JP2000344888A - Crosslinking-group-containing polyimide and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyimide improved especially in mechanical properties and resistances to heat and chemicals by causing a specified proportion of molecular terminals to have crosslinking groups. SOLUTION: This polyimide has crosslinking groups at 1-80 mol% of the molecular terminals. Preferably, the main chain structure of the polyimide is thermoplastic. Preferably, 1-80 mol% of the molecular terminals are crosslinking-group-containing molecular terminals represented by formula I; and 99-20 mol% are molecular terminals containing no crosslinking group, as represented by formula II. The polyimide is preferably melt moldable. In the formulas, Y is a trivalent aromatic group selected from among groups represented by formulas III to VI; T is a divalent aromatic group selected from among groups represented by formulas VII to X; and X is a direct bond or a carbonyl, sulfone, sulfide, ether, isopropylidene, or hexafluoroisopropylidene group. This thermosetting polyimide of a terminal curing type is excellent in sliding-properties, low water absorption, electrical properties, thermal oxidation stability, radiation resistance, etc., in addition to the aforementioned characteristics.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a crosslinkable group-containing polyamic acid or a crosslinkable group-containing polyimide which can be melt-processed, a process for producing the same, and a crosslinked thermoplastic polyimide obtained by heat-treating them. Specifically, polyimide has excellent physical properties inherently, namely, heat resistance, mechanical properties, sliding properties, low water absorption, electrical properties, thermal oxidation stability, chemical resistance, and radiation resistance, among which , Heat-resistant, chemical-resistant, and mechanical properties are significantly improved cross-linked thermoplastic polyimide, and cross-linkable polyimide containing thermoplastic and melt-processable, or cross-linkable polyamic acid that is a precursor thereof As well as their preparation and furthermore their solutions or suspensions.

[0002]

2. Description of the Related Art Conventionally, polyimide has been widely used in various fields as a molding material, a composite material, and an electric / electronic material because it has excellent mechanical properties and electrical properties in addition to its excellent heat resistance. ing.

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

[0004]

Embedded image (Made by DuPont, trade name; Kapton, Vespel) is known. Since this polyimide is non-thermoplastic and insoluble and infusible, there is a great difficulty in molding processability, and there is a problem that mass production of molded products cannot be substantially performed. As a specific processing method, after obtaining a lump using a special molding method called powder sintering molding, mechanical processing such as cutting, cutting, or polishing is performed, thereby obtaining a molded product.

As an amorphous thermoplastic polyimide having improved moldability, a compound represented by the formula (B)

[0006]

Embedded image (Ultem, trade name, manufactured by General Electric Co., Ltd.) are known (US Pat. Nos. 3,847,867 and 3,847,869). However, this polyimide is soluble in amide-based aprotic polar solvents and halogenated hydrocarbon-based solvents and has poor chemical resistance. Further, the glass transition temperature is 215 ° C.,
Depending on the application, further improvement in heat resistance is desired.

Further, a formula (C) having moldability is provided.

[0008]

Embedded image Since the polyimide represented by the formula has a melting point at 385 ° C. while maintaining the properties inherent to polyimide, it exhibits melt fluidity at a temperature higher than the melting point and can be melt-molded (US Pat. No. 5,043,419). . However, although the glass transition temperature of this polyimide is relatively high at 250 ° C., use at a temperature above this temperature causes a remarkable deterioration in properties accompanied by deformation and softening, so that further improvement may be desired depending on the application. Further, the polyimide is inferior in chemical resistance particularly under stress, and therefore, its improvement is strongly desired.

The properties of thermoplastic polyimides depend on the skeleton structure of the polyimides.
Various polyimides have been selected in consideration of the inherent properties of polyimide, such as moldability, mechanical properties, and chemical resistance. However, depending on the application, individual performance may be insufficient, and improvement of the various characteristics described above is desired.

On the other hand, various thermosetting polyimides have been developed and marketed. As a representative example thereof, the formula (D)

[0011]

Embedded image A polyimide obtained from the monomers represented by the following formula (Rhone Poulin Co., trade name; kerimide-
601, F.R. D. Darmory, National
SAMPE Symposium, p. 693, 19th
(1974)). Since this polyimide is thermosetting, it is less likely to be deformed or softened than a thermoplastic polyimide, so that it can be used at a high temperature. However, this polyimide has poor mechanical properties, especially not much toughness, and is weak against external forces such as impact. In addition, since it is thermosetting, melt molding cannot be performed, and it is necessary to perform shaping at the prepolymer stage before curing, and then perform heat treatment.

Further, for the purpose of improving the mechanical properties which have been a drawback of these thermosetting polyimides, there is known a method in which a linear polyimide is used as a main chain and a crosslinking member is introduced into a terminal or a substituent. . For example, US Pat.
No. 028, US Pat. No. 5,478,915, US Pat. No. 5,493,002, US Pat. No. 5,567,800.
No. 5,644,022, U.S. Pat.
No. 2,066, U.S. Pat. No. 5,606,014.

The technical contents are described, for example, in US Pat.
No. 567,800 includes the formula (E)

[0014]

Embedded image Obtained from monomers and a terminal blocking agent represented by
A thermosetting polyimide obtained by heat-treating an imide oligomer having a carbon-carbon triple bond at a molecular terminal is disclosed. Although polyimide disclosed in this patent has excellent physical properties, it can not be melt molded,
It is limited to processing using a solution of a polyamic acid as a precursor. Usually, after shaping with a polyamic acid solution, solvent removal and dehydration imidization reaction are performed by heating. Since the processing involves solvent removal, it is impossible to obtain a thick normal molded product, and the shape of the film or sheet is limited. Problems arise.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide, for each of a variety of known thermoplastic polyimide backbone structures,
Formability, sliding properties, low water absorption,
Crosslinking of the main chain structure, which has significantly better heat resistance, chemical resistance, and mechanical properties than known polyimides having this structure without impairing features such as electrical properties, thermal oxidation stability, and radiation resistance. It is to provide a group-containing polyimide.

The heat resistance, chemical resistance, and mechanical properties, which are one of the problems to be solved by the present invention, specifically indicate, for example, the following physical property values and test results. Typical examples of heat resistance include glass transition temperature, softening temperature in thermomechanical analysis, deflection temperature under load, mechanical properties at high temperatures, retention of mechanical properties in thermal cycle tests, solder heat resistance test, fire resistance test, heated air aging. Tests, etc., among which the problems to be solved by the present invention include, in particular, the deflection temperature under load, the mechanical properties at high temperatures, and the retention rate of the mechanical properties in a heat cycle test. Typical examples of chemical resistance include a solvent solubility test, a solvent immersion test, a solvent immersion test under stress, and various physical property retention rates after immersion in a solvent. Examples thereof include a solvent immersion test under stress and a retention of mechanical properties after immersion in a solvent under stress. Typical mechanical properties include tensile tests,
Compression test, bending test, Izod impact test, fatigue test,
And the like. Among them, the problems to be solved by the present invention include yield strength, tensile modulus, flexural modulus, Izod impact value and the like in a tensile test.

From another point of view, the problems to be solved by the present invention are as follows: excellent physical properties inherent in the terminal-curing type thermosetting polyimide, that is, sliding properties,
It has low water absorption, electrical properties, thermo-oxidative stability, heat resistance, chemical resistance and mechanical properties, and has high moldability that could not be achieved with conventional end-cured polyimides. Another object of the present invention is to provide a crosslinked group-containing polyimide.

Still another object of the present invention is to provide a cross-linking group-containing polyimide which is thermoplastic and can be melt-molded, or a cross-linking group-containing polyamic acid which is a precursor thereof. It is still another object of the present invention to provide a method of manufacturing the same.

According to the present invention, the crosslinkable group-containing polyimide of the present invention can be melt-molded and processed even though it has a crosslinkable crosslinkable group. Is an important feature.
This is completely different from conventional thermosetting resins with crosslinking. The present invention is an invention based on a novel concept that has never been achieved, and achieves the reciprocal events of intermolecular crosslinking and melt flow.

[0020]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, the molecular terminal has a crosslinking group-containing dicarboxylic anhydride of 1 to 80 mol%,
Dicarboxylic anhydride having no crosslinking group 99 to 20 mol%
The cross-linking group-containing polyimide sealed with and achieves the above object, especially heat resistance, chemical resistance, and that the mechanical properties are more remarkably improved and can be melt-molded despite being extremely excellent. We have found and completed the present invention.

That is, the present invention provides the following (1) to (3)
5).

(1) A polyimide containing a cross-linking group, which has a cross-linking group at 1 to 80 mol% of the molecular terminal.

(2) The cross-linking group-containing polyimide according to claim 1, wherein the main chain structure constituting the cross-linking group-containing polyimide has essentially thermoplasticity.

(3) 1 to 80 mol% of the molecular terminal is a cross-linking group-containing molecular terminal represented by the chemical formula (2a),
And 99 to 20 mol% of the molecular terminals are represented by the chemical formula (2b)
The cross-linkable group-containing polyimide according to (1) or (2), which is a molecular terminal containing no cross-linking group represented by the formula:

[0025]

Embedded image (Y in the formula is

[0026]

Embedded image (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Represents a trivalent aromatic group selected from

[0027]

Embedded image (T in the formula is

[0028]

Embedded image (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Represents a divalent aromatic group selected from

(4) It comprises a polyimide molecule having a structure represented by the chemical formula (2c): (1)
A polyimide containing a crosslinking group according to any one of (1) to (3).

[0030]

Embedded image (In the formula, T, PI, and Y are each a group shown below. That is, T is

[0031]

Embedded image (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Represents a divalent aromatic group selected from PI, PI represents a polyimide main chain, and Y represents

[0032]

Embedded image (Wherein, X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group) Shows selected trivalent aromatic group)

(5) In the chemical formula (2b) or (2c), T is a chemical formula (2d),
The crosslinkable group-containing polyimide according to (3) or (4).

[0034]

Embedded image

(6) The polyimide containing a crosslinking group according to any one of (3) to (5), wherein in the chemical formula (2a) or (2c), Y is the chemical formula (2e).

[0036]

Embedded image

(7) The polyimide main chain is represented by the chemical formula (1)
The cross-linking group-containing polyimide according to any one of (1) to (6), which has a repeating structural unit represented by:

[0038]

Embedded image (Wherein, Ar and R are each a group as shown below. That is, Ar in the formula is

[0039]

Embedded image (Wherein, J represents a divalent linking group selected from the group consisting of a carbonyl group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group; K represents a direct bond;
A carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a divalent linking group selected from the group consisting of hexafluorinated isopropylidene groups,
p and q are each independently 0 or 1. Further, the position of the bonding group in which the bonding position is not determined in the formula is a para-position or a meta-position), and represents a divalent aromatic group selected from the group consisting of:

[0040]

Embedded image (Wherein G is a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent aromatic group selected from the group consisting of a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group, and a 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy group; Represents a tetravalent aromatic group selected from the group consisting of

(8) In the repeating structural unit represented by the chemical formula (1), 50 to 100 mol% is represented by the chemical formula (1)
The cross-linking group-containing polyimide according to (7), which has a repeating unit structure represented by (a).

[0042]

Embedded image (Wherein G represents a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent aromatic group selected from the group consisting of a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group, and a 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy group; )

(9) In the chemical formula (1a), G is
The polyimide containing a crosslinking group according to (8), which is a 4'-oxy-4-biphenoxy group.

(10) In the chemical formula (1a), G
Is a 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy group, the polyimide containing a crosslinking group according to (8).

(11) In the above (7), 50 to 100 mol% of the repeating structural units represented by the chemical formula (1) is a repeating unit structure represented by the chemical formula (1b). The crosslinked group-containing polyimide described.

[0046]

Embedded image (Wherein X and R are each a group as shown below: X in the formula is a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group. A divalent linking group selected from the group consisting of a redene group, wherein R in the formula is

[0047]

Embedded image (Wherein G is a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent aromatic group selected from the group consisting of a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group, and a 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy group; ) Represents a tetravalent bonding group selected from the group consisting of: In addition, the position of the bonding group in which the bonding position is not determined is at the para-position or the meta-position.)

(12) In the chemical formula (1b), X
Is an oxygen atom, the bonding positions of the two benzenes to which X is directly bonded to the imide groups are m-position and p-position, respectively, and R is 3,4,3 ′ , 4′-substituted biphenyl, the polyimide containing a crosslinking group according to (11).

(13) The repeating structural unit represented by the chemical formula (1), wherein 50 to 100 mol% of the repeating structural unit represented by the chemical formula (1c) is a repeating unit structure represented by the chemical formula (1c). The crosslinked group-containing polyimide described.

[0050]

Embedded image (Wherein X and R are each a group as shown below: X in the formula is a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group. A divalent linking group selected from the group consisting of a redene group, wherein R in the formula is

[0051]

Embedded image (Wherein G is a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent aromatic group selected from the group consisting of a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group, and a 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy group; ) Represents a tetravalent bonding group selected from the group consisting of: In addition, the position of the bonding group in which the bonding position is not determined is at the para-position or the meta-position.)

(14) In the chemical formula (1c), X
Is a cross-linking group-containing polyimide according to (13), wherein

(15) In the chemical formula (1c), X
Is an oxygen atom, the bond position of the benzene ring to which two Xs are directly bonded is the m-position, and the bond position of the two benzenes to which X and the imide group are directly bonded is Is a p-position and R is 3,4,3 ′, 4′-substituted biphenyl, wherein the polyimide containing a crosslinking group according to (13).

(16) Of the repeating structural units represented by the chemical formula (1), 50 to 100 mol% are the repeating unit structures represented by the chemical formula (1e). The crosslinked group-containing polyimide described.

[0055]

Embedded image (In the formula, Q, Z, and R are each a group shown below. That is, Q represents a divalent aromatic group selected from the group consisting of an ether group and an isopropylidene group. Wherein Z is a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group,
And a hexafluorinated isopropylidene group, and

[0056]

Embedded image Represents a divalent aromatic group selected from the group consisting of: wherein R in the formula is

[0057]

Embedded image (Wherein G is a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent aromatic group selected from the group consisting of a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group, and a 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy group; ) Represents a tetravalent aromatic group selected from the group consisting of: In addition, the position of the bonding group in which the bonding position is not determined is at the para-position or the meta-position.)

(17) In the chemical formula (1e), Q
Is an oxygen atom, and Z is at least one divalent selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group. The polyimide containing a crosslinking group according to (16), which is a group represented by the formula:

(18) In the chemical formula (1e), Q
Is an oxygen atom, Z is a direct bond, R is
The crosslinkable group-containing polyimide according to (16), which is a 1,2,4,5-substituted benzene.

(19) The terminal of the polyimide main chain is end-blocked by using a dicarboxylic anhydride represented by the chemical formula (3a) or (3b) as a terminal capping agent. 1 to 80 mol% of the molecular terminals are the crosslinkable group-containing molecular terminals represented by the chemical formula (2a), and 99 to 20 mol% of the molecular terminals are the crosslinkable groups represented by the chemical formula (2b). A method for producing a polyimide containing a crosslinkable group, which can be melt-molded and processed, characterized in that it is a molecular terminal not containing.

[0061]

Embedded image (Y in the formula is

[0062]

Embedded image (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Represents a trivalent aromatic group selected from

[0063]

Embedded image (T in the formula is

[0064]

Embedded image (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Represents a divalent aromatic group selected from

[0065]

Embedded image (Y in the formula is

[0066]

Embedded image (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Represents a trivalent aromatic group selected from

[0067]

Embedded image (T in the formula is

[0068]

Embedded image (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Represents a divalent aromatic group selected from

(20) Chemical formula (3a) and chemical formula (3
The crosslinking group according to (19), wherein the amount of the dicarboxylic anhydride represented by b) is represented by (Formula 1) [Equation 1] on a molar ratio basis. Production method of contained polyimide. 1/99 ≦ [dicarboxylic anhydride represented by chemical formula (3a)] / [dicarboxylic anhydride represented by chemical formula (3b)] ≦ 80/20 (Formula 1)

[0070]

Embedded image (Y in the formula is

[0071]

Embedded image (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Represents a trivalent aromatic group selected from

[0072]

Embedded image (T in the formula is

[0073]

Embedded image (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Represents a divalent aromatic group selected from

(21) In the chemical formula (3a) and / or the chemical formula (3b), T represents the chemical formula (2d) and / or Y
Is a chemical formula (2e), The manufacturing method of the polyimide containing a crosslinking group as described in (19) or (20) characterized by the above-mentioned. Bridge-containing polyimide.

[0075]

Embedded image

[0076]

Embedded image

(22) Polyamide acid, which is a polyimide precursor obtained by polymerizing a diamine component and a tetracarboxylic anhydride component in a polyimide main chain, is thermally and / or chemically imidized. The method for producing a cross-linking group-containing polyimide according to any one of (19) to (21), which is obtained.

(23) The diamine component is represented by the chemical formula (4)
At least one selected from the diamine component group represented by
The method according to (22), which is a seed.

[0079]

Embedded image (Where Ar is

[0080]

Embedded image (Wherein, J represents a divalent linking group selected from the group consisting of a carbonyl group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group; K represents a direct bond;
A carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a divalent linking group selected from the group consisting of hexafluorinated isopropylidene groups,
p and q are each independently 0 or 1. The position of the bonding group in which the bonding position is not determined in the formula is a para-position or a meta-position), which indicates a divalent aromatic group selected from the group consisting of:

(24) In the diamine component represented by the chemical formula (4), 50 to 100 mol% is represented by the chemical formula (4)
(23) characterized by being represented by c)
3. The method for producing a polyimide containing a cross-linking group described in 1. above.

[0082]

Embedded image (In the formula, X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group. The position of the bonding group in which the bonding position is not determined is in the para or meta position.)

(25) In the chemical formula (4c), X
Is a oxygen atom, The manufacturing method of the polyimide containing a crosslinking group as described in (24).

(26) In the chemical formula (4c), X
Is an oxygen atom, the bonding position of the benzene ring to which two Xs are directly bonded is at the m-position, and the bonding position of the two benzenes to which X and the amino group are directly bonded are both p −
(24). The method for producing a polyimide containing a cross-linking group according to (24).

(27) The crosslinking group according to (24), wherein 50 to 100 mol% of the diamine component represented by the chemical formula (4) is represented by the chemical formula (4d). Production method of contained polyimide.

[0086]

Embedded image (In the formula, X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group.)

(28) In the chemical formula (4d), X
Is a direct bond, the method for producing a polyimide containing a crosslinking group according to (27).

(29) The production method according to (22), wherein the tetracarboxylic dianhydride component is represented by the chemical formula (5).

[0089]

Embedded image (Where R is

[0090]

Embedded image (Wherein G is a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent aromatic group selected from the group consisting of a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group, and a 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy group; Represents a tetravalent linking group selected from the group consisting of

(30) Melting while holding at a temperature T [° C.] for 5 minutes, and a melt viscosity MV 5 (T) [Pa · sec] measured at an arbitrary constant shear stress in the range of 0.1 to 1 [MPa]. And kept at a temperature T [° C.] for 30 minutes to be melted.
When the melt viscosity is MV30 (T) [Pa · sec] measured at an arbitrary constant shear stress in the range of 1 [MPa],
The crosslinkable group-containing polyimide according to any one of (1) to (18), wherein there is a temperature T that satisfies (Formula 2) and (Formula 3) at the same time. [Equation 2] 1 ≦ MV30 (T) / MV5 (T) ≦ 10 (Equation 2) [Equation 3] 10 ≦ MV5 (T) ≦ 10000 (Equation 3)

(31) Melting while holding at a temperature T [° C.] for 5 minutes, and a melt viscosity MV 5 (T) [Pa · sec] measured at an arbitrary constant shear stress in the range of 0.1 to 1 [MPa]. And kept at a temperature of T + 20 [° C.] for 5 minutes to melt.
The melt viscosity is MV5 (T + 20) [Pa · sec] measured at an arbitrary constant shear stress in the range of 1 to 1 [MPa]. 1 [MP
a] Melt viscosity M measured at any constant shear stress in the range of
V30 (T) [Pa · sec], temperature T + 20 [° C]
At a constant shear stress in the range of 0.1 to 1 [MPa].
20) any of (1) to (18), wherein, when [Pa · sec], there is a temperature T that simultaneously satisfies (Equation 2), (Equation 3) and (Equation 4). The crosslinkable group-containing polyimide described in 1. [Equation 4] 1 ≦ MV30 (T) / MV5 (T) ≦ 10 (Equation 2) [Equation 5] 10 ≦ MV5 (T) ≦ 10000 (Equation 3) [Equation 6] MV30 (T + 20) / MV5 ( T + 20) ≦ 20 (Equation 4)

(32) Melting was carried out at 360 ° C. for 5 minutes, and the melt viscosity MV5 (360) [Pa · sec] measured at an arbitrary constant shearing stress in the range of 0.1 to 1 [MPa].
And kept at 360 [° C.] for 30 minutes to melt,
When the melt viscosity is MV30 (360) [Pa · sec] measured at an arbitrary constant shear stress in the range of １1 [MPa], (Equation 5) and (Equation 6) are simultaneously satisfied, (1) The polyimide containing a crosslinking group according to any one of (1) to (18). [Equation 7] 1 ≦ MV30 (360) / MV5 (360) ≦ 10 (Equation 5) [Equation 8] 10 ≦ MV5 (360) ≦ 10000 (Equation 6)

(33) When the storage elasticity after the time t [minutes] measured at 360 ° C. and 1 Hz elapses is represented by G ′ (t), and the loss elasticity is expressed by G ″ (t), The crosslinkable group-containing polyimide according to any one of (1) to (18), wherein the filled t [minute] is 10 [minutes] or more, [Equation 9] G ′ (t) = G ″ ( t) (Equation 7)

(34) (1) to (18) and (3)
A crosslinked polyimide obtained by heat-treating the crosslinkable group-containing polyimide according to any one of (0) to (33).

(35) (1) to (18) and (3)
A solution or suspension containing the cross-linking group-containing polyimide according to any one of 0) to (33).

[0097]

BEST MODE FOR CARRYING OUT THE INVENTION The polyimide of the present invention is a cross-linking group-containing polyimide having a cross-linking group at 1 to 80 mol% of the molecular terminals.

[Molecular end] Here, the molecular end refers to a molecular end not included in the repeating structural unit in the polyimide molecular chain, and typically corresponds to "-End" in the general chemical formula (6a). . When two types of units A and B are present in the repeating structural unit as described in general chemical formula (6b), and one unit (A in this case) is more than one, the molecular terminal is Specifically, it corresponds to "-End" in the general chemical formula (6b). Note that "-E
It is assumed that the structure of “nd” does not include the structural units of A and B.

[0099]

Embedded image

[Cross-Linking Group] The cross-linking group means that a certain bond is formed between molecular chains by a reaction between the cross-linking groups or a cross-linking group and a group in the polyimide main chain under specific cross-linking conditions. Shows the groups that can be obtained. In the present invention, the crosslinking group is present at the molecular end of the polyimide chain. The crosslinking conditions are not limited,
Known crosslinking reactions such as heat curing and light curing can be applied. In addition, a cross-linking group which can be applied under such a condition that the polyimide main chain is not decomposed under the cross-linking condition is preferable in use. In the case of a crosslinking group in which the crosslinking group reacts with a group in the polyimide main chain, the group used as the crosslinking group differs depending on the polyimide main chain used.

As the crosslinking group, known ones can be arbitrarily selected and used. The type of the cross-linking group is not limited, but typical examples include an ethynyl group, a benzocyclobuten-4′-yl group, a vinyl group, an allyl group, a cyano group, an isocyanate group, a nitrilo group, an amino group, Examples include an isopropenyl group, a vinylene group, a vinylidene group, an ethynylidene group, and a biphenylenyl group.

[Molecular Terminal Having Preferred Crosslinking Group] The molecular terminal having a crosslinkable group used in the present invention is preferably one represented by the above general formula (2a).
The polyimide of the present invention has a total number of terminal groups of 1 to 8 in the polymer chain.
0 mol% is this cross-linking group-containing terminal group, and 99 to
20 mol% is a terminal group having no crosslinking group, preferably a terminal group having no crosslinking group represented by the chemical formula (2b). As the terminal structure represented by the general chemical formula (2a), specifically,

[0103]

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[0104]

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[0105]

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[0106]

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Is exemplified. The cross-linking group-containing terminal group is not limited to these, and any known one may be used.
It can be used alone or in combination.

As the most preferred cross-linking group-containing terminal group, those in which Y is the above-mentioned chemical formula (2e) in the above-mentioned general chemical formula (2a) are used. In particular,

[0109]

Embedded image It is.

[Molecule Terminal Having No Crosslinking Group] The crosslinkable group-containing polyimide of the present invention is used in an amount of 1 to 80 mol% of the molecular terminal.
Is characterized by having a cross-linking group, and 99 to 20 mol% of the molecular terminals are molecular terminals having no cross-linking group. The molecular terminal without a cross-linking group, the molecular terminal between each other, or the molecular terminal and the group in the polyimide main chain,
It is a molecular terminal group that does not react under any conditions, such as molding and post-treatment steps, and cannot generate any kind of bond between molecular chains.

[Case where a molecular terminal having a cross-linking group functions as a molecular terminal having no cross-linking group] In the present invention, as described above, a molecular terminal having no cross-linking group refers to a molecular terminal having no cross-linking process or a post-processing step. Since it indicates a molecular terminal group that cannot be crosslinked under any of the conditions, the structure that becomes a crosslinkable group under certain conditions may not have a crosslinkable group when used under mild conditions. Can function as

[Preferable molecular terminal having no cross-linking group] The molecular terminal having no preferable cross-linking group may be any of those having a known structure, singly or as a mixture, and is not limited. The one represented by the chemical formula (2b) is used. Most preferably, in the chemical formula (2b), T is the chemical formula (2d). In particular,

[0113]

Embedded image It is.

[Quantitative Ratio of Molecular Terminal Having Crosslinking Group to Molecular Terminal Having No Crosslinking Group] The present invention relates to a polyimide containing a crosslinking group, which has a crosslinking group at 1 to 80 mol% of the molecular terminal. is there. Therefore, the molar ratio of the molecular terminal having a cross-linking group to the molecular terminal having no cross-linking group is [E'1], and the molar amount of the molecular terminal having no cross-linking group is [E'1]. [2], 1/99 ≦ [E′1] / [E′2] ≦ 80/2
It must be in the range of 0. If the value of [E'1] / [E'2] is less than 1/99 outside this range, the crosslink density is not sufficient, and the improvement in chemical resistance, heat resistance and mechanical properties becomes insufficient. '1] / [E'2] is 80 /
If it exceeds 20, the crosslink density is sufficient, but the viscosity rise during molding is so large that melt molding cannot be performed.

The range of the value of [E'1] / [E'2] must be properly selected according to the molding conditions. Generally, preferably, 5/95 ≦ [E′1] / [E′2] ≦ 70/3.
0, more preferably 10/90 ≦ [E′1] / [E′2] ≦ 70 /
30.

Although the range of the more preferable value varies depending on the processing method, it is more preferable in the batch-type molding method that the stagnation occurs in a molten state such as press molding, for example. 30/70 ≦ [E′1] / [E′2] ] ≦ 70 /
30 and most preferably 40/60 ≦ [E′1] / [E′2] ≦ 60 /
40. Further, for example, in a molding method such as injection molding or extrusion molding which requires continuous operation with stagnation in a molten state, preferably 10/90 ≦ [E′1] / [E′2] ≦ 50 /
50, most preferably 20/80 ≦ [E′1] / [E′2] ≦ 40 /
60. Further, for example, in a molding method in which stagnation in a molten state is small, preferably 20/80 ≦ [E′1] / [E′2] ≦ 60 /
40, and most preferably 30/70 ≦ [E′1] / [E′2] ≦ 50 /
50.

[Structure of cross-linking group-containing polyimide] The main chain structure of the cross-linking group-containing polyimide of the present invention is a known polyimide used alone, mixed at an arbitrary ratio, or copolymerized at an arbitrary ratio. .

[Structure of Preferred Crosslinking Group-Containing Polyimide-
(1)] The main chain structure of the cross-linking group-containing polyimide of the present invention is not limited, but preferably the main chain structure of the cross-linking group-containing polyimide is essentially thermoplastic. It is a group-containing polyimide.

[What essentially has thermoplasticity] Here, that a certain main chain structure has essentially thermoplasticity means that the main chain structure shows thermoplasticity as a characteristic. This shows that a polyimide having no crosslinking group-containing terminal obtained by polymerizing the polyimide having the main chain structure with an excess of diamine and closing the polyimide molecular chain terminal with a stoichiometric amount or more of phthalic anhydride exhibits thermoplasticity.

[Structure of Preferred Crosslinking Group-Containing Polyimide-
(2)] Further, the polyimide is preferably a crosslinkable group-containing polyimide that can be melt-molded.

[Melting Molding] Here, the term "melting molding" refers to a processing method involving the flow of resin in a molten state in at least one step of polyimide molding. The molten state of the polyimide can be realized only at a temperature higher than the crystal melting temperature or the glass transition temperature. In order for the resin to be able to flow, it is necessary to have an appropriate melt viscosity in accordance with the shear stress depending on the processing method. In addition,
Temperature, shear stress and melt viscosity vary depending on the processing method. Processing methods include, for example, extrusion, injection molding, compression molding, blow molding, vacuum molding, rotational molding, reaction injection molding,
Lamination molding, casting and the like.

[Melt Viscosity Change] In order to carry out processing continuously and continuously, the melt viscosity change needs to be small. The term “melt viscosity change” refers to a change in viscosity when maintained at a processing temperature and a processing shear stress.

[Melt Viscosity] From the above, although the viscosity of the polyimide of the present invention is not limited, it is preferable that the polyimide be melted by keeping it at a temperature T [° C.] for 5 minutes.
A melt viscosity MV5 (T) [Pa · sec] measured at an arbitrary constant shear stress in the range of 0.1 to 1 [MPa] is maintained at a temperature T [° C] for 30 minutes to melt. 1 [MP
a] Melt viscosity M measured at any constant shear stress in the range of
When V30 (T) [Pa · sec], (Equation 2)
Is a cross-linking group-containing polyimide having a temperature T that simultaneously satisfies (Formula 3) and (Formula 3), and 1 ≦ MV30 (T) / MV5 (T) ≦ 10 (Formula 2) 10 ≦ MV5 (T) ≦ 10000 (Formula 3) Preferably, the melt is held at a temperature T [° C.] for 5 minutes to be melted, and has a melt viscosity MV5 (T) [Pa · sec] measured at an arbitrary constant shear stress in a range of 0.1 to 1 [MPa].
The temperature is kept at T + 20 [° C.] for 5 minutes and melted.
Melt viscosity MV5 (T + 20) [Pa · sec] measured at an arbitrary constant shear stress in the range of 1 [MPa], and temperature T
[° C.] for 30 minutes to melt, 0.1 to 1 [MP
a] Melt viscosity M measured at any constant shear stress in the range of
V30 (T) [Pa · sec], temperature T + 20 [° C]
For 30 minutes, and melted at an arbitrary constant shear stress in the range of 0.1 to 1 [MPa].
20) A cross-linking group-containing polyimide characterized by having a temperature T that satisfies (Equation 2), (Equation 3) and (Equation 4) at the same time when [Pa · sec], and 1 ≦ MV30 ( T) / MV5 (T) ≦ 10 (Equation 2) 10 ≦ MV5 (T) ≦ 10000 (Equation 3) MV30 (T + 20) / MV5 (T + 20) ≦ 20 (Equation 4) Most preferably, the temperature T [° C.] for 5 minutes to melt, and a melt viscosity MV5 (T) [Pa · sec] measured at an arbitrary constant shear stress in the range of 0.1 to 1 [MPa].
The temperature is kept at T + 20 [° C.] for 5 minutes and melted.
Melt viscosity MV5 (T + 20) [Pa · sec] measured at an arbitrary constant shear stress in the range of 1 [MPa], and temperature T
[° C.] for 30 minutes to melt, 0.1 to 1 [MP
a] Melt viscosity M measured at any constant shear stress in the range of
V30 (T) [Pa · sec], temperature T + 20 [° C]
For 30 minutes, and melted at an arbitrary constant shear stress in the range of 0.1 to 1 [MPa].
20) A polyimide containing a crosslinking group, characterized in that there is a temperature T that satisfies (Equation 2), (Equation 3) and (Equation 4b) at the same time when [Pa · sec] is satisfied. 1 ≦ MV30 (T) / MV5 (T) ≦ 10 (Equation 2) 10 ≦ MV5 (T) ≦ 10000 (Equation 3) MV30 (T + 20) / MV5 (T + 20) ≦ 10 (Equation 4b)

In the case where a cross-linking group-containing terminal group having a structure represented by the general formula (2) is used, considering that the cross-linking condition of the cross-linking group is about 360 ° C. or higher, the above ( The range of the temperature T [° C.] that satisfies the equations (2), (3), (4) and (4b) is 3
Preferably, the temperature is 60 ° C.

In other words, the melt is held at 360 ° C. for 5 minutes and melted, and the melt viscosity MV5 (360) [Pa · se] measured at an arbitrary constant shear stress in the range of 0.1 to 1 MPa.
c] and held at 360 [° C.] for 30 minutes to melt,
When the melt viscosity is MV30 (360) [Pa · sec] measured at an arbitrary constant shearing stress in the range of 0.1 to 1 [MPa], the crosslinking group content satisfying (Equation 5) and (Equation 6) at the same time 1 ≦ MV30 (360) / MV5 (360) ≦ 10 (Equation 5) 10 ≦ MV5 (360) ≦ 10000 (Equation 6) More preferably, it is held at 360 [° C.] for 5 minutes to melt it. The melt viscosity is MV5 (360) [Pa · sec] measured at an arbitrary constant shear stress in the range of 0.1 to 1 [MPa], and the melt is held at 380 [° C] for 5 minutes to melt.
The melt viscosity measured at an arbitrary constant shear stress in the range of [MPa] is MV5 (380) [Pa · sec] and 360 [° C.].
At a constant shear stress in the range of 0.1 to 1 [MPa].
0) [Pa · sec], melted while maintaining at 380 [° C.] for 30 minutes, and melt viscosity MV30 (380) [Pa · sec] measured at an arbitrary constant shear stress in the range of 0.1 to 1 [MPa].
sec], it is a polyimide containing a crosslinking group that simultaneously satisfies (Equation 5), (Equation 6) and (Equation 8), and 1 ≦ MV30 (360) / MV5 (360) ≦ 10 (Equation 5) 10 ≦ MV5 (360) ≦ 10000 (Equation 6) MV30 (380) / MV5 (380) ≦ 20 (Equation 8) Most preferably, it is kept at 360 [° C.] for 5 minutes to be melted, and 0.1 to 1 [MPa]. The melt viscosity was MV5 (360) [Pa · sec] measured at an arbitrary constant shearing stress in the range of 1 to 3 and held at 380 [° C] for 5 minutes to melt.
The melt viscosity measured at an arbitrary constant shear stress in the range of [MPa] is MV5 (380) [Pa · sec] and 360 [° C.].
At a constant shear stress in the range of 0.1 to 1 [MPa].
0) [Pa · sec], melted while maintaining at 380 [° C.] for 30 minutes, and melt viscosity MV30 (380) [Pa · sec] measured at an arbitrary constant shear stress in the range of 0.1 to 1 [MPa].
sec], the cross-linking group-containing polyimide simultaneously satisfies (Equation 5), (Equation 6) and (Equation 8b). 1 ≦ MV30 (360) / MV5 (360) ≦ 10 (Equation 5) 10 ≦ MV5 (360) ≦ 10000 (Equation 6) MV30 (380) / MV5 (380) ≦ 10 (Equation 8b)

[Measurement Method of Melt Viscosity] The method of measuring the melt viscosity is not particularly limited.
Koka type flow tester (for example, Shimadzu Corporation CFT50
0A) orifice 1.0mm (diameter) x 10mm
(Long), it can be measured under the condition of a load of 100 kgf. In this case, the shear stress (Tw) [Pa]
The calculated values are obtained by calculating the apparent shear stress of the tube wall. The calculated values are as follows: the extrusion pressure is P [Pa], the nozzle diameter (diameter) is 2R [cm], and the nozzle length is Lc [c].
m], it is known that Tw = P × R / 2Lc. (According to the Rheology Committee of the Society of Polymer Science, based on “Rheology Measurement Method”), the shear stress in this measurement method is 0.245 [MPa].

[Geling time] Another parameter indicating whether or not melt flow is possible is the gelling time. The gelation time at a certain temperature means that the storage elastic modulus after a lapse of time t [minutes] measured at a certain frequency at that temperature is represented by G ′ (t), and the loss elastic modulus is represented by G ″ (t). G ′ (t) = G ″ (t) (Formula 7) The sample temperature and the measurement frequency when the gelation time is measured based on the processing method and the characteristics of the resin need to be changed. Although not limited, in the case of the polyimide of the present application, the gel time measured at a sample temperature of 360 ° C. and a constant temperature of 1 Hz is preferably 10 minutes or more, and more preferably 20 minutes or more. is there. The method for measuring the storage elastic modulus and the loss elastic modulus is not particularly limited, for example, using a melt viscoelasticity measuring device (for example, RDS-II, Rheometrics Co.)
It can be measured with a parallel plate (for example, 25 mm disposable).

[Structure of Preferred Crosslinking Group-Containing Polyimide-
(3)] The cross-linking group-containing polyimide of the present invention further preferably comprises a molecular chain having a terminal having a cross-linking group at one end of one molecular chain and a terminal having no cross-linking group at the other end. It is a polyimide containing a crosslinking group. The content of the molecular chain is not limited, but is preferably 0.2 mol% or more, more preferably 1 mol% or more, and most preferably 5 mol% or more. Further, as a cross-linking group-containing polyimide, having a terminal having a cross-linking group at one end of one molecular chain and comprising a molecular chain having a terminal having no cross-linking group at the other end, more preferably, A polyimide containing a crosslinking group having a structure represented by the general chemical formula (2c) is shown. Similarly, the content of the molecular chain is not limited, but is preferably 0.2 mol% or more, more preferably 1 mol% or more, and most preferably 5 mol% or more.

[Structure of Preferred Crosslinking Group-Containing Polyimide-
(4)] The polyimide containing a crosslinking group of the present invention preferably has a repeating structural unit represented by the general chemical formula (1) in the polyimide main chain.

[Structure of More Preferred Crosslinking Group-Containing Polyimide- (1)] One of the more preferred crosslinking group-containing polyimides of the present invention having a repeating structural unit represented by the above general formula (1) is one of the repeating structural units Of these, 50 to 100 mol% is a repeating unit structure represented by the general chemical formula (1a). Among them, 50 to 100 mol% of the repeating structural units are

[0131]

Embedded image Most preferably, it has any of the following structures.

[Structure of More Preferred Crosslinking Group-Containing Polyimide- (2)] One of the more preferred crosslinking group-containing polyimides of the present invention having a repeating structural unit represented by the above general formula (1) is one of the repeating structural units Of these, 50 to 100 mol% is a repeating unit structure represented by the general chemical formula (1b). Among them, 50 to 100 mol% of the repeating structural units are

[0133]

Embedded image Most preferably, the structure represented by

[Structure of More Preferred Crosslinking Group-Containing Polyimide- (3)] One of the more preferred crosslinking group-containing polyimides of the present invention having a repeating structural unit represented by the general formula (1) is one of the repeating structural units Of these, 50 to 100 mol% is a repeating unit structure represented by the general chemical formula (1c). Among these, those having a repeating structural unit in which X is an oxygen atom in the general chemical formula (1c) in an amount of 50 to 100 mol% of the repeating structural units are preferable. 100 mol%

[0135]

Embedded image Most preferably, the structure represented by

[Structure of More Preferred Crosslinking Group-Containing Polyimide- (4)] One of the more preferred crosslinking group-containing polyimides of the present invention having a repeating structural unit represented by the general formula (1) is a repeating structural unit. Of these, 50 to 100 mol% is a repeating unit structure represented by the general formula (1e). Among these, those having a repeating unit structure represented by the general chemical formula (1d) in which 50 to 100 mol% of the repeating structural units are preferable.

[0137]

Embedded image (Wherein, X and R are each a group as shown below: X in the formula is a direct bond, a carbonyl group,
A sulfonate group, a sulfide group, an ether group, an isopropylidene group, and a divalent linking group selected from the group consisting of a hexafluorinated isopropylidene group, wherein R in the formula is

[0138]

Embedded image (Wherein G is a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent aromatic group selected from the group consisting of a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group, and a 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy group; ) Represents a tetravalent aromatic group selected from the group consisting of: The position of the bonding group in which the bonding position is not determined in the formula is at the para-position or the meta-position).
In the general formula (1d), a compound having a repeating structural unit in which Z2 is an oxygen atom is preferable, and 50 to 100 mol% of the repeating structural unit is preferably

[0139]

Embedded image Those having a repeating unit structure represented by the following formula are most preferred.

[Molecular Weight of Cross-Linking Group-Containing Polyimide] Logarithmic viscosity is used as an index of the molecular weight of cross-linking group-containing polyimide.

[Logarithmic viscosity of cross-linking group-containing polyimide] The logarithmic viscosity of the cross-linking group-containing polyimide is 0.1 to 1.5 dl.
/ G range. If the logarithmic viscosity is less than 0.1, the mechanical properties are significantly reduced because the molecular weight between crosslinking points is reduced,
If it exceeds 1.5, the melt viscosity will be high, and the melt moldability will be extremely reduced. Preferred logarithmic viscosities are from 0.2 to 1.2.
, More preferably from 0.3 to 0.8, and most preferably from 0.4 to 0.6.

[Measurement Method of Logarithmic Viscosity] The logarithmic viscosity is determined by a solution concentration of 0.5 g / 100 ml in a mixed solvent of p-chlorophenol / phenol = 9/1 by weight, at 35 ° C.
Can be measured using, for example, an Ubbelohde viscometer.

[Regularity when the crosslinkable group-containing polyimide is a copolymer] When the crosslinkable group-containing polyimide of the present invention is a copolymer, the order of two or more kinds of repeating units constituting the copolymer is specified. The nature and regularity may or may not be limited, and the type of copolymer may be random, alternating or block.

[Method for Producing Cross-Linking Group-Containing Polyimide] Here, the method for producing the cross-linking group-containing polyimide of the present invention will be described in detail, but the production method is not limited in the present invention.

[Raw Materials] The polyimide containing a crosslinking group of the present invention is generally obtained from the following raw materials. (A) Diamine component (B) Tetracarboxylic dianhydride component (C) Terminal blocking agent having a crosslinking group (D) Terminal blocking agent having no crosslinking group.

[Diamine Component] The diamine component used to obtain the polyimide containing a cross-linking group of the present invention is not limited, but an aromatic diamine is preferable.

Examples of the aromatic diamine include: a) p-phenylenediamine and m-phenylenediamine having one benzene ring; b) 3,3'-diaminodiphenyl ether having 3, and 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, 4,4′-diaminobenzophenone, 3,
4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4 -Aminophenyl) propane, 2- (3-aminophenyl)
-2- (4-aminophenyl) propane, 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-
Phenylethane, 1- (3-aminophenyl) -1-
(4-aminophenyl) -1-phenylethane, c) 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene having three benzene rings, 1,4 -Bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl)
Benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene,
1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene,
1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-
α, α-ditrifluoromethylbenzyl) benzene,
1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-
α, α-ditrifluoromethylbenzyl) benzene,
2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine, d) 4,4′-bis (3-aminophenoxy) biphenyl having 4 benzene rings, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-amino) Phenoxy) phenyl] sulfide, bis [4-
(4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone,
Bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 2,2-bis [3- (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, e) 1,3-bis [4- (3
-Aminophenoxy) benzoyl] benzene, 1,3-
Bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4
-(3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4
-Bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, f) benzene ring 6 4,4′-bis [4-
(4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone,
4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, g) aromatic substituent 3,3′-diamino-4,
4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 3,
3′-diamino-4-phenoxybenzophenone, 3,
3'-diamino-4-biphenoxybenzophenone, and h) 6,6'-bis (3
-Aminophenoxy) 3,3,3, '3'-tetramethyl-1,1'-spirobiindane 6,6'-bis (4
-Aminophenoxy) 3,3,3, '3'-tetramethyl-1,1'-spirobiindane.

Further, a diamine in which part or all of the hydrogen atoms on the aromatic ring of the above diamine is substituted with a substituent selected from a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group and a trifluoromethoxy group is also used. Can be used.

Further, an ethynyl group, a benzocyclobuten-4'-yl group, a vinyl group, an allyl group, a cyano group, an isocyanate group, a nitrile group, An isopropenyl group may be used by introducing a part or all of hydrogen atoms on the aromatic ring of the diamine as a substituent. Furthermore, preferably within a range that does not impair the moldability,
A vinylene group, a vinylidene group, and an ethynylidene group which are cross-linking points can be incorporated into the main chain skeleton instead of the substituent.

In addition, copolymerization can be carried out using one or more aliphatic diamines together with the above-mentioned diamines for the purpose of improving or modifying the performance, or within a range that does not impair good physical properties. . For example: i) 1,3-bis (3-siloxanediamines
Aminopropyl) tetramethyldisiloxane, 1,3-
Bis (4-aminobutyl) tetramethyldisiloxane,
α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3-aminobutyl) polydimethylsiloxane, j) bis (aminomethyl) ether and bis (2- Aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-
Aminomethoxy) ethyl] ether, bis [2- (2-
Aminoethoxy) ethyl] ether, bis [2- (3-
Aminoprotoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1, 2-bis [2- (2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, k ) Methylenediamines, ethylenediamine,
1,3-diaminopropane, 1,4-diaminobutane,
1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1, 12-diaminododecane, 1) alicyclic diamines, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-
Diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl)
Cyclohexane, 1,4-di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2.2.
1] heptane and 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane are exemplified.

These diamines can be used alone or in combination as necessary.

[Preferred Diamine Component] Among the diamine components exemplified above, a preferred diamine is a diamine represented by the general formula (4).

[More Preferred Diamine Component (1)] Among the diamines represented by the general formula (4), one of the more preferred diamines is the diamine represented by the general formula (4c). In particular, the use amount is preferably 50 to 100 mol%.

Examples of the diamine represented by the general formula (4c) include, for example, 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, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene,
1,4-bis (4-aminobenzoyl) benzene,
3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α,
α-dimethylbenzyl) benzene, 1,4-bis (4-
Amino-α, α-dimethylbenzyl) benzene, 1,3
-Bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α
-Ditrifluoromethylbenzyl) benzene, 1,4-
Bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-
Ditrifluoromethylbenzyl) benzene, 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-
Bis (3-aminophenoxy) pyridine can be used.

Among them, particularly preferred diamines are 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, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene, the most preferred diamine being 1,
3-bis (4-aminophenoxy) benzene.

[More Preferred Diamine Component (2)] Among the diamines represented by the general formula (4), one of the more preferred diamines is the diamine represented by the general formula (4d). In particular, the use amount is preferably 50 to 100 mol%.

Examples of the diamine represented by the general formula (4d) include, for example, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3
-Aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3 , 3,3-hexafluoropropane.

Of these, particularly preferred diamine components are:
4,4′-bis (3-aminophenoxy) biphenyl,
It is.

[Tetracarboxylic dianhydride component] The tetracarboxylic dianhydride component used to obtain the polyimide of the present invention is not limited. For example, pyromellitic dianhydride, 3,3 ', 4,4 4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4- Dicarboxyphenyl) sulfide 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 (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxy) Phenoxy) benzene dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, , 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-
Naphthalenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 2,
2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride Anhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride Product, bis (2,3-dicarboxyphenyl) sulfide dianhydride, bis (2,3-
Dicarboxyphenyl) sulfone dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (2,3-dicarboxyphenoxy)
Benzene dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, and the like can be used alone or in combination as appropriate.

For all of the above-mentioned tetracarboxylic dianhydride components, part or all of the hydrogen atoms on their aromatic rings may be replaced with fluoro, methyl, methoxy, trifluoromethyl, Alternatively, a diamine substituted with a substituent selected from a trifluoromethoxy group can be used.

Further, an ethynyl group, a benzocyclobuten-4'-yl group, a vinyl group, an allyl group, a cyano group, an isocyanate group, a nitrile group, and a crosslinking point which are preferably within the range not impairing the moldability. An isopropenyl group may be used by introducing a part or all of hydrogen atoms on the aromatic ring of the diamine as a substituent. Furthermore, preferably within a range that does not impair the moldability,
A vinylene group, a vinylidene group, and an ethynylidene group which are cross-linking points can be incorporated into the main chain skeleton instead of the substituent.

These tetracarboxylic dianhydride components can be used alone or in combination as necessary.

Further, depending on the production method, instead of dianhydride,
A monoanhydride or a compound which is not an anhydride, or a derivative thereof such as a salt thereof can be optionally used.

[Preferred tetracarboxylic dianhydride component] Among the tetracarboxylic dianhydride components exemplified above, preferred tetracarboxylic dianhydrides are tetracarboxylic dianhydrides represented by the above general formula (5). It is anhydrous.
Specific examples include pyromellitic dianhydride, 3,3 ′,
4,4′-biphenyltetracarboxylic dianhydride, 3,
3 ', 4,4'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide 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 (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy)
Benzene dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,3 , 6,7-Naphthalenetetracarboxylic dianhydride and 1,4,5,8-naphthalenetetracarboxylic dianhydride are exemplified.

[Further preferable tetracarboxylic dianhydride component] Among the diamines represented by the general formula (5), more preferable tetracarboxylic dianhydride is pyromellitic dianhydride, 3,3 ', 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3 4
-Dicarboxyphenyl) sulfide dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride,
2,2-bis (3,4-dicarboxyphenyl) -1,
1,1,3,3,3-hexafluoropropane dianhydride, 1,4-bis (3,4-dicarboxyphenoxy)
One or more tetracarboxylic dianhydride components selected from the group consisting of benzene dianhydride are used.

[Use amount of tetracarboxylic dianhydride component] The total amount of the tetracarboxylic dianhydride component is from 0.8 to 1.25 per mole of the total amount of the diamine component used.
It is a molar ratio. By changing the molar ratio, the molecular weight of the obtained cross-linking group-containing polyimide can be controlled. If the molar ratio is less than 0.8, a molecular weight sufficient to bring out sufficient characteristics cannot be obtained, and if the molar ratio exceeds 1.25, the molecular weight is reduced.

When a dicarboxylic acid or an anhydride or derivative thereof is used as the terminal blocking agent, the total amount of the tetracarboxylic dianhydride component is preferably from 0.8 to 0.1 per mole of the total amount of the diamine component used. 99 molar ratio,
More preferably, the molar ratio is from 0.85 to 0.97,
Most preferably, it is in the range of 0.90 to 0.95. In this case, when a tetracarboxylic dianhydride component exceeding these ranges is used, the end capping becomes insufficient, and the heat stability and processability are adversely affected.

When monoamines are used as the terminal blocking agent, the total amount of the tetracarboxylic dianhydride component is preferably 1.0 mol per mol of the total amount of the diamine component used.
1 to 1.25 mole ratio, more preferably 1.0
5 to 1.20 molar ratio, most preferably 1.07
From 1.15 to 1.15. In this case, when using less tetracarboxylic dianhydride component than these ranges,
Insufficient terminal sealing adversely affects thermal stability and processability.

The molecular weight of the crosslinking group-containing polyimide can be achieved by controlling the molar ratio of the total amount of the tetracarboxylic dianhydride component to 1 mol of the total amount of the diamine component to be used. The optimum charging ratio may vary depending on the temperature, polymerization time and the like.

[Terminal blocking agent having a cross-linking group] The terminal blocking agent having a cross-linking group used in the present invention is not limited. Depending on the method for synthesizing the polyimide, various types of end-capping agents having a cross-linking group are used.Typically, monoamine or dicarboxylic anhydride is used. Various known crosslinking groups can be selected in accordance with the conditions. The type of the cross-linking group is not limited, but typical examples include an ethynyl group, a benzocyclobuten-4′-yl group, a vinyl group, an allyl group, a cyano group, an isocyanate group, a nitrilo group, an amino group, Examples include an isopropenyl group, a vinylene group, a vinylidene group, and an ethynylidene group.

[Preferred Terminal Capping Agent Having Crosslinking Group] The terminal blocking agent having a crosslinking group used in the present invention is preferably a dicarboxylic anhydride having a crosslinking group. Depending on the synthesis method, a derivative such as a ring-opened product or a salt thereof is used. For example:-unsaturated aliphatic dicarboxylic anhydrides represented by maleic anhydride and nadic anhydride-1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride, ethynylphthalic anhydride And 6-
A dicarboxylic anhydride containing an ethynyl group represented by ethynyl-2,3-dicarboxynaphthalene anhydride; a phthalate containing a benzocyclobuten-4'-yl group, a vinyl group, an allyl group, and an isopropenyl group And acid anhydride derivatives or 2,3-dicarboxynaphthalene anhydride derivatives.

[Terminal blocking agent having more preferable cross-linking group] The cross-linking group contained in the structure is preferably an ethynyl group, more preferably a structure containing phenylethynylbenzene.

[Further preferable terminal blocking agent having a crosslinking group] The terminal blocking agent having a cross-linking group used in the present invention includes:
More preferably, it is a dicarboxylic anhydride represented by the general chemical formula (3a).

Specifically, 1-phenyl-2-
(3,4-dicarboxyphenyl) acetylene anhydride,
1-phenyl-2- (3- (3,4-dicarboxyphenoxy) phenyl) acetylene anhydride, 1-phenyl-
2- (3- (3,4-dicarboxyphenylcarbonyl) phenyl) acetylene anhydride, 1-phenyl-2-
(3- (3,4-dicarboxyphenylsulfonyl) phenyl) acetylene anhydride, 1-phenyl-2- (3-
(3,4-dicarboxyphenylsulfinyl) phenyl) acetylene anhydride, 1-phenyl-2- (3- (2
-(3,4-dicarboxyphenyl) isopropanyl)
Phenyl) acetylene anhydride, 1-phenyl-2- (3
-(1,1,1,3,3,3, -hexafluoro-2-
(3,4-dicarboxyphenyl) isopropanyl) phenyl) acetylene anhydride, 1-phenyl-2- (3-
(3,4-dicarboxyphenyl) phenyl) acetylene anhydride, 1-phenyl-2- (4- (3,4-dicarboxyphenoxy) phenyl) acetylene anhydride, 1-phenyl-2- (4- (3,4-dicarboxyphenoxy) phenyl) acetylene anhydride
Phenyl-2- (4- (3,4-dicarboxyphenylcarbonyl) phenyl) acetylene anhydride, 1-phenyl-2- (4- (3,4-dicarboxyphenylsulfonyl) phenyl) acetylene anhydride, 1-phenyl-2- (4- (3,4-dicarboxyphenylsulfonyl) phenyl) acetylene anhydride Phenyl-2
-(4- (3,4-dicarboxyphenylsulfinyl) phenyl) acetylene anhydride, 1-phenyl-2-
(4- (2- (3,4-dicarboxyphenyl) isopropanyl) phenyl) acetylene anhydride, 1-phenyl-2- (4- (1,1,1,3,3,3, -hexafluoro-2 -(3,4-dicarboxyphenyl) isopropanyl) phenyl) acetylene anhydride, 1-phenyl-
2- (4- (3,4-dicarboxyphenyl) phenyl) acetylene anhydride and 2,3-dicarboxy-
6-phenylethynyl) naphthalene anhydride.

The above terminal blocking agents having a cross-linking group may be used alone or in combination of two or more. Also,
A terminal blocking agent having a cross-linking group in which part or all of the hydrogen atoms on those aromatic rings has been substituted with a substituent selected from a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, or a trifluoromethoxy group Can also be used.

Further, an ethynyl group and a benzocyclobutene-4′- which serve as a crosslinking point within a range where the moldability is not impaired.
An yl group, a vinyl group, an allyl group, a cyano group, an isocyanate group, a nitrile group, and an isopropenyl group are introduced as a substituent into a part or all of the hydrogen atoms on the aromatic ring of the above-mentioned dicarboxylic anhydride containing a crosslinking group. Can also be used.

[Most Preferred Terminal Capping Agent Having Cross-Linking Group] Among the above terminal capping agents having a cross-linking group, 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride is used in the present invention. Is most preferable from the viewpoint of the properties of the cross-linking group-containing polyimide and the implementation.

[Terminal blocking agent having no cross-linking group] The terminal blocking agent having no cross-linking group used in the present invention is not limited. Depending on the method of synthesizing the polyimide, various types of terminal blocking agents having no cross-linking group are used.Typical ones are monoamines or dicarboxylic anhydrides, and the structure includes a molding process or a post-treatment condition. It is essential that the group functioning as a crosslinking group is not included. Examples of the crosslinking group include an ethynyl group, a benzocyclobuten-4′-yl group, a vinyl group, an allyl group, a cyano group, an isocyanate group, a nitrilo group, an amino group, an isopropenyl group, a vinylene group, a vinylidene group, and an ethynylidene group. Groups are exemplified.

[Preferred terminal blocking agent having no crosslinking group]
The terminal blocking agent having no crosslinking group used in the present invention is preferably a dicarboxylic anhydride. Depending on the synthesis method, a derivative such as a ring-opened product or a salt thereof is used. It is essential that the structure does not include a group that functions as a cross-linking group under the conditions of the molding or post-treatment step.

[Further preferable terminal blocking agent having no cross-linking group] The terminal blocking agent having no cross-linking group used in the present invention is more preferably a dicarboxylic anhydride represented by the aforementioned general formula (3b). It is.

More specifically, phthalic anhydride, 4-phenylphthalic anhydride, 4-phenoxyphthalic anhydride,
-Phenylsulfinylphthalic anhydride, 4-phenylsulfonylphthalic anhydride, 4-phenylcarbonylphthalic anhydride, 4- (2-phenylisopropyl) phthalic anhydride, 4- (1,1,1,3, 3,3-hexafluoro-2-phenylisopropyl) phthalic anhydride,
2,3-naphthalenedicarboxylic anhydride and 1,8
-Naphthalenedicarboxylic acid anhydride.

The above dicarboxylic anhydrides may be used alone or in combination.
A mixture of more than one species may be used. Also, some or all of the hydrogen atoms on those aromatic rings are fluoro groups,
A diamine substituted with a substituent selected from a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group can also be used.

[Most Preferred Terminal Capping Agent Having No Crosslinking Group] Among the above dicarboxylic anhydrides, phthalic anhydride is most preferred from the viewpoint of the properties of the polyimide containing a crosslinking group of the present invention and the practical aspects.

[Quantitative Ratio of Terminal Blocking Agent Having Crosslinking Group to Terminal Blocking Agent Having No Crosslinking Group] Quantitative Ratio of Terminal Blocking Agent Having Crosslinking Group and Terminal Blocking Agent Having No Crosslinking Group Used as Raw Materials Is not limited as long as the terminal of the synthesized cross-linking group-containing polyimide satisfies the condition of “having a cross-linking group at 1 to 80 mol% of molecular ends”, but preferably, the terminal blocking having a cross-linking group [E]
1], the molar amount of the terminal blocking agent having no cross-linking group was [E
2], it is in the range of 1/99 ≦ [E1] / [E2] ≦ 80/20. [E1] / [E2] out of this range
Is less than 1/99, the crosslink density is not sufficient, and the improvement in chemical resistance, heat resistance, and mechanical properties becomes insufficient.
When the value of [1] / [E2] exceeds 80/20, the crosslink density is sufficient, but the viscosity rise at the time of molding is so large that melt molding becomes impossible.

The range of the value of [E1] / [E2] must be properly selected according to the molding conditions. Generally, it is preferably in the range of 5/95 ≦ [E1] / [E2] ≦ 70/30, more preferably in the range of 10/90 ≦ [E1] / [E2] ≦ 70/30.

Although the range of the more preferable value varies depending on the processing method, for example, although it is accompanied by stagnation in a molten state such as press molding, it is more preferably 30/70 ≦ [E1] / [E2] ≦ 70 / in the batch molding method. 30 and most preferably 40/60 ≦ [E1] / [E2] ≦ 60/40.

For example, in a molding method such as injection molding or extrusion molding which requires stagnation in a molten state and requires continuous operation, the range is preferably 10/90 ≦ [E1] / [E2] ≦ 50/50. , And most preferably 20/80 ≦ [E1] / [E2] ≦ 40/60.

Further, for example, in a molding method in which the retention in the molten state is small, the range is preferably 20/80 ≦ [E1] / [E2] ≦ 60/40, and most preferably 30/70 ≦ [E1] / [ E2] ≦ 50/50.

[Amount of Terminal Capping Agent] The amount of the terminal capping agent used is such that the terminal of the synthesized cross-linking group-containing polyimide has “a cross-linking group at 1 to 80 mol% of the molecular terminals”. It is not limited as long as it is satisfied.
However, preferably, the total amount of the diamine component is [Da]
(Mol) and the total amount of the tetracarboxylic dianhydride component (or the ring-opened product or derivative thereof) [Tc] (mo
l) The total amount of the monoamine component used as the terminal capping agent is [Ma] (mol), and the total amount of the dicarboxylic anhydride component (or the ring-opened product or derivative thereof) used as the terminal capping agent is [Dc]. ] (Mol), ([Dc]-[Ma]) / ([Da]-[Tc])> 2, more preferably 20> ([Dc]-[Ma] ) / ([Da]-[T
c])> 3. [Dc]-[Ma]) / ([Da]-
When the value of [Tc]) deviates from this value and is small, sufficient molecular terminal sealing cannot be performed, and thermal stability, thermal oxidation stability, and moldability deteriorate. On the other hand, if the amount is too large, it becomes difficult to control the molecular weight and to wash the excess terminal blocking agent.

[Production Method of Crosslinking Group-Containing Polyimide] Using the above-mentioned raw materials, polymerization and imidization can be carried out by a known method to obtain a polyimide. Although the production method is not limited, the polymerization is usually performed in a solvent. For example, a) First, a diamine component / tetracarboxylic dianhydride component is stirred in a solvent to obtain a crosslinkable group-containing polyamic acid, and this is thermally or chemically dehydrated and imidized. A direct polymerization method in which the carboxylic acid dianhydride component is dissolved or suspended in a solvent and immediately heated to thermally dehydrate imidize it (the charging timing of the terminal blocking agent is limited in each case) Is not common).

[Polymerization solvent] Examples of the solvent include: m) phenolic solvents such as phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol, m-cresol, p-cresol, 3-xylenol, 2,4-xylenol,
2,5-xylenol, 2,6-xylenol, 3,4
-Xylenol, 3,5-xylenol, n) N, N-dimethylformamide, N, N-dimethylacetamide, N, N
N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotriamide, o) 1,2-dimethoxyethane which is an ether solvent , Bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane, p) amine-based solvent Pyridine, quinoline, isoquinoline, α-picoline, β-picoline, γ-picoline,
Isophorone, piperidine, 2,4-lutidine, 2,6-
Lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine q) Other solvents such as dimethylsulfoxide, dimethylsulfone, diphenylether, sulfolane, diphenylsulfone, tetramethylurea, anisole and water.

These solvents may be used alone or in combination of two or more. Also, r), s),
Using one of t) and the solvent shown in item u),
More than one species can be used as a mixture. When used as a mixture, it is not always necessary to select a combination of solvents that mutually dissolve at an arbitrary ratio, and they may be mixed and non-uniform.

[Polymerization Concentration] The concentration of polymerization performed in these solvents is not particularly limited. When the ratio of the total weight of all the diamine components and all the tetracarboxylic dianhydride components with respect to the total weight of all the solvents, all the diamine components and all the tetracarboxylic dianhydride components used is expressed as a percentage, preferred polymerization is performed. Is from 5 to 50%, more preferably
10 to 30%.

[Charging Order] The charging order of the diamine component, the tetracarboxylic dianhydride component and the terminal blocking agent is not limited. When the diamine component, the tetracarboxylic dianhydride component, and the terminal blocking agent are each composed of two or more kinds, the order of addition is arbitrary, and it is also optional to add one addition at a time or to split.

[Polymerization conditions] The polymerization temperature, polymerization time and polymerization pressure are not particularly limited, and known conditions can be applied.
The polymerization temperature is generally in the range of −10 ° C. to 100 ° C. for the polymerization of the cross-linking group-containing polyamic acid, and in the range of 50 ° C. to 250 ° C. for the imidization. , And the reaction temperature,
Generally, it is 1 to 48 hours. Still further, the reaction pressure is sufficient at normal pressure.

[Logarithmic viscosity of crosslinkable group-containing polyamic acid] The logarithmic viscosity of crosslinkable group-containing polyamic acid when polymerized via the crosslinkable group-containing polyamic acid is 0.1 to 2.0 dl / g.
(Concentration of 0.5 g / d in N, N-dimethylacetamide
1, measured at 35 ° C. Is preferred. Logarithmic viscosity is
If it is less than 0.1, the molecular weight between cross-linking points will be low, so that the mechanical properties will be remarkably reduced. If it exceeds 2.0, the melt viscosity will be high, and the melt moldability will be extremely reduced. Preferred logarithmic viscosities are in the range from 0.3 to 1.2, more preferably in the range from 0.4 to 0.7.

[Chemical imidization] Chemical imidization is a method in which a crosslinking group-containing polyamic acid is reacted with a dehydrating agent having a hydrolytic ability to chemically dehydrate.

The dehydrating agent used is an aliphatic carboxylic anhydride represented by acetic anhydride or trifluoroacetic anhydride;
Examples thereof include polyphosphoric acid and phosphoric acid derivatives represented by phosphorus pentoxide, or mixed acid anhydrides of these acids, and acid chlorides represented by methanesulfonic acid chloride, phosphorus pentachloride and thionyl chloride. These dehydrating agents may be used alone or in combination of two or more. These dehydrating agents are used in an amount of 2 moles per mole of the diamine component used.
〜１０10 molar ratio. Preferably it is a 2.1 to 4 molar ratio.

The chemical imidization method can be carried out in the presence of a base catalyst. As the base catalyst to be used, the amine-based solvent described in the above section p) can be used as the base catalyst. In addition, they are represented by organic bases such as imidazole, N, N-dimethylaniline, N, N-diethylaniline, potassium hydroxide and sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate. And inorganic bases. The amount of these catalysts used is 0.001 to 0.50 mole ratio based on 1 mole of the total amount of the diamine component used. Preferably, the molar ratio is 0.05 to 0.2.

The reaction temperature, reaction time and reaction pressure in the chemical imidization method are not particularly limited, and known conditions can be applied. That is, the reaction temperature is preferably from −10 ° C. to about 120 ° C., more preferably from about room temperature to about 70 ° C., and room temperature is the most preferable and practical in practical aspects. The reaction time varies depending on the type of solvent used and other reaction conditions, but is preferably about 1 to 24 hours. More preferably, it is about 2 to 10 hours. Normal reaction pressure is sufficient. The atmosphere is air, nitrogen, helium, neon, or argon, and is not particularly limited. Preferably, an inert gas such as nitrogen or argon is selected.

[Thermal imidization] The thermal imidization is achieved by heating the polyamic acid or its solution, generally at 100 ° C to 300 ° C.

The thermal imidization can be carried out in the presence of the same base catalyst as used in the chemical imidization method.

The reaction temperature, reaction time and reaction pressure in the thermal imidization method are not particularly limited, and known conditions can be applied. That is, a reaction temperature of about 80 ° C to about 400 ° C can be applied, and preferably about 100 ° C to about 300 ° C. The reaction time varies depending on the type of the solvent used and other reaction conditions, but is generally 0.5 to 24 hours. Furthermore, the reaction pressure is sufficient at normal pressure. The atmosphere is air, nitrogen, helium, neon, or argon, and is not particularly limited. Preferably, an inert gas such as nitrogen or argon is selected.

[Combination of chemical imidization and thermal imidization] The chemical imidization method and the thermal imidization method can be used in combination.

For example, a) a method in which heating is performed simultaneously in the above-mentioned chemical imidization method, and b) a method in which a dehydrating agent used in the chemical imidization coexists when performing the above-mentioned thermal imidization method.

[Direct Polymerization Method] In the direct polymerization method, the diamine component and the tetracarboxylic dianhydride component are dissolved or suspended in a solvent and immediately heated to immediately perform thermal dehydration imidization. Here's how to do it. It is achieved by performing polymerization and imidization in a solvent in the same manner as thermal imidization.

As in the chemical imidization method, the reaction can be carried out in the presence of a base catalyst. The base catalyst used and the amount used are the same as those described in the chemical imidization method.

Further, in order to remove water generated by the dehydration imidization reaction out of the system, another solvent may be coexisted. The solvents used here are: r) benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene,
Bromobenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, and p-bromotoluene No. These solvents may be used alone or
A mixture of more than one species may be used. In addition, the above m)
To q) and the following solvents s) to u), and one or more of them may be used as a mixture. When used as a mixture, it is not always necessary to select a combination of solvents that mutually dissolve at an arbitrary ratio, and they may be mixed and non-uniform. The amount of these dehydrating agents used is not limited at all.

The reaction temperature, reaction time and reaction pressure are as follows:
There is no particular limitation, and known conditions can be applied. That is, a reaction temperature of about 100 ° C. to about 300 ° C. can be applied, and preferably about 120 ° C. to about 250 ° C. The reaction time varies depending on the type of the solvent used and other reaction conditions, but is generally 0.5 to 24 hours. Furthermore, the reaction pressure is sufficient at normal pressure. The atmosphere is air, nitrogen, helium, neon, or argon, and is not particularly limited. Preferably, an inert gas such as nitrogen or argon is selected.

[Treatment of Crosslinking Group-Containing Polyimide] The crosslinking group-containing polyimide is improved in chemical resistance, heat resistance, mechanical properties and the like by crosslinking between molecular chains during or after the molding process. The conditions for these crosslinking reactions are not limited, and can be set arbitrarily. These conditions vary greatly depending on the type and amount of the crosslinking group used. For example, when the molecular terminal having a cross-linking group is represented by the general chemical formula (2a), a preferable cross-linking method is heat treatment, and the heat treatment causes a carbon-carbon triple bond to thermally react, thereby forming a cross-link between molecular chains. Generate.

[Heat treatment conditions] A molecular terminal having a crosslinking group is
The temperature, time and pressure of the heat treatment in the case of the general formula (2a) are not particularly limited, and are determined according to the required properties for the obtained crosslinked thermoplastic polyimide. The temperature of the heat treatment can be applied at about 250 ° C. to 450 ° C., preferably about 300 ° C. to 400 ° C., and most preferably practically 330 ° C. to 380 ° C.
Before and after. If the temperature is lower than 250 ° C., the crosslinking reaction is unlikely to occur, and if the temperature exceeds 450 ° C., the polyimide main chain is denatured, and its properties cannot be sufficiently obtained.

The heat treatment time varies depending on other heat treatment conditions and the like, but is preferably 0.1 hour or more, more preferably 0.2 hour or more, and most preferably 1 hour or more. If the heat treatment time is shorter than this time, the crosslinking density becomes insufficient, and almost no improvement in physical properties is observed.

If the crosslinking time is too long, processing efficiency is disadvantageous, and modification may occur depending on the main chain structure. The preferred upper limit of the heat treatment time is 100 hours.

The pressure at the time of the heat treatment is sufficient at normal pressure. However, if necessary, a method of performing a heat treatment while performing degassing or the like under pressure can be adopted. The atmosphere is air, nitrogen, helium, neon, or argon, and is not particularly limited. Preferably, an inert gas such as nitrogen or argon is selected.

[Heat Treatment Method] The heat treatment method is not limited by the form of the cross-linking group-containing polyimide. In other words, using a cross-linking group-containing polyimide obtained as a powder or granules, a) a method of performing a heat treatment as it is, b) once performing a melt molding process to obtain a molded product having a desired shape, and then forming the molded product. A) a method of heat-treating the product; c) a method of performing the heat treatment simultaneously with the melt-forming process; d) performing the heat-treatment as it is, then performing the melt-forming process once to obtain a molded product having the desired shape. And a method of heat treating the molded article again.

[0216] The respective applications are as follows: a) Since the crosslinked thermoplastic polyimide can be obtained in the form of powder or granules, it can be added to other resins as a filler as it is, or it can be molded by sintering. General melt-forming processing, c) Forming a film or sheet by pressing, especially as an adhesive, d) General-purpose melt forming, especially forming a film or sheet by pressing, using as an adhesive, etc. Is possible.

[Treatment Methods Other than Heat Treatment] In addition to heat treatment, various energy sources that cause crosslinking can be used. For example, irradiation with visible light, infrared rays, ultraviolet rays, radiation such as α, β, and γ rays, electron beams, and X-rays, and plasma treatment and doping treatment are also included.

[Crosslinking Accelerator and Crosslinking Inhibitor] For the purpose of controlling the rate of the crosslinking reaction, a crosslinking accelerator or a crosslinking inhibitor can be used. The crosslinking accelerator and the crosslinking inhibitor are not limited,
When used together with the cross-linking group-containing polyimide, compounds capable of substantially promoting or suppressing the cross-linking reaction can be used in any combination.

For example, metal catalysts containing gallium, germanium, indium and lead, molybdenum, manganese, nickel, cadmium, cobalt, chromium, iron,
It is possible to add transition metal catalysts including copper, tin and platinum, and phosphorus compounds, silicon compounds, nitrogen compounds, and sulfur compounds.

[Solution or Suspension Containing Cross-Linking Group-Containing Polyimide] The solution or suspension containing the cross-linking group-containing polyimide is used in the pretreatment step of shaping or melt-forming the cross-linking group-containing polyimide of the present invention. Can be used.

A solution or a suspension is prepared by using a solvent which does not cause a chemical reaction with the polyimide containing a crosslinking group of the present invention.
Can be prepared.

Solvents that can be used include the solvents described in the above items m) to q) and r), s) acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol , Pentane, hexane, heptane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, fluorobenzene,
Methyl acetate, ethyl acetate, butyl acetate, methyl formate, ethyl formate, t) water, and the amine solvent described in the above item p), imidazole, N, N-dimethylaniline, N, N-diethylaniline, potassium hydroxide , Sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate, u) silicone oil, machine oil, hydraulic oil, kerosene, gasoline, jet fuel. These solvents may be used alone or in combination of two or more. Further, one or two or more of the solvents described in the above m) to r) can be used as a mixture. When used as a mixture, it is not always necessary to select a combination of solvents that mutually dissolve at an arbitrary ratio, and they may be mixed and non-uniform. The concentration of the aqueous solution described in the above item t) is not limited and can be arbitrarily determined.

The concentration of the solution or suspension containing the crosslinking group-containing polyimide is not limited, and can be arbitrarily determined. Generally, it is in the range of 1 to 60%.

The method for preparing the solution or suspension containing the polyimide of the present invention is not limited, and all known methods can be applied.

For example, a) a method in which a solution or suspension after polymerization is used as it is, b) a method in which a polyimide containing a cross-linking group is obtained in the form of powder, granules, or lump and then dissolved or dispersed in the above-mentioned solvent. ,
Is mentioned.

There are no restrictions on the conditions for preparing the solution or suspension, such as temperature, time and stirring method. In the case of a suspension, there is no limitation on the particle size or particle size distribution of the powder or granules to be dispersed, and a dispersion accelerator or an emulsifier can be added during preparation.

[Alloys and Blends with Other Resins] The crosslinking group-containing polyimide of the present invention may be a thermoplastic resin such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polybutadiene, or the like as long as the object of the present invention is not impaired. Polystyrene, polyvinyl acetate ABS resin,
Polybutylene terephthalate, polyethylene terephthalate, polyphenylene oxide, polycarbonate, P
TFE, celluloid, polyarylate, polyether nitrile, polyamide, polysulfone, polyether sulfone, polyether ketone, polyphenyl sulfide,
Polyamide imide, polyether imide, modified polyphenylene oxide and polyimide, or thermosetting resin such as thermosetting polybutadiene, formaldehyde resin, amino resin, polyurethane, silicone resin, SB
It is also possible to blend or alloy an appropriate amount of one or more resins with R, NBR, unsaturated polyester, epoxy resin, polycyanate, phenol resin, polybismaleimide and the like according to the purpose.
The method is not particularly limited, and a known method can be applied.

[Fillers and Additives] The crosslinkable group-containing polyimide of the present invention may be mixed with various fillers or additives as long as the object of the present invention is not impaired. Examples thereof include graphite, carborundum, silica stone powder, molybdenum disulfide, an abrasion resistance improver such as a fluororesin,
Flame retardant improvers such as antimony trioxide, magnesium carbonate and calcium carbonate, electric property improvers such as clay and mica, tracking resistance improvers such as asbestos, silica and graphite, barium sulfate, silica and calcium metasilicate Acid resistance improver, thermal conductivity improver such as iron powder, zinc powder, aluminum powder, copper powder, other glass beads, glass spheres, talc, diatomaceous, alumina, shirasubarun,
Hydrated alumina, metal oxides, coloring agents, pigments and the like. The mixing method is not particularly limited, and a known method can be applied.

[0229]

EXAMPLES The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the present invention. Test methods of various tests common to Examples and Comparative Examples are as follows. 1) Logarithmic viscosity of polyimide powder 0.50 g of a sample was dissolved by heating in 100 ml of a mixed solvent of p-chlorophenol and phenol (90:10 weight ratio), and then cooled to 35 ° C and measured. 2) Melt viscosity Orifice 1.0 mm (diameter) x 10 mm (long), load 10 using Shimadzu Koka flow tester (CFT500A).
0 kgf, measured at 360 ° C x 5 minutes unless otherwise specified. 3) 5% weight loss temperature DTA-TG (Shimadzu DT-40 series, 4
0M) at a rate of temperature rise of 10 ° C./min. Measured with 4) Glass transition temperature / crystal melting temperature DSC (Shimadzu DT-40 series, DSC-41M) was used to raise the temperature at a rate of 10 ° C / min. Measured with 5) Tensile strength of molded article According to ASTM-D-638. 6) Logarithmic viscosity of polyamic acid varnish An amount of varnish containing 0.50 g of solid content was N-methyl-2-
After dissolving to a total of 100 ml in pyrrolidone,
Measured at 35 ° C. 7) Mechanical properties of film Measured according to ASTM D-822. 8) Heat distortion temperature According to ASTM D-648.

Experiment A Series In Examples A1 to A91, in the present invention, 50 to 100 mol% of the repeating structural units having a main chain structure were used.
But,

[0231]

Embedded image (Wherein X is a direct bond, a carbonyl group, a sulfone group,
A divalent linking group selected from a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group, wherein R in the formula is

[0232]

Embedded image (Wherein G is a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent linking group selected from the group consisting of 4-oxyphenoxy, 4'-oxy-4-biphenoxy, and 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy. Which represents a tetravalent aromatic group selected from the group consisting of).

Examples A1 to A7, Comparative Examples A1 to A3 In a vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube, 4,4'-bis (3-aminophenoxy) biphenyl was used as a monomer. 368.43 g (1.0
00 mol), pyromellitic dianhydride, 102.52
g (0.470 mol), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 138.28 g (0.
470 mol), 1830 g of m-cresol as a solvent and a terminal-capping agent of the type and amount shown in Table A1, and stirring under a nitrogen atmosphere to 200 ° C. for 2 hours 3
The temperature was increased by heating over 0 minutes, and the reaction was carried out at 200 ° C. under reflux conditions for 4 hours.

[0234] [Legend] In Table A1, “PA” indicates phthalic anhydride, and “PCE” indicates 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.

Subsequently, the temperature was lowered to 190 ° C., the terminal blocking agent described in Table A1 was charged again, and the temperature was raised again to 200 ° C.
The reaction was further carried out under a reflux condition at 4 ° C. for 4 hours. Then 10
After cooling to 0 ° C., the resulting viscous polymer solution was discharged into 10 liters of vigorously stirred toluene, and the precipitate was separated by filtration. This was further sludged in 4 liters of toluene, separated by filtration, preliminarily dried at 50 ° C. for 24 hours, and then dried at 220 ° C. for 12 hours under a nitrogen stream. Table A2 shows the yield of the obtained powder, the logarithmic viscosity of the polyimide powder, the glass transition temperature, the 5% weight loss temperature, and the melt viscosity (360 ° C / 5 minutes). In the present invention, the ratio of the chemical formula (2a) / chemical formula (2b) at the molecular terminal in the claims is from 1/99 to 80.
/ 20, but from the above results, the ratio of chemical formula (2a) / chemical formula (2b) is 80/2
It is clear that those having a value of more than 0 are inferior in moldability as compared with those having a ratio of 80/20 or less.

[0236]

Examples A8 to A12, Comparative Examples A4 and A5 Press molding was performed using the powders obtained in Examples A2 to A6 and Comparative Example 3. Here each example
The powder used in the comparative example is shown in the following Table A3.

[0238] Specifically, it was extruded into pellets at 355 ° C. using a 25 mm uniaxial extruder, and this beret was subjected to ASTM-D
After loading into a press die having a mold having a shape defined in -638, Examples A8 to A12 and Comparative Example A4 have 360
Press molding was performed at a temperature of 360 ° C. for 5 minutes at 12 ° C. for 12 hours and Comparative Example A5. In each case, good molded products were obtained. Using this molded product, a tensile test was performed at normal temperature (23 ° C.). The results are shown in Table A4. The present invention is characterized in that the ratio of the chemical formula (2a) / chemical formula (2b) at the molecular end in the claims is from 1/99 to 80/20, but from the above results, the chemical formula (2a) / chemical formula ( 2
It is apparent that those having a ratio of b) of less than 1/99 have inferior mechanical properties as compared with those having a ratio of 1/99 or more.

[0239] [Legend] In Table A4, “PA / PCE molar ratio” indicates the molar ratio of phthalic anhydride to 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.

Examples A13 to A17, Comparative Examples A6 to A8 In a vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube, 4,4'-bis (3-aminophenoxy) biphenyl was used as a monomer. 368.43 g (1.0
00 mol), pyromellitic dianhydride, 102.52
g (0.470 mol), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 138.28 g (0.
470 mol), 1630 g of m-cresol as a solvent
And stirring at 200 ° C. under a nitrogen atmosphere.
The temperature was raised for 2 hours and 30 minutes until the temperature reached 200 ° C., and the reaction was carried out under a reflux condition of 200 ° C. for 2 hours to obtain a polymer solution having a non-capped terminal. During the reaction, the terminal blocking agent described in Table A5 and m were placed in a separate container.
-200.0 ml of cresol was charged and dissolved by heating at 100 ° C for 1 hour in advance in a nitrogen atmosphere. The whole solution of the terminal blocking agent was charged into a polymer solution having no terminal blocking, and further reacted at 200 ° C. under reflux condition for 2 hours.

[0241] [Legend] In Table A5, “PA” indicates phthalic anhydride, and “PCE” indicates 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.

Thereafter, the mixture was cooled to 100 ° C., and while maintaining the obtained viscous polymer solution at 100 ° C., 4 liters of toluene was added dropwise thereto over 4 hours. 8 more
After charging 3 liters of toluene heated to 0 ° C., the mixture was cooled to room temperature, 3 liters of toluene was further added, the mixture was stirred for 1 hour, and the precipitate was separated by filtration. This is further sludged in 4 liters of toluene.
After pre-drying at 0 ° C for 24 hours, 200 ° C under a nitrogen stream
For 12 hours under reduced pressure. Table A6 shows the yield of the obtained powder, the logarithmic viscosity of the polyimide powder, the glass transition temperature, the 5% weight loss temperature, and the melt viscosity (360 ° C / 5 minutes). The present invention is characterized in that the ratio of the chemical formula (2a) / chemical formula (2b) at the molecular end in the claims is from 1/99 to 80/20.
It is apparent that those having a ratio of a) / chemical formula (2b) of more than 80/20 are larger than those having a ratio of 80/20 or less and have poor moldability.

[0243]

Examples A18 to A22, Comparative Examples A9, A1
0 Press molding was performed using the powders obtained in Examples A13 to A17 and Comparative Example A8. The powder used in each of the examples and comparative examples is shown in the following Table A7.

[0245] Specifically, it was extruded into pellets at 355 ° C. using a 25 mm uniaxial extruder, and the pellets were 10.0 m wide.
Examples A18 to A22 and Comparative Example A9 were loaded in a press die having a mold having a size of 80.0 mm in length m.
Press molding was performed at 60 ° C. for 12 hours and for Comparative Example A10 at 360 ° C. for 5 minutes. In each case, good molded products were obtained. Each of the test pieces had a width of 10.0 mm ± 0.
010 mm, length was 80.0 mm ± 0.010 mm, and thickness was 1.500 mm ± 0.010 mm.
Using this molded product, a chemical resistance test was performed by the following method. Specifically, a portion of 5.00 mm from both ends of the test piece is fixed, and a jig is applied to the center of the test piece (a portion of 40.0 mm from both ends) to bend the test piece, thereby obtaining a thickness of 3.00 in the thickness direction.
It was adjusted to give a displacement of 50 mm and fixed. In this state, immersed in toluene and methyl ethyl ketone,
After 1 hour, 24 hours, and 168 hours, the test piece was taken out.
The presence or absence of cracks was visually observed. The results of the chemical resistance test are shown in Table A8. In the present invention, the ratio of chemical formula (2a) / chemical formula (2b) at the molecular end in the claims is 1/9.
9 to 80/20. From the above results, the ratio of the chemical formula (2a) / the chemical formula (2b) is
It is clear that those not reaching 1/99 have inferior chemical resistance as compared with those having 1/99 or more.

[0246] [Legend] In Table A8, “○”, “Δ”, and “×” indicate, respectively, those having no cracks, those having slight cracks, and those having many cracks, respectively. The term “PA / PCE molar ratio” indicates the molar ratio of phthalic anhydride to 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride, and “MEK” indicates methyl ethyl ketone.

Examples A23 to A32, Comparative Examples A11 to A
16 The following two reactions (A) and (B) were performed.

(A) In a vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube, 4,4'-bis (3-aminophenoxy) biphenyl as a monomer
368.43 g (1.000 mol), pyromellitic dianhydride, 102.52 g (0.470 mol), 3,
138.28 g (0.470 mol) of 3 ', 4,4'-biphenyltetracarboxylic dianhydride, 10.66 g (72.00 mmol) of phthalic anhydride as a terminal blocking agent
l), 11.92 g of 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride (48.00 mm
ol), 1830 g of m-cresol as a solvent, 13.970 g of γ-picoline as a catalyst (0.1500 mo
l) and stirring under a nitrogen atmosphere for 15 hours.
The temperature was raised to 0 ° C. over 2 hours, and the reaction was carried out at 150 ° C. for 2 hours. Subsequently, 5.33 g (36.00 mmol) of phthalic anhydride and 1-phenyl-2 were used as terminal blocking agents.
5.96 g (24.00 mmol) of-(3,4-dicarboxyphenyl) acetylene anhydride was charged, and 150 ° C.
For a further 8 hours. Thereafter, the mixture was cooled to 60 ° C., and the obtained viscous polymer solution was discharged into 10 liters of vigorously stirred methyl ethyl ketone, and the precipitate was separated by filtration. This was further sludged in 4 liters of methyl ethyl ketone, filtered and, after preliminary drying at 50 ° C. for 24 hours, dried at 220 ° C. for 12 hours under a nitrogen stream to obtain a polyimide powder.

(B) At the time of charging the kind and amount of the terminal blocking agent, only 17.77 g (120.00 mmol) of phthalic anhydride was used.
1) During the reaction, only 8.89 g of phthalic anhydride (6.
Polyimide powder was obtained in exactly the same manner as in (A) except that the amount was changed to 0.00 mmol). (A), the yield of the powder obtained by the two reactions (B), logarithmic viscosity of polyimide powder, glass transition temperature, 5% weight loss temperature, melt viscosity (36
(0 ° C./5 min) is shown in Table A9. In addition, 25
The pellets were extruded into pellets at 355 ° C. using a single-screw extruder at 355 ° C., and the pellets were charged into a press die having a mold having a shape specified in ASTM-D-638.
Press molding was performed under the conditions described in Example 10.

[0250]

[0251] Room temperature (23 ° C) and 177 ° C using the obtained test piece
At high temperature. The results are shown in Table A11. From the above, it is clear that the cross-linking group-containing polyimide of the present invention significantly improves the mechanical properties at room temperature and high temperature by annealing, and it can be seen that this effect cannot be expected with the general polyimides of Comparative Examples.

[0252]

Examples A28 to A32, Comparative Examples A14 to A
16 In a vessel equipped with a stirrer, reflux condenser, water separator and nitrogen inlet tube, 4,4'-bis (3-aminophenoxy) biphenyl as a monomer, 368.43 g (1.0
00 mol), pyromellitic dianhydride, 3,3 ′,
4,4′-biphenyltetracarboxylic dianhydride, the amount shown in Table A12, and m-cresol as a solvent in the amount shown in Table A12 were charged, and the mixture was stirred at 200 ° C. for 2 hours 30 minutes under a nitrogen atmosphere. And heated to 20
The reaction was carried out for 2 hours under the reflux condition of 0 ° C. to obtain a polymer solution having a terminal unblocked. During the reaction, another container was charged with the terminal blocking agent described in Table A13 and 200.0 ml of m-cresol,
In a nitrogen atmosphere, the mixture was previously heated and dissolved at 100 ° C. for 1 hour. The whole solution of the terminal blocking agent was charged into a polymer solution having no terminal blocking, and further reacted at 200 ° C. under reflux condition for 2 hours.

[0254] [Legend] In Table A12, “PMDA” indicates pyromellitic dianhydride, and “BPDA” indicates 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride.

[0255] [Legend] In Table A13, “PA” indicates phthalic anhydride, and “PCE” indicates 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.

Thereafter, the mixture was cooled to 60 ° C., and the obtained viscous polymer solution was stirred vigorously with methyl ethyl ketone 1
The mixture was discharged into 0 liter, and the precipitate was separated by filtration. This was further sludged in 4 liters of methyl ethyl ketone, filtered, and then pre-dried at 50 ° C. for 24 hours.
After drying at 220 ° C. for 12 hours, a polyimide powder was obtained. The logarithmic viscosity, glass transition temperature, and melt viscosity (360 ° C./5 minutes, 15 minutes, 30 minutes) of the obtained polyimide powder are shown in Table A14. From this result, it can be seen that the cross-linking group-containing polyimide of the present invention has good melt fluidity even with various molecular weights, and has better moldability than the comparative examples.

[0257]

Examples A33 to A37, Comparative Examples A17 to A
19 In a container equipped with a stirrer and nitrogen inlet tube, add 4,4 '
-Bis (3-aminophenoxy) biphenyl, 368.
43 g (1.000 mol) of pyromellitic dianhydride and N-methyl-2-pyrrolidone were charged in the amounts shown in Table A15, and reacted at room temperature for 12 hours while stirring under a nitrogen atmosphere to obtain a polyamide acid varnish. Obtained. Further, the obtained varnish was charged with the type and amount of terminal blocking agent shown in Table A15, and further reacted at room temperature for 12 hours.

[0259] [Legend] In Table A15, “PMDA”, “NMP”, “PA” and “PCE” are pyromellitic dianhydride, N-methyl-2-pyrrolidone, phthalic anhydride, and 1-phenyl-2, respectively. -(3,4-Dicarboxyphenyl) acetylene anhydride is shown.

The logarithmic viscosity of the obtained polyamic acid varnish is shown in Table A16. A film was produced using these varnishes. Specifically, a varnish is uniformly cast on a soft glass, and is heated from 50 ° C to 200 ° C in an oven under a nitrogen stream.
The temperature was raised at a rate of 1 ° C. per minute until the temperature reached 200 ° C. for 2 hours. 15 ℃ per minute from 200 ℃ to 370 ℃
And annealed at 370 ° C. for 4 hours. After quenching the resulting film, it was heated and stripped from the glass plate. The film of Comparative Example A19 was brittle, and was finely broken during quenching, and a film could not be obtained. The film obtained by this operation was subjected to a tensile test at normal temperature (23 ° C.). The results are shown in Table A16. From the above results, it is apparent that the cross-linking group-containing polyimide of the present invention exhibits better physical properties at various molecular weights as compared with Comparative Examples.

[0261]

Examples A38 to A42, Comparative Examples A20 to A
22 Methanol 1 in which 500 ml of the varnishes obtained in Examples A33 to A37 and Comparative Examples A17 to A19 was strongly stirred.
The mixture was discharged into 0 liter, and the precipitate was separated by filtration. This was further washed with 800 ml of methanol, and preliminarily dried at 50 ° C. for 24 hours under reduced pressure.
Dehydration and imidation were performed for 2 hours to obtain a polyimide powder. Glass transition temperature of varnish used and polyimide powder obtained and 5
The% weight loss temperatures are shown in Table A17. Further, the powder was placed in a heat-resistant dish, annealed under nitrogen at 380 ° C. for 2 hours, rapidly cooled, and then measured for a glass transition temperature and a 5% weight loss temperature.
The results are shown in Table A17. From the above results, it can be seen that the glass transition temperature of the polyimide containing a crosslinking group of the present invention is significantly improved by annealing, but is not improved in the comparative example.

[0263] [Legend] In Table A17, “Tg” indicates a glass transition temperature, and “Td5” indicates a 5% weight reduction temperature.

Examples A43 to A45, Comparative Example A23 In a vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube, 4,4'-bis (3-aminophenoxy) biphenyl as a monomer was added. 43g (1.0
00 mol), pyromellitic dianhydride 205.03 g
(0.940 mol), 1520 g of m-cresol was further charged as a solvent, and the mixture was heated and heated to 200 ° C. over 2 hours and 30 minutes while stirring under a nitrogen atmosphere.
The reaction was carried out for 2 hours under the reflux condition of 0 ° C. to obtain a polymer solution having a terminal unblocked. During the reaction, another container was charged with 200.0 ml of the terminal blocking agent described in Table A18 and m-cresol,
In a nitrogen atmosphere, the mixture was previously heated and dissolved at 100 ° C. for 1 hour. The whole solution of the terminal blocking agent was charged into a polymer solution having no terminal blocking, and further reacted at 200 ° C. under reflux condition for 2 hours.

[0265] [Legend] In Table A18, “PA” indicates phthalic anhydride, and “PCE” indicates 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.

Thereafter, the mixture was cooled to 100 ° C., and while maintaining the obtained viscous polymer solution at 100 ° C., 4 liters of toluene was dropwise added thereto over 4 hours. 8 more
After charging 3 liters of toluene heated to 0 ° C., the mixture was cooled to room temperature, 3 liters of toluene was further added, the mixture was stirred for 1 hour, and the precipitate was separated by filtration. This is further sludged in 4 liters of toluene, filtered, and then filtered.
After preliminary drying at 24 ° C. for 24 hours, the substrate was dried under reduced pressure at 200 ° C. for 12 hours under a nitrogen stream. Table A19 shows the logarithmic viscosity, glass transition temperature, crystal melting temperature, 5% weight loss temperature, and melt viscosity (410 ° C./5 minutes) of the obtained polyimide powder. Further, the obtained polyimide powder was extruded into pellets at 400 ° C., and the resin temperature was 380 to 410 ° C., the injection pressure was 1400 to 1600 kg / cm ² , and the mold temperature was 170 ° C.
Was performed to obtain an amorphous test piece having a shape defined by ASTM-D-638. Further, the temperature of the obtained amorphous test piece was increased from room temperature to 220 ° C. at a rate of 5 ° C./min under a nitrogen stream, and annealing was performed at 220 ° C. for 5 hours.
Temperature rise from 20 ° C to 280 ° C at a rate of 5 ° C / min,
280 ° C 5 hours annealing, 280 ° C to 320 ° C
Temperature at a rate of 5 ° C./min, annealing at 320 ° C. for 5 hours, annealing from 320 ° C. to 350 ° C. at a rate of 5 ° C./min, annealing at 350 ° C. for 24 hours, 5 ° C.
An annealing process consisting of 9 steps of cooling to room temperature at a temperature drop rate of / min was performed to crystallize, and the examples were crosslinked. A tensile test was performed using this test piece. The results are shown in Table A20.

[0267]

[0268] From the above results, it is clear that the crosslinked group-containing polyimide of the present invention has good mechanical properties even when crystallized.

Examples A46 to A49, Comparative Examples A24 to A
27 Two reactions of (A) and (B) were performed.

(A) In a vessel equipped with a stirrer, reflux condenser, water separator and nitrogen inlet tube,
4'-bis (3-aminophenoxy) biphenyl, 36
8.43 g (1.000 mol), pyromellitic dianhydride, 101.43 g (0.465 mol), 3,
136.81 g (0.465 mol) of 3 ', 4,4'-biphenyltetracarboxylic dianhydride and 1820 g of m-cresol as a solvent were charged, and the mixture was stirred at 200 ° C. for 3 hours under a nitrogen atmosphere. The temperature was raised by heating, and the reaction was carried out at 200 ° C. under reflux for 2 hours to obtain a polymer solution having an unsealed end. During the reaction, 20.74 g of phthalic anhydride (140.0 mmol
l), 34.75 g of 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride (140.0 mm
ol) and 200.0 ml of m-cresol, and dissolved by heating at 100 ° C. for 1 hour in advance in a nitrogen atmosphere. The whole solution of the terminal blocking agent was charged into a polymer solution having no terminal blocking, and further reacted at 200 ° C. under reflux condition for 2 hours. Thereafter, the mixture was cooled to 60 ° C., and the obtained viscous polymer solution was discharged into 10 liters of methanol with vigorous stirring, and the precipitate was separated by filtration. This is further sludged in 4 liters of methanol, filtered, and then cooled to 50 ° C.
After 24 hours of preliminary drying, 12 hours at 220 ° C. under a nitrogen stream.
After drying for a time, a polyimide powder was obtained.

(B) A polyimide powder was obtained in exactly the same manner as in (A), except that the type and amount of the terminal blocking agent were changed to 41.47 g (280.00 mmol) of phthalic anhydride alone.

The logarithmic viscosity, glass transition temperature, 5% weight loss temperature, and melt viscosity (360 ° C./5 minutes) of the powders obtained by the two reactions (A) and (B) are shown in Table A21. Further, each of them was 35 mm using a 25 mm single screw extruder.
Extrude and pelletize at 5 ° C.
After being charged into a press die having a mold having a shape defined in MD-638, press molding was performed under the conditions shown in Table A22. A chemical resistance test was performed using the obtained test pieces.
Specifically, at room temperature (23 ° C.),
The sample was fixed to a jig in a stretched state, and immersed in toluene and methyl ethyl ketone for 24 hours. A tensile test was performed at room temperature (23 ° C.) using the test piece after immersion, and the tensile strength retention was calculated by comparing with a tensile test result using the test piece before immersion. Here, the breaking strength retention is a percentage of the breaking strength of the test piece after immersion compared to the breaking strength of the test piece before immersion. The results are shown in Table A22.

[0273]

[0274] [Legend] In Table A22, “MEK” indicates methyl ethyl ketone.

From the above results, it is clear that the cross-linking group-containing polyimide of the present invention has greatly improved chemical resistance by various annealing conditions regardless of the annealing temperature. It turns out that this effect cannot be expected.

Examples A50 to A54, Comparative Examples A28 to A
32 In exactly the same manner as in Examples A13 to A17, various diamines and pyromellitic dianhydride 202.8 as monomers.
5 g (0.930 mol), 20.74 g of phthalic anhydride (140.0 mmol
1) and 34.75 g of 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride (140.0 mm
ol), and as a comparative example, only phthalic anhydride was 41.47.
g (280.00 mmol) was used to synthesize a polyimide powder. Furthermore, each was extruded at 325 ° C. to 365 ° C. using a 25 mm uniaxial extruder, and pelletized.
This beret was loaded into a press die having a die having a shape defined by ASTM-D-648, and then press-formed at 360 ° C. for 6 hours. The heat distortion temperature was measured using the obtained test piece. Table A23 shows the types and amounts of the diamines and the heat distortion temperatures used in the examples and comparative examples.

[0277] [Legend] In Table A23, diamines are shown by the following symbols. b) bis [4- (3-aminophenoxy) phenyl] ketone c) bis [4- (3-aminophenoxy) phenyl] sulfone d) bis [4- (3-aminophenoxy) phenyl] sulfide e) bis [4 -(3-Aminophenoxy) phenyl] ether f) 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane.

Examples A55 to A59, Comparative Examples A33 to A
37 In exactly the same manner as in Examples A13 to A17, various diamines as monomers and 331.59 g (0.900 mol) of 4,4′-bis (3-aminophenoxy) biphenyl
And pyromellitic dianhydride 202.85 g (0.930
mol), 20.74 g (140.0 mmol) of phthalic anhydride and 34.75 g (140.0 mmol) of 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride as examples of the terminal capping agent. As a comparative example, 41.47 g (280.00
mmol) to synthesize a polyimide powder. further,
Test pieces were obtained in the same manner as in Examples A50 to A54, and the heat distortion temperature was measured. Table A24 shows the types and amounts of the diamines and the heat distortion temperatures used in the examples.

[0279] [Legend] In Table A24, diamines are indicated by the following symbols. a) 4,4'-bis (3-aminophenoxy) biphenyl g) 3,4'-diaminodiphenyl ether h) 4,4'-diaminodiphenyl ether i) 3,3'-diaminodiphenylsulfone j) 1,3-bis (3-aminophenoxy) benzene k) 1,3-bis (3-aminophenoxy) -4-trifluoromethylbenzene

Examples A60 to A64, Comparative Examples A38 to A
42 In exactly the same manner as in Examples A13 to A17, various diamines as monomers and 22,4'-bis (3-aminophenoxy) biphenyl 221.058 g (0.600 mo
l) and 202.85 g of pyromellitic dianhydride (0.9
30mol), 20.74 g (140.0 mmol) of phthalic anhydride and 34.75 g (140.0 mmol) of 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride as examples of the terminal blocking agent. As a comparative example, 41.47 g of phthalic anhydride alone (280.
00 mmol) to synthesize a polyimide powder. Furthermore, test pieces were obtained in the same manner as in Examples A50 to A54, and the heat distortion temperature was measured. Table A25 shows the type and amount of the diamine used in each Example and Comparative Example, and the heat distortion temperature.
Shown in

[0281] [Legend] In Table A25, diamines are shown by the following symbols. a) 4,4'-bis (3-aminophenoxy) biphenyl m) 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene n) 4,4'-bis [4 -(4-aminophenoxy) benzoyl] diphenylether o) 3,3'-diamino-4,4'-diphenoxybenzophenone p) 3,3'-diamino-4-phenoxybenzophenone q) 6,6'-bis (3-aminophenoxy) 3,3,3, '3'-tetramethyl-1,1'-spirobiindane

Examples A65 to A69, Comparative Examples A43 to A
47 In exactly the same manner as in Examples A13 to A17, 368.43 g (1.000 mol) of 4,4′-bis (3-aminophenoxy) biphenyl as a monomer and various acid anhydrides, and as an end capping agent, Is phthalic anhydride 2
0.74 g (140.0 mmol) and 1-phenyl-2
34.75 g (140.0 mmol) of-(3,4-dicarboxyphenyl) acetylene anhydride and 41.47 g (280.00 mmol) of phthalic anhydride alone as a comparative example
A polyimide powder was synthesized using l). Further, each obtained a test piece in the same manner as in Examples A50 to A54,
The heat distortion temperature was measured. Table A26 shows the types and amounts of the acid anhydrides and the heat distortion temperatures used in the examples and comparative examples.

[0283] [Legend] In Table A26, the acid anhydrides are indicated by the following symbols. s) 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride t) 3,3', 4,4'-benzophenonetetracarboxylic dianhydride u) bis (3,4-dicarboxyphenyl) Ether dianhydride v) 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride w) 1,4-bis (3,4 -Dicarboxyphenoxy) benzene dianhydride

From the above tests, it is clear that the polyimide containing a cross-linking group having various structures according to the present invention is significantly higher in heat resistance than a similar polymer having no cross-linking group. Examples A70 to A75, Comparative Examples A43 to A48 Dimethylacetamide was used as a solvent, and the type and amount of diamine and acid anhydride shown in Table A27 were used as monomers.
10. Phthalic anhydride for Examples as end capping agent.
66 g (72.00 mmol) and 1-phenyl-2-
(3,4-dicarboxyphenyl) acetylene anhydride 1
1.92 g (48.00 mmol), and 17.77 g (120.00 mmol) of phthalic anhydride alone as a comparative example.
15% in the same manner as in Examples A33 to A37 using l)
(W / w) Polyamic acid varnish was obtained.

[0285] [Legend] In Table A27, diamines and acid anhydrides are indicated by the following symbols. a) 4,4'-bis (3-aminophenoxy) biphenyl b) bis [4- (3-aminophenoxy) phenyl] ketone c) bis [4- (3-aminophenoxy) phenyl] sulfone h) 4,4 '-Diaminodiphenyl ether i) 3,3'-diaminodiphenylsulfone j) 1,3-bis (3-aminophenoxy) benzene o) 3,3'-diamino-4,4'-diphenoxybenzophenone r) pyromellitic acid Dianhydride s) 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride t) 3,3', 4,4'-benzophenonetetracarboxylic dianhydride

Further, Example 33 was carried out using the obtained varnish.
A film was produced under the same conditions as those of Nos. To 37. Furthermore, this is punched out with a mold and the width is 5.00 mm and the length is 260.00 m
m-shaped test piece was obtained. A chemical resistance test was performed using this test piece. Specifically, 5. from both ends of the film.
The distance between them was set to 251.75 mm using an instrument that fixed the 00 mm portion and that could finely adjust the distance between them. In this state, the entire device was immersed in toluene or methyl ethyl ketone, and after 1 hour, 24 hours, and 16 hours.
After 8 hours, it was taken out and visually checked for cracks. The results are shown in Table A28 together with the logarithmic viscosity of the varnish. In Table A28, “○”, “△”, and “×” indicate, respectively, those having no cracks, those having slight cracks, and those having many cracks, respectively. “MEK” indicates methyl ethyl ketone.

[0287]

Examples A76 to A79 and Comparative Example A54 Using dimethylformamide as a solvent, 368.43 g (1.000 mol) of 4,4'-bis (3-aminophenoxy) biphenyl as a monomer and pyromellitic dianhydride 142 were used. 0.000 g (0.651 mol), 3,
Examples A33 to A37 using 89.90 g (0.279 mol) of 3 ', 4,4'-benzophenonetetracarboxylic dianhydride and the types and amounts of terminal blocking agents shown in Table A29.
15% (w / w) of a polyamic acid varnish was obtained in the same manner as described above. Examples A33 to A using the obtained varnish
A film was produced under the same conditions as in 37. Further, a chemical resistance test in toluene was carried out in the same manner as in Examples A70 to A75 using this. The results are shown in Table A29 together with the logarithmic viscosity of the varnish. In Table A28, “○”, “△”, and “×” indicate, respectively, those having no cracks, those having slight cracks, and those having many cracks, respectively.

[0289] [Legend] In Table A29, the terminal blocking agent is indicated by the following symbols. A) Phthalic anhydride B) 1-Phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride C) 1-Phenyl-2- (4- (3,4-dicarboxyphenoxy) phenyl) acetylene anhydride Compound D) 1-phenyl-2- (4- (3,4-dicarboxybenzoyl) phenyl) acetylene anhydride E) 2,3-dicarboxy-6- (phenylethynyl) naphthalene anhydride

From the above results, it is clear that the cross-linking group-containing polyimides of the present invention having various structures have higher chemical resistance than those of similar polymers having no cross-linking group.

Examples A80 to A82 Using the polyimide powders used in Examples A28 to A30, the melt viscosity was measured at 300 ° C. to 400 ° C. while changing the measurement temperature / residence time variously. Table A3 shows the results.
0 is shown. The shear stress under this measurement condition was 0.24.
It is constant at 5 MPa.

[0292]

Comparative Examples A55 to A57 The temperature dependence of melt viscosity and melt viscosity stability was obtained in the same manner as in Examples A80 to A82 using the polyimide powders used in Comparative Examples A14 to A16. The results are shown in Table A31.

[0294] Examples A80 to A82 and Comparative Examples A55 to A57
From the results, it is clear that the crosslinkable group-containing polyimide of the present invention has high melt viscosity stability over a wide temperature range and excellent moldability.

Examples A83 to A87 Using a melt viscoelasticity meter (RDS-II, Rheometrics)
By parallel plate (25mm disposable)
The gelation time at each temperature of the powder polymerized in Examples A13 to A17 was measured. In addition, the gel time is
It is the time required to reach the gel point at a certain frequency at that temperature, and the gel point is the storage elastic modulus G ',
This is the point where the lines of G ′ and G ″ intersect when the loss modulus is graphed as a function of time t (minutes). The measurement was performed at each temperature for up to 2 hours. The results are shown in Table A32.
Shown in In Table A32, “> 120” indicates that the gel point was not reached within the measurement time.

[0296]

Comparative Examples A58 to A59 The gelling time at each temperature of the powder polymerized in Comparative Examples A6 to A7 was measured in the same manner as in Examples A83 to A87. The results are shown in Table A33.

[0298] Examples A83 to A87 and Comparative Examples A58 to A59
From the results, it is clear that the cross-linking group-containing polyimide of the present invention has a slow gelation over a wide temperature range and is excellent in moldability.

Examples A88 to A91 and Comparative Examples A60 to A6
3 The type and amount of terminal blocking were determined by adding 1-phenyl-2- (3,4-
Dicarboxyphenyl) acetylene anhydride only 69.5
Example A except that the amount was changed to 0 g (280.0 mmol).
Polyimide powder was obtained in exactly the same manner as (A) described in Nos. 46 to A49. This polyimide powder is designated as (C). Furthermore, the polyimide powder obtained in (B) of Examples A46 to A49 and the polyimide of (C) were blended at a weight ratio shown in Table A34 to obtain a uniform mixed powder. This mixed powder is designated as (D) and (E).
Table A34 shows the physical properties of (C) to (E).

[0300] The obtained polyimide powders (D) and (E) were extruded into pellets in the same manner as in Examples A46 to A49, and subjected to a press molding / chemical resistance test. The results are shown in Table A35.

[0301] [Legend] In Table A35, “MEK” indicates methyl ethyl ketone.

From the above results, it is clear that the cross-linking group-containing polyimide of the present invention obtained by blending is also significantly improved in chemical resistance by treatment under various annealing conditions regardless of the annealing temperature. It can be seen that this effect cannot be expected with polyimide.

Experiment B Series In Examples B1 to B61, in the present invention, 50 to 100 mol% of the repeating structural units having a main chain structure were used.
But,

[0304]

Embedded image (Wherein X is a direct bond, a carbonyl group, a sulfone group,
A sulfide group, an ether group, an isopropylidene group, and a divalent linking group selected from a hexafluorinated isopropylidene group, wherein R is

[0305]

Embedded image (In the formula, G is a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluorinated isopropylidene group, and at least one divalent group selected from a substituent group represented by the following formula. Is a bonding group.

[0306]

Embedded image ) Represents a tetravalent aromatic group selected from the group consisting of)).

Examples B1 to B7 and Comparative Examples B1 to B3 In a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, 3,4'-diaminodiphenyl ether as a monomer, 200.24 g ( 1.000mo
l), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 138.28 g (0.470 mol), bis (3,4-dicarboxyphenyl) ether dianhydride, 145.80 g (0 .470 mol), 1937 g of m-cresol as a terminal blocking agent and a solvent of the type and amount shown in Table B1, and heating to 200 ° C. over 2 hours and 30 minutes while stirring under a nitrogen atmosphere, 200
The reaction was carried out under a reflux condition at 4 ° C for 4 hours. In Table B1, "PA" indicates phthalic anhydride, and "PCE" indicates 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.

[0308] Subsequently, the temperature was lowered to 190 ° C., the terminal capping agent shown in Table B1 was charged again, the temperature was raised again, and the reaction was further performed under a reflux condition of 200 ° C. for 4 hours. Thereafter, the mixture was cooled to 100 ° C., and the obtained viscous polymer solution was discharged into 10 liters of vigorously stirred toluene, and the precipitate was separated by filtration. This was further sludged in 4 liters of toluene, filtered, and preliminarily dried at 50 ° C. for 24 hours.
Dry at 10 ° C. for 12 hours. Yield of powder obtained
Table B2 shows the logarithmic viscosity, glass transition temperature, 5% weight loss temperature, and melt viscosity (360 ° C./5 minutes) of the polyimide powder.

[0309] In the present invention, the chemical formula (2a) /
The molar ratio of the chemical formula (2b) is characterized by being from 1/99 to 80/20. From the above results, the molar ratio of the chemical formula (2a) / the chemical formula (2b) exceeds 80/20. It is clear that the moldability is large and the moldability is inferior to those of 80/20 or less.

Examples B8 to B12, Comparative Examples B4 and B5 Press molding was performed using the powders obtained in Examples B2 to B6 and Comparative Example B3. Here, the powders used in the respective examples and comparative examples are shown in the following Table B3.

[0311] Specifically, it was extruded into pellets at 355 ° C. using a single-screw extruder having a diameter of 25 mm, and this pellet was subjected to ASTM-D
After loading into a press die having a mold having a shape defined in -638, Examples B8 to B12 and Comparative Example B4 were 360
Press molding was performed at 12 ° C. for 12 hours and for Comparative Example 5 at 360 ° C. for 5 minutes. In each case, good molded products were obtained. Using this molded product, a tensile test was performed at normal temperature (23 ° C.). The results are shown in Table B4. In Table B4, “PA /
"PCE molar ratio" indicates the molar ratio of phthalic anhydride to 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.

[0312] In the present invention, the chemical formula (2a) /
The molar ratio of the chemical formula (2b) is characterized by being from 1/99 to 80/20. From the above results, the molar ratio of the chemical formula (2a) / the chemical formula (2b) does not reach 1/99. It is clear that the material has inferior mechanical properties as compared with 1/99 or more.

Examples B13 to B17, Comparative Examples B6 to B8 In a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, 3,4'-diaminodiphenyl ether as a monomer, 200.24 g ( 1.000mo
l), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 138.28 g (0.470 mol), bis (3,4-dicarboxyphenyl) ether dianhydride, 145.80 g (0 .470 mol), and 1737 g of m-cresol was charged as a solvent, and the mixture was heated to 200 ° C. over 2 hours and 30 minutes with stirring under a nitrogen atmosphere, and reacted at 200 ° C. under reflux for 2 hours to carry out the reaction. A sealed polymer solution was obtained. Table B in another container during the reaction
5. The terminal blocking agent according to 5 and 200.0 ml of m-cresol
And heated and dissolved in advance in a nitrogen atmosphere at 100 ° C. for 1 hour. The whole solution of the terminal blocking agent was charged into a polymer solution having no terminal blocking, and further reacted at 200 ° C. under reflux condition for 2 hours. In Table B5, “PA” indicates phthalic anhydride, and “PCE” indicates 1
-Phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.

[0314] Thereafter, the mixture was cooled to 100 ° C., and while keeping the obtained viscous polymer solution at 100 ° C., 2 liters of toluene heated to 100 ° C. were charged therein, and 6 liters of toluene were added dropwise over 4 hours. Charged. After charging 4 liters of toluene, the mixture was cooled to room temperature, and the precipitate was separated by filtration. This was further sludged in 4 liters of toluene, separated by filtration, preliminarily dried at 50 ° C. for 24 hours, and then dried under reduced pressure at 200 ° C. for 12 hours under a stream of nitrogen. Yield of obtained powder ・ Logarithmic viscosity of polyimide powder ・ Glass transition temperature ・ 5% weight loss temperature ・ Melting viscosity (360 ° C./5 minutes)
Is shown in Table B6.

[0315] In the present invention, the chemical formula (2a) /
The molar ratio of the chemical formula (2b) is characterized by being from 1/99 to 80/20, and from the above results, the molar ratio of the chemical formula (2a) / the chemical formula (2b) exceeds 80/20. It is clear that the moldability is large and the moldability is inferior to those of 80/20 or less.

Examples B18 to B22, Comparative Examples B9 and B1
0 Press molding was performed using the powders obtained in Examples B13 to B17 and Comparative Example B8. Here, the powders used in the respective examples and comparative examples are shown in the following Table B7.

[0317] Specifically, it was extruded into pellets at 355 ° C. using a single screw extruder having a diameter of 25 mm, and this beret was formed to a width of 10.0 m.
Examples B18 to B22 and Comparative Example B9 were loaded into a press die having a mold having a size of 80.0 mm in m length.
Press molding was performed at 60 ° C. for 12 hours and for Comparative Example 10 at 360 ° C. for 5 minutes. In each case, good molded products were obtained. Each specimen has a width of 10.0 mm ± 0.0
The length was 10 mm, the length was 80.0 mm ± 0.010 mm, and the thickness was 1.500 mm ± 0.010 mm.
Using this molded product, a chemical resistance test was performed. Specifically, a portion of 5.00 mm from both ends of the test piece is fixed, and a jig is applied to the center of the test piece (a portion of 40.0 mm from both ends) to bend, thereby displacing 3.50 mm in the thickness direction. Adjusted to give and fixed. In this state, immersed in toluene and methyl ethyl ketone,
After 4 hours and 168 hours, the test piece was taken out, and the presence or absence of cracks was visually observed. Table B shows the results of the chemical resistance test.
8 is shown. In Table B8, “○”, “△”,
“X” indicates, in order, those having no cracks, those having slight cracks, and those having many cracks. In addition, "PA / PCE molar ratio"
There is phthalic anhydride and 1-phenyl-2- (3,4
The molar ratio of (-dicarboxyphenyl) acetylene anhydride is indicated, and "MEK" indicates methyl ethyl ketone.

[0318] In the present invention, the chemical formula (2a) /
The molar ratio of the chemical formula (2b) is characterized by being from 1/99 to 80/20. From the above results, the molar ratio of the chemical formula (2a) / the chemical formula (2b) does not reach 1/99. It is evident that the product has inferior chemical resistance as compared with 1/99 or more.

Examples B23 to B32 and Comparative Examples B11 to B
16 Two reactions (A) and (B) were performed. (A) In a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, 3,4'-diaminodiphenyl ether as a monomer, 200.24 g (1.000 g)
mol), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 138.28 g (0.470 mol
l), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 151.45 g (0.470 mol
l), 10.66 g of phthalic anhydride (7
2.00 mmol), 11.92 g of 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride
(48.00 mmol), m-cresol 1 as a solvent
960 g, 13.970 g of γ-picoline as a catalyst
(0.1500 mol), and heated to 150 ° C. over 2 hours while stirring under a nitrogen atmosphere,
The reaction was performed at 150 ° C. for 2 hours. Subsequently, 5.33 g (36.00 mmol) of phthalic anhydride was used as a terminal blocking agent,
1-phenyl-2- (3,4-dicarboxyphenyl)
5.96 g (24.00 mmol) of acetylene anhydride was charged, and the reaction was further performed at 150 ° C. for 8 hours. Thereafter, the mixture was cooled to 60 ° C., and the obtained viscous polymer solution was discharged into 10 liters of vigorously stirred methyl ethyl ketone, and the precipitate was separated by filtration. This was further sludged in 4 liters of methyl ethyl ketone, filtered and then treated at 50 ° C. 24
After preliminary drying for a period of time, the mixture was dried at 220 ° C. for 12 hours under a nitrogen stream to obtain a polyimide powder. (B) At the time of charging the kind and amount of the terminal blocking agent, 17.77 g (120.00 mmol) of only phthalic anhydride, and 8.89 g (60.00 mmol) of phthalic anhydride alone during the reaction were charged.
A polyimide powder was obtained in exactly the same manner as in (A), except for changing to l). Table B9 shows the yield of the powder obtained by the two reactions (A) and (B), the logarithmic viscosity of the polyimide powder, the glass transition temperature, the 5% weight loss temperature, and the melt viscosity (360 ° C / 5 minutes). Furthermore, each was extruded and pelletized at 355 ° C. using a single-screw extruder having a diameter of 25 mm, and this bellet was charged into a press die having a mold having a shape specified in ASTM-D-638. Press molding was performed.

[0320]

[0321] Room temperature (23 ° C.) and 177
A high temperature tensile test at ℃ was performed. The results are shown in Table B11.

[0322] From the above, it is apparent that the room temperature and high temperature mechanical properties of the polyimide containing a cross-linking group of the present invention are greatly improved by annealing, and it can be seen that this effect cannot be expected with the general polyimides of Comparative Examples.

Examples B28 to B32, Comparative Examples B14 to B
16 In a container equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, 4,4'-diaminodiphenyl ether as a monomer, 200.24 g (1.000 mo
l), bis (3,4-dicarboxyphenyl) ether dianhydride and 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride in the amounts shown in Table B12 and m-cresol as a solvent Are charged as shown in Table B12,
The mixture was heated to 200 ° C. over 2 hours and 30 minutes while stirring under a nitrogen atmosphere, and reacted at 200 ° C. under reflux for 2 hours to obtain a polymer solution having an unsealed end. Table B1
2, "ODPA" indicates bis (3,4-dicarboxyphenyl) ether dianhydride, and "HQDA" indicates 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride. Indicates an object.

[0324] During the reaction, the terminal blocking agent described in Table B13 and m-
200.0 ml of cresol was charged and dissolved by heating at 100 ° C. for 1 hour in advance in a nitrogen atmosphere. The whole solution of the terminal blocking agent was charged into a polymer solution having no terminal blocking, and further reacted at 200 ° C. under reflux condition for 2 hours.
In Table B13, “PA” indicates phthalic anhydride, and “PCE” indicates 1-phenyl-2- (3,4
-Dicarboxyphenyl) acetylene anhydride.

[0325] Thereafter, the mixture was cooled to 60 ° C., and the obtained viscous polymer solution was discharged into 10 liters of vigorously stirred methyl ethyl ketone, and the precipitate was separated by filtration. This is further sludged in 4 liters of methyl ethyl ketone, filtered, and then filtered.
After predrying for 24 hours at 220 ° C, 1 hour at 220 ° C under a nitrogen stream.
After drying for 2 hours, a polyimide powder was obtained. Logarithmic viscosity, glass transition temperature, melt viscosity (360 ° C
/ 5 minutes, 15 minutes, 30 minutes) are shown in Table B14.

[0326] [Legend] “←”; “Same on the left. "Meaning of.

From these results, it was found that the polyimide containing a crosslinking group of the present invention has various molecular weights (or logarithmic viscosities correlated with the molecular weights).
It can be seen that those having a good melt flowability also have good moldability as compared with the comparative examples.

Examples B33 to B37, Comparative Examples B17 to B
19 In a container equipped with a stirrer and nitrogen introduction tube,
4'-diaminodiphenyl ether, 200.24 g
(1.000 mol), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and N-methyl-2-pyrrolidone were charged in the amounts shown in Table B15, and stirred at room temperature under a nitrogen atmosphere. The reaction was carried out for 12 hours to obtain a polyamic acid varnish. Further, the obtained varnish was charged with the end capping agent of the kind and amount shown in Table B15, and further reacted at room temperature for 12 hours. "BPDA" and "NMP" in Table B15
“PA” and “PCE” indicate pyromellitic dianhydride, N-methyl-2-pyrrolidone, phthalic anhydride, and 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride, respectively. .

[0329] The logarithmic viscosity of the resulting polyamic acid varnish is shown in Table B16. A film was produced using these varnishes. Specifically, a varnish is uniformly cast on soft glass, and is heated from 50 ° C. to 200 ° C. in an oven under a nitrogen stream at 1 ° C. per minute.
At 200 ° C. for 2 hours. Further, the temperature was raised from 200 ° C. to 410 ° C. at a rate of 20 ° C./min, and annealing was performed at 410 ° C. for 30 minutes. After quenching the resulting film, it was heated and stripped from the glass plate. The film of Comparative Example 19 was brittle, and was finely broken during quenching, so that a film could not be obtained. However, other films obtained good films.
The film obtained by this operation was subjected to a tensile test at normal temperature (23 ° C.). The results are shown in Table B16.

[0330] From the above results, it is clear that the cross-linking group-containing polyimide of the present invention exhibits better physical properties at various molecular weights (or logarithmic viscosity correlated with the molecular weight) as compared with Comparative Examples.

Examples B38 to B42, Comparative Examples B20 to B
22 Methanol 1 in which 500 ml of the varnishes obtained in Examples B33 to B37 and Comparative Examples B17 to B19 was strongly stirred.
The mixture was discharged into 0 liter, and the precipitate was separated by filtration. This was further washed with 800 ml of methanol, and preliminarily dried at 50 ° C. for 24 hours under reduced pressure.
Dehydration and imidation were performed for 2 hours to obtain a polyimide powder. Glass transition temperature of varnish used and polyimide powder obtained and 5
The% weight loss temperatures are shown in Table B17. Further, the powder was placed in a heat-resistant dish, annealed at 420 ° C. for 1 hour under nitrogen, rapidly cooled, and then measured for a glass transition temperature and a 5% weight loss temperature.
The results are shown in Table B17. In Table B17, "Tg" indicates a glass transition temperature, and "Td5" indicates a 5% weight loss temperature.

[0332] From the above results, it can be seen that the glass transition temperature of the polyimide containing a crosslinking group of the present invention is significantly improved by annealing, but is not improved in the comparative example.

Examples B43 to B45, Comparative Example B23 In a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, 200.24 g of 3,4'-diaminodiphenyl ether as a monomer (1. 000mo
l), 276.57 g (0.940 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 1707 g of m-cresol as a solvent were charged, and the mixture was stirred at 200 ° C. under a nitrogen atmosphere. 2 hours 30 until
The mixture was heated and heated for 2 minutes, and reacted at 200 ° C. under reflux conditions for 2 hours to obtain a polymer solution having an unblocked end. During the reaction, another container was charged with the terminal blocking agent described in Table B18 and 200.0 ml of m-cresol, and 1
The mixture was heated at 00 ° C. for 1 hour to dissolve. The whole solution of the terminal blocking agent was charged into a polymer solution having no terminal blocking, and further reacted at 200 ° C. under reflux condition for 2 hours. Table B
18, "PA" indicates phthalic anhydride, and "PC"
"E" indicates 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.

[0334] Thereafter, the mixture was cooled to 100 ° C., and while maintaining the obtained viscous polymer solution at 100 ° C., 4 liters of toluene was dropped therein over 4 hours. After 3 liters of toluene heated to 80 ° C. were further charged, the mixture was cooled to room temperature, further 3 liters of toluene was added, and the mixture was stirred for 1 hour, and the precipitate was separated by filtration. This was further sludged in 4 liters of toluene, separated by filtration, preliminarily dried at 50 ° C. for 24 hours, and then dried under reduced pressure at 200 ° C. for 12 hours under a stream of nitrogen. Table B19 shows the logarithmic viscosity, glass transition temperature, crystal melting temperature, 5% weight loss temperature, and melt viscosity (420 ° C / 5 minutes) of the obtained polyimide powder.

[0335] Further, the obtained polyimide powder was extruded into pellets at 420 ° C., the resin temperature was 315 to 425 ° C., the injection pressure was 1400 to 1600 kg / cm 2, and the mold temperature was 22.
Injection molding was performed at 0 ° C. to obtain a test piece having a shape defined by ASTM-D-638. Further, the temperature of the obtained test piece was increased from room temperature to 240 ° C. at a rate of 5 ° C./min under a nitrogen stream, annealing treatment at 240 ° C. for 5 hours, and a temperature increase rate of 5 ° C./min from 240 ° C. to 300 ° C. Temperature rise, 300 ℃ 5
Time annealing, 5 ℃ / 300 ℃ to 380 ℃
Temperature at 380 ° C for 3 hours,
An annealing process consisting of seven steps of cooling to room temperature at a cooling rate of 5 ° C./min was added to crystallize, and the examples were crosslinked. A tensile test was performed using this test piece. The results are shown in Table B20.

[0336] From the above results, it is clear that the crosslinked group-containing polyimide of the present invention has good mechanical properties even when crystallized.

Examples B46 to B49, Comparative Examples B24 to B
27 Two reactions of (A) and (B) were performed. (A) In a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, 3,4'-diaminodiphenyl ether as a monomer, 200.24 g (1.000 g)
mol), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 136.81 g (0.465 mol
l), bis (3,4-dicarboxyphenyl) ether dianhydride, 144.25 g (0.465 mol) and 1,925 g of m-cresol as a solvent were charged, and the mixture was stirred at 200 ° C. for 3 hours under a nitrogen atmosphere. The mixture was heated and heated at 200 ° C. under reflux for 2 hours to obtain a polymer solution having an unsealed end. During the reaction, 20.74 g of phthalic anhydride (140.0 m
mol), 34.75 g of 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride (140.0 g).
mmol), 200.0 ml of m-cresol,
In a nitrogen atmosphere, the mixture was previously heated and dissolved at 100 ° C. for 1 hour. The whole solution of the terminal blocking agent was charged into a polymer solution having no terminal blocking, and further reacted at 200 ° C. under reflux condition for 2 hours. Thereafter, the mixture was cooled to 60 ° C., and the obtained viscous polymer solution was discharged into 10 liters of vigorously stirred methanol, and the precipitate was separated by filtration. This is further sludged in 4 liters of methanol.
After predrying for 24 hours at 220 ° C, 1 hour at 220 ° C under a nitrogen stream.
After drying for 2 hours, a polyimide powder was obtained. (B) The type and amount of the terminal blocking agent were phthalic anhydride only. 41.
(A) except that it was changed to 47 g (280.00 mmol)
In the same manner as above, a polyimide powder was obtained. (A),
The logarithmic viscosity of the powder obtained by the two reactions (B)
Glass transition temperature, 5% weight loss temperature, melt viscosity (360
C / 5 min) is shown in Table B21. Furthermore, each was extruded and pelletized at 355 ° C. using a single screw extruder having a diameter of 25 mm, and this bellet was charged into a press mold having a mold having a shape defined in ASTM-D-638.
Press molding was performed under the conditions described in No. 22. A chemical resistance test was performed using the obtained test pieces. Specifically, at room temperature (2
(3 ° C.), the test piece was fixed to a jig in a 0.5% extended state, and the test piece was added to toluene and methyl ethyl ketone for 24 hours.
Soaked for hours. At room temperature (23
C), and the tensile strength retention was calculated by comparing with a tensile test result using a test piece before immersion. Here, the breaking strength retention is a percentage of the breaking strength of the test piece after immersion compared to the breaking strength of the test piece before immersion. The results are shown in Table B22. Table B
In 22, "MEK" indicates methyl ethyl ketone.

[0338]

[0339] From the above results, it is clear that the crosslinking group-containing polyimide of the present invention has greatly improved chemical resistance by treatment under various annealing conditions regardless of the annealing temperature. It turns out that it cannot be expected.

Examples B50 to B54, Comparative Examples B28 to B
32 In exactly the same manner as in Examples B13 to B17, various diamines and bis (3,4-dicarboxyphenyl) ether dianhydride 288.50 g (0.930 mol) were used as monomers.
1) As an end capping agent, 20.74 g (140.0 mmol) of phthalic anhydride and 1-phenyl-
34.75 g (140.0 mmol) of 2- (3,4-dicarboxyphenyl) acetylene anhydride, and 41.47 g (280.00 mm) of phthalic anhydride alone as a comparative example
ol) to synthesize a polyimide powder. Further, each of them was 325 ° C. to 36 ° C. using a single screw extruder having a diameter of 25 mm.
Extrude and pelletize at 5 ° C.
After being charged into a press die having a mold having a shape defined by MD-648, press molding was performed at 360 ° C. for 6 hours. The heat distortion temperature was measured using the obtained test piece. Table B23 shows the types and amounts of the diamines and the heat distortion temperatures used in the examples and the comparative examples. In Table B23,
Diamines are indicated by the following symbols. a) 3,3'-diaminodiphenyl ether, b) 3,4'-diaminodiphenyl ether, c) 4,4'-diaminodiphenyl ether, e) 3,3'-diaminodiphenylsulfone, h) 4,4'-diaminodiphenylmethane ,

[0341]

Examples B55 to B59, Comparative Examples B33 to B
37 In exactly the same manner as in Examples 23 to 32, various diamines, 180.22 g (0.900 mol) of 4,4′-diaminodiphenyl ether and 1,4-bis (3,4-dicarboxyphenoxy) benzene 374.16 g (0.930 mol) of anhydride, 20.74 g of phthalic anhydride (14
0.0 mmol) and 34.75 g of 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride (1
40.0 mmol) and 41.47 g (280.00 mmol) of phthalic anhydride alone as a comparative example to synthesize a polyimide powder. Further, each was prepared in Example B50.
A test piece was obtained in the same manner as in B54 to B54, and the heat distortion temperature was measured. Table B24 shows the type and amount of the diamine used in each Example, and the heat distortion temperature. In Table B24, diamines are indicated by the following symbols. a) 3,3'-diaminodiphenyl ether, b) 4,4'-diaminodiphenyl ether, c) 3,3'-diaminodiphenyl sulfide, d) 3,3'-diaminobenzophenone, e) 3,3'-diaminodiphenylmethane F) 2,2-di (4-aminophenyl) propane;

[0343] From the above tests, it is clear that the polyimide containing a cross-linking group having various structures according to the present invention is significantly higher in heat resistance than a similar polymer having no cross-linking group.

Examples B60 to B61, Comparative Example B38 The melt viscosity was measured in the same manner as in Examples A80 to A82 using the polyimide powders used in Examples B30 and B32 and Comparative Example B16. The gelation time at each temperature was measured for these powders in the same manner as in Examples A83 to A87. The results are shown in Table B25.
In Table B25, ">120" indicates that the gel point was not reached within the measurement time.

[0345] From these results, it is clear that the cross-linking group-containing polyimide of the present invention has high melt viscosity stability over a wide temperature range, is unlikely to gel, and has excellent moldability.

Experiment C Series In Examples C1 to C39, 50 to 100 mol% of the repeating structural units having a main chain structure in the present invention were used.
But,

[0347]

Embedded image (Wherein X is a direct bond, a carbonyl group, a sulfone group,
A sulfide group, an ether group, an isopropylidene group, and a divalent linking group selected from a hexafluorinated isopropylidene group, wherein R is

[0348]

Embedded image (In the formula, G is a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluorinated isopropylidene group, and at least one divalent group selected from a substituent group represented by the following formula. Is a bonding group.

[0349]

Embedded image ) Represents a tetravalent aromatic group selected from the group consisting of)).

Examples C1 to C7, Comparative Examples C1 to C3 1,3-bis (4-aminophenoxy) benzene as a monomer was placed in a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube. , 292.34 g (1.00
0 mol), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 138.28 g (0.470 mol
l), bis (3,4-dicarboxyphenyl) ether dianhydride, 145.80 g (0.470 mol), Table C
3266 g of m-cresol as a type and amount of a terminal blocking agent and a solvent shown in 1 were charged and heated to 200 ° C. over 2 hours and 30 minutes while stirring under a nitrogen atmosphere.
The reaction was carried out at 200 ° C. under reflux for 4 hours. Table C
1, "PA" indicates phthalic anhydride, and "PC"
"E" indicates 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.

[0351] Subsequently, the temperature was lowered to 190 ° C., the end capping agent of the type and amount described in Table C1 was charged again, and the temperature was raised again to 200 ° C.
The reaction was further performed under reflux conditions for 4 hours. Then 100
After cooling to ℃, the obtained viscous polymer solution was discharged into 20 liters of vigorously stirred toluene, and the precipitate was separated by filtration. This was further sludged in 4 liters of toluene, separated by filtration, preliminarily dried at 50 ° C. for 24 hours, and then dried at 210 ° C. for 12 hours under a nitrogen stream. Yield of obtained powder ・ Logarithmic viscosity of polyimide powder ・ Glass transition temperature ・
Table C shows 5% weight loss temperature and melt viscosity (360 ° C / 5 min)
It is shown in FIG.

[0352] In the present invention, the chemical formula (2)
The molar ratio of a) / chemical formula (2b) is from 1/99 to 80 /
It is characterized by being 20, but from the above results,
The molar ratio of the chemical formula (2a) / the chemical formula (2b) is 80/2
It is clear that those having a value of more than 0 are inferior in moldability as compared with those having a ratio of 80/20 or less.

Examples C8 to C12, Comparative Examples C4 and C5 Press molding was performed using the powders obtained in Examples C2 to C6 and Comparative Example C3. The powder used in each of the examples and comparative examples is shown in the following Table C3.

[0354] Specifically, using a 25 mm diameter single screw extruder, 355
Extruded pellets at ℃ and cast this bellet into ASTM
After loading into a press die having a mold having a shape defined in D-638, Examples C8 to C12 and Comparative Example C4
Press molding was performed at 60 ° C. for 12 hours and for Comparative Example C5 at 360 ° C. for 5 minutes. In each case, good molded products were obtained. Using this molded product, a tensile test was performed at normal temperature (23 ° C.). The results are shown in Table C4. In Table C4, "PA / PCE molar ratio" refers to phthalic anhydride and 1-
The molar ratio of phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride is shown.

[0355] In the present invention, the chemical formula (2a) /
The molar ratio of the chemical formula (2b) is characterized by being from 1/99 to 80/20. From the above results, the molar ratio of the chemical formula (2a) / the chemical formula (2b) does not reach 1/99. It is clear that the material has inferior mechanical properties as compared with 1/99 or more.

Examples C13 to C17, Comparative Examples C6 to C8 1,4-bis (4-aminophenoxy) benzene as a monomer was placed in a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube. , 292.34 g (1.00
0 mol), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 138.28 g (0.470 mol
l), bis (3,4-dicarboxyphenyl) ether dianhydride, 145.80 g (0.470 mol), and m-cresol 2105 g as a solvent were charged, and the mixture was stirred at 200 ° C. for 2 hours under a nitrogen atmosphere. The temperature was increased by heating over 30 minutes, and the reaction was carried out under a reflux condition of 200 ° C. for 2 hours to obtain a polymer solution having an unsealed end. During the reaction, the terminal blocking agent described in Table C5 and m-cresol 200.
0 ml, 100 ° C. in advance in a nitrogen atmosphere,
Heated for 1 hour to dissolve. A total amount of the solution of the terminal blocking agent was charged into a polymer solution having no terminal blocking, and further 200 ° C.
The reaction was performed under reflux conditions for 2 hours. In Table C5, "P
"A" indicates phthalic anhydride, and "PCE" indicates 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.

[0357] Thereafter, the mixture was cooled to 100 ° C., and while keeping the obtained viscous polymer solution at 100 ° C., 2 liters of toluene heated to 100 ° C. were charged therein, and 6 liters of toluene were added dropwise over 4 hours. Charged. After charging 4 liters of toluene, the mixture was cooled to room temperature, and the precipitate was separated by filtration. This was further sludged in 4 liters of toluene, separated by filtration, preliminarily dried at 50 ° C. for 24 hours, and then dried under reduced pressure at 200 ° C. for 12 hours under a stream of nitrogen. Yield of obtained powder ・ Logarithmic viscosity of polyimide powder ・ Glass transition temperature ・ 5% weight loss temperature ・ Melting viscosity (360 ° C./5 minutes)
Is shown in Table C6.

[0358] In the present invention, the chemical formula (2a) /
The molar ratio of the chemical formula (2b) is characterized by being from 1/99 to 80/20. From the above results, the molar ratio of the chemical formula (2a) / the chemical formula (2b) [Formula 2] is 80 /.
It is clear that those having more than 20 are inferior in moldability as compared with those having 80/20 or less.

Examples C18 to C22, Comparative Examples C9 and C1
0 Press molding was performed using the powders obtained in Examples C13 to C17 and Comparative Example C8. Here, the powders used in the respective Examples and Comparative Examples are shown in the following Table C7.

[0360] Specifically, using a 25 mm diameter single screw extruder, 355
Extruded pellets at a temperature of 10.degree.
After loading into a press die having a mold having a size of 0 mm and a length of 80.0 mm, Examples 18 to 22 and Comparative Example 9
Press molding was performed at 0 ° C. for 12 hours and for Comparative Example 10 at 360 ° C. for 5 minutes. In each case, good molded products were obtained. Each test piece had a width of 10.0 mm ± 0.01.
0mm, length is 80.0mm ± 0.010mm,
The thickness was 1.500 mm ± 0.010 mm. Using this molded product, a chemical resistance test was performed. In particular,
A portion of 5.00 mm from both ends of the test piece is fixed, and a jig is applied to the center of the test piece (a portion of 40.0 mm from both ends) to bend so as to give a displacement of 3.50 mm in the thickness direction. Fixed. In this state, the test piece was immersed in toluene and methyl ethyl ketone, taken out after 1 hour, 24 hours, and 168 hours, and the presence or absence of cracks was visually observed. The results of the chemical resistance test are shown in Table C8. In Table C8, “○”, “△”, “×”
Indicates, in order, those having no cracks, those having slight cracks, and those having many cracks. The term “PA / PCE molar ratio” refers to the molar ratio of phthalic anhydride to 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride,
“MEK” indicates methyl ethyl ketone.

[0361] In the present invention, the chemical formula (2a) /
The molar ratio of the chemical formula (2b) is characterized by being from 1/99 to 80/20. From the above results, the molar ratio of the chemical formula (2a) / the chemical formula (2b) does not reach 1/99. It is evident that the product has inferior chemical resistance as compared with 1/99 or more.

Examples C23 to C27, Comparative Examples C11 to C
13 Two reactions of (A) and (B) were performed. (A) In a container equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, 292.34 g of 1,3-bis (3-aminophenoxy) benzene as a monomer was placed.
(1.000 mol), pyromellitic dianhydride, 10
2.52 g (0.470 mol), 3,3 ', 4,4'
-Benzophenonetetracarboxylic dianhydride, 151.
45 g (0.470 mol), 10.66 g (72.00 mmol) of phthalic anhydride as a terminal blocking agent, 11.92 g (48.00 mmol) of 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride Then, 2185 g of m-cresol as a solvent and 13.970 g (0.1500 mol) of γ-picoline as a catalyst were charged and heated to 150 ° C. over 2 hours while stirring under a nitrogen atmosphere, and heated at 150 ° C. for 2 hours. The reaction was performed. Subsequently, 5.33 g of phthalic anhydride (36.
00 mmol), 5.96 g of 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride (24.
00 mmol) and reacted at 150 ° C. for another 8 hours. Thereafter, the mixture was cooled to 60 ° C., and the resulting viscous polymer solution was vigorously stirred with methyl ethyl ketone 10
The mixture was discharged into a liter, and the precipitate was separated by filtration. This was further sludged in 4 liters of methyl ethyl ketone, filtered and then pre-dried at 50 ° C. for 24 hours.
It was dried at 20 ° C. for 12 hours to obtain a polyimide powder. (B) At the time of charging the kind and amount of the terminal blocking agent, 17.77 g (120.00 mmol) of only phthalic anhydride, and 8.89 g (60.00 mmol) of phthalic anhydride alone during the reaction were charged.
A polyimide powder was obtained in exactly the same manner as in (A), except for changing to l). Logarithmic viscosity, glass transition temperature, 5 of powdered polyimide powder obtained by two reactions (A) and (B)
Table C9 shows% weight loss temperature and melt viscosity (360 ° C / 5 minutes).
Shown in Furthermore, each was extruded into pellets at 355 ° C. using a single-screw extruder having a diameter of 25 mm, and this bellet was loaded into a press die having a mold having a shape specified in ASTM-D-638. Press molding was performed.

[0363]

[0364] A high-temperature tensile test at normal temperature (23 ° C.) was performed using the obtained test piece. The results are shown in Table C11.

[0365] From the above, it is clear that the mechanical properties of the cross-linking group-containing polyimide of the present invention are greatly improved by annealing, and it can be seen that this effect cannot be expected with the general polyimides of Comparative Examples.

Examples C28 to C32, Comparative Examples C14 to C
16 In a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, 292.34 g (1.00%) of 1,3-bis (4-aminophenoxy) benzene as a monomer was placed.
0 mol), bis (3,4-dicarboxyphenyl) ether dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride in the amounts shown in Table C12,
Further, m-cresol was charged as a solvent in an amount shown in Table C12, and the mixture was heated to 200 ° C. over 2 hours and 30 minutes while stirring under a nitrogen atmosphere, and reacted at 200 ° C. under reflux for 2 hours to perform terminal reaction. An unsealed polymer solution was obtained.
“ODPA” in Table C12 indicates bis (3,4-dicarboxyphenyl) ether dianhydride, and “HQD”
"A" indicates 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride.

[0367] During the reaction, the end-capping agent described in Table C13 and m-
200.0 ml of cresol was charged and dissolved by heating at 100 ° C. for 1 hour in advance in a nitrogen atmosphere. The whole solution of the terminal blocking agent was charged into a polymer solution having no terminal blocking, and further reacted at 200 ° C. under reflux condition for 2 hours.
In Table C13, “PA” indicates phthalic anhydride, and “PCE” indicates 1-phenyl-2- (3,4
-Dicarboxyphenyl) acetylene anhydride.

[0368] Thereafter, the mixture was cooled to 60 ° C., and the obtained viscous polymer solution was discharged into 10 liters of vigorously stirred methyl ethyl ketone, and the precipitate was separated by filtration. This is further sludged in 4 liters of methyl ethyl ketone, filtered, and then filtered.
After predrying for 24 hours at 220 ° C, 1 hour at 220 ° C under a nitrogen stream.
After drying for 2 hours, a polyimide powder was obtained. Logarithmic viscosity, glass transition temperature, melt viscosity (360 ° C
/ 5 minutes, 15 minutes, and 30 minutes) are shown in Table C14.

[0369] [Legend] “←”; “Same on the left. "Meaning of.

From these results, the cross-linking group-containing polyimide of the present invention has various molecular weights (or logarithmic viscosities correlated with the molecular weight)
It can be seen that those having a good melt flowability also have good moldability as compared with the comparative examples.

Examples C33 to C37, Comparative Examples C17 to C
19 The powders obtained in Examples C28 to C32 and Comparative Examples C14 to C16 were placed in a heat-resistant dish, annealed at 420 ° C. for 1 hour under nitrogen, quenched, and the glass transition temperature and the 5% weight loss temperature were measured. The results are shown in Table C15. Table C
In "15,""Tg" indicates the glass transition temperature, and "Td5"
Indicates a 5% weight loss temperature.

[0372] From the above results, it can be seen that the glass transition temperature of the polyimide containing a crosslinking group of the present invention is significantly improved by annealing, but is not improved in the comparative example.

Examples C38 to C39, Comparative Example C20 The melt viscosity was measured in the same manner as in Examples A80 to A82 using the polyimide powders used in Examples C29, C31 and Comparative Example C15. The gelation time at each temperature was measured for these powders in the same manner as in Examples A83 to A87. The results are shown in Table C16.
In Table C16, “> 120” indicates that the gel point was not reached within the measurement time.

[0374] From these results, it is clear that the cross-linking group-containing polyimide of the present invention has high melt viscosity stability over a wide temperature range, is unlikely to gel, and has excellent moldability.

Experiment D Series In Examples D1 to D25, in the present invention, 50 to 100 mol% of the repeating structural units having a main chain structure were used.
But,

[0376]

Embedded image (Wherein G represents a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent linking group selected from the group consisting of 4-oxyphenoxy, 4'-oxy-4-biphenoxy, and 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy. An example of a repeating unit structure represented by is described.

Examples D1 to D7 and Comparative Examples D1 to D3 In a vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube, m-phenylenediamine was used as a monomer.
108.14 g (1.000 mol), 378.18 g (0.940 mol) of 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, end-capping agent of the type and amount shown in Table D1, M-cresol 1 as solvent
750 g and N, N-dimethylacetamide (195 g) were charged, and the mixture was heated to 200 ° C. over 2 hours and 30 minutes while stirring under a nitrogen atmosphere, and reacted at 200 ° C. under reflux for 4 hours. In Table D1, “PA” indicates phthalic anhydride, and “PCE” indicates 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.

[0378] Subsequently, the temperature was lowered to 190 ° C., the terminal blocking agent described in Table D1 was charged again, the temperature was raised again, and the reaction was further performed under a reflux condition of 200 ° C. for 4 hours. Thereafter, the mixture was cooled to 100 ° C., discharged into 10 l of vigorously stirred toluene, and the precipitate was separated by filtration. This was further sludged in 4 liters of toluene, separated by filtration, preliminarily dried at 50 ° C. for 24 hours, and then dried at 220 ° C. for 12 hours under a nitrogen stream. Logarithmic viscosity, glass transition temperature, 5% weight loss temperature, melt viscosity (360 ° C /
5 min) is shown in Table D2.

[0379] In the present invention, the chemical formula (2a) /
The molar ratio of the chemical formula (2b) is characterized by being from 1/99 to 80/20. From the above results, the molar ratio of the chemical formula (2a) / the chemical formula (2b) exceeds 80/20. It is clear that the moldability is large and the moldability is inferior to those of 80/20 or less.

Examples D8 to D12, Comparative Examples D4 and D5 Press molding was performed using the powders obtained in Examples D2 to D6 and Comparative Example D3. Here, the powder used in each Example and Comparative Example is shown in the following Table D3.

[0381] Specifically, it was extruded into pellets at 355 ° C. using a 25 mm uniaxial extruder, and this beret was subjected to ASTM-D
Examples D8 to D12 and Comparative Example D4 were loaded into a press die having a mold having a shape defined in -638,
Press molding was performed at 12 ° C. for 12 hours and for Comparative Example 5 at 360 ° C. for 5 minutes. In each case, good molded products were obtained. Using this molded product, a tensile test was performed at normal temperature (23 ° C.). The results are shown in Table D4. In Table D4, “PA /
"PCE molar ratio" indicates the molar ratio of phthalic anhydride to 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.

[0382] In the present invention, the chemical formula (2a) /
The molar ratio of the chemical formula (2b) is characterized by being from 1/99 to 80/20. From the above results, the molar ratio of the chemical formula (2a) / the chemical formula (2b) does not reach 1/99. It is clear that the material has inferior mechanical properties as compared with 1/99 or more.

Examples D13 to D22, Comparative Examples D6 to D1
0 Two reactions of (A) and (B) were performed. (A) In a vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube, 108.14 g (1.000 mol) of m-phenylenediamine as a monomer, 3,4 ′
-Diaminodiphenyl ether 80.10 g (0.4
00 mol), bis (3,4-dicarboxyphenyl)
336.78 g of sulfone dianhydride (0.940 mo
l), 10.66 g of phthalic anhydride (7
2.00 mmol), 11.92 g of 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride
(48.00 mmol), m-cresol 2 as a solvent
730 g, 13.970 g of γ-picoline as a catalyst
(0.1500 mol), and heated to 150 ° C. over 2 hours while stirring under a nitrogen atmosphere.
The reaction was performed at 150 ° C. for 2 hours. Subsequently, 5.33 g (36.00 mmol) of phthalic anhydride was used as a terminal blocking agent.
l), 5.96 g of 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride (24.00 mmol)
1) was charged, and the reaction was further performed at 150 ° C. for 8 hours.
Thereafter, the mixture was cooled to 60 ° C., discharged into 10 liters of vigorously stirred methyl ethyl ketone, and the precipitate was separated by filtration. This was further sludged in 4 liters of methyl ethyl ketone, filtered and, after preliminary drying at 50 ° C. for 24 hours, dried at 220 ° C. for 12 hours under a nitrogen stream to obtain a polyimide powder. (B) At the time of charging the kind and amount of the terminal blocking agent, 17.77 g (120.00 mmol) of only phthalic anhydride, and 8.89 g (60.00 mmol) of phthalic anhydride alone during the reaction were charged.
A polyimide powder was obtained in exactly the same manner as in (A), except for changing to l). Table D5 shows the yield of the powder obtained by the two reactions (A) and (B), the logarithmic viscosity of the polyimide powder, the glass transition temperature, the 5% weight loss temperature, and the melt viscosity (360 ° C / 5 minutes). Furthermore, each was extruded and pelletized at 355 ° C. using a 25 mm uniaxial extruder, and this bellet was loaded into a press die having a mold having a shape specified in ASTM-D-638, and then subjected to the conditions described in Table D6. Press molding was performed.

[0384]

[0385] A high-temperature tensile test was performed at room temperature (23 ° C.) and 177 ° C. using the obtained test piece. The results are shown in Table D7.

[0386] From the above, it is clear that the room-temperature and high-temperature mechanical properties of the polyimide containing a cross-linking group of the present invention are greatly improved by annealing, and it can be seen that this effect cannot be expected with the general polyimides of Comparative Examples.

Examples D23 to D25, Comparative Examples D12 to 13 The melt viscosities were measured in the same manner as in Examples A80 to A82 using the polyimide powders used in Examples D4 to D6 and Comparative Examples D1 and D3. The gelation time at each temperature was measured for these powders in the same manner as in Examples A83 to A87. In addition, this powder
Extruded and pelletized under the conditions of ℃ to 360 ℃, Example A
Press forming and MEK resistance tests were performed in the same manner as in Examples 18 to 22. The results are shown in Table D8. In Table D8,
">120" indicates that the gel point was not reached within the measurement time.

[0388] From these results, it is clear that the cross-linking group-containing polyimide of the present invention has high stability of melt viscosity in a wide temperature range, is unlikely to cause gelation, and is excellent in moldability, but also excellent in chemical resistance. is there.

Experiment E Series In Examples E1 to E22, in the present invention, 50 to 100 mol% of the repeating structural units having a main chain structure were used.
But,

[0390]

Embedded image (Wherein, X, Z, and R are each a group as shown below. That is, X in the formula represents a divalent linking group selected from the group consisting of an ether group and an isopropylidene group;
Z in the formula is

[0391]

Embedded image Represents a divalent aromatic group selected from the group consisting of: wherein R in the formula is

[0392]

Embedded image (Wherein G is a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent linking group selected from the group consisting of 4-oxyphenoxy, 4'-oxy-4-biphenoxy, and 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy. And a tetravalent aromatic group selected from the group consisting of: In addition, a position of a bonding group in which a bonding position is not determined in the formula is a para-position or a meta-position) will be described.

Examples E1 to E7 and Comparative Examples E1 to E3 In a vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube, 1,3-bis [4- (4-
Aminophenoxy) -α, α-dimethylbenzyl] benzene 528.69 g (1.000 mol), 3,
276.57 g (0.940 mol) of 3 ', 4,4'-biphenyltetracarboxylic dianhydride, end capping agent of the kind and amount shown in Table E1, m-cresol 3 as a solvent
220 g, and heated to 200 ° C. over 2 hours and 30 minutes while stirring under a nitrogen atmosphere.
The reaction was performed for 4 hours under reflux conditions. In Table E1, "P
"A" indicates phthalic anhydride, and "PCE" indicates 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.

[0394] Subsequently, the temperature was lowered to 190 ° C., the terminal capping agent shown in Table E1 was charged again, the temperature was raised again, and the reaction was further carried out at 200 ° C. under reflux conditions for 4 hours. Thereafter, the mixture was cooled to 100 ° C., discharged into 10 l of vigorously stirred toluene, and the precipitate was separated by filtration. This was further sludged in 4 liters of toluene, separated by filtration, preliminarily dried at 50 ° C. for 24 hours, and then dried at 220 ° C. for 12 hours under a nitrogen stream.
Logarithmic viscosity, glass transition temperature, 5% weight loss temperature, melt viscosity (360 ° C./5
Min) are shown in Table E2.

[0395] In the present invention, the chemical formula (2a) /
The molar ratio of the chemical formula (2b) is characterized by being from 1/99 to 80/20. From the above results, the molar ratio of the chemical formula (2a) / the chemical formula (2b) exceeds 80/20. It is clear that the moldability is large and the moldability is inferior to those of 80/20 or less.

Examples E8 to E12, Comparative Examples E4 and E5 Press molding was performed using the powders obtained in Examples E2 to E6 and Comparative Example E3. Here, the powders used in the respective Examples and Comparative Examples are shown in the following Table E3. Specifically, it was extruded into pellets at 355 ° C. using a 25 mm uniaxial extruder, and this beret was subjected to ASTM-D
After loading into a press die having a mold having a shape defined in -638, Examples E8 to E12 and Comparative Example E4 were 360
Press molding was performed at a temperature of 360 ° C. for 5 minutes at 12 ° C. for 12 hours and Comparative Example E5. In each case, good molded products were obtained. Using this molded product, a tensile test was performed at normal temperature (23 ° C.). The results are shown in Table E4. In Table E4, “PA
"/ PCE molar ratio" indicates the molar ratio of phthalic anhydride to 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.

[0397] In the present invention, the chemical formula (2a) /
The molar ratio of the chemical formula (2b) is characterized by being from 1/99 to 80/20. From the above results, the molar ratio of the chemical formula (2a) / the chemical formula (2b) does not reach 1/99. It is clear that the material has inferior mechanical properties as compared with 1/99 or more.

Examples E13 to E22, Comparative Examples E6 to E1
1 Two reactions of (A) and (B) were performed. (A) In a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, 4,4′-bis [4
-(4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone 668.85 g (1.000
mol), pyromellitic dianhydride 205.03 g
(0.940 mol), 10.66 g (72.00 mmol) of phthalic anhydride as a terminal blocking agent, 1-phenyl-
11.92 g (48.00 mmol) of 2- (3,4-dicarboxyphenyl) acetylene anhydride, m as a solvent
2730 g of cresol, γ-picoline 1 as a catalyst
After charging 3.970 g (0.1500 mol), the mixture was heated to 150 ° C. over 2 hours while stirring under a nitrogen atmosphere, and reacted at 150 ° C. for 2 hours. Subsequently, 5.33 g (36.00) of phthalic anhydride was used as a terminal blocking agent.
mmol), 5.96 g (24.00) of 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride.
mmol) and reacted at 150 ° C. for a further 8 hours. Thereafter, the mixture was cooled to 60 ° C., discharged into 10 liters of vigorously stirred methyl ethyl ketone, and the precipitate was separated by filtration. This was further sludged in 4 liters of methyl ethyl ketone, filtered and, after preliminary drying at 50 ° C. for 24 hours, dried at 220 ° C. for 12 hours under a nitrogen stream to obtain a polyimide powder. (B) At the time of charging the kind and amount of the terminal blocking agent, 17.77 g (120.00 mmol) of only phthalic anhydride, and 8.89 g (60.00 mmol) of phthalic anhydride alone during the reaction were charged.
A polyimide powder was obtained in exactly the same manner as in (A), except for changing to l). Table E5 shows the yield of the powder obtained by the two reactions (A) and (B), the logarithmic viscosity of the polyimide powder, the glass transition temperature, the 5% weight loss temperature, and the melt viscosity (360 ° C./5 minutes). Furthermore, each was extruded and pelletized at 355 ° C. using a 25 mm uniaxial extruder, and this bellet was loaded into a press die having a mold having a shape specified in ASTM-D-638, and then subjected to the conditions shown in Table E6. Press molding was performed.

[0399]

[0400] A high-temperature tensile test was performed at room temperature (23 ° C.) and 177 ° C. using the obtained test piece. The results are shown in Table E7.

[0401] From the above, it is clear that the room-temperature and high-temperature mechanical properties of the polyimide containing a cross-linking group of the present invention are greatly improved by annealing, and it can be seen that this effect cannot be expected with the general polyimides of Comparative Examples.

Experiment F Series In Examples F1 to F16, a crosslinking group-containing end capping agent other than that represented by the above general formula (2a) in the present invention is used, or the crosslinkable group-containing end capping agent is represented by the general formula (2a). An example of using a combination other than the above will be described.

Examples F1 to F6 and Comparative Example F1 Using dimethylacetamide as a solvent, 368.43 g (1.000 mol) of 4,4′-bis (3-aminophenoxy) biphenyl as a monomer and pyromellitic dianhydride 142 were used. 0.000 g (0.651 mol), 3,
3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 89.90 g (0.279 mol), 15% in the same manner as in Examples A33 to A37 by using the types and amounts of terminal blocking agents shown in Table A29. (W / w) Polyamic acid varnish was obtained. Examples A33 to A37 using the obtained varnish
A film was produced under the same conditions as described above. Further, a chemical resistance test in toluene was carried out in the same manner as in Examples A70 to A75 using this. The results are shown together with the logarithmic viscosity of the varnish in Table F1. In Table F1, “○”, “△”,
“X” indicates, in order, those having no cracks, those having slight cracks, and those having many cracks.

[0404] [Legend] In Table F1, the terminal blocking agents are indicated by the following symbols. A) Phthalic anhydride B) 1-Phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride F) 4-Ethynylphthalic anhydride G) 3- (Phenylethynyl) phthalic anhydride H) 5- Norbornene-2,3-dicarboxylic anhydride I) Maleic anhydride J) 2-Methylmaleic anhydride K) 2- (3,4-Dicarboxyphenoxy) biphenylene anhydride

From the above results, it is clear that the polyimide containing a cross-linking group having various structures according to the present invention is significantly higher in chemical resistance than a similar polymer having no cross-linking group.

Examples F7 to F10 and Comparative Example F2 In a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, 1,3-bis (4-aminophenoxy) benzene, 292 .34 g (1.00
0 mol), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 158.87 g (0.540 mol)
l), 167.51 g (0.540 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride, and 3506 g of N-methyl-2-pyrrolidone as a solvent were charged, and the mixture was stirred under a nitrogen atmosphere for 12 hours. . Further, the end capping agent of the type and amount shown in Table F2 was charged therein,
The mixture was stirred under a nitrogen atmosphere for 12 hours. Further, 408 g of acetic anhydride and γ-picoline 2 were added to the obtained polymer solution.
3.53 g was added, and the mixture was added
Stirred for hours. The resulting viscous polymer solution was discharged into 20 liters of vigorously stirred toluene, and the precipitate was separated by filtration. This was further sludged in 4 liters of toluene, separated by filtration, preliminarily dried at 50 ° C. for 24 hours, and then dried under reduced pressure at 150 ° C. for 12 hours under a nitrogen stream. Using the obtained polyimide powder, the gelation temperature at 360 ° C. was measured in exactly the same manner as in Examples A83 to A87. The results are shown in Table F2 together with the logarithmic viscosity of the obtained polyimide powder. In Table F2, ">120" indicates that the gel point was not reached within the measurement time.

[0407] [Legend] In Table F2, the terminal blocking agents are indicated by the following symbols. L) aniline M) 3- (phenylethynyl) aniline N) 3-ethynylaniline O) 3-aminostyrene P) 2-aminobiphenylene

From these results, it is clear that the cross-linking group-containing polyimide of the present invention hardly causes gelation and has excellent moldability.

Examples F11 to F16 and Comparative Example F3 In a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube, 4,4'-bis (3-aminophenoxy) biphenyl as a monomer was prepared. 43g (1.0
00 mol), pyromellitic dianhydride, 102.52
g (0.470 mol), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 138.28 g (0.
470 mol), 1630 g of m-cresol as a solvent
And stirring at 200 ° C. under a nitrogen atmosphere.
The temperature was raised for 2 hours and 30 minutes until the temperature reached 200 ° C., and the reaction was carried out under a reflux condition of 200 ° C. for 2 hours to obtain a polymer solution having a non-capped terminal. During the reaction, the endcapping agent described in Table F3 and m
-200.0 ml of cresol was charged and dissolved by heating at 100 ° C for 1 hour in advance in a nitrogen atmosphere. The whole solution of the terminal blocking agent was charged into a polymer solution having no terminal blocking, and further reacted at 200 ° C. under reflux condition for 2 hours. Thereafter, the mixture was cooled to 100 ° C., and while maintaining the obtained viscous polymer solution at 100 ° C., 4 liters of toluene was dropwise added thereto over 4 hours. After 3 liters of toluene heated to 80 ° C. were further charged, the mixture was cooled to room temperature, further 3 liters of toluene was added, and the mixture was stirred for 1 hour, and the precipitate was separated by filtration. Add this to toluene 4
After sludge filtration in a liter, filtration followed by preliminary drying at 50 ° C. for 24 hours, and drying under reduced pressure at 200 ° C. for 12 hours under a nitrogen stream. Using the obtained polyimide powder, the gelation temperature at 360 ° C. was measured in exactly the same manner as in Examples A83 to A87. The results are shown in Table F3 together with the logarithmic viscosity of the obtained polyimide powder.

[0410] [Legend] In Table F1, the terminal blocking agents are indicated by the following symbols. A) Phthalic anhydride B) 1-Phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride F) 4-Ethynylphthalic anhydride G) 3- (Phenylethynyl) phthalic anhydride H) 5- Norbornene-2,3-dicarboxylic anhydride I) Maleic anhydride J) 2-Methylmaleic anhydride K) 2- (3,4-Dicarboxyphenoxy) biphenylene anhydride

From the above, although a slight difference is observed in the gelation time depending on the crosslinking group, it is clear that the polyimide containing a crosslinking group of the present invention has excellent moldability, and the polyimide of the comparative example has a rapid gelation. It turns out that the melt moldability is extremely poor. Excellent physical properties inherent to polyimide according to the present invention, namely, heat resistance, mechanical properties, sliding properties, low water absorption, electrical properties, thermal oxidation stability, chemical resistance, and radiation resistance, especially heat resistance, It is possible to provide a crosslinked thermoplastic polyimide having significantly improved chemical resistance and mechanical properties, a crosslinkable polyimide containing a melt-processable crosslinkable group, a crosslinkable polyamic acid that is a precursor thereof, and a method for producing them. became.

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

[Procedure amendment]

[Submission date] February 21, 2000 (200.2.2
1)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction contents]

[0014]

Embedded image Obtained from monomers and a terminal blocking agent represented by
A thermosetting polyimide obtained by heat-treating an imide oligomer having a carbon-carbon triple bond at a molecular terminal is disclosed. Although this polyimide <br/> de disclosed in patent has various excellent properties, can not be carried out again melt molding, it is limited to processing using a solution of a polyamic acid which is a precursor. Usually, after shaping with a polyamic acid solution, solvent removal and dehydration imidization reaction are performed by heating. Since the processing involves solvent removal, it is impossible to obtain a thick normal molded product, the shape of the film or sheet is limited,
Further, problems such as foaming due to the residual solvent and necessity of collecting a large amount of the solvent are caused.

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. Hei 11-90454 (32) Priority date March 31, 1999 (March 31, 1999) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. Hei 11-90455 (32) Priority date March 31, 1999 (March 31, 1999) (33) Country claiming priority Japan (JP) (72) Inventor Tomomi Okumura 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Yoshihiro Sakata 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemicals Co., Ltd. No. Mitsui Chemicals Co., Ltd. (72) Inventor Yuichi Okawa 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Prefecture Within Mitsui Chemicals Co., Ltd. (Ref.) UA132 UA141 UA142 UA151 UA152 UA161 UA171 UA211 UA221 UA231 UA262 UA361 UA662 UA672 UB011 UB021 UB022 UB061 UB062 UB121 UB122 UB131 UB132 UB141 UB151 UB152 UB281 UB282 UB301 UB302 UB401 UB402 VA011 VA021 VA022 VA031 VA032 VA041 VA051 VA061 VA062 VA071 VA072 VA081 XA03 XA17 XB20 XB35 YA06 YA08 ZA04 ZA05 ZA06 ZA12 ZA31 ZA41 ZB52

Claims (35)

[Claims] 1. A cross-linking group-containing polyimide having a cross-linking group at 1 to 80 mol% of molecular terminals. 2. The cross-linking group-containing polyimide according to claim 1, wherein the main chain structure constituting the cross-linking group-containing polyimide has essentially thermoplasticity. 3. 1 to 80 mol% of the molecular terminals are the cross-linking group-containing molecular terminals represented by the chemical formula (2a), and 99 to 20 mol% of the molecular terminals are represented by the chemical formula (2b). The crosslinkable group-containing polyimide according to claim 1, wherein the polyimide is a molecular terminal that does not contain a crosslinkable group to be melt-processed. Embedded image (Y in the formula is (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Represents a trivalent aromatic group selected from the following): (T in the formula is (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Represents a divalent aromatic group selected from 4. The cross-linking group-containing polyimide according to claim 1, comprising a polyimide molecule having a structure represented by the chemical formula (2c). Embedded image (In the formula, T, PI, and Y are each a group shown below. That is, T is (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Represents a divalent aromatic group selected from the following, PI represents a polyimide main chain, and Y represents (Wherein, X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group) Shows selected trivalent aromatic group) 5. The cross-linking group-containing polyimide according to claim 3, wherein in the chemical formula (2b) or (2c), T is the following chemical formula (2d). Embedded image 6. The cross-linking group-containing polyimide according to claim 3, wherein in the chemical formula (2a) or (2c), Y is the chemical formula (2e). Embedded image 7. The crosslinkable group-containing polyimide according to claim 1, wherein the polyimide main chain has a repeating structural unit represented by the chemical formula (1). Embedded image (Wherein, Ar and R are each a group as shown below. That is, Ar in the formula is (Wherein, J represents a divalent linking group selected from the group consisting of a carbonyl group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group; K represents a direct bond;
A carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a divalent linking group selected from the group consisting of hexafluorinated isopropylidene groups,
p and q are each independently 0 or 1. The position of the bonding group in which the bonding position is not determined in the formula is a para-position or a meta-position), and represents a divalent aromatic group selected from the group consisting of: 12] (Wherein G is a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent aromatic group selected from the group consisting of a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group, and a 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy group; Represents a tetravalent aromatic group selected from the group consisting of 8. The repeating unit according to claim 7, wherein 50 to 100 mol% of the repeating unit represented by the chemical formula (1) is a repeating unit structure represented by the chemical formula (1a). Crosslinked group-containing polyimide. Embedded image (Wherein G represents a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent aromatic group selected from the group consisting of a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group, and a 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy group; ) 9. In the chemical formula (1a), G is 4′-
Oxy-4-biphenoxy group,
The polyimide containing a crosslinking group according to claim 8. 10. In the chemical formula (1a), G is 4-
The cross-linking group-containing polyimide according to claim 8, which is a [1- (4-oxyphenyl) -1-methylethyl] phenoxy group. 11. In the repeating structural unit represented by the chemical formula (1), 50 to 100 mol% of the repeating structural unit is represented by the chemical formula (1b)
Characterized by having a repeating unit structure represented by
The polyimide containing a crosslinking group according to claim 7. Embedded image (Wherein X and R are each a group as shown below: X in the formula is a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group. And a divalent linking group selected from the group consisting of a lidene group, wherein R in the formula is (Wherein G is a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent aromatic group selected from the group consisting of a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group, and a 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy group; ) Represents a tetravalent bonding group selected from the group consisting of: In addition, the position of the bonding group in which the bonding position is not determined is at the para-position or the meta-position.) 12. In the chemical formula (1b), X is an oxygen atom, and the bonding positions of the two benzenes to which X is directly bonded to the imide groups are m-position and p-position, respectively. The crosslinking group-containing polyimide according to claim 11, wherein R is 3,4,3 ', 4'-substituted biphenyl. 13. The repeating structural unit represented by the chemical formula (1), wherein 50 to 100 mol% of the repeating structural unit is represented by the chemical formula (1c):
Characterized by having a repeating unit structure represented by
The polyimide containing a crosslinking group according to claim 7. Embedded image (Wherein X and R are each a group as shown below: X in the formula is a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group. Represents a divalent linking group selected from the group consisting of a lidene group, wherein R in the formula is (Wherein G is a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent aromatic group selected from the group consisting of a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group, and a 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy group; ) Represents a tetravalent bonding group selected from the group consisting of: In addition, the position of the bonding group in which the bonding position is not determined is at the para-position or the meta-position.) 14. The crosslinkable group-containing polyimide according to claim 13, wherein in the chemical formula (1c), X is an oxygen atom. 15. In the chemical formula (1c), X is an oxygen atom, the bonding position of a benzene ring to which two Xs are directly bonded is the m-position, and X and the imide group are directly bonded. The bonding position of the two benzenes is in the p-position, and R is 3,4,3 ', 4'-substituted biphenyl. Crosslinked group-containing polyimide. 16. In the repeating structural unit represented by the chemical formula (1), 50 to 100% by mole of the repeating structural unit represented by the chemical formula (1e)
Characterized by having a repeating unit structure represented by
The polyimide containing a crosslinking group according to claim 7. Embedded image (In the formula, Q, Z, and R are each a group shown below. That is, Q represents a divalent aromatic group selected from the group consisting of an ether group and an isopropylidene group. Wherein Z is a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group,
And a hexafluorinated isopropylidene group, and Represents a divalent aromatic group selected from the group consisting of: wherein R in the formula is (Wherein G is a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent aromatic group selected from the group consisting of a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group, and a 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy group; ) Represents a tetravalent aromatic group selected from the group consisting of: In addition, the position of the bonding group in which the bonding position is not determined is at the para-position or the meta-position.) 17. In the chemical formula (1e), Q is an oxygen atom, and Z is a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group. 17. The cross-linking group-containing polyimide according to claim 16, wherein the polyimide is at least one divalent group selected from the group consisting of: 18. In the chemical formula (1e), Q is an oxygen atom, Z is a direct bond, and R is 1,2,2
17. The crosslinked group-containing polyimide according to claim 16, wherein the benzene is a 4,5-substituted benzene. 19. A molecule characterized in that the terminal of the polyimide main chain is blocked using a dicarboxylic anhydride represented by the chemical formula (3a) or (3b) as a terminal blocking agent. 1 to 80 mol% of the terminal is represented by the chemical formula (2a)
A cross-linking group-containing molecular terminal represented by the formula: wherein 99 to 20 mol% of the molecular terminals are molecular terminals that do not contain the cross-linking group represented by the chemical formula (2b). Process for producing processable cross-linking group-containing polyimide. Embedded image (Y in the formula is (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Which represents a trivalent aromatic group selected from (T in the formula is (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Which represents a divalent aromatic group selected from the following): (Y in the formula is (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Represents a trivalent aromatic group selected from the following): (T in the formula is (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Represents a divalent aromatic group selected from 20. The use amount of the dicarboxylic anhydride represented by the chemical formulas (3a) and (3b) is represented by (Formula 1) [Equation 1] on a molar ratio basis. 20. The method for producing a cross-linking group-containing polyimide according to claim 19, wherein: [Formula 1] 1/99 ≦ [dicarboxylic anhydride represented by chemical formula (3a)] / [dicarboxylic anhydride represented by chemical formula (3b)] ≦ 80/20 (Formula 1) (Y in the formula is (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Which represents a trivalent aromatic group selected from (T in the formula is (Wherein X represents a direct bond, a divalent linking group selected from the group consisting of a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group). Represents a divalent aromatic group selected from 21. Chemical formula (3a) and / or chemical formula (3)
20. The method according to claim 19, wherein in b) T is a chemical formula (2d) and / or Y is a chemical formula (2e).
0. The method for producing a cross-linking group-containing polyimide described in 0. Embedded image Embedded image 22. A polyimide main chain obtained by thermally and / or chemically imidizing a polyamic acid as a polyimide precursor obtained by polymerizing a diamine component and a tetracarboxylic anhydride component. 22. The method for producing a cross-linking group-containing polyimide according to claim 19, wherein the polyimide is a cross-linked polyimide. 23. The method according to claim 22, wherein the diamine component is at least one selected from a group of diamine components represented by the chemical formula (4). Embedded image (In the formula, Ar is (Wherein, J represents a divalent linking group selected from the group consisting of a carbonyl group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group; K represents a direct bond;
A carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a divalent linking group selected from the group consisting of hexafluorinated isopropylidene groups,
p and q are each independently 0 or 1. The position of the bonding group in which the bonding position is not determined in the formula is a para-position or a meta-position), which indicates a divalent aromatic group selected from the group consisting of: 24. The crosslinking group according to claim 23, wherein 50 to 100 mol% of the diamine component represented by the chemical formula (4) is represented by the chemical formula (4c). Production method of contained polyimide. Embedded image (In the formula, X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group. The position of the bonding group in which the bonding position is not determined is in the para or meta position.) 25. The method for producing a crosslinking group-containing polyimide according to claim 24, wherein in the chemical formula (4c), X is an oxygen atom. 26. In the chemical formula (4c), X is an oxygen atom, the bonding position of a benzene ring to which two Xs are directly bonded is m-position, and X and an amino group are directly bonded. The method for producing a polyimide containing a cross-linking group according to claim 24, wherein the bonding positions of the benzenes are all at the p-position. 27. The crosslinkable group-containing polyimide according to claim 24, wherein 50 to 100 mol% of the diamine component represented by the chemical formula (4) is represented by the chemical formula (4d). Production method. Embedded image (In the formula, X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluorinated isopropylidene group.) 28. The method according to claim 27, wherein in the chemical formula (4d), X is a direct bond. 29. The method according to claim 22, wherein the tetracarboxylic dianhydride component is represented by the chemical formula (5). Embedded image (Wherein R is (Wherein G is a direct bond, a carbonyl group, a sulfone group,
Sulfide group, ether group, isopropylidene group, hexafluorinated isopropylidene group, 3-oxyphenoxy group,
A divalent aromatic group selected from the group consisting of a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group, and a 4- [1- (4-oxyphenyl) -1-methylethyl] phenoxy group; Represents a tetravalent linking group selected from the group consisting of 30. Melting while maintaining at a temperature T [° C.] for 5 minutes to obtain a melt viscosity MV5 (T) [Pa · sec] measured at an arbitrary constant shear stress in the range of 0.1 to 1 [MPa]. ,
It is kept at a temperature T [° C.] for 30 minutes and melted,
When the melt viscosity is MV30 (T) [Pa · sec] measured at an arbitrary constant shear stress in the range of [MPa], there is a temperature T that satisfies (Equation 2) and (Equation 3) simultaneously. The crosslinking group-containing polyimide according to any one of claims 1 to 18, wherein [Equation 2] 1 ≦ MV30 (T) / MV5 (T) ≦ 10 (Equation 2) [Equation 3] 10 ≦ MV5 (T) ≦ 10000 (Equation 3) 31. Melting while holding at a temperature T [° C.] for 5 minutes to obtain a melt viscosity MV5 (T) [Pa · sec] measured at an arbitrary constant shear stress in the range of 0.1 to 1 [MPa]. ,
The temperature is kept at T + 20 [° C.] for 5 minutes and melted.
Melt viscosity MV5 (T + 20) [Pa · sec] measured at an arbitrary constant shear stress in the range of 1 [MPa], and temperature T
[° C.] for 30 minutes to melt, 0.1 to 1 [MP
a] Melt viscosity M measured at any constant shear stress in the range of
V30 (T) [Pa · sec], temperature T + 20 [° C]
For 30 minutes, and melted at an arbitrary constant shear stress in the range of 0.1 to 1 [MPa].
20) A temperature T that satisfies (Equation 2), (Equation 3) and (Equation 4) at the same time when [Pa · sec] is set, wherein: Crosslinked group-containing polyimide. [Equation 4] 1 ≦ MV30 (T) / MV5 (T) ≦ 10 (Equation 2) [Equation 5] 10 ≦ MV5 (T) ≦ 10000 (Equation 3) [Equation 6] MV30 (T + 20) / MV5 ( T + 20) ≦ 20 (Equation 4) 32. Melting while maintaining at 360 [° C.] for 5 minutes to obtain a melt viscosity MV5 (360) [Pa · sec] measured at an arbitrary constant shear stress in a range of 0.1 to 1 [MPa]; It is kept at 360 [° C.] for 30 minutes to be melted,
When the melt viscosity is MV30 (360) [Pa · sec] measured at an arbitrary constant shear stress in the range of 1 [MPa],
The polyimide containing a crosslinking group according to any one of claims 1 to 18, wherein (Formula 5) and (Formula 6) are simultaneously satisfied. [Equation 7] 1 ≦ MV30 (360) / MV5 (360) ≦ 10 (Equation 5) [Equation 8] 10 ≦ MV5 (360) ≦ 10000 (Equation 6) 33. When the storage elastic modulus after a lapse of time t [minutes] measured at 360 ° C. and 1 Hz is represented by G ′ (t) and the loss elastic modulus is represented by G ″ (t), Formula 7 is satisfied. t
19. The crosslinkable group-containing polyimide according to claim 1, wherein [minute] is 10 minutes or more. [Equation 9] G ′ (t) = G ″ (t) (Equation 7) 34. Claims 1 to 18 and 30 to 33
A cross-linked polyimide obtained by heat-treating the cross-linking group-containing polyimide according to any one of the above. 35. Claims 1 to 18 and 30 to 33
A solution or suspension containing the cross-linking group-containing polyimide according to any one of the above.