 ° C.

As a method for molding a resin composition capable of being melt-molded according to the present invention, a uniform molten blend is formed,
Injection molding or extrusion molding, which is a molding method with high productivity, is suitable, but other compression molding, transfer molding, sintering, and the like may be used. Other thermoplastic resins within a range that does not impair the purpose of the present invention, for example,
Polystyrene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, polyethersulfone, polyetherketone, polyphenylene sulfide, polyamideimide, polyetherimide, modified polyphenylene oxide, other polyimide and thermosetting resin according to purpose It is also possible to mix. Further, one or more solid lubricants, for example, molybdenum disulfide, graphite, boron nitride, lead monoxide, lead powder and the like can be added to the polyimide resin composition of the present invention.

Further, reinforcing materials such as glass fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber,
One or more kinds of glass beads or the like can be added. Furthermore, as long as the object of the present invention is not impaired with respect to the resin composition of the present invention, an antioxidant, a heat stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant auxiliary, an antistatic agent, a coloring agent, etc. One or more additives can be added.

[0077]

The present invention will be described in more detail 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 heating and dissolving 0.50 g of polyimide powder in 100 ml of a mixed solvent of p-chlorophenol and phenol (90:10 by weight) and cooling to 35 ° C. Glass transition temperature (Tg); DSC (measured by 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 was placed in a vessel equipped with a stirrer, reflux condenser, water separator and nitrogen inlet tube. .29k
g (10.0 mol), pyromellitic dianhydride 2.0
94 kg (9.6 mol), 138 g of γ-picoline
(1.5 mol) and 23.0 kg of m-cresol, and heated to 145 ° C. while stirring under a nitrogen atmosphere. During this time, distillation of about 340 g of water was confirmed. Further, the reaction was performed at 140 to 150 ° C. for 4 hours. Thereafter, the mixture was cooled to room temperature, discharged into 81.2 kg of methyl ethyl ketone, and filtered. This polyimide powder was further washed with methyl ethyl ketone, preliminarily dried at 50 ° C. for 24 hours under a nitrogen atmosphere, and then dried at 200 ° C. for 6 hours to obtain 6.85 kg (yield 97.3%) of polyimide powder. . The logarithmic viscosity of this polyimide powder is 0.4
9 dl / g, measured at 274 ° C and 294 ° C by DSC
An endothermic peak of the book was observed. The 5% weight loss temperature in air was 525 ° C.

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

[0080]

[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'-benzophenonetetracarboxylic dianhydride ODPA: bis (3,4-dicarboxyphenyl) ether dianhydride

Synthesis Example -7 When performing the reaction, 118.49 g (0.8%) of phthalic anhydride was used.
0 mol), and reacted in the same manner as in Synthesis Example-1 to give 6.93 kg of polyimide powder (yield 97.0%).
I 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.

Synthesis Example 8 A reaction was carried out in the same manner as in Synthesis Example 1 except that 158.54 g (0.80 mol) of 1,8-naphthalenedicarboxylic anhydride was added during the reaction. 7.02
kg (97.0% yield). The logarithmic viscosity of this polyimide powder is 0.50 dl / g, and 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 When carrying out the reaction, 148.11 g of phthalic anhydride (1.0
(0 mol), and the reaction was carried out in the same manner as in Synthesis Example-2 to obtain a polyimide powder. Table 2 shows the polyimide synthesis conditions, the logarithmic viscosity, glass transition temperature, and 5% weight loss temperature of the resulting polyimide powder.

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

Synthesis Example 11 When carrying out the reaction, 88.87 g of phthalic anhydride (0.60 g
(Mol) was added, and a reaction was conducted in the same manner as in Synthesis Example-4 to obtain a polyimide powder. Table 2 shows polyimide synthesis conditions, logarithmic viscosity, glass transition temperature and 5
Indicates the% weight loss temperature.

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

[0087]

[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 * 2) PMDA: pyromellitic dianhydride

Synthesis Example 13 3.50 kg (9.5 mol) of 4,4′-bis (3-aminophenoxy) biphenyl was added to a vessel equipped with a stirrer, reflux condenser, water separator and nitrogen inlet tube. 2.18 kg (10.0 mol) of melitic dianhydride, 140 g (1.5 mol) of γ-picoline, 93.0 g (1.0 mol) of aniline
Mol) and 23.0 kg of m-cresol, and heated to 145 ° C. while stirring under a nitrogen atmosphere. During this time, distillation of about 360 g of water was confirmed. Further, the reaction was performed at 140 to 150 ° C. for 4 hours. afterwards,
After cooling to room temperature and discharging into 81.2 kg of methyl ethyl ketone, the mixture was separated by filtration. This polyimide powder is further washed with methyl ethyl ketone, and at 50 ° C. under a nitrogen atmosphere.
4. After pre-drying for 24 hours, dry at 200 ° C. for 6 hours.
25 kg (97.0% yield) 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:
555 ° C.

Synthesis Example-14 In Synthesis Example-13, instead of 93.0 g (1.0 mol) of aniline, 107.15 g of p-toluidine (1.
0 mol) to obtain 52.6 kg (yield: 97.0%) of polyimide powder in the same manner as in Synthesis Example-13. The logarithmic viscosity of this polyimide powder is 0.47 dl / g, the glass transition temperature is 245 ° C, and the 5% weight loss temperature in air is 552 ° C.
Met.

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

Synthesis Example -16 In Synthesis Example 15, instead of 74.4 g (0.8 mol) of aniline, 85.72 g (0.8 mol) of p-toluidine was used.
Mol) and 6.77 kg (yield 97.0%) of polyimide powder was obtained in the same manner as in Synthesis Example-15. 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.

Synthesis Example-17 In Synthesis Example-13, instead of 3.50 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 carried out in the same manner as in Synthesis Example 13 to obtain a polyimide powder 5.7.
0 kg (97.3% yield) was obtained. This polyimide powder has a logarithmic viscosity of 0.54 dl / g and a glass transition temperature of 217.
° C, 5% weight loss temperature in air was 534 ° C.

Synthesis Example 18 3,3′-Diaminebenzophenone 2.12 was placed in a vessel equipped with a stirrer, reflux condenser, water separator and nitrogen inlet tube.
3 kg (10.0 mol), 3.03 kg of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride
(9.6 mol), 138 g (1.5 mol) of γ-picoline
And 20.9 kg of m-cresol, and heated to 145 ° C. while stirring under a nitrogen atmosphere.
During this time, distillation of about 340 g of water was confirmed. Further 140
The reaction was carried out at a temperature between 150C and 150C for 4 hours. Thereafter, the mixture was cooled to room temperature, discharged into 81.2 kg of methyl ethyl ketone, and filtered. This polyimide powder was washed with methyl ethyl ketone, preliminarily dried at 50 ° C. for 24 hours under a nitrogen atmosphere, and then dried at 200 ° C. for 6 hours to obtain 4.74 kg.
(Yield 97.3%) 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 When performing the reaction, 118.49 g (0.8%) of phthalic anhydride was used.
088), and reacted in the same manner as in Synthesis Example-18, except that 4.88 kg of polyimide powder was obtained (yield 98.0%).
I got The logarithmic viscosity of this polyimide powder is 0.48 dl /
g, the glass transition temperature was 245 ° C, and the 5% weight loss temperature in air was 550 ° C.

Synthesis Example -20 The reaction was carried out in the same manner 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 (97.0% yield) were obtained. This polyimide powder has a logarithmic 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 A container equipped with a stirrer, a reflux condenser, a water separator and a nitrogen introducing tube was charged with 3,3′-diaminebenzophenone 2.03.
8 kg (9.6 mol), 3,3 ′, 4,4′-benzophenonetetracarboxylic 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 heated to 145 ° C. while stirring under a nitrogen atmosphere. About 340g during this time
Distillation of water was confirmed. Furthermore, at 140 ° C to 150 ° C, 4
A time reaction was performed. Thereafter, the mixture was cooled to room temperature and 81.2
After discharging into kg of methyl ethyl ketone, the mixture was filtered off. The polyimide powder was further washed with methyl ethyl ketone, preliminarily dried at 50 ° C. for 24 hours under a nitrogen atmosphere, and then dried at 200 ° C. for 6 hours to obtain 4.74 kg (yield 9).
7.3%) of a polyimide powder. The logarithmic viscosity of this polyimide powder was 0.48 dl / g. The glass transition temperature of this polyimide powder is 240 ° C. and 5% in air.
The weight loss temperature was 548 ° C.

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

Synthesis Example 23 A container equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube was charged with 3.316 kg (9.00 mol) of 4,4′-bis (3-aminophenoxy) biphenyl, 0.200 kg (1.00 mol) of 4'-diaminodiphenyl ether,
2.072 kg (9.50 mol) of pyromellitic dianhydride, 140 g (1.5 mol) of γ-picoline and m-
22.4 kg of cresol was charged and heated to 145 ° C. while stirring under a nitrogen atmosphere. During this time, distillation of about 340 g of water was confirmed. Furthermore, 140 to 15
The reaction was performed at 0 ° C. for 4 hours. Then cool to room temperature
After discharging into 6.1 kg of methyl ethyl ketone, the mixture was filtered off. This polyimide powder was further washed with methyl ethyl ketone, preliminarily dried at 50 ° C. for 24 hours under a nitrogen atmosphere, and then dried at 200 ° C. for 6 hours to obtain 5.09 kg (yield 97.0%) of polyimide powder. . This polyimide powder has a logarithmic viscosity of 0.50 dl / g and a glass transition temperature of 2
The temperature was 58 ° C., and Tc and Tm were not observed. Also,
The 5% weight loss temperature in air was 542 ° C.

Synthesis Example -24 In Synthesis Example 23, 3.316 kg (9.00 mol) of 4,4′-bis (3-aminophenoxy) biphenyl, 4,4 ′
0.200 kg of diaminodiphenyl ether (1.0
0 mol), 2.072 kg of pyromellitic dianhydride
2.579 kg (7.00 mol) of 4,4'-bis (3-aminophenoxy) biphenyl instead of (9.50 mol), bis [4- (3-aminophenoxy) phenyl]
Except that 1.297 kg (3.00 mol) of sulfone and 2.094 kg (9.60 mol) of pyromellitic dianhydride were used, the reaction was carried out in the same manner as in Synthesis Example-23 to obtain 5.51 of polyimide powder (yield). 98.0%) of a polyimide powder. The logarithmic viscosity of this polyimide powder was 0.51 dl / g, the glass transition temperature was 253 ° C., and Tc and Tm were not observed. The 5% weight loss temperature in air was 539 ° C.

Synthesis Example 25 A reaction was carried out in the same manner as in Synthesis Example 23 except that 148.11 g (1.00 mol) of phthalic anhydride was added in the reaction in Synthesis Example 23 to obtain a polyimide powder. 5.26
g (97.8% yield). The logarithmic viscosity of this polyimide powder was 0.50 dl / g, the glass transition temperature was 254 ° C., and Tc and Tm were not observed. The 5% weight loss temperature in air was 546 ° C.

Synthesis Example 26 In Synthesis Example 23, 195.68 g (1.00 mol) of 1.8-naphthalenedicarboxylic anhydride was used when the reaction was carried out.
The reaction was carried out in the same manner as in Synthesis Example 23 except that was added, to obtain 5.31 g (yield 98.0%) of polyimide powder. 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 vessel equipped with stirring, a reflux condenser, a water separator, and a nitrogen inlet tube, 3.150 kg (8.55 mol) of 4,4′-bis (3-aminophenoxy) biphenyl was added. 0.190 kg (0.95 mol) of 4,4′-diaminodiphenyl ether, 2.18 kg of pyromellitic dianhydride (10.
0 mol), 140 g (1.5 mol) of γ-picoline, 93.12 g (1.0 mol) of aniline and 23.0 kg of m-cresol, and heated to 145 ° C. while stirring under a nitrogen atmosphere. did. During this time, about 360
Distillation of water was confirmed. Further, the reaction was performed at 140 to 150 ° C. for 4 hours. Thereafter, the mixture was cooled to room temperature.
After discharging into 2 kg of methyl ethyl ketone, the mixture was filtered off.
The polyimide powder was further washed with methyl ethyl ketone, preliminarily dried at 50 ° C. for 24 hours under a nitrogen atmosphere, and then dried at 200 ° C. for 6 hours to obtain 5.16 kg (yield 98.2%) of polyimide powder. . This polyimide powder has a logarithmic viscosity of 0.49 dl / g and a glass transition temperature of 25.
The 5% weight loss temperature in air at 6 ° C was 549 ° C.

Synthesis Example-28 In Synthesis Example 27, 107.15 g of p-toluidine (1.10 g) was used instead of 93.12 g (1.0 mol) of aniline.
0 mol) to obtain 5.16 kg of polyimide powder (yield 98.0%) in the same manner as in Synthesis Example 27. The logarithmic viscosity of this polyimide powder was 0.49 dl / g, the glass transition temperature was 255 ° C., and the 5% weight loss temperature in air was 547 ° C.

Synthesis Example 29 In Synthesis Example 27, 3.150 kg (8.55 mol) of 4,4′-bis (3-aminophenoxy) biphenyl, 4,4 ′
0.190 kg of diaminodiphenyl ether (0.9
5 mol), instead of 93.12 g (1.0 mol) of aniline, 2.476 kg (6.72 mol) of 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) Phenyl] sulfone 1.246kg
(2.88 mol) and 74.50 g (0.80 mol) of aniline were reacted in the same manner as in Synthesis Example 27 to obtain 5.49 g (yield 97.8%) of polyimide powder. The logarithmic viscosity of this polyimide powder is 0.50 dl / g, the glass transition temperature is 251 ° C., and the 5% weight loss temperature in air is 54.
4 ° C.

Synthesis Example-30 In Synthesis Example-29, 74.50 g (0.8%) of aniline was used.
0. mol) instead of 85.72 g of p-toluidine
The reaction was carried out in the same manner as in Synthesis Example 29 except that (0.80 mol) was used, and 5.52 kg of a polyimide powder (yield 98.0) was obtained.
%). The logarithmic viscosity of this polyimide powder is 0.50 d
1 / g, the glass transition temperature was 252 ° C, and the 5% weight loss temperature in air was 540 ° C.

Examples -1 to 8 The polyimide powder obtained in Synthesis Examples 2 and 3 and the liquid crystalline polyimide powder obtained in Synthesis Example 1 were dry-blended in 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). Table 3 shows the measurement results.

Comparative Examples 1 to 8 Table 3 shows the results of measuring the melt viscosities in the same manner as in Examples 1 to 8 using compositions outside the scope of the present invention.

[0108]

[Table 3]

Examples 9 to 16 After the polyimide powder obtained in Synthesis Examples -4 and 5 and the liquid crystalline polyimide powder obtained in Synthesis Example 1 were dry-blended in 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 ). Table 4 shows the measurement results.

Comparative Examples 9 to 16 Table 4 shows the results of measuring the melt viscosities in the same manner as in Examples -9 to 16 using compositions outside the range of the present invention.

[0111]

[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 in various compositions as shown in Table 5, and then mixed with each other. Chemical flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1c)
m, length 1 cm, pressure 100 kg / cm ² ). Table 5 shows the measurement results.

Comparative Examples 17 to 20 Table 5 shows the results of melt viscosity measurement of the compositions outside the range of the present invention by the same operation as in Examples 17 to 20.

[0114]

[Table 5]

Examples 21 to 28 Polyimide powders obtained in Synthesis Examples -9 and 10 and Synthesis Example -7
After dry-blending the liquid crystalline polyimide powder obtained in the above with various compositions as shown in Table 6, a Koka type flow tester (Shimadzu Corporation, CFT-500, orifice diameter of 0.1) was used.
The melt viscosity was measured at 1 cm, length 1 cm, and pressure 100 kg / cm ² ). Table 6 shows the measurement results.

Comparative Examples 21 to 28 Table 6 shows the results of measuring the melt viscosities of the compositions outside the range of the present invention by the same operation as in Examples 21 to 28.

[0117]

[Table 6]

Examples 29 to 32 The polyimide powder obtained in Synthesis Example-11 and the liquid crystalline polyimide powder obtained in Synthesis Example-7 were dry-blended in various compositions as shown in Table 7 and Flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1)
cm, length 1 cm, pressure 100 kg / cm ² ). Table 7 shows the measurement results.

Comparative Examples -29 to 32 Table 7 shows the results of melt viscosity measurement of the compositions outside the range of the present invention by the same operation as in Examples -29 to 32.

[0120]

[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 in various compositions as shown in Table 8, and then mixed. Chemical flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1
cm, length 1 cm, pressure 100 kg / cm ² ). Table 8 shows the measurement results.

Comparative Examples 33 to 36 Table 8 shows the results of melt viscosity measurement of the compositions outside the range of the present invention by the same operation as in Examples 33 to 36.

[0123]

[Table 8]

Examples 37 to 44 Polyimide Powders Obtained in Synthesis Examples 13 and 17 and Synthesis Examples
After dry blending the liquid crystalline polyimide powder obtained in No. 15 with various compositions as shown in Table 9, 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 ). Table 9 shows the measurement results.

Comparative Examples 37-44 Table 9 shows the results of melt viscosity measurement of the compositions outside the range of the present invention by the same operation as in Examples 37-44.

[0126]

[Table 9]

Examples 45 to 48 After the polyimide powder obtained in Synthesis Example -14 and the liquid crystalline polyimide powder obtained in Synthesis Example -16 were dry-blended in various compositions as shown in Table 10, the resulting mixture was subjected to dry blending. 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 measurement results.

Comparative Examples 45 to 48 Table 10 shows the results of measuring the melt viscosities of the compositions outside the range of the present invention by the same operation as in Examples 45 to 48.

[0129]

[Table 10]

Examples 49-56 The polyimide powders obtained in Synthesis Examples -9, 10, 11 and 12 and the liquid crystalline polyimide powders obtained in Synthesis Examples -7 and 8 were mixed with various polyimides as shown in Table 11. After dry blending with the composition,
The mixture was melt-kneaded and extruded with an extruder (with a screw having a diameter of 40 mm and a compression ratio of 3.0 / 1.0) to obtain uniform compounded pellets. Next, the pellets obtained above were molded using a usual 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 compositions outside the scope of the present invention in the same manner as in Examples -49 to 56.

[0132]

[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 in various compositions as shown in Table 12, and then mixed. Chemical flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1
cm, length 1 cm, 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 viscosities of the compositions outside the range of the present invention by the same operation as in Examples -57 to 60.

[0135]

[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 in various compositions as shown in Table 13 and then mixed with each other. Chemical flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1
cm, length 1 cm, pressure 100 kg / cm ² ). Table 13 shows the measurement results.

Comparative Examples 61-64 Table 13 shows the results of measuring the melt viscosities of the compositions outside the range of the present invention in the same manner as in Examples 61-64.

[0138]

[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 in various compositions as shown in Table 14 and then mixed with each other. Chemical flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1
cm, length 1 cm, pressure 100 kg / cm ² ). Table 14 shows the measurement results.

Comparative Examples 55 to 68 Table 14 shows the results of measuring the melt viscosities of the compositions outside the range of the present invention by the same operation as in Examples 65 to 68.

[0141]

[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 then mixed. 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 15 shows the measurement results.

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

[0144]

[Table 15]

Examples-73 to 76 After the polyimide powder obtained in Synthesis Example-22 and the liquid crystalline polyimide powder obtained in Synthesis Example-16 were dry-blended in various compositions as shown in Table 16, the mixture was mixed with 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 16 shows the measurement results.

Comparative Examples 73 to 76 Table 16 shows the results of measuring the melt viscosities in the same manner as in Examples 73 to 76 using compositions outside the scope of the present invention.

[0147]

[Table 16]

Examples -77 to 80 Synthesis Examples -Polyimide powder obtained in Examples 19 and 21 and Synthesis Examples-
After the liquid crystalline polyimide powder obtained in 7, 15 was dry-blended with various compositions as shown in Tables 17 and 18, an extruder (with a screw having a diameter of 40 mm and a compression ratio of 3.0 / 1.0) was used. The mixture was extruded while being melt-kneaded to obtain a uniform compounded pellet. Next, the pellets obtained above were molded using a usual injection molding machine, and the minimum injection pressure of the molded product was measured. The results are shown in Tables 17 and 18 in Examples-77 to 8
Shown as 0.

Comparative Examples 77 to 80 Table 17 and Table 1 show the results of measuring the melt viscosities of the compositions outside the range of the present invention by the same operation as in Examples 77 to 80.
FIG.

[0150]

[Table 17]

[0151]

[Table 18]

Examples 81 to 88 Synthetic Examples 23 and 24 and Polyimide Powder Obtained in Synthetic Examples 23 and 24
After dry-blending the liquid crystalline polyimide powder obtained in 1 with various compositions as shown in Tables 19 and 20, a Koka type flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1 cm, length 1 cm) , Pressure 100kg / cm
^The melt viscosity was measured in ² ). Tables 19 and 2 show the measured results.
Shown in 0. Tables 19 and 20 also show the results of DSC measurement of the transition temperature (Tg) of the strand obtained by the flow tester. The mixture of the aromatic polyimide copolymer and the liquid crystalline aromatic polyimide at the ratio of this example has a lower melt viscosity than the aromatic polyimide copolymer alone, and a Tg that is not different from the aromatic polyimide copolymer. Had.

Comparative Examples 81-88 Tables 19 and 20 show the results obtained by measuring the melt viscosities of the compositions outside the range of the present invention in the same manner as in Examples 81-88.

[0154]

[Table 19]

[0155]

[Table 20]

Examples-89 to 96-Synthetic Examples-Polyimide powders obtained in 25 and 29 and Synthetic Examples-
After dry-blending the liquid crystalline polyimide powder obtained in 7 with various compositions as shown in Tables 21 and 22, a Koka type flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1 cm, length 1 cm) , Pressure 100kg / cm
^The melt viscosity was measured in ² ). Table 21 and Table 2
Shown in 2. Tables 21 and 22 also show the results of DSC measurement of the transition temperature (Tg) of the strand obtained by the flow tester. The mixture of the aromatic polyimide copolymer and the liquid crystalline aromatic polyimide at the ratio of this example has a lower melt viscosity than the aromatic polyimide copolymer alone, and still has a Tg that is not different from that of the aromatic polyimide copolymer. Had.

Comparative Examples -89 to 96 Tables 21 and 22 show the results of measuring the melt viscosities of the compositions outside the range of the present invention by the same operation as in Examples -89 to 96.

[0158]

[Table 21]

[0159]

[Table 22]

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

Comparative Examples -97 to 100 Examples -97 to 100 using compositions outside the scope of the present invention
Table 23 shows the results of the melt viscosity measurement performed in the same manner as in the above.

[0162]

[Table 23]

Examples 101 to 108 Synthetic Examples-Polyimide Powders Obtained in 27 and 30 and Synthetic Examples-
After dry blending the liquid crystalline polyimide powder obtained in No. 15 with various compositions as shown in Tables 24 and 25, a Koka type flow tester (CFT-500, Shimadzu Corporation, orifice diameter 0.1 cm, length 1 cm) , Pressure 100kg / c
The melt viscosity was measured in m ² ). Tables 24 and 25 show the measurement results.
Shown in Tables 24 and 25 also show the results of measuring the transition temperature (Tg) of the strand obtained by the flow tester by DSC. The mixture of the aromatic polyimide copolymer and the liquid crystalline aromatic polyimide at the ratio of this example has a lower melt viscosity than that of the aromatic polyimide copolymer alone, and is not different from that of the aromatic polyimide copolymer.
g.

Comparative Examples 101-108 Examples 101-101 to 108 using compositions outside the scope of the present invention.
Tables 24 and 25 show the results of melt viscosity measurement by the same operation as in Table 8.
Shown in

[0165]

[Table 24]

[0166]

[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 in various compositions as shown in Table 26, and the 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 26 shows the measurement results. In addition, the transition temperature of the strand obtained by the flow tester (T
Table 26 also shows the results of measuring g) by DSC. The mixture of the aromatic polyimide copolymer and the liquid crystalline aromatic polyimide at the ratio of this example has a lower melt viscosity than the aromatic polyimide copolymer alone, and a Tg that is not different from the aromatic polyimide copolymer. Had.

Comparative Examples 109-112 Examples 109-111 using compositions outside the scope of the present invention.
Table 26 shows the results of measuring the melt viscosity in the same manner as in Example 2.

[0169]

[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 were prepared as shown in Tables 27 and 28. After dry blending with various compositions, an extruder (40 mm diameter, compression ratio = 3.0 /
Extrusion while melting and kneading with a screw of 1.0)
Uniform blended pellets were obtained. Next, the pellets obtained above were molded using a usual injection molding machine, and the minimum injection pressure of the molded product was measured. The results are shown in Tables 27 and 28 in Example-11.
Shown as 3-120. It can be seen that the mixture obtained by mixing the aromatic polyimide copolymer and the liquid crystalline aromatic polyimide at the ratio of this example has a lower minimum injection pressure than the aromatic polyimide copolymer alone and has good moldability.

Comparative Examples-113 to 120 Examples 1-113 to 12 using compositions outside the scope of the present invention
Table 27 in which the minimum injection pressure was measured by performing the same operation as in Table 27,
28. Those containing no liquid crystalline aromatic polyimide have a high minimum injection pressure, and the aromatic polyimide copolymer 5
When the amount of the liquid crystalline aromatic polyimide exceeds 50 parts by weight with respect to 0 parts by weight, the melt viscosity was too low, and the minimum injection pressure could not be measured. That is, the melt viscosity is too high and injection molding becomes difficult.

[0172]

[Table 27]

[0173]

[Table 28]

Examples 121 and 122 The pellets obtained by blending the aromatic polyimide copolymer and the liquid crystalline aromatic polyimide in Examples 113 and 115 at a mixing ratio of 90:10 were processed by a usual 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. Table 29 shows the results.
Examples 121 and 122 are shown in FIGS. 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 at the ratio of the present example was obtained in Comparative Examples 121 and 122.
The mechanical properties are equivalent to those of the above-mentioned aromatic polyimide copolymer alone, and no decrease in mechanical properties is observed even when a liquid crystalline aromatic polyimide is mixed within the range of the present application.

Comparative Examples 121 and 122 The pellets obtained in Comparative Examples 113 and 115 were formed into a molded article in the same manner as in Examples 121 and 122, and the mechanical properties of the molded article were measured. The results are shown in Table 29 as Comparative Examples-121 and 122.

[0176]

[Table 29]

Examples -123 to 142 Aromatic polyetherimides (Ultem 1000, trade name, manufactured by G.E. USA) and Synthesis Examples 1, 7, 8, 15, and 16
After dry-blending the liquid crystal aromatic polyimide obtained in the above with various compositions as shown in Tables 30 to 34, a Koka type flow tester (Shimadzu Corporation, CFT-500, orifice diameter 0.1 cm, length 1 cm, pressure 100kg / c
The melt viscosity was measured in m ² ). Table 30-
34. Tables 30 to 34 also show the results of measuring the glass transition temperature (Tg) of the strand obtained by the flow tester by DSC. The mixture of the aromatic polyetherimide and the liquid crystalline aromatic polyimide at the ratio 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. Was. The strand obtained by the flow tester was as tough as the aromatic polyetherimide alone.

Comparative Examples 123 to 142 Examples 123 to 14 using compositions outside the scope of the present invention
Tables 30 to 3 show the results of measuring the melt viscosity in the same operation as in Table 2.
It is shown in FIG. Those containing no liquid crystalline aromatic polyimide at all have a high melt viscosity. When the liquid crystalline aromatic polyimide mixed with 50 parts by weight of the aromatic polyetherimide is more than 50 parts by weight, the melt viscosity becomes low, but the flow tester is reduced. The resulting tetrand was brittle.

[0179]

[Table 30]

[0180]

[Table 31]

[0181]

[Table 32]

[0182]

[Table 33]

[0183]

[Table 34]

Examples 143 to 146 An aromatic polyetherimide (Ultem 1000, trade name, manufactured by GE Corporation) and the polyimide powders obtained in Synthesis Examples 7 and 15 were dried in various compositions as shown in Table 35. After blending, an extruder (40 mm diameter, compression ratio = 3.0)
/ With screw of 1.0) and extruded while melt-kneading to obtain uniform blended pellets. Next, the pellets obtained above were molded using a usual injection molding machine, and the minimum injection pressure of the molded product was measured. The results are shown in Table 35 in Example-143.
146. It can be seen that the mixture obtained by mixing the aromatic polyetherimide and the liquid crystalline aromatic polyimide in the proportion of this example has a lower minimum injection pressure than the aromatic polyetherimide alone, and has good moldability.

Comparative Examples -143 to 146 Examples -143 to 14 using compositions outside the scope of the present invention
By performing the same operation as in Step 6, the minimum injection pressure was measured. Those containing no 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 pressure becomes low. Pressure could not be measured. That is, the melt viscosity is too low, making injection molding difficult.

[0186]

[Table 35]

[0187]

According to the present invention, there is provided a thermoplastic resin composition excellent in molding workability and excellent in thermal stability, in addition to the excellent characteristics inherent to the thermoplastic resin.

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 4-160807 (32) Priority date Hei 4 (1992) June 19 (33) Priority claim country Japan (JP) (31) Priority Claim Number Japanese Patent Application No. 4-275916 (32) Priority Date Hei 4 (1992) October 14 (33) Priority Country Japan (JP) (72) Inventor Tadashi Asanuma 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Within Chemical Co., Ltd. (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals Co., Ltd.

Claims (11)

[Claims] 1. A method according to claim 1, wherein 99.9 to 50 parts by weight of at least one thermoplastic resin selected from the group consisting of aromatic polyimides and aromatic polyetherimides and the following (1) and (2):
A thermoplastic resin composition having good moldability and processability, comprising 0.1 to 50 parts by weight of at least one kind of liquid crystalline aromatic polyimide selected from the group consisting of (3) and (3). (1) Formula (1) (Wherein, R _{1 to} R ₅ are hydrogen, fluorine, trifluoromethyl, methyl, ethyl or a cyano group, which may be the same or different from each other; R has 2 to 27 carbon atoms; A tetravalent group selected from the group consisting of a formula 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 liquid crystalline aromatic polyimide having a repeating structural unit represented as a basic skeleton, (2) a repeating structural unit represented by the above formula (1) as a basic skeleton, and the terminal of the polymer molecule having the formula (2) Formula 2 (Wherein, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group,
A condensed polycyclic aromatic group, or a divalent 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) (3) a liquid crystalline aromatic polyimide obtained by sealing with a dicarboxylic anhydride, (3) having a repeating structural unit represented by the above formula (1) as a basic skeleton, and the polymer molecule having a terminal represented by the formula (3) V —NH ₂ (3) (wherein V has 6 to 15 carbon atoms, a monocyclic aromatic group,
Represented by a condensed polycyclic aromatic group or a monovalent 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) Liquid crystalline aromatic polyimide obtained by sealing with a monoamine, 2. The liquid-crystalline aromatic polyimide is at least one liquid-crystalline aromatic polyimide selected from the group consisting of the following (4), (5) and (6).
The thermoplastic resin composition according to the above. (4) Formula (4) (5) a liquid crystalline aromatic polyimide having a repeating structural unit represented by the formula (4) as a basic skeleton, (5) having a repeating structural unit represented by the above formula (4) as a basic skeleton, and a polymer molecule having the formula (2) Embedded image (Wherein, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group,
Represented by a condensed polycyclic aromatic group, or a divalent 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 bridge member) (6) a liquid crystalline aromatic polyimide obtained by sealing with a dicarboxylic anhydride, (6) having a repeating structural unit represented by the above formula (4) as a basic skeleton, and the terminal of the polymer molecule having the formula (3) V —NH ₂ (3) (wherein V has 6 to 15 carbon atoms, a monocyclic aromatic group,
Represented by a condensed polycyclic aromatic group or a monovalent 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) Liquid crystalline aromatic polyimide obtained by sealing with a monoamine. 3. The liquid-crystalline aromatic polyimide is at least one liquid-crystalline aromatic polyimide selected from the group consisting of the following (7), (8) and (9).
The thermoplastic resin composition according to the above. (7) Formula (4) Basic skeletons 1 to 99 having a repeating structural unit represented by
Mol% and the formula (1) (Wherein, R _{1 to} R ₅ are hydrogen, fluorine, trifluoromethyl, methyl, ethyl or a cyano group, which may be the same or different from each other; R has 2 to 27 carbon atoms; A tetravalent group selected from the group consisting of a formula 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 liquid crystalline aromatic polyimide copolymer comprising 99 to 1 mol% of a basic skeleton having a repeating structural unit represented by the formula (excluding the same repeating structural unit as formula (4)); The terminal of the polymer molecule of the liquid crystalline aromatic polyimide copolymer is represented by the formula (2). (Wherein, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group,
Represented by a condensed polycyclic aromatic group, or a divalent 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 bridge member) A liquid crystalline aromatic polyimide copolymer obtained by being sealed with a dicarboxylic anhydride; (9) the terminal of the polymer molecule of the above liquid crystalline 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,
Represented by a condensed polycyclic aromatic group, or a monovalent group selected from the group consisting of a non-fused polycyclic aromatic group in which the aromatic groups are directly or mutually linked by a bridge member) A liquid crystalline aromatic polyimide copolymer obtained by being sealed with a monoamine. 4. An aromatic polyimide according to the following (10):
The thermoplastic resin composition according to claim 1, which is at least one aromatic polyimide selected from the group consisting of (11) and (12). (10) Formula (5) (Wherein, 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;
Has 6 to 27 carbon atoms, and is 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 bridge member. 4
(11) an aromatic polyimide having a repeating structural unit represented by the following formula (5) as a basic skeleton; (11) an aromatic polyimide having a repeating structural unit represented by the above formula (5) as a basic skeleton; Formula (2) (Wherein 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 the aromatic groups are directly or mutually linked by a bridge member. An aromatic polyimide obtained by sealing with an aromatic dicarboxylic anhydride represented by the following formula (5): Having a polymer skeleton represented by the formula (3) V—NH ₂ (3) (wherein V has 6 to 15 carbon atoms, and is a monocyclic aromatic group;
Represented by a condensed polycyclic aromatic group or a monovalent 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) Aromatic polyimide obtained by sealing with a monoamine. 5. The repeating structural unit of the aromatic polyimide is represented by the formula (6): The thermoplastic fat composition according to claim 6, which is a repeating structural unit represented by the formula: 6. An aromatic polyimide according to the following (13):
The thermoplastic resin composition according to claim 4, which is at least one aromatic polyimide selected from the group consisting of (14) and (15). (13) Formula (7) (14) an aromatic polyimide having a repeating structural unit represented by the formula (7) as a basic skeleton, (14) having a repeating structural unit represented by the above formula (7) as a basic skeleton, and a polymer molecule having a terminal represented by the formula (2) 12] (Wherein 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 the aromatic groups are directly or mutually linked by a bridge member. An aromatic polyimide obtained by sealing with an aromatic dicarboxylic anhydride represented by the following formula (7): (15) a repeating structural unit represented by the above formula (7) Having a polymer skeleton represented by the formula (3) V—NH ₂ (3) (wherein V has 6 to 15 carbon atoms, and is a monocyclic aromatic group;
Represented by a condensed polycyclic aromatic group or a monovalent 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) Aromatic polyimide obtained by sealing with a monoamine. 7. An aromatic polyimide according to the following (16):
At least one selected from the group consisting of (17) and (18)
2. The heat-treatable material according to claim 1, wherein both are one kind of aromatic polyimide
Plastic resin composition. (16) Formula (6)The basic skeleton of a repeating structural unit represented by
And the formula (8)Wherein R isAnd n is an integer of 0, 1, 2, and 3, Q is directly connected, -O-,-
S-, -CO-, -SO ₂-, -CH₂-, -C (CH
₃)₂-Or -C (CF₃)₂-Represents an aromatic ring
When there are a plurality of linking groups Q connecting
May be the same or different combinations, and R ″ is(Where M isAt least one divalent group selected from the group consisting of
At least one tetravalent group selected from the group consisting of
Represents a repeating structural unit represented by the formula (6)
1 to 99 mol% of the basic skeleton
(17) Polymer molecules of the above aromatic polyimide copolymer
Is the end of formula (2)Wherein Z is a monocyclic aromatic group having 6 to 15 carbon atoms,
Cyclic aromatic group, aromatic group
Selected from the group consisting of non-fused polycyclic aromatic groups linked to
Aromatic dicarboxylic acid represented by
Aromatic polyimide copolymer obtained by sealing with water, (18) Polymer molecule of the aromatic polyimide copolymer
Is terminated by the formula (3) V-NH₂ (3) (wherein, V has 6 to 15 carbon atoms, a monocyclic aromatic group,
Fused polycyclic aromatic group, aromatic group directly or
The group consisting of interconnected non-fused polycyclic aromatic groups?
An aromatic monoamine represented by the following formula:
Aromatic polyimide copolymer obtained by sealing with a resin. 8. The repeating structural unit represented by the formula (8) is represented by the formula (9): The thermoplastic resin composition according to claim 7, which is a repeating structural unit represented by the formula (wherein R is as defined above) (however, excluding the same structural unit as in the formula (6)). 9. An aromatic polyetherimide having the formula (2)
1) (Wherein X is And Y is The thermoplastic resin composition according to claim 1, which is an aromatic polyetherimide having at least one kind of repeating structural unit represented by the following formula: 10. The thermoplastic resin composition according to claim 1, wherein the aromatic dicarboxylic anhydride is phthalic anhydride. 11. The thermoplastic resin composition according to claim 1, wherein the aromatic monoamine is aniline.