JPH0881556A - Polyimide - Google Patents

Abstract

PURPOSE: To obtain a polyimide which is essentially thermoplastic and has excellent properties by using a long-chain aromatic diamine composed of four benzene rings, one pyridine nucleus or benzonitrile nucleus bonded to each other through specified organic groups as a monomer component. CONSTITUTION: A hydroxy aromatic amino compound such as 2-(4- aminophenyl)-2-(4'-hydroxyphenyl)propane is condensed with a dihalogenopyridine or a dihalogenobenzonitrile to obtain an aromatic diamino compound represented by formula I (wherein L is O, carbpnyl or isopropylidene; X is a group of formula II or III; and Ar is a 6-27 C aromatic group), An aromatic diamine component based on this compound is reacted with an aromatic tetracarboxylic dianhydride to make a polyamic acid. This acid is imidated thermally or chemically to obtain a polyimide comprising repeating units of formula IV. The new polyimide which is one having a specified structure having a pyridine nucleus or a benzonitrile nucleus is essentially thermoplastic and is an injection-moldable material of excellent processability.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyimide, a method for producing the same, a novel aromatic diamino compound used for producing the polyimide, and a method for producing the same. More specifically, it relates to a thermoplastic polyimide having excellent heat resistance and a method for producing the same. Further, it is a polyimide resin composition containing these polyimide and a fibrous reinforcing material. The novel aromatic diamino compound having a pyridine skeleton represented by the general formula (3-1) and the novel aromatic diamino compound having a cyano group represented by the general formula (3-2) of the present invention are It is not only useful as a raw material for the polyimide of the present invention, but also used as a raw material for other polyimides, polyamides, polyamideimides, bismaleimides and epoxy resins.

[0002]

2. Description of the Related Art Conventionally, polyimide has excellent properties such as mechanical properties, chemical resistance, flame retardancy, and electrical properties in addition to its excellent heat resistance.
Widely used in the fields of composite materials, electric and electronic parts, etc.

For example, a typical polyimide has the formula
(A)

[Chemical 27] A polyimide having a repeating structural unit represented by the following formula is known (trade name: Kapton, Ve manufactured by DuPont).
However, since this polyimide is insoluble and infusible, it has to be molded by a special method such as sinter molding via a polyamic acid as a precursor, resulting in poor moldability. With this method, it is difficult to obtain processed products with complicated shapes,
In order to obtain a satisfactory molded product, it is necessary to further finish the molded product by cutting or the like, so that there is a big drawback that the processing cost becomes high.

Similarly, the formula (B), which is generally known as a film application,

[Chemical 28] A polyimide having a repeating structural unit represented by (Upilex, Ube Industries) cannot be extruded because it has no melt fluidity. Therefore, there is a problem that these polyimides can only be formed into a film by a method such as a casting method.

Further, as a thermoplastic polyimide having improved glass transition temperature, melt fluidity and molding processability, a compound represented by the formula (C)

[Chemical 29] There is known a polyimide having a repeating structural unit represented by (JP-A-62-205124). This polyimide has a good melt flowability and is capable of melt injection molding. However, since this polyimide is crystalline in nature, crystallization proceeds by heat treatment under certain specific conditions. Once crystallized, it must be above the melting point of the polymer to remelt (390 ° C or above for this polyimide)
Molding processing temperature is required. In addition, not only for polyimide, but for polymer film applications, the flexibility of the polymer itself, that is, flexibility is an important factor. A crystallized film is not sufficiently flexible and may be broken or microcracked by an external force or the like.

From the above viewpoints, in an application field where crystallization is basically not desired, an essentially amorphous thermoplastic polyimide resin which does not crystallize even after melt molding and has flexibility is desired. There is. For the purpose of improving such a defect of polyimide, a method for improving the diamine component as a raw material has been tried. For example, attempts have been made to control the glass transition temperature and melt fluidity of polyimide by means of the bonding group in the monomer unit, the extension or broken structure of the molecular chain, and the like. For example, regarding the method based on the broken structure of the molecular chain, 3,3′-diaminobenzophenone and 3,3′-diaminobenzophenone
A polyimide (NASA, LARC-TPI) composed of 3 ', 4,4'-benzophenone tetracarboxylic dianhydride has been developed as a thermoplastic polyimide. However, although this polyimide exhibits excellent heat resistance and adhesiveness, it still lacks fluidity when melted, and currently adhesives are mainly used. Several structures have been proposed for methods such as molecular chain extension, but none satisfying all the conditions has been obtained yet because of deterioration of physical properties.

Among the studies of diamino compounds as monomers for such polyimides, regarding polyimides containing a pyridine skeleton, Japanese Patent Application Laid-Open No. 62-116563 discloses a polyimide using bis (aminophenoxy) pyridine as a diamine component. Is disclosed. However, the polyimide having this compound as a monomer has a short molecular chain unit of the monomer, and therefore has insufficient melt fluidity,
Moldability is difficult. Regarding the polyimide containing a cyano group, Japanese Patent Application Laid-Open No. 3-17129 discloses a polyimide containing bis (aminophenoxy) benzonitrile as a monomer. This cyano group-containing polyimide has high heat resistance, but its melt flowability is insufficient due to the short molecular chain unit of the monomer, and moldability is poor. As described above, the properties such as heat resistance, molding processability, mechanical properties and crystallinity of a polyimide containing a nitrogen atom in a polymer molecule and using a raw material diamine having a long molecular chain as a monomer are still well known. Has not been done.

[0008]

An object of the present invention is to provide, in addition to the excellent heat resistance inherent in polyimide, an essentially thermoplastic polyimide having good moldability and an aromatic diamine useful as a raw material for the polyimide. To provide. Another object of the present invention is to provide an aromatic diamino compound which is sufficiently excellent in flexibility and molding processability and is extremely excellent as a raw material for a heat resistant polyimide and its polyimide resin.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to achieve the above-mentioned object, and as a result, four benzene nuclei and one pyridine nuclei are linked by a specific divalent organic group. In addition, the polyimide containing a long-chain aromatic diamine having a specific structure as a monomer component is essentially a thermoplastic polyimide having various properties unique to polyimide and excellent moldability, and four benzene nuclei And one benzonitrile nucleus linked by a specific divalent organic group,
The present invention was completed by finding that a polyimide containing a long-chain aromatic diamine having a specific structure as a monomer component is an essentially thermoplastic polyimide having excellent moldability and extremely high heat resistance.

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

[Chemical 30] (In the formula, L represents an oxygen atom, a carbonyl group, an isopropylidene group or a hexafluoroisopropylidene group, and X is

[Chemical 31] Ar has a carbon number of 6 to 27 and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member. A polyimide having at least one repeating structural unit represented by the formula (1) as an essential structural unit,

(2) General formula (1)

[Chemical 32] Having at least one repeating structural unit represented by the formula (wherein L, X and Ar are the same as those described above) as an essential structural unit, and the end of the polymer molecule has essentially no substituents, or A polyimide which is an aromatic ring substituted with a group having no reactivity with an amine or a dicarboxylic acid anhydride,

(3) General formula (1-1)

[Chemical 33] (Wherein Ar is the same as in the case of the general formula (1)), the polyimide of the above (1) or (2) having at least one repeating structural unit as an essential structural unit,

(4) General formula (1-2)

Embedded image (In the formula, L and Ar are the same as in the case of the general formula (1)) A polyimide of the above (1) or (2), which has at least one repeating structural unit as an essential structural unit,

(5) General formula (1)

Embedded image (Wherein L, X and Ar are the same as above) and 1 to 100 mol% of the repeating structural unit represented by the general formula (2)

Embedded image (In the formula, n represents an integer of 0 to 6, Q is a direct bond, -O-, -S-
, -CO-, -SO _2- , -CH _2- , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2-
In the case where there are a plurality of bonding groups Q that connect aromatic rings to each other, the bonding groups may be the same or different combinations. Ar ′ has 6 to 27 carbon atoms and is a monocyclic aromatic group. Group, a condensed polycyclic aromatic group, or a tetravalent group which is a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a cross-linking member). A polyimide or polyimide copolymer containing 0 mol% as an essential structural unit, or a group in which the terminal of the polymer molecule has essentially no substituent or is not reactive with an amine or a dicarboxylic acid anhydride. A substituted polyimide or polyimide copolymer,

(6) In addition, the general formula (3)

Embedded image (In the formula, L represents an oxygen atom, a carbonyl group, an isopropylidene group or a hexafluoroisopropylidene group, and X is

[Chemical 38] And an aromatic diamine mainly composed of at least one aromatic diamino compound represented by the general formula (4)

[Chemical Formula 39] (In the formula, Ar is a monocyclic aromatic group having 6 to 27 carbon atoms, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member. A tetracarboxylic acid dianhydride represented by the formula (4) is reacted to thermally or chemically imidize the resulting polyamic acid.

[Chemical 40] (Wherein L, X and Ar are the same as above), a method for producing a polyimide having at least one repeating structural unit as an essential structural unit,

(7) General formula (3)

Embedded image An aromatic diamine mainly composed of at least one aromatic diamino compound represented by the formula (wherein L and X are the same as defined above);

Embedded image (Wherein Ar is the same as the above), a tetracarboxylic dianhydride represented by the general formula (5)

[Chemical 43] (In the formula, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are directly or cross-linked to each other. An aromatic dicarboxylic acid anhydride represented by a divalent group which is a group or a general formula (6) Z ₁ -NH ₂ (6) (in the formula, Z ₁ has 6 to 15 carbon atoms, and Aromatic group represented by a cyclic aromatic group, a condensed polycyclic aromatic group, or a monovalent group which is a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a bridging member) General formula characterized by reacting in the presence of a group monoamine to thermally or chemically imidize the resulting polyamic acid
(1)

[Chemical 44] (Wherein, L, X and Ar are the same as the above) has at least one kind of repeating structural unit as an essential structural unit, and the end of the polymer molecule has essentially no substituent, Alternatively, a method for producing a polyimide which is an aromatic ring substituted with a group having no reactivity with an amine or a dicarboxylic acid anhydride,

(8) General formula (3)

[Chemical formula 45] (In the formula, L and X are the same as above) 1 to 0.01 parts by mole of the aromatic diamine, mainly represented by the general formula
(4)

[Chemical formula 46] (In the formula, Ar is the same as above) 1 to 0.01 part by mole of tetracarboxylic dianhydride, and further, the general formula (9)

[Chemical 47] (In the formula, n is an integer of 0 to 6, Q is a direct connection, -O-, -S-, -C
Represents O-, -SO _2- , -CH ₂ , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- , and when there are a plurality of bonding groups Q connecting the aromatic rings, they are At least one aromatic diamine represented by the same group or different kinds of bonding groups)
0.99 parts by mole and general formula (10)

[Chemical 48] (In the formula, Ar ′ has a carbon number of 6 to 27, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are directly or cross-linked by a bridging member. A tetracarboxylic dianhydride represented by the formula (which represents a tetravalent group which is an aromatic group) is reacted with 0 to 0.99 parts by mole of the tetracarboxylic acid dianhydride.

(9) The above reaction is carried out by adding the compound of the general formula (5) to 1 mol of the total amount of the aromatic diamine.

[Chemical 49] (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are directly or crosslinked with each other. aromatic dicarboxylic anhydride of 0.001 to 1.0 mol represented by represents a divalent group which is an aromatic group) or the total amount to 1 mole of the aromatic tetracarboxylic dianhydride, the general formula (6) Z ₁ -NH ₂ (6) (In the formula, Z ₁ has 6 to 15 carbon atoms, and a monocyclic aromatic group, a condensed polycyclic aromatic group or an aromatic group is directly or cross-linked to each other. Aromatic monoamine represented by a monovalent group which is a non-fused polycyclic aromatic group)
A method for producing the polyimide or polyimide copolymer according to the above (8), wherein the polyamic acid obtained is reacted in the presence of 0.001 to 1.0 mol to thermally or chemically imidize the polyamic acid.

(10) Further, the novel aromatic diamino compound used as a monomer of the polyimide of the present invention has the general formula (3)

Embedded image An aromatic diamino compound represented by the formula (wherein L and X are the same as above),

(11) Formula (3-1) as a particularly preferred diamine compound

[Chemical 51] And the general formula (3-2)

[Chemical 52] (Wherein L is the same as in the case of the general formula (3)), an aromatic diamino compound,

(12) General formula (7)

Embedded image (In the formula, L represents an oxygen atom, a carbonyl group, an isopropylidene group or a hexafluoroisopropylidene group) and a hydroxyl group-containing aromatic amino compound represented by the general formula (8) Y-X-Y (8) , X is

[Chemical 54] In which Y represents a halogen atom) and is condensed in the presence of a base in an aprotic polar solvent.

[Chemical 55] (Wherein L and X are the same as above), a method for producing an aromatic diamino compound,

(13) 100 parts by weight of the polyimide or polyimide copolymer described in (5) above and 5 to 70 parts by weight of a fibrous reinforcing material selected from carbon fiber, glass fiber, aromatic polyamide fiber and potassium titanate fiber. A polyimide resin composition containing

(14) An injection molded product obtained from this polyimide resin composition,

(15) A polyimide film containing the polyimide or polyimide copolymer of the present invention.
Polyimide or polyimide copolymer obtained by the present invention, in addition to excellent heat resistance, excellent melt flow stability,
It has greatly improved moldability and can be applied to structural materials.

The polyimide of the present invention has the general formula (1)

[Chemical 56] (In the formula, L, X and Ar are the same as described above) A polyimide having at least one repeating structural unit as an essential structural unit.

Particularly preferred repeating structural unit of the polyimide is represented by the general formula (1-1) among the repeating structural units represented by the general formula (1).

[Chemical 57] (In the formula, Ar is the same as the above) A polyimide having at least one repeating structural unit represented by the formula as an essential structural unit, or the general formula (1-2)

[Chemical 58] (In the formula, L and Ar are the same as described above) A polyimide having at least one repeating structural unit as an essential structural unit.

The polyimide having the repeating structural unit represented by the above general formula (1-1) has particularly excellent melt flowability and good injection moldability and extrusion moldability. Further, the polyimide having the repeating structural unit represented by the general formula (1-2) has excellent heat resistance and a high glass transition temperature. Further, 1 to 100 mol% of the repeating structural unit represented by the general formula (1) and the general formula (2)

Embedded image (In the formula, n, Q and Ar ′ are the same as the above), which is a polyimide or a polyimide copolymer containing 99 to 0 mol% of repeating structural units as essential structural units. The polyimide copolymer has a repeating structural unit represented by the general formula (1) in the polyimide copolymer,
It is preferably a polyimide copolymer containing 50 mol% or more, more preferably 70 mol% or more.

These polyimides or polyimide copolymers have an aromatic ring in which the end of the polymer molecule has essentially no substituent or is substituted with a group having no reactivity with amine or dicarboxylic acid anhydride. The polyimide may be The polyimide having the repeating structural unit represented by the general formula (1) is represented by the general formula (3)

Embedded image An aromatic diamine mainly composed of at least one aromatic diamino compound represented by the formula (wherein L and X are the same as defined above);

[Chemical formula 61] (In the formula, Ar is a monocyclic aromatic group having 6 to 27 carbon atoms, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member. The tetracarboxylic acid dianhydride represented by the formula (4) is reacted, and the resulting polyamic acid is thermally or chemically imidized to produce the compound.

The aromatic diamino compound of the present invention used for producing the polyimide of the present invention has the general formula (3):

Embedded image An aromatic diamine represented by the formula (wherein L and X are the same as defined above), preferably represented by the formula (3-1)

[Chemical formula 63] Or general formula (3-2)

[Chemical 64] (In the formula, L is the same as the above) and is an aromatic diamino compound.

These compounds are represented by the general formula (7)

[Chemical 65] (Wherein L is the same as above) and a hydroxyl group-containing aromatic amino compound represented by the general formula (8) Y-XY (8) (wherein X and Y are the same as above). It can be prepared by condensing the represented compound in an aprotic polar solvent in the presence of a base. The aromatic diamine of the present invention has four benzene nuclei and a pyridine skeleton or a benzonitrile nucleus, and a polyimide having the aromatic diamine as a monomer is amorphous and has excellent heat fluidity and molding processability. I understood.

The method for producing the aromatic diamine of the present invention will be specifically described below. The hydroxyl group-containing aromatic amino compound used as the raw material of the aromatic diamine of the present invention has the general formula (7)

[Chemical formula 66] (Wherein L is the same as above), for example, 4-amino-4′-hydroxydiphenyl ether, 2- (4-aminophenyl) -2- (4′-hydroxyphenyl) propane. , 2- (4-aminophenyl) -2- (4'-hydroxyphenyl) hexafluoropropane, 4-amino-4'-hydroxybenzophenone. Preferred is 2- (4-aminophenyl) -2- (4'-hydroxyphenyl) propane.

Further, the compound represented by the general formula (8) has the general formula (8-1)

Embedded image (Wherein Y represents a halogen atom) or a dihalogenopyridine represented by the general formula (8-2)

[Chemical 68] (Wherein Y represents a halogen atom), and examples of the dihalogenopyridine include 2,6-dichloropyridine, 2,6-dibromopyridine, and 2,6-diiodopyridine. Etc., but 2,6-dichloropyridine is preferably used because of easy availability of raw materials. Further, as dihalogenobenzonitrile, 2,6-dichlorobenzonitrile, 2,
2,6-Dichlorobenzonitrile is preferably used from the viewpoint of easy availability of raw materials such as 6-dibromobenzonitrile and 2,6-diiodobenzonitrile.

In the method of the present invention, the amount of the hydroxyl group-containing aromatic amino compound should be at least twice the equivalent amount of dihalogenopyridine or dihalogenobenzonitrile. Considering the complexity of post-treatment, cost, etc. It is preferably used in the range of 2.5 times equivalent. The base used in the method of the present invention is an alkali metal carbonate, hydrogen carbonate, hydroxide or alkoxide, and potassium carbonate, potassium hydrogen carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, carbonic acid. Examples thereof include sodium hydrogen, lithium carbonate, lithium hydroxide, sodium methoxide, potassium isopropoxide and the like. The amount of these bases used is equivalent to or more than the halogen group of the starting dihalogenopyridine or dihalogenobenzonitrile, and preferably 1
~ 2 equivalents.

The solvent used in the method of the present invention includes:
Examples include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, sulfolane and the like. The amount of these solvents to be used is not particularly limited, but usually 1 to 10 times by weight of the raw material is sufficient. Also,
In the method of the present invention, as a catalyst for promoting the reaction,
Copper powder or copper compound, or crown ether,
Even if a phase transfer catalyst such as polyethylene glycol, a quaternary ammonium salt or a quaternary phosphonium salt is used, there is no problem. The reaction temperature is usually 40 to 250.
The temperature is in the range of 100 ° C, preferably 100 to 200 ° C.

As the reaction method of the present invention, a predetermined amount of a hydroxyl group-containing aromatic amino compound, a base and a solvent are charged, the hydroxyl group-containing aromatic amino compound is converted to an alkali metal salt, and then dihalogenopyridine or diamine is added. Either a method in which halogenobenzonitrile is added for the reaction or a method in which all raw materials containing dihalogenopyridine or dihalogenobenzonitrile are simultaneously added in advance and the temperature is allowed to rise and the reaction is performed may be employed. Moreover, the present invention is not limited to these and can be appropriately implemented by other methods. As a removal method when water is present in the reaction system,
There is a method of venting out of the system during the reaction by passing nitrogen gas or the like, but generally, a method of using a small amount of benzene, toluene, xylene, chlorobenzene, etc. to remove it outside the system by azeotropic distillation. Is often used. The end point of the reaction can be determined by thin layer chromatography or high performance liquid chromatography while observing the reduction of the raw materials. After the completion of the reaction, the crude aromatic diamine is obtained after being concentrated or discharged as it is into water or the like.
This product can be purified by a method such as recrystallization with a solvent or sludging, and mineralization with hydrochloric acid.

In the polyimide of the present invention, the aromatic diamine obtained as described above is used as an essential monomer, but other aromatic diamines may be mixed and used as long as the good physical properties of the polyimide are not impaired. .

The aromatic tetracarboxylic dianhydride used in the production of the polyimide of the present invention has the general formula (4)

[Chemical 69] At least one tetracarboxylic dianhydride represented by the formula (wherein Ar is the same as above) is used.

Specifically, in the general formula (4), Ar is represented by the formula (a)

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

[Chemical 71] A condensed polycyclic aromatic group represented by or a formula (c)

[Chemical 72] [In the formula, X'is a direct bond, -CO-, -O-, -S-,
_{-SO 2 -, - CH 2 -} , - C (CH 3) 2 -, - C
(CF _{3) 2} -

Embedded image

[Chemical 74] (Here, Y'is a direct bond, -CO-, -O-, -S-,
_{-SO 2 -, - CH 2 -} , - C (CH 3) 2 -, - C
(Representing a divalent group represented by (CF ₃ ) _2- )] A tetravalent group such as a non-condensed polycyclic aromatic group in which an aromatic group represented by The tetracarboxylic dianhydride is used.

The tetracarboxylic acid dianhydride represented by the general formula (4) used in the present invention is, for example,
Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3
3'-benzophenone tetracarboxylic dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride Anhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4
-Dicarboxyphenyl) sulfone dianhydride, 1,1-
Bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5 , 8-Naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10 -Perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride and the like. These may be used alone or in combination of two or more.

In the production of polyimide, it is usual to adjust the amount ratio of aromatic tetracarboxylic dianhydride and aromatic diamine in order to adjust the molecular weight of the produced polyimide. In the method of the present invention, the molar ratio of the aromatic tetracarboxylic dianhydride to the aromatic diamine suitable for obtaining a polyimide having good melt fluidity is 0.
It is in the range of 9 to 1.0.

The polyimide of the present invention obtained by using the above aromatic diamine and aromatic tetracarboxylic dianhydride as monomer components is mainly a polyimide having an essential structural unit having a repeating structural unit represented by the general formula (1). Is. In addition, a mixture of the aromatic diamine of the present invention and one or more kinds of other aromatic diamines and one or more kinds of aromatic tetracarboxylic dianhydrides as monomers are used and the repeating unit represented by the above general formula (1) is used. A polyimide copolymer having a structural unit and a repeating structural unit represented by the general formula (2) is obtained.

The polyimide copolymer composed of the repeating structural unit represented by the general formula (1) and the repeating structural unit represented by the general formula (2) has the general formula (3):

[Chemical 75] (Wherein L and X are the same as above) and the general formula (9)

[Chemical 76] (In the formula, n is an integer of 0 to 6, Q is a direct connection, -O-, -S-, -C
Represents O-, -SO _2- , -CH ₂ , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- , and when there are a plurality of bonding groups Q connecting the aromatic rings, they are In the coexistence of at least one aromatic diamine represented by the formula (10)

Embedded image (In the formula, Ar ′ has a carbon number of 6 to 27, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are connected to each other directly or by a crosslinking member. It is obtained by reacting with at least one aromatic tetracarboxylic dianhydride represented by the formula (which represents a tetravalent group which is an aromatic group).

As the aromatic diamine of the general formula (9) used here, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 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'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3 '
-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis
(4-Aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) )-
1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-amino Phenyl) -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, 3,3'-diamino-4
-Phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 4,4'-bis (4- Aminophenoxy) biphenyl, 3,3'-bis (4-aminophenoxy) biphenyl, 3,
4'-bis (3-aminophenoxy) biphenyl,

Bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] ketone, bis [3- (4-aminophenoxy) phenyl] ketone, bis [3- ( 3-Aminophenoxy) phenyl] ketone, 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5,5'-diphenoxybenzophenone, 3,4'-diamino-4, 5'-diphenoxybenzophenone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [3- (4-aminophenoxy) phenyl]
Sulfide, bis [3- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4 -Aminophenoxy) phenyl] sulfone, bis [3- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, Bis [3- (3-aminophenoxy) phenyl] ether, bis [3- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-amino Phenoxy) phenyl] methane, bis [3- (3-aminophenoxy) phenyl] methane, bis [3- (4-aminophenoxy) phenyl] methane, 2,2-bis [4- (3-aminophenoxy) phenyl L] propane, 2,2-bis [4- (4-aminophenoxy)
Phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] propane, 2,2-bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3 -Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3, 3-Hexafluoropropane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-
Hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane

1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis (3-amino-4) -Phenoxybenzoyl) benzene, 1,4-bis (3-amino-4)
-Phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) benzene, 1,4-bis (4-
Amino-5-phenoxybenzoyl) benzene, 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4 '-Bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [ Four-
4- (4-aminophenoxy) phenoxyphenyl] sulfone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4'- Diamino-4,5'-dibiphenoxybenzophenone,

1,3-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5) -Biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5)
-Biphenoxybenzoyl) benzene 1,4-bis [4- (4-
Aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy)
Phenoxy-α, α-dimethylbenzyl] benzene, 1,
3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-fluorophenoxy) -α, α -Dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-
Methylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-cyanophenoxy)-
α, α-Dimethylbenzyl] benzene, 1,3-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis
(3-Amino-4-biphenoxybenzoyl) benzene, 1,
3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5-biphenoxybenzoyl)
Examples thereof include benzene. These may be used alone or in combination of two or more.

As the tetracarboxylic dianhydride of the general formula (10) used as one of the monomers, any of the compounds listed as the specific examples of the general formula (4) can be used. The tetracarboxylic dianhydride of the general formula (10) may be the same as or different from the tetracarboxylic dianhydride of the general formula (4), and the tetracarboxylic dianhydride used in the production of the polyimide copolymer may be used. The acid dianhydrides may be used alone or in combination of two or more.
In the production of polyimide or polyimide copolymer,
The amounts of the aromatic diamine component and the aromatic tetracarboxylic dianhydride used are 1 to 0.01 parts by mole of the aromatic diamine represented by the general formula (3) and the aromatic tetracarboxylic dianhydride represented by the general formula (4). 1 to 0.01 parts by mole, further 0 to 0.99 parts by mole of the aromatic diamine represented by the general formula (9) and 0 to 0.99 parts by mole of the aromatic tetracarboxylic dianhydride represented by the general formula (10). In the case of a polyimide copolymer, the aromatic diamine represented by the general formula (3) is preferably 0.5 part by mole or more, more preferably 0.7 part by mole or more in the aromatic diamine component.

Further, the polyimide of the present invention is a polyimide or polyimide copolymer having an aromatic ring whose polymer terminal is unsubstituted or substituted with a group having no reactivity with amine or dicarboxylic acid anhydride, or these Compositions containing the polyimides of are also included, and these polyimides may exhibit better performance.

The polyimide or polyimide copolymer having an aromatic ring, which is unsubstituted or substituted with a group having no reactivity with amine or dicarboxylic acid anhydride, at the terminal of the polymer molecule is mainly represented by the formula (3). A mixture of an aromatic diamine or another diamine and one or more tetracarboxylic dianhydrides mainly represented by the general formula (4) are added to the general formula (5)

Embedded image (In the formula, Z has a carbon number of 6 to 15, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are connected to each other directly or by a crosslinking member. An aromatic dicarboxylic acid anhydride represented by an aromatic divalent group) or a general formula (6) Z ₁ -NH ₂ (6) (wherein Z ₁ has 6 to 15 carbon atoms; Represents a monovalent group which is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are directly or linked to each other by a bridging member). It is a polyimide obtained by sealing with an aromatic monoamine, preferably phthalic anhydride or aniline.

This polyimide comprises an aromatic diamine component and an aromatic tetracarboxylic dianhydride component represented by the general formula (5)
An aromatic dicarboxylic acid anhydride represented by or a general formula
It is obtained by reacting in the presence of an aromatic monoamine represented by (6) and thermally or chemically imidizing the resulting polyamic acid.

Specific examples of the aromatic dicarboxylic acid anhydride represented by the general formula (5) include phthalic anhydride and 2,3-
Benzophenone dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride, 2,3-dicarboxyphenyl ether anhydride, 3,4-dicarboxyphenylphenyl ether anhydride, 2,3-biphenyldicarboxylic acid anhydride, 3 , 4-biphenyldicarboxylic acid anhydride, 2,3-dicarboxyphenylphenyl sulfone anhydride, 3,4-dicarboxyphenylphenyl sulfone anhydride, 2,3-dicarboxyphenylphenyl sulfide anhydride, 3,4-di Carboxyphenyl phenyl sulfide anhydride, 1,2-naphthalene dicarboxylic acid anhydride, 2,3-naphthalene dicarboxylic acid anhydride, 1,8-naphthalene dicarboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3 -Anthracene dicarboxylic acid anhydride, 1,
9-anthracene dicarboxylic acid anhydride and the like can be mentioned. These dicarboxylic acid anhydrides may be substituted with groups that are not reactive with amines or dicarboxylic acid anhydrides.

Among these dicarboxylic acid anhydrides, phthalic anhydride is most preferable from the viewpoint of properties and practical use of the polyimide obtained. That is, it is a polyimide having excellent molding stability during high-temperature molding, has excellent heat resistance, and considering the excellent workability, for example, structural materials, base materials for space aircraft, electric Polyimide is extremely useful as an electronic component or adhesive. When phthalic anhydride is used, there is no problem in substituting a part of it with another dicarboxylic acid anhydride as long as the good physical properties of the polyimide are not impaired. The amount of dicarboxylic acid anhydride used is 0.001 to 1.0 mol per mol of the aromatic diamine used. If it is less than 0.001 mol, the viscosity will increase during high temperature molding, which will cause deterioration of molding processability. On the other hand, if it exceeds 1.0 mol, the mechanical properties will deteriorate. The preferred amount used is 0.01 to 0.5 mol.

When an aromatic monoamine is used,
As the aromatic monoamine, 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, m-nitroaniline, p-nitroaniline, o-aminophenol, m- Aminophenol, p-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenidine, m-phenidine, p-phenidine, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl,
4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether, 4-aminophenylphenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenylphenyl sulfide, 3- Aminophenylphenyl sulfide, 4-aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfone, 4-aminophenylphenyl sulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 2 -Amino-1-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 5-amino
-2-naphthol, 7-amino-2-naphthol, 8-amino-1
-Naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like.

These aromatic monoamines may be substituted with a group having no reactivity with the amine or the dicarboxylic acid anhydride. The amount of aromatic monoamine used is 0,0 per 1 mol of the tetracarboxylic dianhydride used.
It is 001 to 1.0 mol. If it is less than 0.001 mol ratio, the viscosity is increased during high temperature molding, which causes deterioration of molding processability. On the other hand, if the molar ratio exceeds 1.0, the mechanical properties will deteriorate. The preferred amount used is 0.01 to 0.5 mol.

As described above, the molar ratio of the aromatic tetracarboxylic dianhydride to the aromatic diamine which is suitable for obtaining the polyimide having good melt fluidity is in the range of 0.9 to 1.0. Therefore, in this way, when producing a polyimide of which the terminal of the polyimide of the present invention is an unsubstituted or substituted aromatic ring, an aromatic tetracarboxylic acid dianhydride, an aromatic diamine, and a dicarboxylic acid anhydride or The molar ratio of the aromatic monoamine is 0.9 to 1.0 mol for the aromatic diamine and 0.001 to 1.1 for the dicarboxylic acid anhydride or the aromatic monoamine, per 1 mol of the tetracarboxylic dianhydride.
It is 0 mol. The method for producing a polyimide of the present invention can be applied to any method capable of producing a polyimide, including known methods, but it is particularly preferable to carry out the reaction in an organic solvent.

The solvent used in such a reaction is preferably N, N-dimethylacetamide,
Other usable solvents include, for example, N, N-dimethylformamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-
Dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl)
Ether, 1,2-bis (2-methoxyethoxy) ethane, bis 2- (2-methoxyethoxy) ethyl ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyrroline, picoline, dimethyl sulfoxide, dimethyl sulfone , Tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, m-cresylic acid, p-chlorophenol, anisole, benzene, toluene, xylene and the like.
In addition, these organic solvents may be used alone or as a mixture of two or more kinds.

In the method of the present invention, aromatic diamine, aromatic tetracarboxylic acid dianhydride, aromatic dicarboxylic acid anhydride, or aromatic monoamine is added to an organic solvent and reacted. After reacting an acid dianhydride and an aromatic diamine, a method of continuing the reaction by adding an aromatic dicarboxylic acid anhydride or an aromatic monoamine, (b) reacting by adding an aromatic dicarboxylic acid anhydride to the aromatic diamine After the reaction, an aromatic tetracarboxylic dianhydride is added, and the reaction is further continued. (C) An aromatic monoamine is added to the aromatic tetracarboxylic dianhydride to react, and then an aromatic diamine is added. Then, the reaction is continued, and (d) the aromatic tetracarboxylic dianhydride, aromatic diamine, aromatic dicarboxylic anhydride or aromatic monoamine is simultaneously added. And pressurizing method, and the like are reacted, really no problem the method of adding Izure. The reaction temperature is usually 250 ° C or lower, preferably 50 ° C or lower.
The reaction pressure is not particularly limited and can be carried out at normal pressure. The reaction time varies depending on the type of aromatic tetracarboxylic dianhydride, the type of solvent and the reaction temperature, and usually 4 to 24 hours is sufficient.

Further, the obtained polyamic acid is added in an amount of 100 to 40.
A polyimide having a repeating unit corresponding to a polyamic acid can be obtained by heating at 0 ° C. for imidization or by chemical imidization using an imidizing agent such as acetic anhydride. Further, an aromatic diamine and an aromatic tetracarboxylic dianhydride, further, when the terminal of the polyimide is an aromatic ring, an aromatic dicarboxylic acid anhydride or an aromatic monoamine, was suspended or dissolved in an organic solvent. It is also possible to obtain a target polyimide by post-heating to generate a polyamic acid as a polyimide precursor and simultaneously perform imidization.

The polyamic acid, which is the precursor of the polyimide of the present invention, was dissolved in N, N-dimethylacetamide at a concentration of 0.5 g / dl, and then the logarithmic viscosity value measured at 35 ° C. was 0.
01-3.0 dl / g, and after further heating and dissolving the present polyimide powder in a mixed solvent of 9 parts by weight of p-chlorophenol and 1 part by weight of phenol at a concentration of 0.5 g / dl, 35
The value of logarithmic viscosity measured at ° C is 0.01 to 3.0 dl
/ G. As a method for producing a polyimide film in the present invention, after coating a varnish of a polyamic acid which is a precursor of the present polyimide on a glass plate, a method of heating and imidizing, a film by directly heating and pressing a polyimide powder It is possible to use a method of forming a film, or a method of dissolving in an organic solvent and removing the solvent to form a film. That is, a film-form or powder-form polyimide can be obtained by using a conventionally known method.

The polyimide resin composition of the present invention comprises a polyimide resin such as the polyimide or polyimide copolymer of the present invention, carbon fiber, and 100 parts by weight of the resin.
It contains 5 to 70 parts by weight, preferably 10 to 50 parts by weight of a fibrous reinforcing material such as glass fiber, aromatic polyamide fiber or potassium titanate fiber. If the content of the fibrous reinforcing material is less than 5 parts by weight, a sufficient reinforcing effect cannot be obtained. Further, if it exceeds 70 parts by weight, it is difficult to obtain a good molded product by melt molding such as injection molding.

The polyimide resin composition of the present invention can be prepared by various methods. It can be prepared by adding a fibrous reinforcing material to a polyimide resin by various commonly known methods. For example, polyimide resin powder and fibrous reinforcing material are pre-kneaded using a mortar, Henschel mixer, drum blender, tampler blender, ball mill, ribbon blender, and the like, and then a melt mixer, pellets or powder using a hot roll or the like. The most common method is to obtain a mixture. The thus obtained polyimide resin composition of the present invention is molded by a known molding method such as an injection molding method, an extrusion molding method, a compression molding method and a rotational molding method, and is put into practical use. Since the polyimide resin composition of the present invention has excellent fluidity, the injection molding method is most preferable from the viewpoint of work efficiency.

When the polyimide resin composition of the present invention is subjected to melt molding, other thermoplastic resin resins such as polyethylene, polypropylene, polycarbonate, polyarylate and polyamide are used within a range not impairing the object of the present invention. , Polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyphenyl sulfide, polyamide imide, polyether imide, modified polyphenylene oxide, polyimide other than the present invention, etc. in an appropriate amount according to the purpose of the present invention May be.

Further, the following fillers and the like used in ordinary resin compositions may be used within the range not impairing the object of the present invention. That is, wear resistance improvers such as graphite, carborundum, silica powder, molybdenum disulfide, and fluororesins, flame retardant improvers such as antimony trioxide, magnesium carbonate, and calcium carbonate, electrical characteristics of clay, mica, etc. Improver, asbestos, silica, cracking resistance improver such as graphite, barium sulfate, silica,
Acid resistance improver such as calcium metasilicate, thermal conductivity improver such as iron powder, zinc powder, aluminum powder and copper powder, other glass beads, glass spheres, talc, diatomaceous earth, alumina, silas baln, hydrated alumina, metal oxide Items, colorants and the like.

[0065]

EXAMPLES The present invention will be described in detail below with reference to examples. The physical properties of the polyimide in the examples were measured by the following methods. Logarithmic viscosity: Polyamic acid in N, N-dimethylacetamide, polyimide in p-chlorophenol / phenol (weight ratio 9/1) mixed solvent, 0.5 g / 10 each
After dissolution at a concentration of 0 ml, measurement was carried out at 35 ° C. Tg: DSC (Shimadzu DT-40 series, DSC-41
Measured by M). 5% weight loss temperature: DTG in the air (Shimadzu DT-40
Series, DTG-40M). Flow starting temperature: Shimadzu Koka type flow tester (CFT50
0A), measured with a load of 100 kg and a heating rate of 5 ° C./min. Melt viscosity: Shimadzu Koka type flow tester (CFT500
Measured with a load of 100 kg according to A). Tensile strength: Measured according to ASTM-D-638. Elongation: Measured according to ASTM-D-638. Tensile elastic modulus: measured according to ASTM-D-638. Bending strength and elastic modulus: measured according to ASTM-790. Izod impact strength: ASTM-D-256 (with notch)
Measured according to. Heat distortion temperature: Measured according to ASTM-D-648. Molding shrinkage ratio: Measured according to ASTM-D-955.

Example 1 A 4-necked flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 1,3-dimethyl-2-imidazolidinone (DMI) 25.
0 g, 2,6-dichlorobenzonitrile 20 g (0.116 mol
), 2- (4-aminophenyl) -2- (4'-hydroxyphenyl) propane 55.5 g (0.244 mol), potassium carbonate 20
g (0.145 mol) was added, the temperature was raised to 140 ° C. with stirring, and the mixture was aged at 140 ° C. for 14 hours. After the reaction,
The inorganic salts were removed by cooling to 90 ° C and filtering. 150 g of water was added to the filtrate, cooled to room temperature, and the organic layer was separated. The obtained organic layer was dissolved in 100 g of isopropyl alcohol (IPA), and 200 g of 36% HCl was added to precipitate the hydrochloride. The hydrochloride was recrystallized from 150 g of water / 45 g of IPA and 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzonitrile hydrochloride (p-COBN-M ・
2HCl) was obtained. 90 g of water and 90 g of IPA were dissolved in p-COBN-M.2HCl, 30 g of 28% NH ₄ OH aqueous solution was added to precipitate, and the crystals were separated by filtration and dried to obtain 2,6-bis [4- ( 4-amino-
α, α-Dimethylbenzyl) phenoxy] benzonitrile (p-COBN-M) was obtained. Yield: 62% Yield: 40 g Melting point: 194.1-194.8 ° C 1H-NMR δ (DMSO-d6, ppm) 1.59 (s, 12H) 4.87 (s, 4H) 6.44-6.59 (m, 6H) 6.86-7.50 (m , 13H)

[Chemical 79]

Example 2 A 3-neck flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 1,3-dimethyl-2-imidazolidinone (DMI) 550.
g, 2,6-dichlorobenzonitrile 51.6 g (0.3 mol), 4
-(4-Aminophenoxy) -phenol 126.8 g (0.63 mo
l) and 53.9 g (0.39 mol) of potassium carbonate were respectively introduced, the mixture was heated to 150 ° C. under stirring, and then aged at 150 ° C. for 6 hours. After completion of the reaction, the inorganic salt was removed by cooling to 90 ° C. and filtering. 120 g of water was added to the filtrate and cooled to room temperature for crystallization. The obtained crystals were separated by filtration and recrystallized with DMF / water to obtain the desired product, 2,6-bis [4- (4-aminophenoxy) phenyloxy] benzonitrile (p-PPBN-M). Yield: 68% Yield: 102 g Melting point: 233.3-234.2 ° C 1H-NMR δ (DMSO-d6, ppm) 4.96 (s, 4H) 6.44-6.57 (m, 4H) 6.62-7.15 (m, 8H) 7.19- 7.28 (m, 2H) 7.31 ~ 7.57 (m, 1H)

Embedded image

Example 3 In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 450 g of N, N-dimethylformamide (DMF), 37 g (0.25 mol) of 2,6-dichloropyridine and 2- ( 4-Aminophenyl) -2- (4'-hydroxyphenyl) propane 119.3g
(0.525 mol), potassium carbonate 44.9 g (0.325 mol),
After charging and heating to 150 ° C under stirring,
It was aged at 150 ° C for 28 hours. After the reaction is complete, cool to 90 ° C,
The inorganic salts were removed by filtration. Water in the filtrate
400 g was added, cooled to room temperature, and the organic layer was separated. The obtained organic layer was dissolved in 250 g of isopropyl alcohol (IPA) and 200 g of 36% HCl was added to precipitate a hydrochloride.
The hydrochloride was recrystallized from 150 g of water and 45 g of IPA to give 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] pyridine hydrochloride (p-COP-M · 2HCl). Obtained. p-CO
PM ・ 2HCl is dissolved in 90 g of water and 90 g of IPA, and 28% NH
90 g of ₄ OH aqueous solution was added for neutralization to precipitate crystals, which was filtered and dried to obtain the desired product p-COP-M (yield 83 g,
Yield 63%). The melting point was 123.3-124.7 ° C.

Example 4 2,6-bis [4- (4-amino-α, α-) obtained in Example 1 was placed in a container equipped with a stirrer, a reflux condenser, and a nitrogen introducing tube.
Dimethylbenzyl) phenoxy] benzonitrile 27.69
g (0.05 mol), pyromellitic dianhydride 10.47 g (0.
048 mol), phthalic anhydride 0.592 g (0.004 mol), γ-picoline 0.70 g and m-cresol 152.6 g were charged, and the mixture was heated to 150 ° C. with stirring under a nitrogen atmosphere.
Then, after reacting at 150 ℃ for 4 hours, about 1.
Distillation of 8 ml of water was confirmed. After completion of the reaction, the mixture was cooled to room temperature, discharged into about 1 L of methyl ethyl ketone, and then the polyimide powder was filtered off. After washing this polyimide powder with methyl ethyl ketone, it was heated in air at 50 ° C for 24 hours and then in nitrogen for 220 hours.
34.66 g of polyimide powder (yield 93.8
%) Was obtained. The polyimide powder thus obtained had an inherent viscosity of 0.61 dl / g. The glass transition temperature of this polyimide powder was 264 ° C, and the 5% weight loss temperature was 504 ° C.

The infrared absorption spectrum of this polyimide powder is shown in FIG. This spectrum diagram, the absorption near 1780 cm ^-1 and 1720 cm ^-1 imide characteristic absorption bands were remarkably observed. The elemental analysis values of the obtained polyimide powder were as follows. CHN calculated value (%) 76.71 4.53 5.71 Measured value (%) 77.54 4.63 5.42 When the flow starting temperature of this polyimide powder was measured using a Koka type flow tester, flow was observed at 345 ° C. Furthermore, the molding stability of the polyimide was measured by changing the residence time in the cylinder of the flow tester. Temperature 38
The results at 0 ° C. and a load of 100 kg are shown in FIG. Even if the residence time in the cylinder becomes long, the melt viscosity hardly changes, and it can be seen that the molding stability is good. The strand obtained here was highly flexible.

Examples 5 to 9 By the same method as in Example 4, various polyimide powders were obtained using the diamine component and the acid anhydride component shown in Table 1 (Table 1). Table 1 (Table 1) shows the results of basic physical properties such as diamine component, acid anhydride component, yield, logarithmic viscosity, and Tg together with the results of Example 4.

Example 10 27.69 g (0.05 mo) of 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzonitrile was placed in a flask equipped with a stirrer, a reflux condenser, and a nitrogen introducing tube.
l) and 154.4 g of N, N-dimethylacetamide were charged and pyromellitic dianhydride 10.91 g (0.05 m
ol) was added in portions while paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for about 30 hours. The polyamic acid thus obtained had an inherent viscosity of 0.88 dl / g. Take a part of this polyamic acid solution, cast it on a glass plate, and then
A polyimide film was obtained by heating each at 1 ° C, 200 ° C and 300 ° C for 1 hour. Tg of this polyimide film is 278 ℃
Met. The tensile strength of this film is 10.28 kg.
/ Mm ² , elongation was 9.7%, and tensile modulus was 298 kg / cm ² .

Examples 11 and 12 Various polyimide films were obtained using the diamine component and the acid anhydride component shown in Table 2 (Table 2) by the same method as in Example 10. Table 2 (Table 2) shows the diamine component, the acid anhydride component, the logarithmic viscosity of amic acid, Tg,
The mechanical properties and the results of Example 10 are also shown.

[0074]

[Table 1]

[0075]

[Table 2]

Example 13 The 2,6-bis [4- (4-amino-α, α-) obtained in Example 3 was placed in a container equipped with a stirrer, a reflux condenser, and a nitrogen introducing tube.
Dimethylbenzyl) phenoxy] pyridine 26.49 g (0.0
5 mol), pyromellitic dianhydride 10.47 g (0.048 mo
l), phthalic anhydride 0.592 g (0.004 mol), γ-picoline
0.70 g and m-cresol 147.84 g were charged, and the mixture was heated to 150 ° C. with stirring under a nitrogen atmosphere. Then, after reacting at 150 ℃ for 4 hours, about 1.8 ml
Distillation of water was confirmed. After completion of the reaction, the mixture was cooled to room temperature, discharged into about 1 L of methyl ethyl ketone, and then the polyimide powder was filtered off. After washing this polyimide powder with methyl ethyl ketone, it was heated in air at 50 ° C for 24 hours and then in nitrogen at 220 ° C.
34.23 g of polyimide powder after drying for 4 hours (yield 95.7%)
I got The polyimide powder thus obtained has an inherent viscosity of 0.
It was 57 dl / g. The glass transition temperature of this polyimide powder was 213 ° C, and the 5% weight loss temperature was 492 ° C.

The infrared absorption spectrum of this polyimide powder is shown in FIG. In this spectrum, absorptions at 1780 cm ^-1 and 1720 cm ^-1 , which are the imide characteristic absorption bands, were remarkably observed. The elemental analysis values of the obtained polyimide powder were as follows. CHN calculated value (%) 75.93 4.68 5.90 Measured value (%) 75.10 4.55 6.01 When the flow starting temperature of this polyimide powder was measured using a Koka type flow tester, flow was observed at 390 ° C. The melt viscosity at 400 ° C. for 5 minutes was 350 poise, which proved to be extremely excellent in melt fluidity.

Example 14 The acid anhydride in Example 13 was replaced with pyromellitic dianhydride 1
A polyimide powder was obtained in exactly the same manner as in Example 13 except that the amount of benzophenonetetracarboxylic dianhydride was changed from 0.47 g (0.048 mol) to 15.47 g (0.048 mol). Various physical properties of the obtained polyimide powder are shown in Table 3 (Table 3) together with the results of Example 13. The polyimide powder obtained in this example had a melt viscosity at 320 ° C. of 10300 poises, and the strands obtained here were highly flexible. Further, the molding stability of this polyimide under heat was measured by changing the residence time in the cylinder of the flow tester. Figure 4 shows the results at a temperature of 320 ° C and a load of 100 kg. It can be seen that the melt viscosity hardly changes even if the residence time in the cylinder becomes long.

Example 15 The acid anhydride in Example 13 was converted to pyromellitic dianhydride 1
Example except that 0.47 g (0.048 mol) was changed to 14.12 g (0.048 mol) of biphenyl tetracarboxylic dianhydride
A polyimide powder was obtained in the same manner as in 13. The physical properties of the obtained polyimide powder are shown in Table 3 (Table 3) in Example 13.
The results are shown together with 14 and 14.

Example 16 A polyimide powder was obtained in exactly the same manner as in Example 14 except that phthalic anhydride was not used. Using the obtained polyimide powder, the molding stability under heat was measured in the same manner as in Example 14 while changing the residence time in the cylinder of the flow tester. FIG.
As shown in (1), it can be seen that the melt viscosity increases as the residence time in the cylinder increases.

Example 17 26.49 g (0.05 mol) of 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] pyridine was added to a flask equipped with a stirrer, a reflux condenser, and a nitrogen introducing tube. , N, N-
Dimethylacetamide (170.4 g) was charged and the mixture was placed under a nitrogen atmosphere to obtain 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride.
16.11 g (0.05 mol) was added in portions while paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for about 30 hours. The polyamic acid thus obtained had an inherent viscosity of 1.81 dl / g.
A part of this polyamic acid solution was taken, cast on a glass plate, and then heated at 100 ° C., 200 ° C., and 300 ° C. for 1 hour to obtain a polyimide film. The Tg of this polyimide film was 214 ° C. The tensile strength of this film was 10.17 kg / mm ² , the elongation was 4.6%, and the tensile elastic modulus was 319 kg / cm ² .

Example 18 The acid anhydride of Example 17 was converted from 16.3 g (0.05 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic acid dianhydride to 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride 14.71 g
A polyimide film was obtained in the same manner as in Example 17, except that the content was changed to (0.05 mol). Table 4 (Table 4) shows the acid anhydride component, the logarithmic viscosity of the amic acid, the Tg, and the mechanical properties together with the results of Example 17.

[0083]

[Table 3]

[0084]

[Table 4]

Example 19 The 2,6-bis [4- (4-amino-α, α-) obtained in Example 3 was placed in a container equipped with a stirrer, a reflux condenser, and a nitrogen introducing tube.
Dimethylbenzyl) phenoxy] pyridine 18.54 g (0.0
35 mol), and 4,4'-diaminodiphenyl ether
3.00 g (0.015 mol), pyromellitic dianhydride 10.47
g (0.048 mol), phthalic anhydride 0.592 g (0.004 mol), γ-picoline 0.70 g and m-cresol 128.04 g were charged, and the mixture was heated to 150 ° C. with stirring under a nitrogen atmosphere. Then, when the reaction was carried out at 150 ° C. for 4 hours, it was confirmed that about 1.8 ml of water was distilled off. After completion of the reaction, the mixture was cooled to room temperature, discharged into about 1 L of methyl ethyl ketone, and then the polyimide powder was filtered off. This polyimide powder was further washed with methyl ethyl ketone and then dried in air at 50 ° C for 34 hours and in nitrogen at 220 ° C for 4 hours to obtain polyimide powder 29.11.
g (yield 94.5%) was obtained. The polyimide powder thus obtained had an inherent viscosity of 0.55 dl / g. The glass transition temperature of this polyimide powder is 210 ° C, and the 5% weight loss temperature is
It was 503 ° C. Hereinafter, the flow starting temperature and melt viscosity of this polyimide powder were measured in the same manner as in the above example. The results are shown in Table-5 (Table 5 and Table 6).

Examples 20 to 33 In the same manner as in Example 19, various polyimide powders were obtained by using the diamine component and the acid anhydride component as shown in Table 5 (Table 5 and Table 6). Table-5 (Table 5, Table 6)
Include diamine component, acid anhydride component, logarithmic viscosity, Tg,
The 5% weight loss temperature, melt flow onset temperature, and melt viscosity are shown together with the results of Example 19.

Examples 34 to 44 100 parts by weight of each of the various polyimide powders obtained in the above examples were treated with silane having a fiber length of 3 mm and a fiber diameter of 13 μm (trade name: CS3PE-467S, manufactured by Nitto Boseki Co., Ltd.). Table-
6 (Table 7, Table 8 and Table 9) were added in the respective amounts and mixed in a drum blender mixer (Kawata Manufacturing Co., Ltd.)
After melt-kneading at a temperature of 360 to 440 ° C. by a 30 mm single-screw extruder, the strand was air-cooled and cut to obtain pellets. The obtained pellets were injection molded (injection pressure 500 kg / cm ² , cylinder temperature 360-420 ° C, mold temperature 160-180 ° C) with an injection molding machine (Argburg Allround A-220, manufactured by Arburg, Germany). Various measurement test pieces were obtained and measured. Measured tensile strength (according to ASTM-D-638), bending strength and elastic modulus (ASTM-790), Izod impact strength (notched; ASTM-D-256), heat distortion temperature (ASTM-D-648),
Molding shrinkage (ASTM-D-955) is shown in Table-6 (Table 7, Table 8 and Table 9).

Comparative Examples 1-11 Examples were used except that an amount of glass fiber outside the scope of the present invention was used.
The same operation was performed on 34 to 44 to measure each physical property. The results are shown in Table 6 (Table 7, Table 8 and Table 9) together with the examples.

Examples 45 to 55 For each 100 parts by weight of the various polyimide powders obtained in the above examples, the fiber length was 3 mm, the average diameter was 12 μm, and the Asbect ratio
Table 7 shows a carbon fiber having 250 (trade name: Torayca).
(Table 10, Table 11, Table 12) Each amount shown in addition,
After mixing with a drum blender mixer (Kawata Manufacturing),
After melt-kneading with a single-screw extruder having a diameter of 30 mm at a temperature of 360 to 440 ° C., the strand was air-cooled and cut to obtain pellets. The obtained pellets were injection molded (injection pressure 500 kg / cm ² , cylinder temperature 360-420 ° C, mold temperature 160-180 ° C) with an injection molding machine (Argburg Allround A-220, manufactured by Arburg, Germany). Various measurement test pieces were obtained and measured. Table 7 shows the measured tensile strength, bending strength and elastic modulus, Izod impact strength, heat distortion temperature, and molding shrinkage.
(Table 10, Table 11, Table 12).

Comparative Examples 12-22 Except for using an amount of carbon fiber outside the range of the present invention, Examples 45-
The same operation was performed on 55 to measure each physical property. The results are shown in Table 7 (Table 10, Table 11 and Table 12) together with the examples.

[0091]

[Table 5]

[0092]

[Table 6]

[0093]

[Table 7]

[0094]

[Table 8]

[0095]

[Table 9]

[0096]

[Table 10]

[0097]

[Table 11]

[0098]

[Table 12]

[Brief description of drawings]

1 is an infrared absorption spectrum diagram of the polyimide powder obtained in Example 4. FIG.

FIG. 2 is a result of measurement of a relationship between a residence time in a cylinder of a flow tester of polyimide powder obtained in Example 4 and a change in melt viscosity.

3 is an infrared absorption spectrum diagram of the polyimide powder obtained in Example 13. FIG.

FIG. 4 is a result of measuring a relationship between a residence time in a cylinder of a flow tester of the polyimide powder obtained in Examples 14 and 16 and a change in melt viscosity.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] March 10, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

The aromatic diamino compound of the present invention used for producing the polyimide of the present invention has the general formula (3):

Embedded image An aromatic diamine represented by the formula (wherein L and X are the same as defined above), preferably represented by the formula (3-1)

[Chemical formula 63] Or general formula (3-2)

[Chemical 64] (In the formula, L is the same as the above) and is an aromatic diamino compound. Specifically, for example, 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy]
Pyridine, 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzonitrile, 2,6-bis [4- (4-
Amino-α, α-bistrifluoromethylbenzyl) phenoxy] benzonitrile, 2,6-bis [4- (4-aminophenoxy) phenoxy] benzonitrile, 2,6-bis [4- (4
-Aminobenzoyl) phenoxy] benzonitrile and the like.

Continuation of front page (31) Priority claim number Japanese Patent Application No. 6-160960 (32) Priority Day Hei 6 (1994) July 13 (33) Country of priority claim Japan (JP) (72) Inventor Mitsuo Matsuo 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Tsutomu Ishida 1190, Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Akio Karasawa Sakae, Yokohama-shi, Kanagawa 1190, Kasama-cho, Mitsui within Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Keizaburo Yamaguchi 1190, Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Within Mitsui Toatsu Chemicals, Inc. (72) Akihiro Yamaguchi Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa 1190 Mitsui Toatsu Chemical Co., Ltd.

Claims (15)

[Claims] 1. A compound represented by the general formula (1): (In the formula, L represents an oxygen atom, a carbonyl group, an isopropylidene group or a hexafluoroisopropylidene group, and X is Ar has a carbon number of 6 to 27 and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member. A polyimide having at least one repeating structural unit represented by the formula (4) as an essential structural unit. 2. A compound represented by the general formula (1): At least one repeating structural unit represented by the formula (wherein L, X and Ar are the same as those described above) as an essential structural unit, and the end of the polymer molecule has essentially no substituent, or A polyimide having an aromatic ring substituted with a group having no reactivity with an amine or a dicarboxylic acid anhydride. 3. A compound represented by the general formula (1-1): The polyimide according to claim 1 or 2, which has at least one repeating structural unit represented by the formula (wherein Ar is the same as in the general formula (1)) as an essential structural unit. 4. A compound represented by the general formula (1-2): The polyimide according to claim 1 or 2, which has at least one repeating structural unit represented by the formula (wherein L and Ar are the same as those in the general formula (1)) as an essential structural unit. 5. A compound represented by the general formula (1): (Wherein L, X and Ar are the same as above) and 1 to 100 mol% of the repeating structural unit and the general formula (2): (In the formula, n represents an integer of 0 to 6, Q is a direct bond, -O-, -S-
, -CO-, -SO _2- , -CH _2- , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2-
In the case where there are a plurality of bonding groups Q that connect aromatic rings to each other, the bonding groups may be the same or different combinations. Ar ′ has 6 to 27 carbon atoms and is a monocyclic aromatic group. Group, a condensed polycyclic aromatic group, or a tetravalent group which is a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a cross-linking member). Polyimide or polyimide copolymer containing 0 mol% as an essential structural unit, or the end of the polymer molecule thereof has essentially no substituent,
Alternatively, a polyimide or a polyimide copolymer substituted with a group having no reactivity with an amine or a dicarboxylic acid anhydride. 6. A compound represented by the general formula (3): (In the formula, L represents an oxygen atom, a carbonyl group, an isopropylidene group or a hexafluoroisopropylidene group, and X is And an aromatic diamine mainly composed of at least one aromatic diamino compound represented by the following general formula (4): (In the formula, Ar is a monocyclic aromatic group having 6 to 27 carbon atoms, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member. A tetracarboxylic acid dianhydride represented by the formula (4) is reacted to imidize the resulting polyamic acid thermally or chemically. A method for producing a polyimide having at least one repeating structural unit represented by the formula (wherein L, X and Ar are the same as the above) as an essential structural unit. 7. A compound represented by the general formula (3): An aromatic diamine mainly composed of at least one aromatic diamino compound represented by the formula (wherein L and X are the same as above), and mainly represented by the general formula (4): (Wherein Ar is the same as above), a tetracarboxylic dianhydride represented by the general formula (5) (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are directly or crosslinked with each other. An aromatic dicarboxylic acid anhydride represented by a divalent group which is an aromatic group) or a general formula (6) Z ₁ -NH ₂ (6) (in the formula, Z ₁ has 6 to 15 carbon atoms, An aromatic group represented by a monocyclic aromatic group, a condensed polycyclic aromatic group, or a monovalent group which is a non-condensed polycyclic aromatic group in which aromatic groups are directly or cross-linked with each other) Wherein the polyamic acid obtained is reacted in the presence of a group monoamine to thermally or chemically imidize the compound of the general formula (1) (In the formula, L, X and Ar are the same as the above), at least one of the repeating structural units represented by the formula (1) is contained as an essential structural unit, and the end of the polymer molecule has essentially no substituent. A method for producing a polyimide having an aromatic ring substituted with a group having no reactivity with an amine or a dicarboxylic acid anhydride. 8. A compound represented by the general formula (3): (In the formula, L and X are the same as above) 1 to 0.01 parts by mole of the aromatic diamine, mainly represented by the general formula
(4) [Chemical 17] (In the formula, Ar is the same as above) 1 to 0.01 part by mole of tetracarboxylic dianhydride, and further, the compound represented by the general formula (9): (In the formula, n is an integer of 0 to 6, Q is a direct connection, -O-, -S-, -C
_{O -, - SO 2 -,} -CH 2, -C (CH 3) 2 - or -C (CF _{3) 2} - represents, if the linking group Q linking the aromatic rings is a plurality, they At least one aromatic diamine represented by the same group or different kinds of bonding groups)
0.99 parts by mole and general formula (10): (In the formula, Ar ′ has a carbon number of 6 to 27, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are directly or cross-linked by a bridging member. The method for producing a polyimide or polyimide copolymer according to claim 5, which comprises reacting with 0 to 0.99 parts by mol of a tetracarboxylic dianhydride represented by the formula (which represents a tetravalent group which is an aromatic group). 9. The reaction according to the general formula (5): (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are directly or crosslinked with each other. aromatic dicarboxylic anhydride of 0.001 to 1.0 mol represented by represents a divalent group which is an aromatic group) or the total amount to 1 mole of the aromatic tetracarboxylic dianhydride, the general formula (6) Z ₁ -NH ₂ (6) (In the formula, Z ₁ has 6 to 15 carbon atoms, and a monocyclic aromatic group, a condensed polycyclic aromatic group or an aromatic group is directly or cross-linked to each other. Aromatic monoamine represented by a monovalent group which is a non-fused polycyclic aromatic group)
The method for producing a polyimide or a polyimide copolymer according to claim 8, wherein the polyamic acid obtained is reacted in the presence of 0.001 to 1.0 mol to thermally or chemically imidize the polyamic acid. 10. A compound represented by the general formula (3): An aromatic diamino compound represented by the formula: wherein L and X are the same as defined above. 11. The formula (3-1): Or the general formula (3-2) 11. In the formula, L is the same as the above.
Aromatic diamino compounds of. 12. A compound represented by the general formula (7): (In the formula, L represents an oxygen atom, a carbonyl group, an isopropylidene group or a hexafluoroisopropylidene group) and a hydroxyl group-containing aromatic amino compound represented by the general formula (8) Y-X-Y (8) , X is In which Y represents a halogen atom) and is condensed in the presence of a base in an aprotic polar solvent. (In the formula, L and X are the same as the above), and a method for producing an aromatic diamino compound. 13. 100 parts by weight of the polyimide or polyimide copolymer according to claim 5, carbon fiber, glass fiber,
A polyimide resin composition comprising 5 to 70 parts by weight of a fibrous reinforcing material selected from aromatic polyamide fibers and potassium titanate fibers. 14. An injection-molded article obtained from the polyimide resin composition according to claim 13. 15. A polyimide film containing the polyimide or polyimide copolymer according to claim 5.