JPH09104754A - Polyimide polymer and thermosetting polyimide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermosetting polyimide superior in heat resistance, processibility, and mechanical characteristics to a thermoplastic polyimide by selecting a polyimide having a specific backbone and norbornene structures at the molecular ends. SOLUTION: This thermosetting polymidie has repeating structural units, represented by formula I (wherein P1 is a divalent group represented by formula II or III; S1 is at least one kind of a monovalent group represented by formula IV or V; m is an integer of 100-1; n is an integer of 0-99, provided m+n<=100; and when m≠100, there may be some regularity in the arrangement of the two kinds of repeating structural units).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel polyimide-based polymer and a thermosetting polyimide obtained by heat-treating it.

[0002]

2. Description of the Related Art Conventionally, polyimide has excellent properties such as mechanical properties, chemical resistance, flame retardancy, and electrical properties in addition to its excellent heat resistance.
Widely used in the fields of composite materials, electric and electronic parts, etc. For example, a typical polyimide has the formula (5)

[0003]

Embedded image

(Dupont, trade name Vespe
Although l) is known, this polyimide has a drawback that it is poor in moldability because it is non-thermoplastic and insoluble and infusible. As the thermoplastic polyimide having improved moldability, polyimides represented by the following formulas (6) and (7) are known.

[0005]

Embedded image

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The polyimide represented by the above formula (6) (GE
Company name, ULTEM; US Patent 3,847,867
And 3,847,869) have excellent melt moldability, but have a low glass transition temperature of 215 ° C.,
In addition, it has a drawback such as poor chemical resistance to halogenated hydrocarbons. Further, the polyimide represented by the above (7) (manufactured by Mitsui Toatsu Chemicals, Inc., trade name AURUM; US Pat. Nos. 4,847,349, 5,087,689,
Nos. 5,205,894, 5,278,267, etc.) have the heat resistance (glass transition temperature; 250 ° C., melting point; 388 ° C.) originally possessed by polyimide, chemical resistance, mechanical properties, and electrical characteristics. And is a melt-moldable polyimide.

However, there is a problem that the melt viscosity of these thermoplastic polyimides is high as compared with the viscosity of the thermosetting polymer in the B stage state. On the other hand, as the thermosetting polyimide, the following formula (8)

[0008]

Embedded image

Polyimide represented by (Rhone Poulenc Company, trade name; Kelimide-601, FDD
armory. , Int'l. SAMPE Sym
p. , 693, No. 19 (1974)) is known. Although the melt viscosity of this polyimide in the B-stage state is lower than that of the thermoplastic polyimide, the mechanical properties after thermosetting, especially the impact strength such as Izod impact value and the tensile elongation rate are low and not satisfactory. Furthermore, the following formula (9)

[0010]

Embedded image A thermosetting polyimide (US Pat. No. 5,412,066) obtained by heat-treating a polyimide having a carbon-carbon triple bond at the molecular end has a glass transition temperature of 230 to 250 ° C. even after thermosetting. Therefore, the thermosetting polyimide had low heat resistance.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermosetting polyimide which is superior to thermoplastic polyimide in heat resistance, processability and mechanical properties.

[0012]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a polyimide having a basic skeleton claimed in the present application and further containing a norbornene structure at the molecular end portion is used. It was found that the thermosetting polyimide obtained by heat treatment has excellent heat resistance and mechanical properties, and that it can be easily processed in its precursor and B stage state, and completed the present invention.

That is, the present invention is based on the formula (1)

Embedded image (In the formula, P1 is the following formula (A) or (B)

Embedded image

Embedded image Represents a divalent group represented by the following formula, S1 is represented by the following formulas (C) and (D)

Embedded image

Embedded image Represents at least one monovalent group represented by
Is an integer of 0 to 1, n is an integer of 0 to 99,
When m + n ≦ 100 and m ≠ 100, there may or may not be a regularity or regularity between the repeating units of m and n. ) Is a polymer having a repeating structural unit represented by,

The following equation (2)

Embedded image (In the formula, P2 is the following formula (E) or (F)

Embedded image

Embedded image Represents a divalent group represented by and S2 is represented by the following formulas (G) and (H)

Embedded image

Embedded image Represents at least one type of monovalent group represented by and m and n are the same as above. ) 0.05 of polyamic acid having a repeating unit represented by the formula (N, N-dimethylacetamide solvent, concentration 0.5 g / dl, measured at 35 ° C.) 0.05
It is a polyamic acid which is a precursor of the polymer according to claim 1, which is in a range of from 1.0 to 1.0 dl / g,

More specifically, the following equation (3)

Embedded image (In the formula, S1 is (C) and (D)

Embedded image

Embedded image Represents at least one monovalent group represented by
Is an integer from 0 to 70, l is an integer from 0 to 30,
In addition, when k + l ≦ 100 and k ≠ 100, there may or may not be a regularity or regularity between the repeating units of k and l. ) A polymer having a repeating unit represented by and a polyamic acid which is a precursor thereof,

The following equation (4)

Embedded image (In the formula, i is an integer of 100 to 10, j is an integer of 0 to 90, and i + j ≦ 100, and i ≠ 1.
In the case of 00, there may or may not be a regularity or regularity between the repeating units of i and j. ) A thermosetting polyimide obtained by heat-treating a polymer having a repeating unit represented by the formula (1) and a polyamic acid which is a precursor thereof, and a polymer represented by the above-mentioned (1) and a polyamic acid which is a precursor thereof.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The repeating unit in the formula (1) includes 4- (3-aminophenoxy) biphenyl which is an aromatic diamine and pyromellitic dianhydride which is an aromatic tetracarboxylic dianhydride. Used as an essential monomer. Further, 4,4'-diaminodiphenyl ether is added to the aromatic diamine or 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is added to the aromatic tetracarboxylic dianhydride to obtain a copolymer. Is added as an essential monomer of.

The above-mentioned aromatic diamine is used as an essential monomer in the thermosetting polyimide of the present invention, but it may be obtained by further adding other aromatic diamine within the range not impairing its good physical properties.

Examples of diamines that can be added include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3'-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, bis (3-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis (3-
Aminophenyl) sulfoxide, bis (4-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenoxy) sulfoxide, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, (3-amino Phenyl) (4-aminophenyl) sulfone, 3,3′-diaminobenzophenone, 3,4 ′
-Diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-Aminophenoxy) phenyl] ethane, 1,2-bis [4
-(3-Aminophenoxy) phenyl] ethane, 1,1
-Bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane , 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1
1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,
1,1,3,3,3-hexafluoropropane, 1,3
-Bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4
-Aminophenoxy) benzene, 4,4'-bis (4-
Aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-
Aminophenoxy) phenyl] sulfide, bis [4-
(4-Aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] Sulfone, bis [4- (4-aminophenoxy)
Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3
-Aminophenoxy) benzoyl] benzene, 1,3-
Bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [3- (4-aminophenoxy)
Benzoyl] diphenyl ether, 4,4′-bis [3
-(3-Aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α, α-
Dimethylbenzyl) phenoxy] benzophenone, 4,
4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenyl sulfone, bis [4-
{4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4 -Aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3
-Bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene,
1,3-bis [4- (4-amino-6-fluoromethylphenoxy) -α, α-dimethylbenzyl] benzene,
1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-
Bis [4- (4-amino-6-cyanophenoxy)-
α, α-Dimethylbenzyl] benzene, 3,3′-diamino-4,4′-diphenoxybenzophenone, 4,
4'-diamino-5,5'-diphenoxybenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5 -Phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5-phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino -5,5 '
-Dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibiphenoxybenzophenone, 3,3 '
-Diamino-4-biphenoxybenzophenone, 4,
4'-diamino-5-biphenoxybenzophenone,
3,4'-diamino-4-biphenoxybenzophenone, 3,4'-diamino-5-biphenoxybenzophenone, 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3 -Amino-4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) benzene, 1,4-
Bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1 , 4-bis (4-
Amino-5-biphenoxybenzoyl) benzene, 2,
6-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzonitrile, and some or all of the hydrogen atoms on the aromatic ring of the above aromatic diamine are halogen atoms and have 1 to 3 carbon atoms. Aromatic diamine substituted with a halogenated alkyl group having 1 to 3 carbon atoms or an alkoxy group in which part or all of the hydrogen atoms of the alkyl group, alkoxy group, cyano group, or alkyl group or alkoxy group is substituted with a halogen atom. Etc. Furthermore, these aromatic diamines may be used alone or in combination of two or more.

Similarly, another aromatic tetracarboxylic acid dianhydride can be further added. Examples of aromatic tetracarboxylic acid dianhydrides that can be added include 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride and 2,2 ′, 3,3′-benzophenone tetracarboxylic acid dianhydride. Anhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4
-Dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride,
4,4'-bis (3,4-dicarboxyphenoxy) dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropanedi Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride , Bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, and the above aromatics Some or all of the hydrogen atoms on the aromatic ring of the tetracarboxylic dianhydride are halogen atoms, alkyl or alkoxy groups having 1 to 3 carbon atoms, cyano groups, or some of the hydrogen atoms of alkyl or alkoxy groups. Or, an aromatic tetracarboxylic dianhydride substituted with a halogenated alkyl group having 1 to 3 carbon atoms or an alkoxy group, all of which is substituted with a halogen atom, and the like can be mentioned. These may be used alone or in combination of two or more.

The amount of tetracarboxylic dianhydride used is 0.1 per mole of the aromatic diamine component used.
˜1.0 molar ratio. If the amount is less than 0.1 mol, a polymer having a sufficient molecular weight cannot be obtained before the heat treatment, so that the mechanical properties and heat resistance of the resin deteriorate. Also 1.
If it exceeds 0 mol, the tetracarboxylic acid component becomes excessive at the terminal of the polymer molecule, and the dicarboxylic acid dianhydride for introducing the crosslinking factor into the polymer skeleton cannot act. The preferable molar ratio is 0.5 to 0.999, and more preferably 0.8 to 0.99.

The polymer obtained by using the above aromatic diamine component and aromatic tetracarboxylic dianhydride component as the monomer component mainly has a repeating unit represented by the formula (1), and the molecular end of the polymer is Has a double bond.

The double bond introduced at the terminal of this molecule has the formula (10)

Embedded image By using 5-norbornene-2,3-dicarboxyanhydride represented by

The amount of 5-norbornene-2,3-dicarboxyanhydride used is 0.001 to 1.0 mol ratio per mol of the aromatic diamine component used. 0.
If it is less than 001 mol, the thermal crosslinking reaction due to heat treatment does not proceed sufficiently, and a resin having excellent curing characteristics cannot be obtained. Also,
If it exceeds 1.0 mol, the degree of crosslinking after heat treatment will proceed too much, and the mechanical properties such as impact properties and tensile elongation of the resulting resin will deteriorate. The preferred amount is 0.01 to 0.5 mol. More preferably, it is 0.05 to 0.3 mol.

In addition, an aromatic dicarboxylic acid anhydride other than the above-mentioned 5-norbornene-2,3-dicarboxyanhydride may be partially used in combination as long as the characteristics of the thermosetting polyimide of the present invention are not impaired. As the aromatic dicarboxylic acid anhydride used here, for example, phthalic anhydride,
2,3-benzophenone dicarboxylic acid anhydride, 3,4-
Benzophenone dicarboxylic acid anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic acid anhydride, 3,4-biphenyl dicarboxylic acid anhydride, 2,3-dicarboxyphenylphenyl sulfone anhydride, 3,4-dicarboxyphenylphenyl sulfone anhydride, 2,3-dicarboxyphenylphenyl sulfide anhydride, 3,4-dicarboxyphenylphenyl sulfide anhydride, 1, Examples thereof include 2-naphthalenedicarboxylic acid anhydride, 2,3-naphthalenedicarboxylic acid anhydride, and 1,8-naphthalenedicarboxylic acid anhydride. Further, these aromatic dicarboxylic acid anhydrides may be used alone or in combination of two or more kinds.

As a method for adding and reacting 5-norbornene-2,3-dicarboxyanhydride, (a) tetracarboxylic dianhydride and aromatic diamine are reacted, and then 5-norbornene-2,3 -Method of continuing the reaction by adding dicarboxy anhydride, 5) to (b) aromatic diamine
-Norbornene-2,3-dicarboxyanhydride is added and reacted, then tetracarboxylic dianhydride is added, and the reaction is continued, (c) tetracarboxylic dianhydride, aromatic diamine, and 5-norbornene-2,3
-A method of simultaneously adding and reacting with dicarboxy anhydride, and any addition method may be used.

The production of the polymer represented by the formula (1) can be carried out by any known method and is not particularly limited. in this case,
Formula (2) in which the polymer represented by Formula (1) is its precursor
It does not matter even if a part of the polymer is included.

For example, N, N-dimethylacetamide,
N, N-dimethylformamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,2-dimethoxyethane, bis ( 2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy)
Ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyrroline, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide, sulfolane, phenol, o-cresol, m-cresol, The above aromatic tetracarboxylic dianhydride and aromatic diamine in an organic solvent such as p-cresol, m-cresylic acid, p-chlorophenol, anisole, benzene, toluene, xylene, etc., or a mixture of two or more thereof. Are reacted with each other to obtain a precursor of the polymer of the formula (1) represented by the formula (2).

The polymer represented by the formula (2), which is the precursor of the formula (1) thus obtained, has a concentration of 0.5 g / dl of N,
The value of the logarithmic viscosity measured at 35 ° C. in N-dimethylacetamide is in the range of 0.05 to 1.0 dl / g.
If it is less than 0.05 dl / g, the mechanical properties of the thermosetting polyimide of the present invention obtained after heat treatment will deteriorate. 1.0
If it exceeds dl / g, a thermosetting polyimide cannot be obtained even if sufficient heat treatment is performed.

The polymer represented by the formula (2) thus obtained is chemically treated with a dehydrating agent such as acetic anhydride, trifluoroacetic anhydride, polyphosphoric acid, phosphorus pentoxide and thionyl chloride. By imidizing, the polymer represented by the formula (1) is obtained. In this case, pyridine, imidazole, picoline and its isomers, quinoline and its isomers, and organic bases such as alkylamines represented by triethylamine may coexist. Further, after obtaining the precursor of the formula (2), the solution can be heated to thermally imidize to obtain the polymer represented by the formula (1). Also in this case, the above-mentioned base may coexist as in the case of the chemical imidization method.

The reaction temperature for imidization is 0 to 400 ° C., preferably 0 to 250 ° C., and more preferably 25 to 200 ° C. The reaction pressure is not particularly limited, and the reaction can be sufficiently performed at normal pressure. The reaction time varies depending on the type of solvent, the reaction temperature, and the imidization method, but 1 to 48 hours is usually sufficient.

The thermosetting polyimide of the present invention can be obtained by heat-treating the polymer represented by the above formula (1). However, a part of the formula (1) may be a polymer of the formula (2) which is a precursor thereof.

It is also possible to carry out the thermal crosslinking reaction and the thermal imidization reaction at the same time by further heat-treating the precursor represented by the above formula (2). The heat treatment temperature varies depending on the type of polymer, but is usually 200 to 500 ° C., preferably 250 to 450 ° C., and more preferably 350 to
It is in the range of 400 ° C. At a temperature lower than 200 ° C., the thermal crosslinking reaction does not proceed, and at a temperature higher than 500 ° C., the polymer is modified, and the characteristics of the thermosetting polyimide cannot be sufficiently obtained.

The heat treatment time varies depending on the type of polymer and the heat treatment temperature to be carried out, but is usually 0.1 minute to 1 hour, more preferably 5 minutes to 30 minutes. 0.
If the time is shorter than 1 minute, the thermal crosslinking reaction does not sufficiently occur and a thermoset polyimide cannot be obtained. If the time is longer than 24 hours, the thermosetting polyimide obtained will be modified, and the characteristics of the thermosetting polyimide will not be obtained sufficiently. The heat treatment pressure is not particularly limited, and can be sufficiently performed even at normal pressure.

For the purpose of controlling the reaction rate by accelerating or suppressing the thermal crosslinking reaction, a metal catalyst containing gallium, germanium, indium and lead, molybdenum, manganese, nickel, cadmium, cobalt, chromium. It is possible to add transition metal catalysts including iron, copper, tin and platinum, and phosphorus compounds, silicon compounds, nitrogen compounds and sulfur compounds. Irradiation of infrared rays, ultraviolet rays, radiation such as α, β or γ rays, electron beams or x-rays, and plasma treatment or doping treatment may be performed for the same purpose as described above.

When the heat treatment is carried out, the form of the polymer of the above formula (1) or (2) is not particularly limited. After the obtained polymer is made into a solid such as powder, granules or lumps, suspension, and solution, heat treatment can be performed. In the case of a solid body, depending on the required shape, for example, a film,
It is possible to make sheets, fibers and molded bodies with various shapes. In this case, known molding methods such as melting, extrusion, sintering, blowing and calendering can be used.
When a solvent is used, it can be formed into a shape similar to that of a solid body with desolvation depending on heat treatment conditions. Furthermore, solids such as powder, granules, and lumps, suspensions, and solutions obtained by solution are used for carbon fibers, glass fibers, various other inorganic fibers, aramid fibers, heterocyclic polymer fibers, and other various chemical fibers. It is also possible to impregnate a woven cloth or a paper-like sheet covered with these fibers and then heat-treat. Furthermore, applying them to a material such as a plate, foil, and rod made of metal, ceramic, plastic, and glass to heat-treat them, and after applying them, heat-treating them by stacking the same kind or different kinds of materials and sandwiching them. It is possible to bond both at the same time. When gluing,
It is preferably carried out under pressure.

The thermosetting polyimide of the present invention is a thermoplastic resin such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polybutadiene, polystyrene, polyvinyl acetate ABS resin, polybutylene terephthalate as long as the object of the present invention is not impaired. , Polyethylene terephthalate, polyphenylene oxide, polycarbonate, PTFE, celluloid, polyarylate, polyether nitrile, polyamide, polysulfone, polyether sulfone, polyether ketone, polyphenyl sulfide, polyamide imide, polyether imide,
Modified polyphenylene oxide and polyimide etc., or other thermosetting resins such as thermosetting polybutadiene,
Formaldehyde resin, amino resin, polyurethane, silicone resin, SBR, NBR, unsaturated polyester, epoxy resin, polycyanate, phenol resin, etc. can be blended in an appropriate amount of one or more resins depending on the purpose. is there. The compounding method is not particularly limited.

It is also possible to use a mixture of two or more of the thermosetting polyimides of the present invention in suitable amounts depending on the purpose. It is also possible to blend one or two or more of the above-mentioned resins with the mixed thermosetting polyimide within a range that does not impair the object of the present invention.

Further, the following fillers and the like may be used within a range that does not impair the object of the present invention. That is, abrasion resistance improvers such as graphite, carborundum, silica powder, molybdenum disulfide, and fluororesins, reinforcing agents such as glass fibers and carbon fibers, flame retardant properties such as antimony trioxide, magnesium carbonate and calcium carbonate. Improvers, electrical property improvers such as clay and mica, tracking resistance improvers such as asbestos, silica and graphite, acid resistance improvers such as barium sulfate and calcium metasilicate, iron powder, zinc powder, aluminum powder, copper powder Other examples are thermal conductivity improvers such as glass beads, glass spheres, talc, diatomaceous earth, alumina, silasbaln, hydrated alumina, metal oxides, and colorants.

[0040]

EXAMPLES The present invention will be described in detail below with reference to examples. The physical properties of the polyimide in the examples were measured by the following methods. Glass transition temperature; measured by DSC (Shimadzu DT-40 series, DSC-41M) under a nitrogen stream at a temperature rising rate of 16 ° C / min. 5% weight loss temperature; DTG in air (Shimadzu DT-4
0 series, DTG-40M), in air flow, 1
Measured at a heating rate of 0 ° C / min. Logarithmic viscosity; Polyamic acid in N, N-dimethylacetamide at a concentration of 0.5 g / 100 ml at 35 ° C.
Measured at. Mechanical properties of film: tensile strength, tensile elongation and tensile modulus were measured according to ASTM-D882.

Example 1 36.85 g (0.1 mol) of 4,4'-bis (3-aminophenoxy) biphenyl and pyromellitic acid diacid were placed in a container equipped with a stirrer, a reflux condenser, and a nitrogen introducing tube. 21.16 g (0.097 mol) of anhydride and N-methyl-
Charge 2-pyrrolidone (135.0 g) under nitrogen atmosphere 2
Stirred at 5 ° C. After 6 hours, 5-norbornene-2,3
-Dicarboxy anhydride 0.985 g (0.006 mol)
Was added and stirring was continued for 18 hours. The obtained precursor polymer had an inherent viscosity of 0.50 dl / g. The obtained polymer solution was cast on a glass plate using a doctor blade, and then it was heated at 250 ° C. under a nitrogen stream.
And dried for 4 hours to obtain an imide film having a thickness of 40 μm before thermal crosslinking. About this imide film before thermal crosslinking D
SC measurement showed that the glass transition temperature was 250 ° C,
An exothermic peak due to the thermal crosslinking reaction was observed at 375 ° C.
Further, 20 mg of the imide film before thermal crosslinking was added to 5 ml of p-chlorophenol, and when heated, it was completely dissolved at 150 ° C. On the other hand, the imide film before heat-crosslinking treatment was heat-treated at 375 ° C. for 30 minutes in a nitrogen stream to give a thickness of 40 μm.
A polyimide film of m was obtained. When DSC measurement was performed on the polyimide film after the thermal crosslinking treatment, a glass transition temperature was observed at 280 ° C., but no exothermic peak was detected. Further, when a solubility test with p-chlorophenol was conducted by the same method, it was not dissolved even after 1 hour under heating under reflux, and no change was observed by visual observation. The 5% weight loss temperature of the polyimide film after heat treatment was 520 ° C. Furthermore, when the mechanical properties of the polyimide film were measured, the tensile strength was 13.5 Kg / mm ² , the tensile elastic modulus was 350 Kg /
It was mm ² and the tensile elongation was 70%.

Examples 2 to 11 As shown in Table 1, various predetermined amounts of aromatic diamine, aromatic tetracarboxylic dianhydride and 5-norbornene-
Polymers of various precursors were obtained using 2,3-dicarboxyanhydride and various solvents. The logarithmic viscosities thereof were imidized in the same manner as in Example 1 to obtain each imide film. Solubility tests of these films with glass transition temperature, exothermic peaks and p-chlorophenol were carried out in Example 1.
The same was done. Table 2 shows the results. Subsequently, the imide films were subjected to the same heat treatment as in Example 1,
A polyimide film after various heat treatments was obtained. Regarding the obtained polyimide film, the film thickness, glass transition temperature, exothermic peak, solubility test with p-chlorophenol, 5% weight loss temperature, and mechanical properties were measured in the same manner as in Example 1. The results are shown in Table 2 together with the results of Example 1.

Comparative Examples 1 to 4 As shown in Table 3, various predetermined amounts of aromatic diamine, aromatic tetracarboxylic dianhydride and 5-norbornene-
Polymers of various precursors outside the scope of the claims were obtained using 2,3-dicarboxyanhydride and various solvents. The results are shown in Table 5. Subsequently, the precursor polymer was imidized in the same manner as in Example 1 to obtain each imide film. For each of the obtained polyimide films, the same measurement as in Example 1 was performed. The results are shown in Table 4.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

[0047]

[Table 4]

[0048]

[Table 5]

[0049]

INDUSTRIAL APPLICABILITY The thermosetting polyimide obtained by the present invention has excellent heat resistance and can be applied to structural materials, electronic materials and the like having excellent workability and mechanical properties.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Jun Nakajima 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Toatsu Chemical Co., Ltd.

Claims (5)

[Claims] (1) Formula (1) (In the formula, P1 is the following formula (A) or (B) Embedded image Represents a divalent group represented by the following formula, S1 is represented by the following formulas (C) and (D): Embedded image Represents at least one monovalent group represented by
Is an integer of 0 to 1, n is an integer of 0 to 99,
When m + n ≦ 100 and m ≠ 100, there may or may not be a regularity or regularity between the repeating units of m and n. ) A polymer having a repeating structural unit represented by: 2. A formula (2) which is a precursor of the polymer represented by the above formula (1). (Wherein, P2 is the following formula (E) or (F) Embedded image S2 represents a divalent group represented by the following formulas (G) and (H): Embedded image Represents at least one type of monovalent group represented by and m and n are the same as above. ) 0.05 of polyamic acid having a repeating unit represented by the formula (N, N-dimethylacetamide solvent, concentration 0.5 g / dl, measured at 35 ° C.) 0.05
The polyamic acid as a precursor of the polymer according to claim 1, which is in the range of from 1.0 to 1.0 dl / g. 3. Formula (3): Where S1 is (C) and (D) Embedded image Represents at least one monovalent group represented by
M is an integer from 0 to 70, l is an integer from 0 to 30 and k + l ≦ 100, and when k ≠ 100, m
There may or may not be a regularity or regularity between the repeating units of and n. ) A polymer having a repeating unit represented by the formula (1) and a polyamic acid which is a precursor thereof. 4. Formula (4): (In the formula, i is an integer of 100 to 10, j is an integer of 0 to 90, and i + j ≦ 100, and i ≠ 1.
In the case of 00, there may or may not be a regularity or regularity between the repeating units of i and j. ) A polymer having a repeating unit represented by the formula (1) and a polyamic acid which is a precursor thereof. 5. A thermosetting polyimide obtained by heat-treating the polymer according to any one of claims 1 to 4 and a polyamic acid which is a precursor thereof.