JP2002216542A - Transparent conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive film having various physical properties such as heat resistance, mechanical properties, electrical properties, thermal oxidation stability and chemical resistance excellent in transparency. SOLUTION: Using a specific diamine compound and tetracarboxylic dianhydride is an essential condition. A polyimide of a repeating structural unit represented by the general formula (1) [In the formula, X shows a direct bond, -O-, -SO2-, -C(CH3)2 or -C(CF3)2-] gained by using the specific diamine compound and tetracarboxylic dianhydride or a substance that the end of the polyimide is sealed by an aromatic dicaboxylic acid anhydride or an aromatic monoamine are excellent in heat resistance, mechanical properties, electrical properties, thermal oxidation stability and chemical resistance as well as transparency. Accordingly, a polyimide film forming the transparent conductive film is effectively used for the transparent conductive film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transparent conductive film used for a solid display, a liquid crystal display and the like.

[0002]

2. Description of the Related Art Transparent conductive films used for transparent electrodes of various displays are required to be excellent in transparency, electric characteristics and mechanical characteristics. Therefore, highly transparent resins such as polyethylene terephthalate and polycarbonate have been conventionally used as the base film. Specifically, the transparent conductive film is manufactured by forming a metal oxide film on such a film of polyethylene terephthalate or polycarbonate.

However, the film made of polyethylene terephthalate or polycarbonate has low heat resistance, and when heated to 170 ° C. or more, deformation occurs and high-temperature heat treatment cannot be performed. Therefore, on these films, for example, a metal oxide film such as indium oxide is formed by vacuum evaporation, and when this is directly used as a transparent conductive film, the oxidation treatment after vacuum evaporation cannot be sufficiently performed. The obtained metal oxide film has a problem in transparency. That is, the metal oxide film formed by vapor deposition is insufficient in transparency as it is, and good transparency is exhibited by oxidizing under severe conditions, but the above-mentioned polyethylene terephthalate film or polycarbonate film is Since it cannot withstand such severe heat treatment, the transparency of the metal oxide film is not satisfactory. If metal indium is vacuum-deposited in place of vacuum deposition of indium oxide or the like, it is not necessary to oxidize at high temperature after vacuum deposition like vacuum deposition of indium oxide, so even films such as polyethylene terephthalate film or polycarbonate film Although adequately compatible, the metal oxide coatings obtained by this method are not satisfactory because of their transparency problems.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a transparent conductive film using a heat-resistant resin having excellent transparency and having a transparent conductive film having extremely excellent transparency.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have solved the above problem by using a highly transparent polyimide film having a specific structure. I found what I could do. That is, the present invention is a polyimide obtained from a specific aromatic diamine and tetracarboxylic dianhydride, in addition to the excellent physical properties inherent to polyimide, because it is excellent in transparency, metal oxide film by vacuum evaporation It has been found that it is possible to carry out an oxidation treatment at a high temperature after the formation, and that the resulting conductive film is transparent and can be used as a substrate material for a liquid crystal display material, thus completing the present invention. That is, the present invention provides a transparent conductive film obtained using a polyimide resin containing a repeating structural unit represented by the general formula (1) as an essential component.

[0006]

Embedded image [X in the general formula (1) is a direct bond, -O-, -SO2
Represents-, -C (CH3) 2- or -C (CF3) 2-. And when producing the polyimide represented by the general formula (1), the aromatic dicarboxylic anhydride represented by the general formula (2) and / or the aromatic monoamine represented by the general formula (3) It is a transparent conductive film obtained using a polyimide resin obtained by performing a reaction in the presence.

[0007]

Embedded image [In the general formula (2), Ar1 represents one selected from the group of the formula (I), and Y represents one selected from the group of the formula (II). In the general formula (3), Ar2 represents a kind selected from the group of the formula (III), and Z represents a kind selected from the group of the formula (IV). ]

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, it has been found that the polyimide represented by the general formula (1) is suitable for a transparent conductive film. The polyimide represented by the general formula (1) is represented by the general formula (4)

[0009]

Embedded image [X in the general formula (4) is a direct bond, -O-, -SO2
Represents-, -C (CH3) 2- or -C (CF3) 2-. And a diamine component represented by the formula (5):

[0010]

Embedded image And a bis (3,4-dicarboxyphenyl) ether dianhydride represented by the following formula:

[Diamine Component] Examples of the diamine represented by the general formula (4) include 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] sulfone and 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.

The polyimide of the present invention can be used by mixing one or more of the following diamines with the above-mentioned diamine for the purpose of improving or modifying the performance. Examples of the aromatic diamine that can be mixed include a diamine represented by the general formula (4) and diamines a) to l) shown below. Specific examples are shown below.

A) Diamine having one benzene ring. p
-Phenylenediamine, m-phenylenediamine, b) diamine having two benzene rings 4,4'-diaminodiphenylmethane 3,4'-diaminodiphenylmethane 3,3'-diaminodiphenylmethane 4,2'-diaminodiphenylmethane 4,4 ' -Diaminodiphenyl sulfide 3,4'-diaminodiphenyl sulfide 3,3'-diaminodiphenyl sulfide 4,4'-diaminodiphenyl sulfone 3,4'-diaminodiphenyl sulfone 3,3'-diaminodiphenyl sulfone 4,4'-diamino Benzophenone 3,4'-diaminobenzophenone 3,3'-diaminobenzophenone 4,4'-diaminodiphenyl ether 3,4'-diaminodiphenyl ether 3,3'-diaminodiphenyl ether 2,2-bis (4-aminophenoxy ) Propane 2,2-bis (3-aminophenoxy) propane 2- (3-aminophenoxy) -2- (4-aminophenoxy) propane 2,2-bis (4-aminophenoxy) 1,1,1,1
3,3,3-hexafluoropropane 2,2-bis (3-aminophenoxy) 1,1,1,
3,3,3-hexafluoropropane 2- (3-aminophenoxy) -2- (4-aminophenoxy) 1,1,1,3,3,3-hexafluoropropane 4,4′-diamino-2, 2'-dichlorobiphenyl 4,4'-diamino-2,2'-dibromobiphenyl 4,4'-diamino-2,2'-dicyanobiphenyl 4,4'-diamino-2,2'-dimethylbiphenyl 4,4 '-Diamino-3,3'-dimethylbiphenyl 4,4'-diamino-2,2'-ditrifluoromethylbiphenyl 4,4'-diamino-2-trifluoromethyldiphenyl ether 4,4'-diamino-3-tri Fluoromethyl diphenyl ether 4,4'-diamino-2,2'-ditrifluoromethyl diphenyl ether 4,4'-diamino-2,3'-ditrifluoromethyl diphenyl 4,4'-diamino-3,3'-ditrifluoromethyl diphenyl ether 3,4'-diamino-5-trifluoromethyl diphenyl ether 3,4'-diamino-2'-trifluoromethyl diphenyl ether 3,4'-diamino -3'-trifluoromethyldiphenylether 3,4'-diamino-5,2'-ditrifluoromethyldiphenylether 3,4'-diamino-5,3'-ditrifluoromethyldiphenylether 3,3'-diamino-5-tri Fluoromethyl diphenyl ether 3,3'-diamino-5,5'-ditrifluoromethyl diphenyl ether 4,4'-diamino-2-trifluoromethyl diphenyl sulfide 4,4'-diamino-3-trifluoromethyl diphenyl sulfide 4,4 '-Diamino-2,2'-di Trifluoromethyldiphenyl sulfide 4,4'-diamino-2,3'-ditrifluoromethyldiphenyl sulfide 4,4'-diamino-3,3'-ditrifluoromethyldiphenyl sulfide 3,4'-diamino-5-trifluoro Methyl diphenyl sulfide 3,4'-diamino-2'-trifluoromethyl diphenyl sulfide 3,4'-diamino-3'-trifluoromethyl diphenyl sulfide 3,4'-diamino-5,2'-ditrifluoromethyl diphenyl sulfide 3,4'-diamino-5,3'-ditrifluoromethyldiphenyl sulfide 3,3'-diamino-5-trifluoromethyldiphenyl sulfide 3,3'-diamino-5,5'-ditrifluoromethyldiphenyl sulfide 4, 4'-diamino-2-trifluoromethyl Diphenylsulfone 4,4'-diamino-3-trifluoromethyldiphenylsulfone 4,4'-diamino-2,2'-ditrifluoromethyldiphenylsulfone 4,4'-diamino-2,3'-ditrifluoromethyldiphenylsulfone 4,4'-diamino-3,3'-ditrifluoromethyldiphenylsulfone 3,4'-diamino-5-trifluoromethyldiphenylsulfone 3,4'-diamino-2'-trifluoromethyldiphenylsulfone 3,4 '-Diamino-3'-trifluoromethyldiphenyl sulfone 3,4'-diamino-5,2'-ditrifluoromethyldiphenyl sulfone 3,4'-diamino-5,3'-ditrifluoromethyldiphenyl sulfone 3,3'- Diamino-5-trifluoromethyldiphenylsulfone 3,3'-diamino 5,5'-ditrifluoromethyldiphenyl sulfone 4,4'-diamino-2-trifluoromethylbenzophenone 4,4'-diamino-3-trifluoromethylbenzophenone 4,4'-diamino-2,2'-ditrifluoro Methylbenzophenone 4,4'-diamino-2,3'-ditrifluoromethylbenzophenone 4,4'-diamino-3,3'-ditrifluoromethylbenzophenone 3,4'-diamino-5-trifluoromethyldibenzophenone 3, 4'-diamino-2'-trifluoromethyl benzophenone 3,4'-diamino-3'-trifluoromethyl benzophenone 3,4'-diamino-5,2'-ditrifluoromethyl benzophenone 3,4'-diamino-5 , 3'-Ditrifluoromethyl benzophenone 3,3'-diamino-5-to Trifluoromethylbenzophenone 3,3'-diamino-5,5'-ditrifluoromethylbenzophenone 4,4'-diamino-2-methyldiphenyl ether 4,4'-diamino-3-methyldiphenyl ether 4,4'-diamino-2 , 2'-dimethyldiphenyl ether 4,4'-diamino-2,3'-dimethyldiphenyl ether 4,4'-diamino-3,3'-dimethyldiphenyl ether 3,4'-diamino-5-methyldiphenyl ether 3,4'- Diamino-2'-methyldiphenylether 3,4'-diamino-3'-methyldiphenylether 3,4'-diamino-5,2'-dimethyldiphenylether 3,4'-diamino-5,3'-dimethyldiphenylether 3,3 '-Diamino-5-methyldiphenyl ether 3,3'-diamino 5,5'-dimethyldiphenyl ether 4,4'-diamino-2-methyldiphenyl sulfide 4,4'-diamino-3-methyldiphenyl sulfide 4,4'-diamino-2,2'-dimethyldiphenyl sulfide 4,4 '-Diamino-2,3'-dimethyldiphenyl sulfide 4,4'-diamino-3,3'-dimethyldiphenyl sulfide 3,4'-diamino-5-methyldiphenyl sulfide 3,4'-diamino-2'-methyldiphenyl Sulfide 3,4'-diamino-3'-methyldiphenyl sulfide 3,4'-diamino-5,2'-dimethyldiphenyl sulfide 3,4'-diamino-5,3'-dimethyldiphenyl
Sulfide 3,3'-diamino-5-methyldiphenyl sulfide 3,3'-diamino-5,5'-dimethyldiphenyl
Sulfide 4,4'-diamino-2-methyldiphenylsulfone 4,4'-diamino-3-methyldiphenylsulfone 4,4'-diamino-2,2'-dimethyldiphenylsulfone 4,4'-diamino-2,3 '-Dimethyldiphenylsulfone 4,4'-diamino-3,3'-dimethyldiphenylsulfone 3,4'-diamino-5-methyldiphenylsulfone 3,4'-diamino-2'-methyldiphenylsulfone 3,4'- Diamino-3'-methyldiphenyl sulfone 3,4'-diamino-5,2'-dimethyldiphenyl
Sulfone 3,4'-diamino-5,3'-dimethyldiphenyl
Sulfone 3,3'-diamino-5-methyldiphenylsulfone 3,3'-diamino-5,5'-dimethyldiphenyl
Sulfone 4,4'-diamino-2-methylbenzophenone 4,4'-diamino-3-methylbenzophenone 4,4'-diamino-2,2'-dimethylbenzophenone 4,4'-diamino-2,3'-dimethyl Benzophenone 4,4'-diamino-3,3'-dimethylbenzophenone 3,4'-diamino-5-methyldibenzophenone 3,4'-diamino-2'-methylbenzophenone 3,4'-diamino-3'-methyl Benzophenone 3,4'-diamino-5,2'-dimethylbenzophenone 3,4'-diamino-5,3'-dimethylbenzophenone 3,3'-diamino-5-methylbenzophenone 3,3'-diamino-5,5 '-Dimethylbenzophenone 4,4'-diamino-2-bromodiphenyl ether 4,4'-diamino-3-bromodiphenylate 4,4'-diamino-2,2'-dibromodiphenyl ether 4,4'-diamino-2,3'-dibromodiphenyl ether 4,4'-diamino-3,3'-dibromodiphenyl ether 3,4 ' -Diamino-5-bromodiphenyl ether 3,4'-diamino-2'-bromodiphenyl ether 3,4'-diamino-3'-bromodiphenyl ether 3,4'-diamino-5,2'-dibromodiphenyl ether 3,4 '-Diamino-5,3'-dibromodiphenyl ether 3,3'-diamino-5-bromodiphenyl ether 3,3'-diamino-5,5'-dibromodiphenyl ether 4,4'-diamino-2-bromodiphenyl sulfide 4 4,4'-diamino-3-bromodiphenyl sulfide 4,4'-diamino-2,2'-dibromodiphenyl sulfide 4,4'-diamino-2,3'-dibromodiphenyl sulfide 4,4'-diamino-3,3'-dibromodiphenyl sulfide 3,4'-diamino-5-bromodiphenyl sulfide 3,4 '-Diamino-2'-bromodiphenyl sulfide 3,4'-diamino-3'-bromodiphenyl sulfide 3,4'-diamino-5,2'-dibromodiphenyl sulfide 3,4'-diamino-5,3'- Dibromodiphenyl
Sulfide 3,3'-diamino-5-bromodiphenyl sulfide 3,3'-diamino-5,5'-dibromodiphenyl
Sulfide 4,4'-diamino-2-bromodiphenylsulfone 4,4'-diamino-3-bromodiphenylsulfone 4,4'-diamino-2,2'-dibromodiphenylsulfone 4,4'-diamino-2, 3′-dibromodiphenyl sulfone 4,4′-diamino-3,3′-dibromodiphenyl sulfone 3,4′-diamino-5-bromodiphenyl sulfone 3,4′-diamino-2′-bromodiphenyl sulfone 3, 4'-diamino-3'-bromodiphenyl sulfone 3,4'-diamino-5,2'-dibromodiphenyl
Sulfone 3,4'-diamino-5,3'-dibromodiphenyl
Sulfone 3,3'-diamino-5-bromodiphenyl sulfone 3,3'-diamino-5,5'-dibromodiphenyl
Sulfone 4,4'-diamino-2-bromobenzophenone 4,4'-diamino-3-bromobenzophenone 4,4'-diamino-2,2'-dibromobenzophenone 4,4'-diamino-2,3'- Dibromobenzophenone 4,4'-diamino-3,3'-dibromobenzophenone 3,4'-diamino-5-bromobenzophenone 3,4'-diamino-2'-bromobenzophenone 3,4'-diamino-3 ' -Bromobenzophenone 3,4'-diamino-5,2'-dibromobenzophenone 3,4'-diamino-5,3'-dibromobenzophenone 3,3'-diamino-5-bromobenzophenone 3,3'-diamino -5,5'-Dibromobenzophenone 4,4'-diamino-2-chlorodiphenyl ether 4,4'-diamino-3-chlorodiphenyl ether 4 , 4'-Diamino-2,2'-dichlorodiphenyl ether 4,4'-diamino-2,3'-dichlorodiphenyl ether 4,4'-diamino-3,3'-dichlorodiphenyl ether 3,4'-diamino -5-chlorodiphenyl ether 3,4'-diamino-2'-chlorodiphenyl ether 3,4'-diamino-3'-chlorodiphenyl ether 3,4'-diamino-5,2'-dichlorodiphenyl ether 3,4'-diamino -5,3'-dichlorodiphenylether 3,3'-diamino-5-chlorodiphenylether 3,3'-diamino-5,5'-dichlorodiphenylether 4,4'-diamino-2-chlorodiphenylsulfide 4,4 '-Diamino-3-chlorodiphenyl sulfide 4,4'-diamino-2,2'-dichlorodiphenyl sulfide 4,4'-diamino-2,3'-dichlorodiphenyl sulfide 4,4'-diamino-3,3'-dichlorodiphenyl sulfide 3,4'-diamino-5-chlorodiphenyl sulfide 3,4'- Diamino-2'-chlorodiphenyl sulfide 3,4'-diamino-3'-chlorodiphenyl sulfide 3,4'-diamino-5,2'-dichlorodiphenyl sulfide 3,4'-diamino-5,3'-di Chlordiphenyl sulfide 3,3'-diamino-5-chlorodiphenyl sulfide 3,3'-diamino-5,5'-dichlorodiphenyl sulfide 4,4'-diamino-2-chlorodiphenylsulfone 4,4'-diamino- 3-chlorodiphenylsulfone 4,4'-diamino-2,2'-dichlorodiphenylsulfone 4,4'-diamino-2,3'-dic Rudiphenylsulfone 4,4'-diamino-3,3'-dichlorodiphenylsulfone 3,4'-diamino-5-chlorodiphenylsulfone 3,4'-diamino-2'-chlorodiphenylsulfone 3,4'-diamino -3'-chlorodiphenyl sulfone 3,4'-diamino-5,2'-dichlorodiphenyl sulfone 3,4'-diamino-5,3'-dichlorodiphenyl sulfone 3,3'-diamino-5-chlorodiphenyl Sulfone 3,3'-diamino-5,5'-dichlorodiphenyl sulfone 4,4'-diamino-2-chlorobenzophenone 4,4'-diamino-3-chlorobenzophenone 4,4'-diamino-2,2 ' -Dichlorobenzophenone 4,4'-diamino-2,3'-dichlorobenzophenone 4,4'-diamino-3,3'-dichlorobenzof Non 3,4'-diamino-5-chlorobenzophenone 3,4'-diamino-2'-chlorobenzophenone 3,4'-diamino-3'-chlorobenzophenone 3,4'-diamino-5,2'-dichloro Benzophenone 3,4'-diamino-5,3'-dichlorobenzophenone 3,3'-diamino-5-chlorobenzophenone 3,3'-diamino-5,5'-dichlorobenzophenone 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) benzene ring Diamine having three. 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, 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, , 4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2,6-bis (3-aminophenoxy)
Pyridine, 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (4-aminophenoxy) benzonitrile, 1,3-bis (3-aminophenoxy)
-2-chlorobenzene, 1,3-bis (3-aminophenoxy) -5-chlorobenzene, 1,3-bis (4-aminophenoxy) -4-chlorobenzene, 1,3-bis (3-aminophenoxy) ) -2-Brombenzene, 1,
3-bis (3-aminophenoxy) -5-bromobenzene, 1,3-bis (4-aminophenoxy) -4-bromobenzene, 1,3-bis (3-aminophenoxy)-
4-trifluoromethylbenzene, 1,3-bis (4-
Aminophenoxy) -4-trifluoromethylbenzene, 1,3-bis (3-aminophenoxy) -5-trifluoromethylbenzene, 1,3-bis (4-aminophenoxy) -5-trifluoromethylbenzene, 1 , 3
-Bis (3-aminophenoxy-5-trifluoromethyl) benzene, 1,3-bis (4-aminophenoxy-
2-trifluoromethyl) benzene, 1,4-bis (3
-Aminophenoxy-5-trifluoromethyl) benzene, 1,4-bis (4-aminophenoxy-2-trifluoromethyl) benzene, 1,3-bis (3-aminophenoxy-5-trifluoromethyl) -4 -Trifluoromethylbenzene, 1,3-bis (4-aminophenoxy-2-trifluoromethyl) -4-trifluoromethylbenzene, 1,3-bis (3-aminophenoxy-5
-Trifluoromethyl) -5-trifluoromethylbenzene, 1,3-bis (4-aminophenoxy-2-trifluoromethyl) -5-trifluoromethylbenzene d) Diamine having four benzene rings. 4,4′-bis (4-aminophenoxy) biphenyl,
Bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl]
Sulfide, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy)
Phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,
1,3,3,3-hexafluoropropane, 4,4'-
Bis (3-amino-5-trifluoromethylphenoxy) biphenyl 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenylbis [4- (3
-Amino-5-trifluoromethylphenoxy) phenyl] sulfide, bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] sulfide, bis [4- (3-amino-5-trifluoromethylphenoxy)) Phenyl] sulfone, bis [4- (4-amino-2)
-Trifluoromethylphenoxy) phenyl] sulfone, bis [4- (3-amino-5-trifluoromethylphenoxy) phenyl] ether, bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl]
Ether, bis [4- (3-amino-5-trifluoromethylphenoxy) phenyl] ketone, bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl]
Ketone, 2,2-bis [4- (3-amino-5-trifluoromethylphenoxy) phenyl] propane, 2,2
-Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] propane, 2,2-bis [3-
(3-amino-5-trifluoromethylphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) ) 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 Diamines. 4,4'-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4
-Amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (4- Aminophenoxy) phenoxy] diphenylsulfone; g) diamine having an aromatic substituent. 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino -4-biphenoxybenzophenone, h) diamine having a spirobiindane ring. 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; i) Diamines which are siloxane diamines. 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω -Bis (3-aminobutyl) polydimethylsiloxane, j) diamines which are ethylene glycol diamines. Bis (aminomethyl) ether, 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) diamines which are methylene diamines. 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) Diamines which are 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.

[Tetracarboxylic acid component] The tetracarboxylic dianhydride used to obtain the polyimide of the present invention is bis (3,4-dicarboxyphenyl) ether dianhydride represented by the formula (5). However, there is no problem if one or more of the following tetracarboxylic dianhydrides are copolymerized for the purpose of improving or modifying the performance of the polyimide of the present invention. Tetracarboxylic dianhydrides that can be used in combination are pyromellitic dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl)
Sulfide dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane 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, 2,2 -Bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 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, 2,2-bis (2,3-dicarboxyphenyl)- 1,1,1,3,3,3-hexafluoropropane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) sulfide dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, 1,3-bis (2,
3-dicarboxyphenoxy) benzene dianhydride, 1,
Examples include 4-bis (2,3-dicarboxyphenoxy) benzene dianhydride and 1,2,5,6-naphthalenetetracarboxylic dianhydride.

[Terminal Capping] In the production of the polyimide for a transparent conductive film of the present invention, when the amount of the tetracarboxylic dianhydride used is less than 1 mol per 1 mol of the diamine, the end of the resulting polyimide is not more than 1 mol. It remains as an amino group. Therefore, the aromatic dicarboxylic anhydride represented by the general formula (2) used for sealing the terminal amino group is phthalic anhydride, 4-phenylphthalic anhydride,
-Phenoxyphthalic anhydride, 4-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 anhydride Can be.

Among the above-mentioned aromatic dicarboxylic anhydrides,
It is most preferable from the viewpoint of properties and practice of the polyimide of the present invention from which phthalic anhydride can be obtained. The amount of the aromatic dicarboxylic anhydride used is 10 to 100 mol% of the remaining amino groups.
It is. Specifically, when the number of moles of the diamine is A and the number of moles of the tetracarboxylic dianhydride is B, the number of moles of the amino group remaining at the terminal is theoretically represented by the formula (a). That is, assuming that the number of moles of the aromatic dicarboxylic anhydride used is C, the range of C is represented by the formula (b). (AB) × 2 (a) 10 ≦ {C} [(AB) × 2]} × 100 ≦ 100 (b) The amount of the aromatic dicarboxylic anhydride used is less than the amount of the remaining amino group. If the amount is less than 10 mol%, sufficient end capping cannot be performed, and if it exceeds 100 mol%, a molecular weight sufficient to bring out sufficient properties cannot be obtained. Preferably, it is 20 to 100 mol%, more preferably 40 to 100 mol%. When producing the polyimide for a transparent conductive film of the present invention, if the amount of the diamine used is less than 1 mol per 1 mol of the tetracarboxylic dianhydride, the terminal of the obtained polyimide remains as a dicarboxylic anhydride. Thus, the aromatic monoamine represented by the general formula (3) used for sealing the terminal dicarboxylic anhydride is specifically aniline, 2-fluoroaniline, 3-fluoroaniline 4-fluoro Aniline 2-chloroaniline, 3-chloroaniline 4-chloroaniline 2-bromoaniline, 3-chloroaniline
Bromoaniline 4-bromoaniline 2-nitroaniline, 3-nitroaniline 4-nitroaniline 2-cyanoaniline, 3-cyanoaniline 4-cyanoaniline2-
Methylaniline, 3-methylaniline, 4-methylaniline, 2-trifluoromethylaniline, 3-trifluoromethylaniline, 4-trifluoromethylaniline, 2-methoxyaniline, 3-methoxyaniline,
-Methoxyaniline, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminodiphenyl ether, 3-aminodiphenyl ether, 4-
Amino diphenyl ether, 2-amino diphenyl sulfide, 3-amino diphenyl sulfide, 4-amino diphenyl sulfide, 2-amino diphenyl sulfone, 3-amino diphenyl sulfone, 4-amino diphenyl sulfone, 2-amino benzophenone, 3-amino benzophenone, 4 -Aminobenzophenone, 1-aminonaphthalene, and 2-aminonaphthalene.

Among the aromatic monoamines described above, aniline is most preferable from the viewpoint of the properties and practice of the polyimide of the present invention. The amount of aromatic monoamine used is from 10 to 100 mol% of the residual terminal dicarboxylic anhydride. Specifically, assuming that the number of moles of the diamine is A and the number of moles of the tetracarboxylic dianhydride is B, the number of moles of the dicarboxylic anhydride remaining at the terminal is theoretically represented by the formula (c). That is, assuming that the number of moles of the aromatic monoamine used is D,
The range of D is represented by equation (d). (BA) × 2 (c) 10 ≦ {D} [(BA) × 2]} × 100 ≦ 100 (d) The amount of the aromatic monoamine used is less than the amount of the remaining terminal dicarboxylic anhydride. If the amount is less than 10 mol%, sufficient end capping cannot be performed, and if it exceeds 100 mol%, a molecular weight sufficient to bring out sufficient properties cannot be obtained. Preferably, 20 to 1
00 mol%, more preferably 40 to 100 mol%.

[Preparation of polyimide] The tetracarboxylic dianhydride is represented by the formula (5), and one or more kinds are used. The amount is such that the total amount of tetracarboxylic dianhydride per mole of total diamine used is from 0.9 to 1.1.
It is a molar ratio. By changing the molar ratio, the molecular weight of the resulting polyamic acid or polyimide can be controlled. The molar ratio is less than 0.9, or 1.
If it exceeds 1, a molecular weight sufficient to bring out sufficient properties cannot be obtained. Preferably it is 0.92 to 1.08 molar ratio, more preferably 0.94 to 1.06 molar ratio, most preferably in the range of 0.95 to 1.05.

The diamine represented by the general formula (4), the tetracarboxylic dianhydride represented by the general formula (5), the dicarboxylic anhydride represented by the general formula (2), and the diamine represented by the general formula (3) The method of adding the aromatic monoamine to the polymerization system and reacting the same is not particularly limited. I) After reacting the diamine with the tetracarboxylic dianhydride, the dicarboxylic anhydride or the aromatic monoamine B) a method in which dicarboxylic acid anhydrides are added to diamine to cause a reaction, and then tetracarboxylic dianhydride is added and the reaction is further continued; c) a tetracarboxylic dianhydride A method of adding an aromatic monoamine to, reacting, adding a diamine, and continuing the reaction. 2) Dividing the total amount of dicarboxylic anhydrides, adding one of them to the diamine first, reacting, A method in which boric acid dianhydride is added and the reaction is further continued, and then the other is added to continue the reaction. E) The total amount of the aromatic monoamine is divided, and one is added to tetracarboxylic dianhydride first. After the reaction, a method of adding a diamine, further continuing the reaction, and then continuing the reaction by adding the remaining other, and a method of multiplying the methods a) to e) above. Any addition method may be used.

The reaction for producing the polyimide for a transparent conductive film of the present invention is usually carried out in a solvent. Examples of the solvent include: m) phenolic solvents such as phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol, m-cresol, p-cresol, 2,3-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, and anisole. These solvents may be used alone or in combination of two or more. Further, one or two or more of these solvents may be further mixed and used using the solvents described in the following section r). When used as a mixture, it is not necessary to select a combination of solvents that are mutually soluble at an arbitrary ratio, and they may be mixed and non-uniform.

The concentration of the reaction carried out in these solvents (hereinafter referred to as
It is called the polymerization concentration. ) Has no restrictions. In the present invention, the polymerization concentration in the solvent is determined based on the total weight of the total weight of all the solvents used and the total weight of the total weight of all the diamines and all the tetracarboxylic dianhydrides used. The percentage of the total weight of the combined carboxylic dianhydrides is defined as a value expressed as a percentage. Preferred polymerization concentrations are from 5 to 40%, more preferably from 10 to 30%, and most preferred polymerization concentrations are from 15 to 25%.
%.

The reaction for producing the polyimide for an optical material of the present invention is preferably carried out in a solvent. The following method is used: a) Diamine or tetracarboxylic dianhydride is heated in a molten state at a temperature higher than their melting point. B) a method in which a diamine or tetracarboxylic dianhydride is reacted in a state of being vaporized by heating under reduced pressure, etc. c) an external energy such as light, ultrasonic wave or plasma is applied to the diamine or tetracarboxylic dianhydride. And a method of reacting by giving more activation.

In the above-mentioned solvent, a diamine of the general formula (4), a tetracarboxylic dianhydride of the formula (5) and a dicarboxylic anhydride of the general formula (2), or an aromatic monoamine of the general formula (3) Is reacted to obtain the polyimide or polyamic acid of the present invention.

The polyamic acid may be a diamine of the general formula (4), a tetracarboxylic dianhydride of the formula (5) and a dicarboxylic anhydride of the general formula (2) or an aromatic compound of the general formula (3) in the solvent. It is obtained by reacting an aromatic monoamine.
Particularly preferred solvents for this reaction include the aprotic amide solvents described in the above item n) and the ether solvents described in the above item o). The reaction temperature, reaction time and reaction pressure are not particularly limited, and known conditions can be applied. That is, the reaction temperature is preferably in the approximate range of −10 ° C. to 100 ° C., more preferably in the range of around the ice-cooling temperature to about 50 ° C., and most preferably practically room temperature. . The reaction time varies depending on the type of monomer used, the type of solvent, and the reaction temperature, but is preferably 1 to 48 hours. More preferably, it is about 2 to 3 hours to about ten and several hours, and most preferably 4 to 10 hours in practical terms. Still further, the reaction pressure is sufficient at normal pressure. The logarithmic viscosity of the obtained polyamic acid is 0.1 to 2.0 dl.
/ G (in N, N-dimethylacetamide, concentration 0.5g
/ Dl, measured at 35 ° C. ) Range. Logarithmic viscosity is
If it is less than 0.1, the molecular weight is low, so that the mechanical properties are remarkably deteriorated. If it exceeds 2.0, the solution viscosity is high, and it is difficult to cast it into an appropriate shape, which makes the work difficult.

The polyimide for a transparent conductive film of the present invention can be obtained by subjecting the polyamic acid obtained by the above method to a dehydration imidization reaction by a known method. The method can be roughly classified into a chemical imidation method and a thermal imidation method, and all dehydration imidation methods can be applied, including a method using both of them.

In the chemical imidization method, the polyamic acid obtained by the above method is reacted with a dehydrating agent having a hydrolytic ability to chemically dehydrate. The dehydrating agent used is an acetic anhydride, an aliphatic carboxylic anhydride represented by trifluoroacetic anhydride, polyphosphoric acid, a phosphoric acid derivative represented by phosphorus pentoxide, or a mixed acid anhydride of these acids,
Acid chlorides represented by methanesulfonic acid chloride, phosphorus pentachloride and thionyl chloride are exemplified. These dehydrating agents may be used alone or in combination of two or more. The used amount of these dehydrating agents is 2 to 10 mole ratio to 1 mole of the total amount of all diamines used. Preferably it is a 2.1 to 4 molar ratio.

Further, the chemical imidization method can be carried out in the presence of a base catalyst. As the base catalyst to be used, the amine solvent described in the above item p) can be used as the base catalyst. Besides these, 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 are represented. And inorganic bases. The amount of these catalysts used is based on 1 mole of all diamines used.
The molar ratio is from 0.001 to 0.50. Preferably 0.
05 to 0.2 molar ratio.

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.

The thermal imidization method is a) a method in which the polyamic acid is heated and thermally dehydrated by the method described above, and b) a polymerization reaction and a dehydration imidization reaction for obtaining the polyamic acid without obtaining the polyamic acid. In order to proceed simultaneously, it can be carried out by a method in which the monomers used and the dicarboxylic anhydride are dissolved or suspended in a solvent and immediately heated to thermally dehydrate. In the above item a), the polyamic acid may be in any form of a solution dissolved in a solvent, a dispersed suspension, and a solid of the polyamic acid isolated from the solution or suspension. When the solution or suspension is heated, the solvent may be refluxed even if the solvent used is evaporated and removed while accompanied by a dehydration imidization reaction. The former is most often used for film formation and the like, and the latter is suitable for a dehydration imidization reaction in a reactor. Particularly preferred solvents used in the method of the above item b) are the phenolic solvents of the above item m).

The thermal imidization method can be carried out in the presence of a base catalyst, similarly to the chemical imidization method. 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 / imidation 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. Further, m)
One or more of these solvents may be used as a mixture with the solvents described in (1) to (r). When used as a mixture, it is not necessary to select a combination of solvents that are mutually soluble 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 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 400 ° C. can be applied, preferably about 100 ° C. to 300 ° C., and the most preferable and practical in practice is 150 ° C. to 2 ° C.
It is around 50 ° C. The reaction time varies depending on the type of solvent used and other reaction conditions.
It is preferably 4 hours, more preferably around 2 to 10 hours. Furthermore, the reaction pressure is normal 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.

As the method using the chemical imidization method and the thermal imidation method in combination, a) a method in which heating is performed simultaneously in the execution of the chemical imidization method, and b) a chemical imide method in which the thermal imidization method is used. And a method in which a dehydrating agent used in the chemical reaction coexists.

The polyamic acid solution or the polyimide solution obtained by the above method is cast on a glass plate, a metal foil or the like, and dried by heating to obtain a polyimide film. In the case of polyimide powder, it can be formed into a film by extrusion.

The polyimide film thus obtained has a very high transparency and is colorless and transparent, unlike the conventional polyimide film. In the present invention, the term "colorless and transparent polyimide film" means that the visible light transmittance at 500 nm of a polyimide film having a film thickness of 50 ± 5 μm is 80% or more.

[Transparent conductive film] The transparent conductive film is formed on at least one of the front surface and the back surface of the above-mentioned colorless and transparent polyimide film, and is usually formed of a metal oxide film. A general method can be applied as a method for forming such a metal oxide film.

Specifically, In2O3, SnO2, ZnO
Vacuum evaporation of a metal oxide such as or a mixture of any combination thereof, vapor deposition by sputtering, ion plating, chemical vapor deposition, or disperse the metal oxide powder in an appropriate coating agent It is a method of applying a material. For example, a vacuum deposition method using an electron beam gun, a method in which particles sputtered from a metal target by reactive sputtering are oxidized with an oxygen gas to obtain a metal oxide film, and the like can be given.

As another method, there is a method in which the above-mentioned metal oxide film is subjected to a heat treatment at a high temperature of 170 ° C. or higher for a relatively short time to improve transparency and heat resistance.
However, this method cannot be realized as long as a film having no heat resistance such as a polyethylene terephthalate film is used as a base film, but the polyimide film of the present invention has excellent heat resistance as well as transparency. Therefore, these heat treatments were made possible.

[0039]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. Test methods of various tests common to Examples and Comparative Examples are as follows. [Logarithmic viscosity of polyamic acid] (ηinh) 0.50 g / 100 m in N, N-dimethylacetamide
After dissolving at a concentration of 1 l, the value was measured at 35 ° C. [Production method of film] Polyamic acid varnish was cast on a glass plate, and then 100 ° C, 200 ° C under a nitrogen atmosphere.
The resultant was baked at 30 ° C. for 30 minutes and at 250 ° C. for 4 hours to prepare a polyimide film having a thickness of 50 ± 5 μm, which was desolvated and imidized. [Method of Evaluating Film] A film was prepared from a polyamic acid varnish by the above method, and evaluated by the following method. 1) Glass transition temperature (Tg) DSC measurement, heating rate 16 ° C./min, measured in nitrogen 2) 5% weight loss temperature (Td5) DTA-TG measurement, heating rate 10 ° C./min, in air 3) T% 500 nm Light transmittance at 500 nm (Shimadzu UV-3100)
(Measured by PC)

[0040]

Example 1 36.85 g (0.100 mol) of 4,4′-bis (3-aminophenoxy) biphenyl as a solvent was placed in a container equipped with a stirrer, a nitrogen inlet tube, and a thermometer.
156.92 g of N-dimethylacetamide was charged and dissolved under stirring in a nitrogen atmosphere for 30 minutes. Then, bis (3,4-dicarboxyphenyl) ether dianhydride,
After adding 30.40 g (0.098 mol) in portions while paying attention to the rise in the solution temperature, the mixture was stirred at room temperature for 6 hours. The logarithmic viscosity of the polyamic acid thus obtained is 0.8.
It was 2 dl / g. A film was prepared from the obtained polyamic acid varnish by the method described above. Next, a transparent conductive film was formed on one surface of the obtained polyimide film using a reactive magnetron sputtering method. That is,
A polyimide film was mounted on the substrate side of the sputtering apparatus, and an alloy target composed of 90% by weight of metal In and 10% by weight of Sn was mounted on the sputter electrode. And 1
After evacuating to 0-3 Pa, argon gas was
00 cc / min, and oxygen gas at 15 cc / min.
× 10-1Pa. Next, a direct current voltage of 400 V was applied to the sputter electrode to perform glow discharge, and sputtering was performed for 30 seconds to form a transparent conductive film made of In oxide and Sn oxide on the polyimide film. This transparent conductive film showed a surface resistance of 300Ω / □. Table 1 shows the amounts of diamine and tetracarboxylic dianhydride and the physical properties of the obtained polyamic acid varnish, and Table 1 shows the physical properties of the polyimide film on which the transparent conductive film was formed.
It is shown in FIG.

[0041]

Examples 2 to 9 Various polyamic acid varnishes were produced in the same manner as in Example 1 by changing the amount of various diamines and the amount of tetracarboxylic dianhydride used in the reaction, and a polyimide film was prepared from the polyamic acid varnish by the method described above. Was prepared, and thermophysical properties and optical properties were evaluated. The diamine used,
Table 1 shows the amount of tetracarboxylic dianhydride and physical properties of the obtained polyamic acid varnish, and Table 2 shows physical properties of the polyimide film having the transparent conductive film formed thereon.

[0042]

Example 10 A polyamic acid varnish was synthesized in the same manner as in Example 1, and then 0.59 g (0.009 g) of phthalic anhydride was synthesized.
4 mol), and the mixture was further stirred for 6 hours. Using the obtained polyamic acid varnish, a polyimide film was prepared in the same manner as described above, and the thermophysical properties and optical properties were evaluated. Table 3 shows the amounts of the diamine, tetracarboxylic dianhydride and terminal blocking agent used and the physical properties of the obtained polyamic acid varnish.
Table 4 shows the physical properties of the polyimide film having the transparent conductive film formed thereon.

[0043]

EXAMPLES 11-18 Various polyamic acid varnishes were produced in the same manner as in Example 1 using various diamines, dicarboxylic anhydrides and aromatic monoamines. A polyimide film was prepared from the polyamic acid varnish by the method described above, and the thermophysical properties and optical properties were evaluated. Table 3 shows the amounts of the diamine, tetracarboxylic dianhydride and terminal blocking agent used, and the physical properties of the obtained polyamic acid varnish. Table 4 shows the physical properties of the polyimide film on which the transparent conductive film was formed.
Shown in

[0044]

Comparative Examples 1 to 7 A polyamic acid varnish was synthesized using a material other than the polyimide monomer of the present invention. A polyimide film was prepared from the obtained polyamic acid varnish by the method described above, and the thermophysical properties and optical properties were evaluated. Table 5 shows the amounts of the diamine, tetracarboxylic dianhydride and terminal blocking agent used, and the physical properties of the obtained polyamic acid varnish. Table 5 shows the physical properties of the polyimide film on which the transparent conductive film was formed.
6 is shown. [Abbreviations] In Examples and Comparative Examples, diamine components, tetracarboxylic dianhydrides, monoamines, and dicarboxylic anhydride components used are represented by the following abbreviations. m-BP; 4,4'-bis (3-aminophenoxy) biphenyl, m-BS; bis [4- (3-aminophenoxy) phenyl] sulfone, m-BO; bis [4- (3-aminophenoxy) Phenyl] ether, m-BAPP; 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 6F-BAPP; 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1 4,1,3,3-hexafluoropropane p-BP; 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-ODA; 4,4′-diaminodiphenyl ether ODPA; 4-dicarboxyphenyl) ether dianhydride PMDA; pyromellitic dianhydride BTDA; 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride PA; 4-phenylphthalic anhydride DPEA; 3,4-diphenylether dicarboxylic anhydride NDA; 1,8-naphthalenedicarboxylic anhydride AN; aniline CLAN; 4-chloroaniline MAN; 4-methylaniline ABP ; 4-aminobiphenyl

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

[Table 5]

[0050]

[Table 6]

[0051]

From the results of the polyimide of the comparative example having a structure other than that of the present invention, it can be seen that the polyimide having the transparent conductive film of the present invention has a higher light transmittance than the polyimide of the comparative example. . In all cases, the glass transition temperature is 170 ° C. or higher, and the 5% weight loss temperature is 500 ° C.
It has excellent heat resistance as described above, the light transmittance at a wavelength of 500 nm is 80% or more, and has excellent transparency as compared with the polyimide of Comparative Example, and is useful as a transparent conductive film. I understand.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 7/06 C08J 7/06 B // C08L 79:08 C08L 79:08 F term (reference) 4F006 AA39 AB74 BA07 CA08 DA01 4F071 AA60 AF30 AF37 AH12 BB02 BC01 4F100 AA33 AK49A BA02 BA03 BA06 BA07 BA10A BA10B BA10C EH66 GB41 JB01 JG01B JG01C JJ03 JK01 JN01B JN01C 4J043 PA02 PC116 PC42 TA1 1 XA13 XA17 XA19 XB09 ZA44 ZA52 ZB23 5G307 FA02 FB01 FC09

Claims (2)

[Claims] 1. A colorless and transparent polyimide film having a repeating structural unit represented by the general formula (1) as an essential component, and a transparent conductive film formed on at least one of the front and back surfaces of the colorless and transparent polyimide film. A transparent conductive film comprising a conductive film. Embedded image [X in the general formula (1) is a direct bond, -O-, -SO2
Represents-, -C (CH3) 2- or -C (CF3) 2-. ] 2. The method for producing a polyimide represented by the general formula (1) according to claim 1, wherein the aromatic dicarboxylic anhydride and / or the general formula (3) represented by the following general formula (2) is used. A transparent conductive film characterized by using a polyimide resin obtained by performing a reaction in the presence of an aromatic monoamine represented by the formula (1). Embedded image [In the general formula (2), Ar1 represents one selected from the group of the formula (I), and Y represents one selected from the group of the formula (II). In the general formula (3), Ar2 represents a kind selected from the group of the formula (III), and Z represents a kind selected from the group of the formula (IV). ]