JP2011216468A - Electrode, and organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrode having little variation in transmittance even after an environment testing under a high temperature-high humidity environment and excellent in a plane stability, and to provide an organic electroluminescent element excellent in a temporal stability in which the electrode is used.SOLUTION: In the electrode having a conductive metal layer containing a metal fiber on a substrate and a conductive polymer layer, the conductive metal layer contains an antioxidant and moreover the conductive polymer layer contains as a binder resin a polymer (A) containing at least either of a polymer having a structural unit represented by general formula (I) or a co-polymer having a structural unit represented by general formula (I) and general formula (II). The organic electroluminescent element includes this electrode.

Description

  The present invention, when an antioxidant is contained in an electrode, has high planarity even after an environmental test under a high temperature and high humidity environment, an electrode having excellent transparency, and excellent temporal stability using the electrode. The present invention relates to an organic electroluminescence element.

  In recent years, various types of display technologies such as liquid crystal, plasma, organic electroluminescence, and field emission have been developed in response to the increasing demand for thin TVs. In any of these displays with different display methods, the transparent electrode is an essential constituent technology. In addition to televisions, transparent electrodes are an indispensable technical element in touch panels, mobile phones, electronic paper, various solar cells, and various electroluminescence light control elements.

  Conventionally, an ITO transparent electrode in which an indium-tin composite oxide (ITO) film is formed on a transparent substrate such as glass or a transparent plastic film by a vacuum deposition method or a sputtering method has been mainly used. . However, indium used in ITO is a rare metal and removal of indium is desired due to the rising price. In addition, roll-to-roll using a flexible substrate has been desired along with an increase in display screen and productivity.

  Furthermore, electrodes having a smooth surface are required for electrodes for electroluminescence elements and organic thin film solar cells. For example, in the case of an electrode for an organic electroluminescence element, an ultra-thin film of an organic compound is formed on the electrode, so that an excellent surface smoothness is required for the transparent electrode. In organic electroluminescence elements, if the surface height difference (surface irregularities) of the anode is large, the electric field concentrates on the protrusions (protrusions) and the EL element is destroyed, or the organic compound ultra-thin layer formed on the anode There is a problem that non-uniform light emission occurs.

  Thus, for the demand for an electrode having flexibility, for example, a transparent electrode in which silver nanowires are coated on a flexible transparent substrate has been disclosed (for example, see Patent Document 1).

  Since silver inherently has high conductivity, when silver nanowires or silver salt emulsions are used, both good conductivity and transparency can be achieved.

  However, silver suffers from problems such as reduced conductivity and transparency due to oxygen, moisture, sulfide gas, etc. in the atmosphere, and when stored under high temperature and high humidity, the silver surface is corroded and the flatness deteriorates. Have the problem of doing. In order to deal with such problems, a method has been proposed in which aromatic triazole or dithiodiazole is mixed with a resin and coated (for example, see Patent Document 1). However, this method is effective for lowering the conductivity and transparency caused by sulfide gas, but the transparency during storage at high temperature and high humidity, deterioration in flatness, and light emission when it is made into a device. It is not enough for the problem of uniformity.

  On the other hand, a manufacturing method for forming a conductive film by developing and plating an emulsion layer containing a silver salt emulsion has been disclosed, and a method of adding an antioxidant that defines a reduction potential to the emulsion layer is proposed. Has been. (For example, refer to Patent Document 2). Moreover, the method of adding antioxidant to the copper alloy powder containing silver is disclosed. (For example, refer to Patent Document 3). However, the conductive metal fiber layer has not been studied, and the structure in which an antioxidant is added to an emulsion layer containing a silver salt emulsion or the structure in which an antioxidant is added to a copper alloy powder containing silver has a high temperature and high humidity. It cannot be said that it is sufficient for the problems of transparency decrease during storage, deterioration of flatness, and the problem of light emission uniformity when a device is formed.

Special table 2009-505358 JP 2006-228469 A JP-A-10-162647

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an electrode that has little variation in transmittance even after an environmental test in a high-temperature and high-humidity environment, and that has excellent planar stability. is there. Another object of the present invention is to provide an organic electroluminescence device having excellent temporal stability using the electrode.

  The above object of the present invention can be achieved by the following constitution.

  1. In an electrode having a conductive metal layer containing metal fibers on a substrate and a conductive polymer layer, the conductive metal layer contains an antioxidant, and the conductive polymer layer is used as a binder resin. Polymer (A) having at least one of a polymer having a structural unit represented by the following general formula (I) and a copolymer having a structural unit represented by the following general formula (I) and the following general formula (II) An electrode comprising:

[Wherein, R represents a hydrogen atom or a methyl group, and Q represents —C (═O) O— or —C (═O) NRa—. Ra represents a hydrogen atom or an alkyl group, A represents a substituted or unsubstituted alkylene group, — (CH ₂ CHRbO) _x — (CH ₂ CHRb) —, and Rb represents a hydrogen atom or an alkyl group. x is an average number of repeating units of 1 to 100. y represents 0 or 1; Z represents an alkyl group, —C (═O) —Rc, —SO ₂ —Rd, —SiRe ₃ . Rc, Rd, and Re represent an alkyl group, a perfluoroalkyl group, or an aryl group. ]
2. 2. The electrode according to 1 above, wherein the conductive polymer layer is disposed on the conductive metal layer.

  3. 3. The electrode according to 1 or 2, wherein the metal fiber is a silver nanowire.

  4). 4. The electrode according to any one of 1 to 3, wherein the antioxidant is a water-soluble compound.

  5. 5. The electrode according to any one of 1 to 4, wherein the antioxidant is a phenol compound.

6). The additive amount of the antioxidant ^{is, 1 × 10 -4 g / m} 2 ~1g / electrode according to any one of the 1 to 5, wherein the ^m is ^2.

  7). It has an electrode of any one of said 1-6, The organic electroluminescent element characterized by the above-mentioned.

  According to the present invention, it is possible to provide an electrode with little variation in transmittance even after an environmental test in a high-temperature and high-humidity environment, and further having excellent planar stability. Moreover, the organic electroluminescent element excellent in temporal stability using this electrode can be provided.

It is a structural schematic diagram which shows an example of the typical electrode of this invention. It is a structural schematic diagram which shows another example of the typical electrode of this invention. It is a structure schematic diagram which shows another example of the typical electrode of this invention. It is a structural schematic diagram which shows another example of the typical electrode of this invention.

  Hereinafter, although the form for implementing this invention is demonstrated, this invention is not limited to these.

  The present invention is an electrode having a conductive metal layer containing a metal fiber and a conductive polymer layer on a substrate, wherein the conductive metal layer is an antioxidant and the conductive polymer layer is a binder resin. The polymer A is contained.

  In the present invention, by including an antioxidant in the conductive metal layer in particular, an electrode excellent in planar stability can be obtained with little variation in transmittance even after an environmental test under a high temperature and high humidity environment. And the said effect was further improved by containing the polymer A as binder resin. Moreover, the organic electroluminescent element excellent in temporal stability using this electrode is obtained.

  Hereinafter, the present invention, its components, and the best mode and mode for carrying out the present invention will be described in detail.

<< Antioxidant >>
The electrode of the present invention is characterized by containing an antioxidant as a stabilizer in order to prevent deterioration of the electrode-forming material due to heat, oxygen, and moisture during storage and manufacturing processes.

  Preferred examples of the antioxidant of the present invention include phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, acrylate compounds, benzofuranone compounds, oxygen scavengers, and the like. Moreover, a water-soluble compound is mentioned.

  Among these, phenolic compounds and water-soluble compounds are particularly preferable. By blending these compounds, it is possible to obtain an electrode that does not have a decrease in transparency due to heat, oxygen, or moisture, or a decrease in planarity of the conductive layer, and improves the temporal stability of an organic electroluminescence device using this electrode. I can do it.

  These antioxidants can be used alone or in combination of two or more.

  Specific examples of the antioxidant of the present invention include the following compounds, but are not limited thereto.

(Phenolic compounds)
As one of the antioxidants useful in the present invention, a phenol compound represented by the following general formula (A-1) is preferable.

In general formula (A-1), R <_11> , R < ₁₂ > represents a substituent. n1 represents an integer of 1 to 3. m1 represents an integer of 1 to 5. When m1 is 2 or more, they may be connected to each other to form a ring.

  Examples of the substituent include a hydrogen atom, a halogen atom (eg, fluorine atom, chlorine atom, etc.), an alkyl group (eg, methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl). Group), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), aralkyl group (eg benzyl group, 2-phenethyl group etc.), aryl group (eg phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group). Etc.), alkoxy groups (eg methoxy group, ethoxy group, isopropoxy group, butoxy group etc.), aryloxy groups (eg phenoxy group etc.), cyano groups, acylamino groups (eg acetylamino group, propionylamino group etc.), alkylthio Groups (eg methylthio, ethylthio, butylthio, etc.) An arylthio group (for example, phenylthio group), a sulfonylamino group (for example, methanesulfonylamino group, benzenesulfonylamino group, etc.), a ureido group (for example, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethyl) Ureido group etc.), sulfamoylamino group (dimethylsulfamoylamino group etc.), carbamoyl group (eg methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group etc.), sulfamoyl group (eg ethylsulfamoyl group, dimethylsulfamoyl group) Famoyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.), sulfonyl group (eg methanesulfonyl group, butanesulfonyl group, phenoxy group) Sulfonyl group, etc.), acyl group (eg acetyl group, propanoyl group, butyroyl group etc.), amino group (methylamino group, ethylamino group, dimethylamino group etc.), cyano group, hydroxy group, nitro group, nitroso group, Amine oxide groups (for example, pyridine-oxide groups), imide groups (for example, phthalimide groups), disulfide groups (for example, benzene disulfide groups, benzothiazolyl-2-disulfide groups), carboxyl groups, sulfo groups, heterocyclic groups (for example, pyrrole) Group, pyrrolidyl group, pyrazolyl group, imidazolyl group, pyridyl group, benzimidazolyl group, benzthiazolyl group, benzoxazolyl group, etc.). These substituents may be further substituted.

  Phenol compounds are known compounds and are described, for example, in columns 12 to 14 of US Pat. No. 4,839,405, and include 2,6-dialkylphenol derivative compounds. Among these compounds, preferred compounds include compounds represented by the following general formula (A-2).

In formula _{(A-2), R 101} ~R 106 represents a substituent. As this substituent, it is synonymous with the substituent represented by R <_11> , R < ₁₂ > of the said general formula (A-1).

R ₁₀₁ is preferably a hydrogen atom, and a phenol compound in which R ₁₀₂ and R ₁₀₆ are alkyl groups is preferred.

  Specific examples of the phenol compound include n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, n-octadecyl 3- (3,5-di-t-butyl-4 -Hydroxyphenyl) -acetate, n-octadecyl 3,5-di-t-butyl-4-hydroxybenzoate, n-hexyl 3,5-di-t-butyl-4-hydroxyphenylbenzoate, n-dodecyl 3,5 -Di-t-butyl-4-hydroxyphenylbenzoate, neo-dodecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, dodecyl beta (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate, ethyl α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl α- (4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2- (n- Octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-benzoate, 2- (n-octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-phenylacetate, 2- (n-octadecyl) Thio) ethyl 3,5-di-t-butyl-4-hydroxyphenyl acetate, 2- (n-octadecylthio) ethyl 3,5-di-t-butyl-4-hydroxy-benzoate, 2- (2-hydroxy Ethylthio) ethyl 3,5-di-t-butyl-4-hydroxybenzoate, diethyl glycol bis- (3,5-di-t-butyl-4- Droxy-phenyl) propionate, 2- (n-octadecylthio) ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, stearamide N, N-bis- [ethylene 3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], n-butylimino N, N-bis- [ethylene 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2- ( 2-stearoyloxyethylthio) ethyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2- (2-stearoyloxyethylthio) ethyl 7- (3-methyl-5-tert-butyl-4-hydroxy) Phenyl) heptanoate, 1,2-propylene glycol bis- [3- (3,5-di-t-butyl-4-hydroxypheny ) Propionate], ethylene glycol bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], neopentyl glycol bis- [3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate], ethylene glycol bis- (3,5-di-t-butyl-4-hydroxyphenylacetate), glyce (phosphorus-l-n-octadecanoate-2,3-bis- (3 , 5-di-t-butyl-4-hydroxyphenyl acetate), pentaerythritol-tetrakis- [3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate], 1,1, 1-trimethylolethane-tris- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], sorbito Hexa- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2-hydroxyethyl 7- (3-methyl-5-tbutyl-4-hydroxyphenyl) propionate, 2-stearoyl Oxyethyl 7- (3-methyl-5-t-butyl-4-hydroxyphenyl) heptanoate, 1,6-n-hexanediol-bis [(3 ′, 5′-di-t-butyl-4-hydroxyphenyl) ) Propionate], pentaerythritol-tetrakis (3,5-di-t-butyl-4-hydroxyhydrocinnamate). The phenol compound of the above type is commercially available, for example, from BASF Japan Ltd. under the trade names “Irganox 1076” and “Irganox 1010”.

  Further, phenolic compounds represented by the following structural formulas and derivatives thereof can be mentioned.

(Hindered amine compounds)
As one of the antioxidants useful in the present invention, a hindered amine compound represented by the following general formula (B) is preferable.

_Wherein, R 21 _{to R 27} represents a substituent. As a substituent, it is synonymous with the substituent represented by R <_11> , R < ₁₂ > of the said general formula (A-1). R ₂₄ is preferably a hydrogen atom and a methyl group, R ₂₇ is preferably a hydrogen atom, and R ₂₂ , R ₂₃ , R ₂₅ and R ₂₆ are preferably a methyl group.

  Specific examples of hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2) , 6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6- Tramethyl-4-piperidyl) 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2,6,6-pentamethyl-4- Piperidyl) decanedioate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -1- [ 2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2, 6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, and the like.

  Further, it may be a polymer type compound. As specific examples, N, N ′, N ″, N ″ ′-tetrakis- [4,6-bis- [butyl- (N-methyl-2,2,6, 6-tetramethylpiperidin-4-yl) amino] -triazin-2-yl] -4,7-diazadecane-1,10-diamine, dibutylamine and 1,3,5-triazine-N, N′-bis ( 2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, di Polycondensate of butylamine, 1,3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1,1,3,3 -Tetramethylbutyl) amino-1,3,5-tri Gin-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], Between 1,6-hexanediamine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) and morpholine-2,4,6-trichloro-1,3,5-triazine Polycondensate, poly [(6-morpholino-s-triazine-2,4-diyl) [(2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene [(2,2,6 , 6-tetramethyl-4-piperidyl) imino]], etc., high molecular weight HALS in which a plurality of piperidine rings are bonded via a triazine skeleton; dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl- 1-piperidine ester Polymer with diol, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethyl) (Ethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like, and the like are exemplified by compounds in which a piperidine ring is bonded through an ester bond, but the present invention is not limited thereto. It is not a thing.

  Among these, polycondensates of dibutylamine, 1,3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-tetramethyl-4-piperidyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, etc. Those having a molecular weight (Mn) of 2,000 to 5,000 are preferred.

  The hindered amine compound of the above type is commercially available from BASF Japan, for example, under the product names “Tinuvin 144” and “Tinuvin 770” and from ADEKA, Inc., “ADK STAB LA-52”.

(Phosphorus compounds)
As one of the antioxidants useful in the present invention, a moiety represented by the following general formulas (C-1), (C-2), (C-3), (C-4), (C-5) A compound having a structure in the molecule is preferred.

In the formula, Ph ₁ and Ph ′ ₁ represent a substituent. As a substituent, it is synonymous with the substituent represented by R <_11> , R < ₁₂ > of the said general formula (A-1). More preferably, Ph ₁ and Ph ′ ₁ represent a phenylene group, and the hydrogen atom of the phenylene group is a phenyl group, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 to 12 carbon atoms. Or an alkyl cycloalkyl group or an aralkyl group having 7 to 12 carbon atoms. Ph ₁ and Ph ′ ₁ may be the same as or different from each other. X represents a single bond, a sulfur atom or a —CHR ₆ — group. R ₆ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms. Moreover, these may be substituted by a substituent having the same meaning as the substituents represented by R ₁₁ and R ₁₂ in the general formula (A-1).

Wherein, Ph ₂ and Ph _'2 each represent a substituent. As a substituent, it is synonymous with the substituent represented by R <_11> , R < ₁₂ > of the said general formula (A-1). More preferably, Ph ₂ and Ph ′ ₂ represent a phenyl group or a biphenyl group, and the hydrogen atom of the phenyl group or biphenyl group is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a carbon number. It may be substituted with a 6-12 alkylcycloalkyl group or an aralkyl group having 7-12 carbon atoms. Ph ₂ and Ph ′ ₂ may be the same as or different from each other. Moreover, these may be substituted by a substituent having the same meaning as the substituents represented by R ₁₁ and R ₁₂ in the general formula (A-1).

In the formula, Ph ₃ represents a substituent. As a substituent, it is synonymous with the substituent represented by R <_11> , R < ₁₂ > of the said general formula (A-1). More preferably, Ph ₃ represents a phenyl group or a biphenyl group, and the hydrogen atom of the phenyl group or biphenyl group is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a 6 to 12 carbon atom. It may be substituted with an alkylcycloalkyl group or an aralkyl group having 7 to 12 carbon atoms. Moreover, these may be substituted by a substituent having the same meaning as the substituents represented by R ₁₁ and R ₁₂ in the general formula (A-1).

In the formula, Ph ₄ represents a substituent. As a substituent, it is synonymous with the substituent represented by R <_11> , R < ₁₂ > of the said general formula (A-1). More preferably, Ph ₄ represents an alkyl group having 1 to 20 carbon atoms or a phenyl group, and the alkyl group or phenyl group has the same meaning as the substituents represented by R ₁₁ and R ₁₂ in the general formula (A-1). It may be substituted with a substituent.

In the formula, Ph ₅ , Ph ′ ₅ and Ph ″ ₅ represent substituents. The substituents have the same meanings as the substituents represented by R ₁₁ and R ₁₂ in formula (A-1). , Ph ₅ , Ph ′ ₅ and Ph ″ ₅ represent an alkyl group or phenyl group having 1 to 20 carbon atoms, and the alkyl group or phenyl group is represented by R ₁₁ and R ₁₂ in the general formula (A-1). It may be substituted with a substituent having the same meaning as the substituent.

  Specific examples of phosphorus compounds include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-). t-butylphenyl) phosphite, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6- [ 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1.3.2] dioxaphosphine Monophosphite compounds such as pin and tridecyl phosphite; 4,4'-butylidene-bis (3-methyl-6-t-butyl) Diphosphite compounds such as phenyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite); triphenylphosphonite, tetrakis (2,4- Di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) [1,1-biphenyl]- Phosphonite compounds such as 4,4'-diylbisphosphonite; phosphinite compounds such as triphenylphosphinite and 2,6-dimethylphenyldiphenylphosphinite; triphenylphosphine and tris (2,6-dimethoxyphenyl) Phosphine compounds such as phosphine; and the like.

  The phosphorous compounds of the above-mentioned types are, for example, from Sumitomo Chemical Co., Ltd., “Sumilizer GP”, from ADEKA Co., Ltd., “ADK STAB PEP-24G”, “ADK STAB PEP-36” and “ADK STAB 3010”, BASF Japan Co., Ltd. "IRGAFOS P-EPQ" and "GSY-P101" from Sakai Chemical Industry Co., Ltd.

(Acrylate compounds)
The acrylate compound is a known compound, and is described in, for example, JP-A 63-179953 and JP-A 1-168643, and 2-t-butyl-6- (3-t-butyl-2 -Hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate Etc.

  Acrylate compounds of the above type are commercially available from Sumitomo Chemical Co., Ltd. under the trade names “Sumilizer GS” and “Sumilizer GM”, for example.

(Benzofuranone compounds)
A benzofuranone compound is a known compound, and is described in, for example, Japanese Patent Publication No. 63-26771, Japanese Patent Application Laid-Open No. 7-233160 and Japanese Patent Application Laid-Open No. 2003-176417, and 5,7-di-t-butyl. -3- (3,4-dimethylphenyl) -3H-benzofuran-2-one, 5,7-di-t-butyl-3-phenyl-3H-benzofuran-2-one, 5,7-di-t- And butyl-3- (4-methoxyphenyl) -3H-benzofuran-2-one.

  The above type of benzofuranone-based compound is commercially available, for example, from BASF Japan Ltd. under the trade name “HP-136”.

(Sulfur compounds)
As one of the antioxidants useful in the present invention, a sulfur compound represented by the following general formula (D) is preferable.

In the formula, R ₃₁ and R ₃₂ represent a substituent. As a substituent, it is synonymous with the substituent represented by R <_11> , R < ₁₂ > of the said general formula (A-1).

  Specific examples of the sulfur compound include dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thiodipropioate. And pentaerythritol-tetrakis (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like. .

  The above-mentioned type of sulfur-based compound is commercially available from Sumitomo Chemical Co., Ltd. under the trade names “Sumilizer TPL-R” and “Sumilizer TP-D”, for example.

(Water-soluble compounds)
One antioxidant useful in the present invention is a water-soluble antioxidant.

  Ascorbins (for example, L-ascorbic acid and the like), erythorbic acids, sulfites (for example, sodium sulfite and sodium bisulfite), tocopherols, catechins and the like can be mentioned.

In the present invention, the addition amount of these antioxidants is preferably ^{1 × 10 -4 g / m 2} ~1g / m 2, at ^{1 × 10 -3 mg / m 2} ~500mg / m 2 Although it is more preferable, the addition amount may be appropriately selected depending on the kind of the antioxidant and the like. Two or more of these may be used in combination.

  The addition amount of the antioxidant is preferably not less than the lower limit of the above range from the viewpoint of stabilizing action, and is preferably not more than the lower limit of the above range from the viewpoint of transparency.

  The antioxidant may be added to the conductive metal layer after being dissolved in water, alcohol, ether, ester, ketone, hydrocarbon, halogenated hydrocarbon, amide, or a mixed solvent thereof. Or you may add, after melt | dissolving in another organic solvent. Further, it may be added after being dissolved in a high boiling point solvent or the like. Specifically, methyl ethyl ketone, methanol, water, DMSO and the like can be used.

<< Metal fiber >>
(Conductive metal layer)
The conductive metal layer of the present invention is characterized by containing metal fibers.

  In the metal fiber of the present invention, if the minor axis of the fiber diameter is nm, it may be rod-shaped or wire-shaped, but is preferably a wire-shaped metal nanowire from the viewpoint of conductivity and transparency.

  In general, a metal nanowire refers to a linear structure having a diameter from the atomic scale to the nm size, which contains a metal element as a main component.

  As the metal nanowire used in the present invention, in order to form a long conductive path with one metal nanowire, the average length is preferably 3 μm or more, more preferably 3 to 500 μm, and particularly preferably 3 to 300 μm. It is preferable. In addition, the relative standard deviation of the length is preferably 40% or less. Moreover, although there is no restriction | limiting in particular in an average breadth, it is preferable that it is small from a transparency viewpoint, and the larger one is preferable from a conductive viewpoint. In the present invention, the average minor axis of the metal nanowire is preferably 10 to 300 nm, and more preferably 30 to 200 nm. In addition, the relative standard deviation of the minor axis is preferably 20% or less. The metal nanowires of the conductive metal layer are preferably in contact with each other, and more preferably in mesh form. Conductive metal layers in which metal nanowires are brought into contact with each other or meshed can be easily obtained by using the liquid phase film forming method.

  In the present invention, the means for producing the metal nanowire is not particularly limited, and for example, known means such as a liquid phase method and a gas phase method can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used. For example, as a method for producing silver nanowires, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. 2002, 14, 4736-4745, and the like. The method for producing silver nanowires can be easily produced in an aqueous solution, and since the conductivity of silver is the highest in metals, it is preferably applied as a method for producing metal nanowires according to the present invention. Can do.

<< Conductive polymer >>
(Conductive polymer layer)
The conductive polymer layer in the present invention is characterized by containing the polymer (A) as a binder resin, but preferably contains a conductive polymer comprising a π-conjugated conductive polymer and a polyanion. .

  The conductive polymer according to the present invention is easily produced by chemical oxidative polymerization of a precursor monomer that forms a π-conjugated conductive polymer described later in the presence of an appropriate oxidizing agent, an oxidation catalyst, and a polyanion described later. it can.

(Π-conjugated conductive polymer)
The π-conjugated conductive polymer used in the present invention is not particularly limited, and includes polythiophenes (including basic polythiophenes, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans. , Polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyl chain conductive polymers can be used. Of these, polythiophenes and polyanilines are preferable from the viewpoints of conductivity, transparency, stability, and the like. Most preferred is polyethylene dioxythiophene.

(Π-conjugated conductive polymer precursor monomer)
The precursor monomer has a π-conjugated system in the molecule, and a π-conjugated system is formed in the main chain even when polymerized by the action of an appropriate oxidizing agent. Examples thereof include pyrroles and derivatives thereof, thiophenes and derivatives thereof, anilines and derivatives thereof, and the like.

  Specific examples of the precursor monomer include pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, 3, 4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxylpyrrole, 3-methyl-4-carboxylpyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3 -Butylthiophene, 3-hexylchi Phen, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenyl Thiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3- Octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiol 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxy Thiophene, 3,4-didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, 3,4-butenedioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl -4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene, aniline, 2-methylaniline, 3-isobutyl Aniline, 2-aniline sulfonic acid, 3-aniline A sulfonic acid etc. are mentioned.

(Polyanion)
The polyanion is a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester, and a copolymer thereof. It consists of a structural unit having a functional group and a structural unit having no anionic group.

  This polyanion is a solubilized polymer that solubilizes the π-conjugated conductive polymer in a solvent. The anionic group of the polyanion functions as a dopant for the π-conjugated conductive polymer, and improves the conductivity and heat resistance of the π-conjugated conductive polymer.

  The anionic group of the polyanion may be any functional group that can undergo chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a monosubstituted sulfate group A monosubstituted phosphate group, a phosphate group, a carboxy group, a sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.

  Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfone. Examples include acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid and the like. . These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.

  Moreover, the polyanion which has a fluorine (F) in a compound may be sufficient. Specifically, Nafion (manufactured by Dupont) containing a perfluorosulfo group, Flemion (manufactured by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group, and the like can be mentioned.

  Among these, when the compound having a sulfo group is formed by applying and drying the conductive polymer-containing layer, the heat treatment is performed at a temperature of 100 ° C. or more and 200 ° C. or less for 5 minutes or more. It is more preferable because the cleaning resistance and solvent resistance of the coating film are remarkably improved.

  Furthermore, among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethylsulfonic acid, and polyacrylic acid butylsulfonic acid are preferable. These polyanions have high compatibility with the binder resin, and can further increase the conductivity of the obtained conductive polymer.

  The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.

  Examples of the method for producing a polyanion include a method of directly introducing an anionic group into a polymer having no anionic group using an acid, a method of sulfonating a polymer having no anionic group with a sulfonating agent, an anion And a method of producing the polymerizable group-containing polymerizable monomer by polymerization.

  Examples of the method for producing an anionic group-containing polymerizable monomer by polymerization include a method for producing an anionic group-containing polymerizable monomer in a solvent by oxidative polymerization or radical polymerization in the presence of an oxidizing agent and / or a polymerization catalyst. It is done. Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, this is maintained at a constant temperature, and a solution in which a predetermined amount of an oxidizing agent and / or a polymerization catalyst is dissolved in the solvent is added to the solvent. The reaction is performed for a predetermined time. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, a polymerizable monomer having no anionic group may be copolymerized with the anionic group-containing polymerizable monomer. The oxidizing agent, oxidation catalyst, and solvent used in the polymerization of the anionic group-containing polymerizable monomer are the same as those used in the polymerization of the precursor monomer that forms the π-conjugated conductive polymer.

  When the obtained polymer is a polyanionic salt, it is preferably transformed into a polyanionic acid. Examples of the method for converting to an anionic acid include an ion exchange method using an ion exchange resin, a dialysis method, an ultrafiltration method, and the like. Among these, the ultrafiltration method is preferable from the viewpoint of easy work.

  A commercially available material can be preferably used for such a conductive polymer. For example, a conductive polymer (abbreviated as PEDOT-PSS) composed of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid is described in H.C. C. It is commercially available from Starck as the Clevios series, from Aldrich as PEDOT-PSS 483095, 560596, and from Nagase Chemtex as the Denatron series. Polyaniline is also commercially available from Nissan Chemical as the ORMECON series. In the present invention, such an agent can also be preferably used.

  2nd. A water-soluble organic compound may be contained as a dopant. There is no restriction | limiting in particular in the water-soluble organic compound which can be used by this invention, It can select suitably from well-known things, For example, an oxygen containing compound is mentioned suitably. The oxygen-containing compound is not particularly limited as long as it contains oxygen, and examples thereof include a hydroxyl group (hydroxyl group) -containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound. Examples of the hydroxyl group (hydroxyl group) -containing compound include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, and glycerin. Among these, ethylene glycol and diethylene glycol are preferable. Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, and γ-butyrolactone. Examples of the ether group-containing compound include diethylene glycol monoethyl ether. Examples of the sulfoxide group-containing compound include dimethyl sulfoxide. These may be used alone or in combination of two or more, but at least one selected from dimethyl sulfoxide, ethylene glycol, and diethylene glycol is preferably used.

(Polymer (A))
The conductive polymer layer of the present invention includes, as a binder resin, a polymer having a structural unit represented by the general formula (I), and a structural unit represented by the general formula (I) and the general formula (II). It contains the polymer (A) which has at least any one of the copolymer which has these.

  The structural units represented by the general formula (I) and the general formula (II) will be described.

  In the structural unit represented by the general formula (I), R represents a hydrogen atom or a methyl group. Q represents —C (═O) O— or —C (═O) NRa—, and Ra represents a hydrogen atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. These alkyl groups may be substituted with a substituent. Examples of these substituents include alkyl groups, cycloalkyl groups, aryl groups, heterocycloalkyl groups, heteroaryl groups, hydroxy groups, halogen atoms, alkoxy groups, alkylthio groups, arylthio groups, cycloalkoxy groups, aryloxy groups, Acyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, ureido group, aralkyl group, nitro group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbamoyl group, Arylcarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, acyloxy group, alkenyl group, alkynyl group, alkylsulfonyl group, arylsulfonyl group, alkyloxysulfonyl , Aryloxy sulfonyl group, alkylsulfonyloxy group, may be substituted with an aryl sulfonyloxy group. Of these, a hydroxy group and an alkyloxy group are preferable.

  The alkyl group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 8. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, octyl group and the like.

  The number of carbon atoms of the cycloalkyl group is preferably 3-20, more preferably 3-12, and still more preferably 3-8. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The alkoxy group may have a branch, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6, and further preferably 1 to 4. Most preferably. Examples of the alkoxy group include a methoxy group, an ethoxy group, a 2-methoxyethoxy group, a 2-methoxy-2-ethoxyethoxy group, a butyloxy group, a hexyloxy group and an octyloxy group, and preferably an ethoxy group. The number of carbon atoms of the alkylthio group may be branched, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6, Most preferably, it is 1-4. Examples of the alkylthio group include a methylthio group and an ethylthio group. The arylthio group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylthio group include a phenylthio group and a naphthylthio group. The number of carbon atoms of the cycloalkoxy group is preferably 3-12, more preferably 3-8. Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group. The aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group. The aryloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxy group include a phenoxy group and a naphthoxy group. The heterocycloalkyl group preferably has 2 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Examples of the heterocycloalkyl group include a piperidino group, a dioxanyl group, and a 2-morpholinyl group. The heteroaryl group preferably has 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the heteroaryl group include a thienyl group and a pyridyl group. The acyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group. The alkylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylcarbonamide group include an acetamide group. The arylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylcarbonamide group include a benzamide group and the like. The alkylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the sulfonamido group include a methanesulfonamido group and the like, and the arylsulfonamido group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylsulfonamide group include a benzenesulfonamide group and p-toluenesulfonamide group. The number of carbon atoms in the aralkyl group is preferably 7-20, and more preferably 7-12. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group. The alkoxycarbonyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the alkoxycarbonyl group include a methoxycarbonyl group. The aryloxycarbonyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group. The aralkyloxycarbonyl group preferably has 8 to 20 carbon atoms, and more preferably 8 to 12 carbon atoms. Examples of the aralkyloxycarbonyl group include a benzyloxycarbonyl group. The acyloxy group preferably has 1 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group. The alkenyl group has preferably 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group and isopropenyl group. The alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkynyl group include an ethynyl group. The alkylsulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyl group include a methylsulfonyl group and an ethylsulfonyl group. The arylsulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group. The alkyloxysulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkyloxysulfonyl group include a methoxysulfonyl group and an ethoxysulfonyl group. The aryloxysulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxysulfonyl group include a phenoxysulfonyl group and a naphthoxysulfonyl group. The alkylsulfonyloxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyloxy group include a methylsulfonyloxy group and an ethylsulfonyloxy group.

  The number of carbon atoms of the arylsulfonyloxy group is preferably 6-20, and more preferably 6-12. Examples of the arylsulfonyloxy group include a phenylsulfonyloxy group and a naphthylsulfonyloxy group. The substituents may be the same or different, and these substituents may be further substituted.

In the structural unit represented by the general formula (I) of the present invention, A represents a substituted or unsubstituted alkylene group, — (CH ₂ CHRbO) _x — (CH ₂ CHRb) —. The alkylene group preferably has, for example, 1 to 5 carbon atoms, more preferably an ethylene group or a propylene group. These alkylene groups may be substituted with the above-described substituents. Rb represents a hydrogen atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. Further, these alkyl groups may be substituted with the above-described substituents. Furthermore, x represents the average number of repeating units, preferably 1 to 100, more preferably 1 to 10. The number of repeating units has a distribution, the notation indicates an average value, and may be expressed by one digit after the decimal point.

  In the structural unit represented by the general formula (II) of the present invention, R, Q, Ra, A, Rb, and x have the same meaning as defined in the general formula (I).

In the structural unit represented by the general formula (II), y represents 0 or 1. Z represents an alkyl group, —O—C (═O) —Rc, —O—SO ₂ —Rd, —O—SiRe ₃ , and the alkyl group preferably has, for example, 1 to 12 carbon atoms, and more preferably Is a methyl group or an ethyl group, more preferably a methyl group. These alkyl groups may be substituted with the substituent described above. Rc, Rd, and Re represent an alkyl group, a perfluoroalkyl group, and an aryl group. The alkyl group preferably has, for example, 1 to 12 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. . These alkyl groups may be substituted with the substituent described above. The perfluoroalkyl group preferably has, for example, 1 to 8 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, still more preferably a trifluoromethyl group. The aryl group is preferably, for example, a phenyl group or a toluyl group, and more preferably a toluyl group. Furthermore, these alkyl groups, perfluoroalkyl groups, and aryl groups may be substituted with the above-described substituents.

  Typical examples of the structural units represented by general formula (I) and general formula (II) are shown below, but the present invention is not limited thereto.

  In the binder resin according to the present invention, the molar ratio of the structural unit represented by the general formula (I) is preferably 3% to 100%, more preferably 5% to 50%.

  In the binder resin of the present invention, a third structural unit can be used in addition to the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II). In that case, the third structural unit is preferably 50% or less.

  The third structural unit is preferably a polymerizable monomer copolymerizable with the structural units represented by the general formulas (I) and (II). For example, styrene derivatives (for example, styrene, α-methylstyrene, o- Methyl styrene, m-methyl styrene, p-methyl styrene, vinyl naphthalene, etc.), acrylonitrile, methacrylonitrile, vinyl chloride, vinyl acetate and the like.

  In the binder resin according to the present invention, the molar ratio of the structural unit represented by the general formula (I) is preferably 3% to 100%, more preferably 5% to 50%.

  The binder resin of the present invention can be obtained by radical polymerization using a general-purpose polymerization catalyst. Examples of the polymerization mode include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like, preferably solution polymerization. The polymerization temperature varies depending on the initiator used, but is generally -10 to 250 ° C, preferably 0 to 200 ° C, more preferably 10 to 100 ° C.

  The molecular weight of the binder resin of the present invention is preferably in the range of 3,000 to 2,000,000, more preferably 4,000 to 500,000, and still more preferably 5,000 to 100,000.

The number average molecular weight and molecular weight distribution of the binder resin of the present invention can be measured by generally known gel permeation chromatography (GPC). The solvent to be used is not particularly limited as long as the binder resin dissolves, and THF (tetrahydrofuran), DMF (dimethylformamide), and CH ₂ Cl ₂ are preferable, more preferably THF and DMF, and still more preferably DMF. The measurement temperature is not particularly limited, but 40 ° C. is preferable.

  The ratio of the conductive polymer to one polymer (A) is preferably 30 to 900 parts by mass, more preferably 100 parts by mass or more, when the conductive polymer is 100 parts by mass. preferable.

  Thereby, the conductive assist effect with respect to the conductive polymer of the polymer (A) is expressed without reducing the transmittance, and both high transparency and conductivity can be achieved.

  After apply | coating a conductive polymer layer, a drying process is performed suitably. Although there is no restriction | limiting in particular as conditions of a drying process, It is preferable to dry-process at the temperature of the range which does not damage a base material and a conductive polymer content layer. In particular, when the polyanion is a polyanion having a sulfonic acid, it is preferable to perform an additional heat treatment for 3 minutes or more at a temperature in the range of 100 to 200 ° C. after forming a film by coating and drying. Thereby, the washing | cleaning tolerance of a conductive polymer content layer and solvent tolerance improve remarkably. In addition, storage stability is improved. The treatment temperature is more preferably 110 to 160 ° C., and the treatment time is more preferably 5 minutes or more. There is no particular upper limit for the treatment time, but it is preferably 120 minutes or less in view of productivity.

  It is preferable that the coating dry film thickness of a conductive polymer and a polymer (A) content layer is 30-2000 nm. In the region of less than 100 nm, the decrease in conductivity is large, so that it is more preferably 100 nm or more, and from the viewpoint of further improving the leak prevention effect, it is more preferably 200 nm or more. Further, it is more preferably 1000 nm or less from the viewpoint of maintaining high transmittance.

(binder)
The binder of the present invention is not particularly limited as long as it is transparent in the visible region (that is, has sufficient transmittance). A curable resin is preferably used as the binder. Examples of the curable resin include a thermosetting resin, an ultraviolet curable resin, and an electron beam curable resin. The ultraviolet curable resin is a resin that is cured through a crosslinking reaction or the like by ultraviolet irradiation, and a component containing a monomer having an ethylenically unsaturated double bond is preferably used. For example, acrylic urethane type resin, polyester acrylate type resin, epoxy acrylate type resin, polyol acrylate type resin and the like can be mentioned. In the present invention, it is preferable that an acrylic or acrylic urethane-based ultraviolet curable resin is a main component as a binder.

  Acrylic urethane-based resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates including methacrylates) to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used. For example, a mixture of 100 parts of Unidic 17-806 (manufactured by DIC Corporation) and 1 part of Coronate L (manufactured by Nippon Polyurethane Corporation) is preferably used.

  Examples of UV curable polyester acrylate resins include those which are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photoreaction initiator added to the oligomer, and a reaction. Those described in US Pat. No. 105738 can be used.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.

  Examples of the resin monomer may include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  Among these, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolethane (meth) acrylate as the main component of the binder , An acrylic selected from dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate A system active ray curable resin is preferred.

  Specific examples of the photoreaction initiator of these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer. The photoinitiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photoinitiator, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.

  A water-soluble binder resin is also preferably used as the binder of the present invention. The water-soluble binder resin is a water-soluble binder resin, and means a binder resin in which 0.001 g or more is dissolved in 100 g of water at 25 ° C. The dissolution can be measured with a haze meter or a turbidimeter.

  The water-soluble binder resin is preferably transparent. The water-soluble binder resin is not particularly limited as long as it is a medium for forming a natural polymer, a synthetic resin, a polymer and a copolymer, and other films. Examples of water-soluble binders include: gelatin, casein, starch, gum arabic, poly (vinyl alcohol), poly (vinyl pyrrolidone), carboxymethyl ether cellulose, hydroxyethyl cellulose, cellulose such as methyl hydroxyethyl ether cellulose, chitosan, dextran , Guar gum, poly (acrylamide), poly (acrylamide-acrylic acid), poly (acrylic acid), poly (methacrylic acid), poly (allylamine), poly (butadiene-maleic anhydride), poly (n-butyl acrylate-2) -Methacryloyltrimethylammonium bromide), poly (3-chloro-2-hydroxypropyl-2-methacryloxytrimethylammonium bromide), poly (2-dimethylaminoethyl methacrylate) ), Poly (ethylene glycol), poly (ethylene glycol) -bisphenol A-diglycidyl ether adduct, poly (ethylene glycol) bis 2-aminoethyl, poly (ethylene glycol) dimethyl ether, poly (ethylene glycol) monocarboxymethyl ether Monomethyl ether, poly (ethylene glycol) monomethyl ether, poly (ethylene oxide), poly (ethylene oxide-b-propylene oxide), polyethyleneimine, poly (2-ethyl-2-oxazoline), poly (1-glycerol methacrylate), poly ( 2-hydroxyethyl acrylate), poly (2-ethyl methacrylate), poly (2-hydroxyethyl methacrylate-methacrylic acid), poly (maleic acid), poly (methacrylic acid) ), Poly (2-methacryloxyethyltrimethylammonium bromide), poly (N-iso-propylacrylamide), poly (styrenesulfonic acid), poly (N-vinylacetamide), poly (N-methyl-N-vinylacetamide) ), Poly (vinylamine), poly (2-vinyl-1-methylpyridinium bromide), poly (phosphoric acid), poly (2-vinylpyridine), poly (4-vinylpyridine), poly (2-vinylpyridine-N -Oxide), poly (vinylsulfonic acid) and the like. In the above binder, the polymer having carboxylic acid, sulfonic acid, phosphoric acid or the like may have a salt such as lithium, sodium or potassium, and the polymer having a nitrogen atom has a structure such as hydrochloride. Also good. The binder resin can be used alone or in combination.

  Water-soluble binder resins include gelatin, poly (vinyl alcohol), poly (vinyl pyrrolidone), celluloses, poly (acrylic acid), poly (ethylene glycol), poly (2-hydroxyethyl acrylate), poly (2-hydroxy Ethyl methacrylate), poly (2-hydroxyethyl methacrylate), and poly (vinyl sulfonic acid) are preferable. As commercially available products, poly (vinyl pyrrolidone), poly (vinyl alcohol) (manufactured by Polysciences), PVA203, PVA-224, EXEVAL RS-4104 (manufactured by Kuraray), Metroise 90SH-100, Metroise 60SH-50, Metroise 60SH- 06 (manufactured by Shin-Etsu Chemical Co., Ltd.) or the like can be used.

  In the water-soluble binder resin, more preferably, a water-soluble binder resin having a structure having a hydroxyl group in the repeating unit may be mentioned. Specifically, poly (vinyl pyrrolidone), poly (vinyl alcohol), celluloses, poly (2 -Hydroxyethyl acrylate), poly (3-hydroxypropyl acrylate), poly (4-hydroxybutyl acrylate), poly (2-hydroxyethyl methacrylate), poly (3-hydroxypropyl methacrylate) and the like.

  The water-soluble binder resin is preferably crosslinked and cured, and may be crosslinked by a dehydration condensation reaction under acidic conditions such as sulfonic acid and carboxylic acid. Moreover, you may use crosslinking agents, such as an aldehyde type, an epoxy type, a melamine type, and an isocyanate type. The cross-linking agent may contain an acid, an alkali, or a salt as a pH adjuster, and is preferably ammonia or an ammonium salt because it can be easily removed by heating. In order to accelerate the crosslinking reaction, it is preferable to heat at 100 to 150 ° C.

[substrate]
There is no restriction | limiting in particular as a board | substrate used for the electrode of this invention. For example, a glass substrate, a resin substrate, a resin film, and the like are preferable in terms of excellent hardness as a substrate and easy formation of a conductive layer on the surface. It is preferable to use a resin film.

  In the present invention, a transparent substrate is preferable, and a substrate having high light transmittance is more preferable. “Transparent” means the total light transmittance in a visible light wavelength region measured by a method in accordance with “Testing method of total light transmittance of plastic-transparent material” of JIS K 7361-1 (corresponding to ISO 13468-1). Is 60% or more.

  There is no restriction | limiting in particular in the resin film which can be preferably used as a board | substrate in this invention, About the material, a shape, a structure, thickness, etc., it can select suitably from well-known things. For example, polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate, modified polyester, polyethylene (PE) resin films, polypropylene (PP) resin films, polystyrene resin films, polyolefin resin films such as cyclic olefin resins, Vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate (PC) resin film, polyamide resin A film, a polyimide resin film, an acrylic resin film, a triacetyl cellulose (TAC) resin film, and the like can be given. If the resin film transmittance of 80% or more in nm), can be preferably applied to the resin film of the present invention. Among these, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, it is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. More preferred are polyethylene terephthalate films and biaxially stretched polyethylene naphthalate films.

  The substrate used in the present invention can be subjected to a surface treatment or an easy-adhesion layer in order to ensure the wettability and adhesion of the coating solution. A conventionally well-known technique can be used about a surface treatment or an easily bonding layer. For example, the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment. Examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer. When the resin film is a biaxially stretched polyethylene terephthalate film, the interface reflection between the film substrate and the easy adhesion layer is reduced by setting the refractive index of the easy adhesion layer adjacent to the film to 1.57 to 1.63. Therefore, the transmittance can be improved. The method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion. In addition, a barrier coat layer may be previously formed on the substrate.

〔electrode〕
The preferable structural schematic diagram of the electrode of this invention is shown.

  FIG. 1 is a structural schematic diagram showing an example of a representative electrode of the present invention. The electrode has a first conductive metal layer 31 on a substrate 41, and the conductive metal layer 31 contains metal fibers 11.

  FIG. 2 is a structural schematic diagram showing an example of a representative electrode of the present invention. The electrode has a conductive metal layer 31 on a substrate 41, and the conductive metal layer 31 contains the metal fiber 11 and the conductive polymer 21.

  FIG. 3 is a structural schematic view showing another example of a representative electrode of the present invention, which has a first conductive metal layer 31 containing metal fibers 11 on a base material 41, and the first electrode A second conductive layer containing the conductive polymer 21 is formed on the conductive metal layer 31.

  FIG. 4 is a structural schematic diagram showing still another example of a representative electrode of the present invention, which has a first conductive metal layer 31 including a metal fiber 11 on a substrate 41, and the first electrode A second conductive layer 32 containing the conductive polymer 21 is formed on the conductive metal layer 31, and a part of the second conductive layer 32 includes the metal fiber 11. That is, the metal fiber 11 is shared by both the first conductive layer 31 and the second conductive layer 32.

  In the present invention, the conductive polymer 21 preferably contains a polymer represented by the general formula (A).

  In the present invention, the conductive metal layer contains the antioxidant of the present invention.

[Method for producing electrode]
The electrode of the present invention can be produced by the following methods (a) to (c).

  There are no particular restrictions on the method used in the step of forming the layer, but from the viewpoint of improving productivity, improving electrode quality such as smoothness and uniformity, and reducing environmental impact, the liquid phase such as coating and printing methods. It is preferable to use a film forming method.

  As coating methods, roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, bar coating method, gravure coating method, curtain coating method, spray coating method, doctor coating method Etc. can be used. As the printing method, a letterpress (letter) printing method, a stencil (screen) printing method, a lithographic (offset) printing method, an intaglio (gravure) printing method, a spray printing method, an ink jet printing method, and the like can be used.

  As a production method for producing the transparent electrode of the present invention, the following means are particularly preferably used.

B) A production method for forming a conductive metal layer, a layer containing a conductive metal and a conductive polymer, and a conductive polymer layer directly on the substrate. (Direct method)
B) After forming a conductive metal layer, a layer containing a conductive metal and a conductive polymer on the release surface of the release substrate, and a conductive layer containing a conductive polymer on the conductive metal layer, A manufacturing method in which a conductive layer is formed by transferring these layers onto a substrate for transfer. (Transfer method)
C) A manufacturing method in which a conductive metal layer is formed on a release surface of a release substrate and then transferred onto a transfer substrate to form a conductive polymer. (Transfer method + Direct method)
A preferred embodiment is that the composition is an aqueous dispersion.

  In the present invention, the conductive metal layer contains an antioxidant.

There is no particular limitation on the amount of the metal fiber, the conductive polymer, and the polymer represented by the general formula (A), but the metal fiber is preferably 0.50 g / m ² from the relationship between conductivity and transmittance, more preferably. Is 0.10 g / m ² or less.

  The conductive polymer has a solid content of preferably 50 times or less, more preferably 10 times or less, and further preferably 5 times or less of the metal fiber mass.

  In the above-described transparent electrode manufacturing method c), examples of the releasable substrate that can be used include a resin substrate and a resin film. There is no restriction | limiting in particular in this resin, It can select suitably from well-known things, For example, synthesis | combination, such as a polyethylene terephthalate resin, a vinyl chloride resin, an acrylic resin, a polycarbonate resin, a polyimide resin, a polyethylene resin, a polypropylene resin A substrate or film composed of a single layer or multiple layers of resin is preferably used. Furthermore, a glass substrate or a metal substrate can also be used. Further, a surface treatment may be applied to the surface (release surface) of the releasable substrate by applying a release agent such as silicon resin, fluororesin, or wax as necessary.

  Since the surface of the releasable substrate affects the smoothness of the surface after the conductive layer is transferred, it is desirable that the surface of the releasable substrate be highly smooth. Specifically, Ry ≦ 50 nm is preferable, and Ry ≦ 40 nm. It is more preferable that Ry ≦ 30 nm. Further, Ra ≦ 10 nm is preferable, Ra ≦ 5 nm is more preferable, and Ra ≦ 1 nm is further more preferable.

  In the above process, after applying the metal fiber, it is possible to increase the adhesion between the metal fibers by performing a calendar process or a heat treatment, or to reduce the contact resistance between the metal fibers by performing a plasma process. It is effective as a method for improving the electrical conductivity of. In the above step, the release surface of the releasable substrate may be previously hydrophilized by corona discharge (plasma) or the like.

  In the method including the step of transferring, the transfer may be performed via an adhesive layer. The transfer layer may be provided on the releasable substrate side or may be provided on the substrate side. The adhesive used for the adhesive layer is not particularly limited as long as it is a material having transfer ability in the visible region. A curable resin or a thermoplastic resin may be used. As the curable resin, it is preferable to use the compounds mentioned in the description of the binder.

  The release layer substrate on which the conductive layer is formed and the substrate to be transferred are bonded (bonded), and the release layer is peeled off after the adhesive is cured by irradiating ultraviolet rays or the like. Transfer to the substrate side for transfer is possible. Here, the bonding method is not particularly limited and can be performed by a sheet press, a roll press or the like, but is preferably performed using a roll press machine. The roll press is a method in which a film to be bonded is sandwiched between the rolls, and the rolls are rotated. The roll press is uniformly applied with pressure, and has a higher productivity than the sheet press and can be used preferably.

[Patterning method]
The conductive layer according to the present invention can be patterned. There is no particular limitation on the patterning method or process, and a known method can be applied as appropriate. For example, a method of forming a patterned electrode by forming a patterned conductive layer on a release surface and then transferring it onto a substrate can be used. Specifically, the following method is preferable. Can be used.

i) A method of directly forming a conductive layer in a pattern using a printing method on a releasable substrate
ii) A method in which a conductive layer is uniformly formed on a releasable substrate and then patterned using a general photolithography process.
iii) A method of patterning like a photolithography process after uniformly forming a conductive layer using a conductive material containing, for example, an ultraviolet curable resin
iv) A method in which a conductive layer is uniformly formed on a negative pattern previously formed of a photoresist on a releasable substrate and is patterned using a lift-off method [Surface smoothness]
In the present invention, Ra representing the smoothness of the surface of the conductive layer means an arithmetic average roughness and is a value according to the surface roughness defined in JIS B601 (1994). In the electrode of the present invention, the smoothness of the surface of the conductive layer is preferably Ra ≦ 10 nm. In the present invention, for the measurement of Ra, a commercially available atomic force microscope (AFM) can be used. For example, it can be measured by the following method.

  Using an SPI 3800N probe station and SPA400 multifunctional unit manufactured by Seiko Instruments Inc. as the AFM, set the sample cut to a size of about 1 cm square on a horizontal sample stage on the piezo scanner, and place the cantilever on the sample surface. When the region where the atomic force works is reached, scanning is performed in the XY direction, and the unevenness of the sample at that time is captured by the displacement of the piezo in the Z direction. A piezo scanner that can scan XY 20 μm and Z 2 μm is used. The cantilever is a silicon cantilever SI-DF20 manufactured by Seiko Instruments Inc., which has a resonance frequency of 120 to 150 kHz and a spring constant of 12 to 20 N / m, and is measured in a DFM mode (Dynamic Force Mode). A measurement area of 80 × 80 μm is measured at a scanning frequency of 1 Hz.

  In the present invention, the value of Ra is preferably 10 nm or less, and more preferably 5 nm or less.

[Auxiliary electrode]
In order to cope with an increase in area, it is preferable that the electrode having the conductive polymer-containing layer further has an auxiliary electrode including a light-impermeable conductive portion and a light-transmissive window portion.

  The light-impermeable conductive portion of the auxiliary electrode is preferably a metal from the viewpoint of good conductivity, and examples of the metal material include gold, silver, copper, iron, nickel, and chromium. The metal of the conductive part may be an alloy, and the metal layer may be a single layer or a multilayer.

  The shape of the auxiliary electrode is not particularly limited. For example, the conductive portion has a stripe shape, a mesh shape, or a random mesh shape.

  There are no particular limitations on the method of forming the stripe-shaped or mesh-shaped auxiliary electrode with the conductive portion, and a conventionally known method can be used. For example, a metal layer can be formed on the entire surface of the substrate and formed by a known photolithography method. Specifically, a conductor layer is formed on the entire surface of the substrate using one or more physical or chemical forming methods such as vapor deposition, sputtering, and plating, or a metal foil is formed with an adhesive. After being laminated on the material, it can be processed into a desired stripe shape or mesh shape by etching using a known photolithography method.

  As another method, a method of printing an ink containing metal fine particles in a desired shape by screen printing, or applying a plating catalyst ink to a desired shape by gravure printing or an ink jet method, followed by plating treatment As another method, a method using silver salt photographic technology can also be used. About the method to which silver salt photography technology is applied, it can carry out with reference to 0076-0112 of Unexamined-Japanese-Patent No. 2009-140750 and an Example, for example. About the method of carrying out the gravure printing of catalyst ink and plating, it can carry out with reference to Unexamined-Japanese-Patent No. 2007-281290, for example.

  As a random network structure, for example, a method for spontaneously forming a disordered network structure of conductive fine particles by applying and drying a liquid containing metal fine particles as described in JP-T-2005-530005 Can be used.

  As another method, for example, a method of forming a random network structure of metal nanowires by applying and drying a coating solution containing metal nanowires as described in JP-T-2009-505358 can be used.

[Preferred use]
The electrode of the present invention has both high conductivity and transparency, and various optoelectronic devices such as liquid crystal display elements, organic light emitting elements, inorganic electroluminescent elements, electronic paper, organic solar cells, inorganic solar cells, electromagnetic wave shields, touch panels, etc. It can be suitably used in the field. Among these, it can be particularly preferably used as an electrode of an organic electroluminescence element in which the smoothness of the electrode surface is strictly required.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<< Synthesis of Polymer (A) >>
Synthesis Example 1 (Synthesis of A1: within the present invention)
After adding 100 ml of THF to a 200 ml three-necked flask and heating to reflux for 10 minutes, the mixture was cooled to room temperature under nitrogen.

  I-1: 2-hydroxyethyl acrylate (10.0 g, 86 mmol, molecular weight: 116.05) and AIBN (1.41 g, 8.5 mmol, molecular weight: 164.11) were added, and the mixture was heated to reflux for 5 hours. After cooling to room temperature, the reaction solution was dropped into 3000 ml of MEK and stirred for 1 hour. After decantation of MEK (methyl ethyl ketone), the polymer was dissolved three times with 100 ml of MEK, and then the polymer was dissolved in THF (tetrahydrofuran) and transferred to a 100 ml flask. THF was distilled off under reduced pressure using a rotary evaporator and then dried under reduced pressure at 50 ° C. for 3 hours. As a result, 8.9 g (yield 89%) of the present polymer A1 having a number average molecular weight of 370000 and a molecular weight distribution of 2.7 was obtained. The obtained polymer was dissolved in pure water to prepare an aqueous solution of polymer A1 having a solid content of 50%.

  The number average molecular weight was measured by GPC (Waters 2695, manufactured by Waters).

<GPC measurement conditions>
Apparatus: Wagers 2695 (Separations Module)
Detector: Waters 2414 (Refractive Index Detector)
Column: Shodex Asahipak GF-7M HQ
Eluent: Dimethylformamide (20 mM LiBr)
Flow rate: 1.0 ml / min
Temperature: 40 ° C
Synthesis Example 2 (Synthesis of A2: within the present invention)
I-13: Blemmer GLM (0.22 g, 1.5 mmol, molecular weight: 146.06), II-12: Blemmer AE-400 (23.4 g, 48.5 mmol, molecular weight: 482.27) were used as monomers. Except for the above, 21.0 g (yield 89%) of the polymer A2 of the present invention having a number average molecular weight of 27600 and a molecular weight distribution of 3.1 was obtained in the same manner as in Synthesis Example 1.

Synthesis Example 3 (Synthesis of A3: within the present invention)
I-13: Blemmer GLM (0.37 g, 2.5 mmol, molecular weight: 146.06), II-12: Blemmer AE-400 (22.9 g, 47.5 mmol, molecular weight: 482.27) were used as monomers. 19.8 g (yield 85%) of the polymer A3 of the present invention having a number average molecular weight of 31100 and a molecular weight distribution of 2.9 was obtained in the same manner as in Synthesis Example 1 except for the above.

Synthesis Example 4 (Synthesis of A4: within the present invention)
Synthesis example except that I-13: Blemmer GLM (3.56 g, 25 mmol, molecular weight: 146.06), II-12: Blemmer AE-400 (12.1 g, 25 mmol, molecular weight: 482.27) were used as monomers. In the same manner as in Example 1, 14.3 g (yield 91%) of the polymer A4 of the present invention having a number average molecular weight of 23100 and a molecular weight distribution of 2.7 was obtained.

Synthesis Example 5 (Synthesis of A5: within the present invention)
Synthesis Example except that I-13: Blemmer GLM (5.84 g, 40 mmol, molecular weight: 146.06), II-12: Blemmer AE-400 (4.82 g, 10 mmol, molecular weight: 482.27) were used as monomers. In the same manner as in Example 1, 9.38 g (yield 88%) of the polymer A5 of the present invention having a number average molecular weight of 25400 and a molecular weight distribution of 2.6 was obtained.

Synthesis Example 6 (Synthesis of A6: within the present invention)
Except that I-1: 2-hydroxyethyl acrylate (1.74 g, 15 mmol, molecular weight: 116.05), II-6: Blemmer PME-200 (9.7 g, 35 mmol, molecular weight: 276.16) was used as the monomer. In the same manner as in Synthesis Example 1, 10.3 g (yield 90%) of the polymer A6 of the present invention having a number average molecular weight of 33700 and a molecular weight distribution of 2.4 was obtained.

  Polymers A2 to A6 of the present invention were dissolved in pure water to prepare aqueous solutions of polymers A2 to A6 having a solid content of 50%.

<< Preparation of conductive polymer liquids P-1 to P-7 >>
Next, using the polymers A1 to A6 prepared above (aqueous solution having a solid content of 50%), conductive polymer liquids P-1 to P-7 were prepared as follows.

(Conductive polymer liquid P-1)
Polymer A1 (50% solid content aqueous solution) 0.14 g
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
(Conductive polymer liquid P-2)
Polymer A2 (50% solid content aqueous solution): 0.14 g
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
(Conductive polymer liquid P-3)
Polymer A3 (50% solid content aqueous solution) 0.14 g
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
(Conductive polymer liquid P-4)
Polymer A4 (50% solid content aqueous solution) 0.14 g
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
(Conductive polymer liquid P-5)
Polymer A5 (50% solid content aqueous solution) 0.14 g
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
(Conductive polymer liquid P-6)
Polymer A6 (50% solid content aqueous solution) 0.14 g
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
(Conductive polymer liquid P-7)
PEDOT-PSS CLEVIOS PH510 (solid content 1.89%) (manufactured by HC Starck) 1.59 g
<< Preparation of Silver Nanowire Dispersions 1 and 2, Silver Particle Dispersion 3 >>
Examples of conductive metal fibers include Adv. Mater. , 2002, 14, 833 to 837, a silver nanowire having an average minor axis of 75 nm and an average length of 35 μm is produced using polyvinylpyrrolidone K30 (molecular weight: 50,000; manufactured by ISP). After silver nanowires are filtered and washed with an outer filtration membrane, hydroxypropylmethylcellulose 60SH-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) is redispersed in an aqueous solution containing 25% by mass of silver, and the silver nanowires of the present invention Dispersion 1 was prepared.

  Further, the silver nanowire dispersion liquid 2 of the invention and A silver particle dispersion 3 having an average particle size of 80 nm was prepared.

<< Electrode No. 1-No. Production of 35 >>
(Preparation of electrode No. 1; the present invention)
The silver nanowire dispersion 1 prepared above was placed on a 100 μm thick polyethylene terephthalate film support having a gas barrier layer on both sides so that the amount of silver nanowires was 60 mg / m ^2. It was applied using a spin coater and dried. Subsequently, the silver nanowire coating layer is calendered, and the conductive polymer liquid P-1 prepared by the above method is applied onto the silver nanowire coating layer using a spin coater so that the dry film thickness is 300 nm. It was applied and heated at 120 ° C. for 20 minutes on a hot plate, and electrode No. 1 was produced.

To the silver nanowire dispersion 1, the antioxidant PH-18 of the present invention was dissolved in methyl ethyl ketone and added so that the applied amount was 0.5 mg / m ² .

(Production of electrode Nos. 2 to 27 (present invention) and electrode Nos. 28 to 35 (comparative))
Electrode No. 1 except that the types of metal fibers and antioxidants contained in the conductive metal layer, the antioxidant, the addition amount, and the conductive polymer type are changed as shown in Tables 1 and 2 below. Electrode No. 2 to 27, comparative electrode Nos. 28-35 were produced.

<Evaluation>
[Difference in transmittance before and after storage]
The transmittance was determined by measuring the total light transmittance of the conductive portion pattern portion using AUTOMATIC HAZEMETER (MODEL TC-HIIIDP) manufactured by Tokyo Denshoku.

  The electrode No. 1 of the present invention produced as described above. 1-27, comparative electrode No. For 28 to 35, the total light transmittance was measured before and after storage for 7 days under 85 ° C. and 90% RH, the difference before and after storage was determined, and the transmittance before and after storage in a high temperature and high humidity environment based on the following criteria: The difference was evaluated.

◎: Difference in total light transmittance is less than 1% ○: Difference in total light transmittance is 1% or more and less than 3% △: Difference in total light transmittance is 3% or more and less than 5% ×: Difference in total light transmittance Is 5% or more (smoothness)
As an evaluation of smoothness, using an atomic force microscope (AFM) SPI3800N probe station and SPA400 multifunctional unit (manufactured by Seiko Instruments Inc.), the surface roughness Ra was measured (surface roughness Ra is (It is a value according to the surface roughness specified in JIS B601 (1994)). The cantilever uses SI-DF20 (manufactured by Seiko Instruments Inc.), a resonance frequency of 120 to 150 kHz, a spring constant of 12 to 20 N / m, a DFM mode (Dynamic Force Mode), a measurement area of 10 μm square, and a scanning frequency of 1 Hz. The arithmetic average roughness Ra was measured and determined according to JIS B601 (1994).

  The electrode No. 1 of the present invention produced as described above. 1-27, comparative electrode No. For 28 to 35, arithmetic average roughness Ra was measured before and after storage for 7 days under the condition of 85 ° C. and 90% RH, the change ratio due to storage was determined according to the following formula 1, and evaluation was performed based on the following criteria.

Change ratio (%) by storage = ((arithmetic average roughness Ra after storage−arithmetic average roughness Ra before storage) / arithmetic average roughness Ra before storage) × 100
◎: Change ratio by storage is less than 1% ○: Change ratio by storage is 1% or more and less than 3% △: Change ratio by storage is 3% or more and less than 8% ×: Change ratio by storage is 8% or more The results are shown in Tables 1 and 2.

In Table 1 and Table 2,
Irganox 1010: Phenol compound, manufactured by BASF Japan Ltd. Irganox 1076: Phenol compound, manufactured by BASF Japan Ltd. GSY-P101: Phosphorus compound, manufactured by Sakai Chemical Industry Co., Ltd. Sumilizer-GP: Phosphorus compound, Tinvin-144 manufactured by Sumitomo Chemical Co. : Hindered amine compound, BASF Japan Ltd. LA-52: ADK STAB LA-52, hindered amine compound, ADEKA Corporation Sumilizer-GS: Acrylate compound, Sumitomo Chemical Co., Ltd. HP-136: Benzofuranone compound, BASF Japan stock Company comparison compound (1): benzimidazole The structure of the above compound is shown below.

  As shown in Tables 1 and 2, No. 28 to 35, the electrode of the present invention having the antioxidant of the present invention in the conductive metal layer having metal fibers and the polymer (A) of the present invention in the conductive polymer layer is a high temperature and high humidity condition. It can be seen that there is little decrease in transparency and deterioration in smoothness due to storage under.

Example 2
[Production of organic electroluminescence element (organic EL element)]
The electrode No. 1 prepared in Example 1 was used. Organic EL elements 1 to 35 were produced by the following procedure using each of 1 to 35 as an anode electrode.

<Formation of hole transport layer>
Dissolve 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD) as a hole transport material on the anode electrode so as to be 1% by mass in 1.2-dichloroethane. The applied hole transport layer forming coating solution was applied by a spin coater and then dried at 80 ° C. for 60 minutes to form a hole transport layer having a thickness of 40 nm.

<Formation of light emitting layer>
On each film in which the hole transport layer is formed, the red dopant material Btp ₂ Ir (acac) is 1% by mass and the green dopant material Ir (ppy) ₃ is 2% with respect to polyvinylcarbazole (PVK) as the host material. %, Blue dopant material FIr (pic) is mixed so as to be 3% by mass, and the light emission is dissolved in 1.2-dichloroethane so that the total solid concentration of PVK and the three dopants is 1% by mass. The coating liquid for layer formation was applied with a spin coater and then dried at 100 ° C. for 10 minutes to form a light emitting layer having a thickness of 60 nm.

<Formation of electron transport layer>
On the formed light emitting layer, LiF was evaporated as a material for forming an electron transport layer under a vacuum of 5 × 10 ⁻⁴ Pa to form an electron transport layer having a thickness of 0.5 nm.

<Formation of cathode electrode>
On the formed electron transport layer, Al was vapor-deposited under a vacuum of 5 × 10 ⁻⁴ Pa to form a cathode electrode having a thickness of 100 nm.

<Formation of sealing film>
On the formed electron transport layer, a polyethylene terephthalate and the substrate, using a flexible sealing member which is deposited to a thickness 300nm of Al ₂ O _3. Adhesive is applied to the periphery of the cathode electrode except for the ends so that external terminals of the anode electrode and the cathode electrode can be formed, and after the flexible sealing member is bonded, the adhesive is cured by heat treatment and sealed. A film was formed and sealed.

<Evaluation>
<Light emission brightness unevenness>
Using a KEITHLEY source measure unit type 2400, a direct current voltage was applied to the organic EL element to emit light. With respect to the organic EL elements 1 to 35 that emitted light at 200 cd / m ² , each light emission uniformity was observed with a 50 × microscope. Furthermore, the light emission uniformity after emitting the organic EL elements 1 to 35 at 200 cd / m ² for 1000 hours was observed.

(Evaluation criteria for light emission uniformity)
A: The entire EL element emits light uniformly. O: The entire EL element emits light substantially uniformly. Δ: Some unevenness is observed in the light emission of the EL element. X: Clear unevenness is observed in the light emission of the EL element. The evaluation results are shown in Table 3.

  As shown in Table 3, the organic EL elements 28 to 35 (comparative examples) have the antioxidant of the present invention in the conductive metal layer having metal fibers, and the polymer of the present invention in the conductive polymer layer. It can be seen that the organic EL device using the electrode of the present invention having (A) has little decrease in transparency and smoothness due to storage under high temperature and high humidity conditions.

11 Metal Fiber 21 Conductive Polymer 31 First Conductive Metal Layer 32 Second Conductive Layer 41 Substrate

Claims (7)

In an electrode having a conductive metal layer containing metal fibers on a substrate and a conductive polymer layer, the conductive metal layer contains an antioxidant, and the conductive polymer layer is used as a binder resin. Polymer (A) having at least one of a polymer having a structural unit represented by the following general formula (I) and a copolymer having a structural unit represented by the following general formula (I) and the following general formula (II) An electrode comprising:

[Wherein, R represents a hydrogen atom or a methyl group, and Q represents —C (═O) O— or —C (═O) NRa—. Ra represents a hydrogen atom or an alkyl group, A represents a substituted or unsubstituted alkylene group, — (CH ₂ CHRbO) _x — (CH ₂ CHRb) —, and Rb represents a hydrogen atom or an alkyl group. x is an average number of repeating units of 1 to 100. y represents 0 or 1; Z represents an alkyl group, —C (═O) —Rc, —SO ₂ —Rd, —SiRe ₃ . Rc, Rd, and Re represent an alkyl group, a perfluoroalkyl group, or an aryl group. ]   The electrode according to claim 1, wherein the conductive polymer layer is disposed on the conductive metal layer.   The electrode according to claim 1, wherein the metal fiber is a silver nanowire.   The electrode according to any one of claims 1 to 3, wherein the antioxidant is a water-soluble compound.   The electrode according to any one of claims 1 to 4, wherein the antioxidant is a phenol compound. The additive amount of the antioxidant ^{is, 1 × 10 -4 g / m} 2 ~1g / electrode according to any one of claims 1 to 5, characterized in that ^m is ^2.   An organic electroluminescence device comprising the electrode according to claim 1.

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