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WO2012014621A1 - Film conducteur transparent et élément électroluminescent organique - Google Patents

Film conducteur transparent et élément électroluminescent organique Download PDF

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Publication number
WO2012014621A1
WO2012014621A1 PCT/JP2011/065034 JP2011065034W WO2012014621A1 WO 2012014621 A1 WO2012014621 A1 WO 2012014621A1 JP 2011065034 W JP2011065034 W JP 2011065034W WO 2012014621 A1 WO2012014621 A1 WO 2012014621A1
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group
film
organic
molecular weight
conductive layer
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Japanese (ja)
Inventor
中村　和明
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Konica Minolta Inc
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Konica Minolta Inc
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Priority to JP2012526389A priority Critical patent/JP5741581B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H10K50/814—Anodes combined with auxiliary electrodes, e.g. ITO layer combined with metal lines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/287—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polypropylene oxide in the alcohol moiety
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes

Definitions

  • the present invention is a transparent electrode that can be suitably used in various fields such as a liquid crystal display element, an organic light emitting element, an inorganic electroluminescent element, a solar cell, an electromagnetic wave shield, electronic paper, and a touch panel, and further an organic electroluminescence using the transparent electrode
  • the present invention relates to an element (hereinafter also referred to as an organic EL element).
  • the transparent electrode is an essential constituent technology.
  • transparent electrodes are an indispensable technical element in touch panels, mobile phones, electronic paper, various solar cells, and various electroluminescence light control elements.
  • 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. It was. However, indium used in ITO is a rare metal and removal of indium is desired due to the rising price. In addition, with an increase in display screen and productivity, a roll-to-roll production technique using a flexible substrate is desired.
  • ITO indium-tin composite oxide
  • a transparent conductive film such as a conductive polymer is laminated on a thin metal wire formed in a pattern so that it can be used for products requiring such a large area and a low resistance value, and the surface uniformity of current is high.
  • a transparent conductive film having both conductivity has been developed (see, for example, Patent Documents 1 and 2).
  • Patent Documents 1 and 2 it is necessary to smooth the irregularities of the fine metal wires that cause leakage of the organic electronic device with a transparent conductive film such as a conductive polymer, and it is essential to increase the thickness of the conductive polymer.
  • the conductive polymer has absorption in the visible light region, there is a problem that when the film is thickened, the transparency of the transparent electrode is significantly lowered.
  • a technique for laminating a mixture of a conductive polymer and an insulating polymer on a fine wire structure is disclosed as having both conductivity and transparency (for example, Patent Document 3).
  • Patent Document 3 a technique for laminating a mixture of a conductive polymer and an insulating polymer on a fine wire structure.
  • an insulating polymer has a problem that it causes deterioration of optical performance such as haze from the viewpoint of a decrease in conductivity and compatibility with the conductive polymer.
  • polyvinylpyrrolidone PVP
  • a copolymer of poly (vinyl pyridine) and poly (vinyl acetate) PVPy-VAc
  • PMAA polymethacrylic acid
  • PMAA polymethacrylic acid
  • PHEA-MAA poly (methacrylic acid) copolymer
  • PVB polyvinyl butyral
  • the present invention has been made in view of the above-mentioned problems, and the object of the present invention is excellent in transparency, conductivity, and film strength, as well as deterioration in transparency, conductivity, and film strength even in a high temperature and high humidity environment.
  • An object of the present invention is to provide a transparent electrode that provides an organic EL device that is less in stability, excellent in light emission uniformity, and less in light emission uniformity and excellent in light emission life.
  • Another object of the present invention is to provide an organic EL device that has high emission uniformity using the electrode, has little deterioration in emission uniformity, and has an excellent lifetime.
  • the transparent conductive film coating liquid contains a water-dispersible conductive polymer such as 3,4-polyethylenedioxythiophene polysulfonate (PEDOT / PSS) and a water-soluble binder in order to achieve both conductivity and transmittance.
  • a water-dispersible conductive polymer such as 3,4-polyethylenedioxythiophene polysulfonate (PEDOT / PSS)
  • a water-soluble binder in order to achieve both conductivity and transmittance.
  • Compositions have been developed.
  • hydrophilic binders have been studied as water-soluble polymers from the viewpoint of compatibility with water-dispersible conductive polymers.
  • the demand for flexibility as a transparent substrate increases, and when a resin film such as polyethylene terephthalate is used, the drying temperature is lower than that of the glass substrate from the viewpoint of avoiding film deformation.
  • the present invention has been completed using a binder resin containing a structural unit having a hydroxy group and a structural unit not containing a hydroxy group in the repeating unit of the binder.
  • the object of the present invention can be achieved by including a binder resin containing a structural unit having a hydroxy group in a repeating unit and a structural unit not containing a hydroxy group in the second conductive layer, as in the configuration of the present invention.
  • the present invention has been achieved.
  • the present invention uses a conductive polymer and a binder resin in which the number of hydroxy groups is controlled for the second conductive layer to achieve both transparency and conductivity of the transparent conductive film, and excellent film strength, and in a high temperature and high humidity environment. It has been found that a highly stable transparent electrode and a long-life organic electroluminescence device using the transparent electrode, which have both high conductivity, transparency and good film strength even after an environmental test, can be obtained. .
  • the object of the present invention is achieved by adopting the following configuration.
  • a transparent conductive film having a first conductive layer made of a metal material formed in a pattern on a substrate and a second conductive layer containing a conductive polymer, a structural unit having a hydroxy group in the second conductive layer; And a binder resin containing a structural unit that does not have a hydroxy group and has an ester or amide bond.
  • R represents a hydrogen atom or a methyl group
  • 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
  • Rb represents a hydrogen atom or an alkyl group
  • x represents the average number of repeating units. And is a number from 1 to 100.
  • R represents a hydrogen atom or a methyl group
  • 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—
  • Rb represents a hydrogen atom or an alkyl group.
  • x represents the average number of repeating units, and is a number from 1 to 100.
  • y represents 0 or 1;
  • Z represents a hydrogen atom, an alkoxy group, —O—C ( ⁇ O) —Rc, —O—SO 2 —Rd, or —O—SiRe 3 .
  • Rc, Rd, and Re represent a substituted or unsubstituted alkyl group or an aryl group. However, Ra and Z may be bonded to form a morpholine ring with N—A2.
  • An organic electroluminescence device comprising the transparent conductive film according to any one of (1) to (3).
  • the transparency, conductivity and film strength are excellent, and transparency, conductivity and film strength are hardly deteriorated even in a high temperature and high humidity environment, and stability and light emission uniformity are excellent. It is possible to provide a transparent electrode that provides an organic EL device that has little emission uniformity deterioration and excellent emission lifetime.
  • FIG. 1 is a schematic diagram illustrating an example of the transparent conductive film having the configuration of the present invention.
  • FIG. 1 (a) is a top view of the transparent conductive film
  • FIG. 1 (b) is a cross-sectional view taken along line AA ′ of FIG. 1 (a).
  • 1 is a first conductive layer made of a metal material formed in a pattern
  • 2 is a second conductive layer containing a conductive polymer
  • 3 is a substrate.
  • the characteristic in the structure of this invention contains the binder resin containing the structural unit which has a hydroxyl group in a 2nd conductive layer, and the structural unit which does not have a hydroxyl group and has an ester or amide bond.
  • the binder resin according to the present invention is preferably a binder resin that dissolves about 0.001 g or more in 100 g of water at 25 ° C., and specifically has the following structure and has OH in an acidic group, etc. Is not included.
  • the degree of solubility in water can be measured with a haze meter or a turbidimeter.
  • the binder resin according to the present invention is preferably transparent, and specifically has a structure containing a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II). desirable.
  • 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, for example, 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.
  • substituents include cycloalkyl groups, aryl groups, heterocycloalkyl groups, heteroaryl groups, hydroxy groups, halogen atoms, alkoxy groups, alkylthio groups, arylthio groups, cycloalkoxy groups, aryloxy groups, acyl groups, 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, alkyloxys, al
  • the number of carbon atoms of the cycloalkyl group is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 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.
  • alkoxy group examples 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, preferably an ethoxy group.
  • the alkylthio 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 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 to 12, and more preferably 3 to 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, 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 morpholino group.
  • the heteroaryl group preferably has 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms.
  • heteroaryl group examples include a thienyl group and a pyridyl group.
  • the acyl group preferably has 1 to 20 carbon atoms, 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.
  • the sulfonamido group include a methanesulfonamido group and the like
  • the arylsulfonamido group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • the arylsulfonamido group include a benzenesulfonamido group and p-toluenesulfonamido group.
  • the aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms.
  • 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, more preferably 2 to 12 carbon atoms.
  • Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.
  • the alkenyl group preferably has 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.
  • alkyloxysulfonyl group examples 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.
  • alkylsulfonyloxy group examples include a methylsulfonyloxy group and an ethylsulfonyloxy group.
  • the arylsulfonyloxy group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • 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.
  • 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.
  • R b represents a hydrogen atom or an alkyl group.
  • the alkyl group is preferably, for example, a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group.
  • alkyl groups may be substituted with the above-described substituents.
  • 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.
  • R, Q, Ra, A, Rb, and x have the same meanings as defined in the general formula (I).
  • y represents 0 or 1.
  • Z represents a hydrogen atom, an alkoxy group, —O—C ( ⁇ O) —Rc, —O—SO 2 —Rd, or —O—SiRe 3 .
  • Rc, Rd and Re represent a substituted or unsubstituted alkyl group or an aryl group, and the alkyl group preferably has, for example, 1 to 12 carbon atoms, more preferably a methyl group or an ethyl group, still more preferably a methyl group. is there.
  • These alkyl groups may be substituted with the substituent described above.
  • the alkyl group is preferably a halogen-substituted alkyl group, particularly preferably a perfluoroalkyl group, for example, preferably having 1 to 8 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, still more preferably trifluoromethyl. It is a 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 and aryl groups may be substituted with the above-described substituents.
  • the binder resin of the present invention may contain another structural unit in addition to the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II).
  • the binder resin of the present invention may be referred to as the hydroxy group-containing nonconductive polymer of the present invention.
  • the molar ratio of the structural unit having a hydroxy group represented by the general formula (I) is preferably 5 to 90%, more preferably 10 to 50%.
  • the binder resin of the present invention can be obtained by radical polymerization using a general-purpose polymerization catalyst.
  • 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 in the range of 5000 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 if soluble binder resin, THF (tetrahydrofuran), DMF (dimethylformamide), preferably CH 2 Cl 2, more preferably THF, is DMF, still more preferably DMF.
  • the measurement temperature is not particularly limited, but 40 ° C. is preferable.
  • the second conductive layer contains a conductive polymer.
  • the conductive polymer according to the present invention is preferably a conductive polymer having a ⁇ -conjugated conductive polymer and a polyanion.
  • a conductive polymer can be easily produced by chemical oxidative polymerization of a precursor monomer that forms a ⁇ -conjugated conductive polymer described later in the presence of an appropriate oxidizing agent, an oxidation catalyst, and a poly anion described later. .
  • the ⁇ -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, A chain conductive polymer of polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyl compounds 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.
  • Precursor monomers used in the formation of ⁇ -conjugated conductive polymers have a ⁇ -conjugated system in the molecule, and even when polymerized by the action of an appropriate oxidant, a ⁇ -conjugated system is formed in the main chain. It is what is done. Examples thereof include pyrroles and derivatives thereof, thiophenes and derivatives thereof, anilines and derivatives thereof, and the like.
  • the precursor monomer examples 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-hexyl Offene, 3-heptyl
  • the polyanion used in the present invention includes 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 co-polymer thereof.
  • a polymer comprising a structural unit having an anionic group and a structural unit having no anionic group.
  • This poly anion is a solubilized polymer that solubilizes the ⁇ -conjugated conductive polymer in a solvent.
  • the anion group of the polyanion functions as a dopant for the ⁇ -conjugated conductive polymer, and improves the conductivity and heat resistance of the ⁇ -conjugated conductive polymer.
  • the anion group of the polyanion may be any functional group capable of causing chemical oxidation doping to the ⁇ -conjugated conductive polymer.
  • a monosubstituted sulfate ester Group, monosubstituted phosphate group, phosphate group, carboxy group, sulfo group and the like are preferable.
  • a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.
  • 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, poly Isoprene sulfonic 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, etc. Can be mentioned. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
  • it may be a poly anion further having F (fluorine atom) in the compound.
  • F fluorine atom
  • Nafion made by Dupont
  • Flemion made by Asahi Glass Co., Ltd.
  • perfluoro vinyl ether containing a carboxylic acid group
  • the compound having a sulfonic acid is formed by applying and drying the conductive polymer-containing layer, and then subjected to a heat drying treatment at 100 to 120 ° C. for 5 minutes or more before the microwave irradiation. May be. This promotes the crosslinking reaction, which is preferable since the washing resistance and solvent resistance of the coating film are remarkably improved.
  • polystyrene sulfonic acid polyisoprene sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polybutyl acrylate sulfonic acid are preferable.
  • These poly anions have high compatibility with the hydroxy group-containing non-conductive polymer of the present invention, 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, and an anionic group containing The method of manufacturing by superposition
  • Examples of the method for producing an anion group-containing polymerizable monomer by polymerization include a method for producing an anion 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. Specifically, a predetermined amount of the anionic group-containing polymerizable monomer is dissolved in a solvent, kept 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 predetermined amount. React with time. The polymer obtained by the reaction is adjusted to a certain concentration by the solvent. In this production method, an anionic group-containing polymerizable monomer may be copolymerized with a polymerizable monomer having no anionic group.
  • 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 ⁇ -conjugated conductive polymer.
  • the obtained polymer is a polyanionic salt, it is preferably transformed into a polyanionic acid.
  • 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.
  • the ultrafiltration method is preferable from the viewpoint of easy work.
  • the ratio of the ⁇ -conjugated conductive polymer and the poly anion contained in the conductive polymer, “ ⁇ -conjugated conductive polymer”: “poly anion” is preferably 1: 1 to 20 by mass ratio. From the viewpoint of conductivity and dispersibility, the range of 1: 2 to 10 is more preferable.
  • the oxidant used when the precursor monomer forming the ⁇ -conjugated conductive polymer is chemically oxidatively polymerized in the presence of the polyanion to obtain the conductive polymer according to the present invention is, for example, J. Org. Am. Soc. 85, 454 (1963), which is suitable for the oxidative polymerization of pyrrole.
  • oxidants such as iron (III) salts, eg FeCl 3 , Fe (ClO 4 ) 3 , organic acids and iron (III) salts of inorganic acids containing organic residues
  • iron (III) salts eg FeCl 3 , Fe (ClO 4 ) 3
  • organic acids and iron (III) salts of inorganic acids containing organic residues Or use hydrogen peroxide, potassium dichromate, alkali persulfate (eg potassium persulfate, sodium persulfate) or ammonium, alkali perborate, potassium permanganate and copper salts such as copper tetrafluoroborate preferable.
  • air and oxygen in the presence of catalytic amounts of metal ions such as iron, cobalt, nickel, molybdenum and vanadium ions can be used as oxidants at any time.
  • persulfates and the iron (III) salts of inorganic acids containing organic acids and organic residues has great application advantages because they are
  • iron (III) salts of inorganic acids containing organic residues include iron (III) salts of alkanol sulfate hemiesters having 1 to 20 carbon atoms, such as lauryl sulfate; alkyl sulfonic acids having 1 to 20 carbon atoms, such as Methane or dodecanesulfonic acid; carboxylic acid having 1 to 20 aliphatic carbon atoms such as 2-ethylhexyl carboxylic acid; aliphatic perfluorocarboxylic acid such as trifluoroacetic acid and perfluorooctanoic acid; aliphatic dicarboxylic acid such as oxalic acid And especially the aromatic, optionally substituted alkyl sulfonic acids having 1 to 20 carbon atoms, such as the Fe (III) salts of benzesenesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid
  • Such a conductive polymer is preferably a commercially available material.
  • 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 and 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.
  • An organic compound may be contained as the second dopant.
  • 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 hydroxy group-containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound.
  • the hydroxy group-containing compound include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, glycerin and the like. Among these, ethylene glycol and diethylene glycol are preferable.
  • Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, ⁇ -butyrolactone, and the like.
  • 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.
  • the first conductive layer according to the present invention is characterized in that a metal material is formed in a pattern on a film substrate.
  • a metal material is formed in a pattern on a film substrate.
  • a film substrate having both a light-impermeable conductive portion made of a metal material and a light-transmissive window portion is obtained, and an electrode substrate excellent in transparency and conductivity can be produced.
  • the metal material is not particularly limited as long as it is excellent in conductivity.
  • the metal material may be an alloy other than a metal such as gold, silver, copper, iron, nickel, and chromium.
  • the shape of the metal material is preferably metal fine particles or metal nanowires from the viewpoint of ease of pattern formation as described later, and the metal material is preferably silver from the viewpoint of conductivity.
  • the pattern shape is not particularly limited.
  • the conductive portion may be a stripe shape, a mesh shape, or a random network shape, but the aperture ratio is preferably 80% or more from the viewpoint of transparency.
  • the aperture ratio is the ratio of the light transmitting portion excluding the light non-transmitting conductive portion to the whole.
  • the conductive portion has a stripe shape or a mesh shape
  • the aperture ratio of the stripe pattern having a line width of 100 ⁇ m and a line interval of 1 mm is about 90%.
  • the line width of the pattern is preferably 10 to 200 ⁇ m. When the line width of the thin wire is 10 ⁇ m or more, desired conductivity can be obtained, and when it is 200 ⁇ m or less, high transparency can be obtained.
  • the height of the fine wire is preferably 0.1 to 10 ⁇ m.
  • a metal layer can be formed on the entire surface of the substrate and formed by a known photolithography method.
  • a conductor layer is formed on the entire surface using one or more physical or chemical forming methods such as printing, vapor deposition, sputtering, plating, etc., or a metal foil is used as an adhesive.
  • the film After being laminated on the base material, the film can be processed into a desired stripe shape or mesh shape by etching using a known photolithography 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.
  • a method using silver salt photographic technology can be carried out with reference to, for example, [0076]-[0112] of JP-A-2009-140750 and Examples.
  • the method for carrying out the plating process by gravure printing of the catalyst ink can be carried out with reference to, for example, JP-A-2007-281290.
  • 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.
  • a method for 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.
  • Metal nanowire refers to a fibrous structure having a metal element as a main component.
  • the metal nanowire in the present invention means a large number of fibrous structures having a minor axis from the atomic scale to the nm size.
  • the average length is preferably 3 ⁇ m or more, more preferably 3 to 500 ⁇ m, and particularly preferably 3 to 300 ⁇ m.
  • the relative standard deviation of the length is preferably 40% or less.
  • the average minor axis of the metal nanowire is preferably 10 to 300 nm, and more preferably 30 to 200 nm.
  • the relative standard deviation of the minor axis is preferably 20% or less.
  • the basis weight of the metal nanowire is preferably 0.005 to 0.5 g / m 2 , and more preferably 0.01 to 0.2 g / m 2 .
  • metal used for the metal nanowire copper, iron, cobalt, gold, silver or the like can be used, but silver is preferable from the viewpoint of conductivity.
  • a single metal may be used, in order to achieve both conductivity and stability (sulfurization, oxidation resistance, and migration resistance of metal nanowires), the main metal and one or more other metals May be included in any proportion.
  • the method 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
  • a method for producing silver nanowires Adv. Mater. , 2002, 14, 833-837, Chem. Mater. 2002, 14, 4736-4745
  • a method for producing gold nanowires is disclosed in Japanese Patent Application Laid-Open No. 2006-233252
  • a method for producing copper nanowires is disclosed in Japanese Patent Application Laid-Open No. 2002-266007, and the like. Reference can be made to 2004-149871.
  • the above-described method for producing silver nanowires can be preferably applied because silver nanowires can be easily produced in an aqueous solution, and the conductivity of silver is maximum in metals.
  • the surface specific resistance of the thin wire portion of the first conductive layer is preferably 100 ⁇ / ⁇ or less, and more preferably 20 ⁇ / ⁇ or less for increasing the area.
  • the surface specific resistance can be measured, for example, according to JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.
  • the first conductive layer is heat-treated within a range that does not damage the film substrate. Thereby, fusion of metal fine particles and metal nanowires progresses and the first conductive layer becomes highly conductive, which is particularly preferable.
  • the second conductive layer may completely cover the patterned first conductive layer, or may partially cover or contact it.
  • the second conductive layer is formed into a film by applying and drying a dispersion composed of a conductive polymer and the hydroxy group-containing non-conductive polymer of the present invention.
  • the second conductive layer is applied by roll coating, bar coating, dip coating, spin coating, casting, and die coating.
  • a coating method such as a blade coating method, a bar coating method, a gravure coating method, a curtain coating method, a spray coating method, a doctor coating method, or an inkjet method can be used.
  • the first conductive layer is formed on the transfer film by the above-described method, and the second conductive layer is further formed.
  • the method etc. which form a 2nd conductive layer by the well-known method by the inkjet method etc. in the nonelectroconductive part of a 1st conductive layer are mentioned.
  • the second conductive layer is further characterized by including the hydroxy group-containing nonconductive polymer of the present invention. Thereby, high electroconductivity, high transparency, and strong film
  • the conductive layer of the present invention By forming the conductive layer of the present invention having such a structure, high conductivity that cannot be obtained with a metal or metal oxide fine wire or a conductive polymer layer alone can be obtained uniformly in the electrode plane. .
  • the ratio of the conductive polymer of the second conductive layer to the hydroxy group-containing nonconductive polymer of the present invention is such that the hydroxy group-containing nonconductive polymer is 30 to 900 parts by mass when the conductive polymer is 100 parts by mass. It is preferable that the hydroxy group-containing nonconductive polymer is 100 parts by mass or more from the viewpoints of preventing current leakage, the conductivity enhancing effect of the hydroxy group-containing nonconductive polymer, and transparency.
  • the dry film thickness of the second conductive layer is preferably 30 to 2000 nm. From the viewpoint of conductivity, the thickness is more preferably 100 nm or more, and from the viewpoint of the surface smoothness of the electrode, it is further preferably 200 nm or more. Moreover, it is more preferable that it is 1000 nm or less from the point of transparency.
  • the second conductive layer After applying the second conductive layer, it can be appropriately dried.
  • a drying process it is preferable to dry-process at the temperature of the range which does not damage a base material or a conductive layer.
  • a drying treatment can be performed at 80 to 120 ° C. for 10 seconds to 10 minutes.
  • the cleaning resistance and solvent resistance of the electrode are remarkably improved, and the device performance is further improved.
  • effects such as reduction in driving voltage and improvement in life can be obtained.
  • additives examples include plasticizers, stabilizers such as antioxidants and sulfurization inhibitors, surfactants, dissolution accelerators, polymerization inhibitors, and colorants such as dyes and pigments.
  • solvents for example, organic solvents such as water, alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons, etc. are used. May be included.
  • the base material used for the transparent electrode of the present invention is also called a film substrate, has high light transparency, excellent flexibility, a sufficiently small dielectric loss coefficient, and a conductive material whose microwave absorption is to be heated. If it is a material smaller than a layer, there will be no restriction
  • a resin substrate, a resin film, etc. are mentioned suitably, it is preferable to use a transparent resin film from a viewpoint of productivity, a viewpoint of performance, such as lightness and a softness
  • the transparent resin film If it is a transparent resin film, it is resistant to deformation and impact caused by external force and is not easily broken. There is no restriction
  • 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 Examples thereof include a film, a polyimide resin film, an acrylic resin film, and a triacetyl cellulose (TAC) resin film.
  • PET polyethylene terephthalate
  • PE polyethylene
  • PP polypropylene
  • polystyrene resin films polyolefin resin films such as cyclic olefin resins
  • Vinyl resin films such as polyvinyl chloride and polyviny
  • Any resin film having a transmittance of 80% or more at a visible wavelength (380 to 780 nm) is preferably used as the film substrate used in the present invention.
  • a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, and a polycarbonate film are preferable, and a biaxially stretched polyethylene terephthalate film.
  • a biaxially stretched polyethylene naphthalate film is more preferred.
  • the film 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.
  • examples of the surface treatment include 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, epoxy copolymer and the like.
  • the easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.
  • an inorganic film, an organic film, or a hybrid film of both may be formed on the front surface or the back surface of the film substrate, and the water vapor transmission rate (25 ⁇ 0. 5 ° C. and relative humidity (90 ⁇ 2)% RH) are preferably 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less of a barrier film, and further conform to JIS K 7126-1987.
  • oxygen permeability was measured by the method is, 1 ⁇ 10 -3 ml / m 2 ⁇ 24h ⁇ atm or less, the water vapor transmission rate (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) is, 1 ⁇ 10
  • a high barrier film of ⁇ 3 g / (m 2 ⁇ 24 h) or less is preferable.
  • any material may be used as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like can be used.
  • Organic electroluminescence device is characterized by having an organic layer including an organic light emitting layer and the transparent electrode of the present invention.
  • the organic electroluminescent device in the present invention preferably uses the transparent electrode of the present invention as an anode, and the organic light-emitting layer and the cathode are made of any material or configuration generally used in organic electroluminescent devices. Can be used.
  • Anode / organic light emitting layer / cathode As an element configuration of the organic electroluminescence element, Anode / organic light emitting layer / cathode, anode / hole transport layer / organic light emitting layer / electron transport layer / cathode, Anode / hole injection layer / hole transport layer / organic light emitting layer / electron transport layer / cathode, Anode / hole injection layer / organic light emitting layer / electron transport layer / electron injection layer / cathode, Anode / hole injection layer / organic light emitting layer / electron injection layer / cathode, The thing of various structures, such as these, can be mentioned.
  • the organic light emitting layer is prepared by a known method using the above materials and the like, and examples thereof include vapor deposition, coating, and transfer.
  • the thickness of the organic light emitting layer is preferably 0.5 to 500 nm, particularly preferably 0.5 to 200 nm.
  • the organic electroluminescence element of the present invention can be used for a self-luminous display, a liquid crystal backlight, illumination, and the like. Since the organic electroluminescence element of the present invention can emit light uniformly and without unevenness, it is preferably used for lighting purposes.
  • the transparent 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. It can be suitably used in such fields. Among these, it can use especially preferably as a transparent electrode of the organic electroluminescent element and organic thin-film solar cell element by which the smoothness of the transparent electrode surface is calculated
  • the molecular weight was measured by GPC (Waters 2695, manufactured by Waters).
  • Synthesis Example 3 (Synthesis of P-3: within the present invention) Except that I-8: Blemmer AE-200 (7.10 g, 25 mmol, molecular weight: 284.16), II-21: N-methylacrylamide (2.13 g, 25 mmol, molecular weight: 85.05) was used as the monomer. In the same manner as in Synthesis Example 1, 7.75 g (yield 84%) of water-soluble binder resin P-3 having a number average molecular weight of 31700 and a molecular weight distribution of 2.1 was obtained.
  • Synthesis Example 4 (Synthesis of P-4: within the present invention) Except that I-12: Blemmer PP-500 (3.04 g, 5 mmol, molecular weight: 608.41), II-7: Blemmer PME-400 (22.3 g, 45 mmol, molecular weight: 496.59) were used as monomers. In the same manner as in Synthesis Example 1, 22.0 g (yield 87%) of water-soluble binder resin P-4 having a number average molecular weight of 33200 and a molecular weight distribution of 2.7 was obtained.
  • Synthesis Example 5 (Synthesis of P-5: 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. Otherwise, 21.0 g (yield 89%) of water-soluble binder resin P-5 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 6 (Synthesis of P-6: 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. Otherwise, 19.8 g (yield: 85%) of water-soluble binder resin P-6 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.
  • Synthesis Example 7 (Synthesis of P-7: 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. 1 and the number average molecular weight 23100 Thus, 14.3 g (yield 91%) of water-soluble binder resin P-7 having a molecular weight distribution of 2.7 was obtained.
  • Synthesis Example 8 (Synthesis of P-8: 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 No. 1, 9.38 g (yield 88%) of water-soluble binder resin P-8 having a number average molecular weight of 25400 and a molecular weight distribution of 2.6 was obtained.
  • Synthesis Example 9 (Synthesis of P-9: within the present invention) After adding 200 ml of THF to a 500 ml three-necked flask and heating to reflux for 10 minutes, it was cooled to room temperature under nitrogen. 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 added dropwise into 5000 ml of MEK and stirred for 1 hour.
  • a water-soluble binder resin Z3.0 g and dehydrated tetrahydrofuran 30 ml were charged into a 100 ml flask and completely dissolved, and then the internal temperature was reduced to 10 ° C. or lower with an ice bath.
  • a solution prepared by dissolving trifluoromethanesulfonyl chloride (0.65 g, 3.9 mmol, molecular weight: 167.93) in 10 ml of dehydrated tetrahydrofuran was separately prepared, and dropped into the water-soluble binder resin Z solution over 30 minutes. The internal temperature was maintained at 10 ° C. or lower.
  • Synthesis Example 10 (Synthesis of P-10: within the present invention) A number average molecular weight of 32200 and a molecular weight distribution of 2.200 were obtained in the same manner as in Synthesis Example 9 except that 4-methylbenzoyl chloride (0.30 g, 1.9 mmol, molecular weight: 154.02) was used instead of trifluoromethanesulfonyl chloride. As a result, 2.84 g (yield 90%) of water-soluble binder resin P-10 was obtained. The structure was confirmed by 1 H-NMR.
  • Synthesis Example 11 (Synthesis of P-11: within the present invention) I-15: N-methylolacrylamide (0.25 g, 2.5 mmol, molecular weight: 101.05), II-6: Blemmer PME-200 (13.1 g, 47.5 mmol, molecular weight: 276.16) as monomers 11.7 g of a water-soluble binder resin P-11 having a number average molecular weight of 35900 and a molecular weight distribution of 2.7 was obtained in the same manner as in Synthesis Example 1 except that it was used. (Yield 88%).
  • Synthesis Example 12 (Synthesis of P-12: within the present invention) Synthesis Example 1 except that I-19: hydroxyethylacrylamide (0.58 g, 5 mmol, molecular weight: 115.06) and II-24: acryloylmorpholine (6.35 g, 45 mmol, molecular weight: 141.08) were used as monomers. By the same method, 6.03 g (yield 87%) of water-soluble binder resin P-12 having a number average molecular weight of 35,900 and a molecular weight distribution of 2.7 was obtained.
  • Synthesis Example 13 (Synthesis of P-13: outside the present invention) 4.50 g of binder resin P-13 having a number average molecular weight of 37,000 and a molecular weight distribution of 2.7 was obtained in the same manner as in Synthesis Example 1 except that 5.06 g of only I-8 was used as a monomer (yield 89%). Obtained.
  • Synthesis Example 14 (Synthesis of P-14: outside the present invention) 4.80 g of binder resin P-14 having a number average molecular weight of 39000 and a molecular weight distribution of 2.8 was obtained in the same manner as in Synthesis Example 1 except that 5.33 g of II-7 alone was used as a monomer (yield 90%). Obtained.
  • Synthesis Example 15 (Synthesis of PB: outside the present invention) According to the same method as in Synthesis Example 1, except that 2-hydroxyethyl acrylate (3.48 g, 30 mmol, molecular weight: 116.05) and acrylic acid (2.16 g, 30 mmol, molecular weight: 72.02) were used as monomers. 4.29 g (yield 76%) of a binder resin PB having a number average molecular weight of 37100 and a molecular weight distribution of 2.6 was obtained using a resin having a hydroxy group.
  • the dried sample was further dehumidified by being held for 10 minutes in an atmosphere at a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature ⁇ 8 ° C.).
  • Modification A The sample subjected to the dehumidification treatment was modified under the following conditions to form a gas barrier layer.
  • the dew point temperature during the reforming process was -8 ° C.
  • a first conductive layer was formed on the non-barrier surface of the transparent electrode film substrate having gas barrier properties obtained above by the following method.
  • the fine wire lattice (metal material) was prepared by gravure printing or silver nanowire as shown below.
  • the silver nanowire dispersion liquid is applied using a bar coating method so that the basis weight of the silver nanowires is 0.06 g / m 2 , dried at 110 ° C. for 5 minutes, and heated to form a silver nanowire substrate. Produced.
  • Silver nanowire dispersions are available from Adv. Mater. , 2002, 14, 833 to 837 with reference to the method described in PVP K30 (molecular weight 50,000; manufactured by ISP), silver nanowires having an average minor axis of 75 nm and an average length of 35 ⁇ m were produced. Silver nanowires are filtered off using a filtration membrane, washed, and then redispersed in an aqueous solution containing 25% by mass of hydroxypropylmethylcellulose 60SH-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) to prepare a silver nanowire dispersion. did.
  • Example 1 ⁇ Preparation of transparent electrode >> ⁇ Preparation of transparent electrode TC-101>
  • the following coating liquid A is extruded on the transparent electrode in which the first conductive layer is formed by gravure printing on the film substrate for the transparent electrode having gas barrier properties, using an extrusion method so as to have a dry film thickness of 300 nm.
  • the slit gap was adjusted and applied, dried by heating at 110 ° C. for 5 minutes to form a second conductive layer comprising a conductive polymer and a water-soluble binder resin P-1, and the obtained electrode was 8 ⁇ 8 cm. Cut out.
  • the obtained electrode was heated in an oven at 110 ° C. for 30 minutes to produce a transparent electrode TC-101.
  • Silver nanowire dispersions are described in Adv. Mater. , 2002, 14, 833 to 837 with reference to the method described in PVP K30 (molecular weight 50,000; manufactured by ISP), silver nanowires having an average minor axis of 75 nm and an average length of 35 ⁇ m were produced. Silver nanowires are filtered off using a filtration membrane, washed, and then redispersed in an aqueous solution containing 25% by mass of hydroxypropylmethylcellulose 60SH-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) to prepare a silver nanowire dispersion. did.
  • the random network structure was prepared using silver nanowires as shown below.
  • the silver nanowire dispersion liquid is applied using a bar coating method so that the basis weight of the silver nanowires is 0.06 g / m 2 , dried at 110 ° C. for 5 minutes, and heated to form a silver nanowire substrate. Produced.
  • a second conductive layer was formed using a coating liquid A on a transparent electrode in which a random network structure was formed by silver nanowires, and cut into 8 ⁇ 8 cm.
  • the obtained electrode was heated in an oven at 110 ° C. for 30 minutes to produce a transparent electrode TC-114.
  • a transparent electrode TC-115 was prepared in the same manner as the transparent electrode TC-101 except that P-1 in the coating solution A was changed to P-13 in the production of the transparent electrode TC-101.
  • a transparent electrode TC-116 was prepared in the same manner as the transparent electrode TC-101 except that P-1 in the coating solution A was changed to P-14 in the production of the transparent electrode TC-101.
  • surface resistance was measured using a resistivity meter (Loresta GP (MCP-T610 type): manufactured by Dia Instruments Co., Ltd.).
  • the surface resistance is preferably 100 ⁇ / ⁇ or less, and preferably 30 ⁇ / ⁇ or less in order to increase the area of the organic electronic device.
  • Crimping / peeling was repeated 10 times on the conductive layer using a Scotch tape manufactured by Sumitomo 3M Co., and the dropping of the conductive layer was visually observed and evaluated according to the following criteria.
  • the transparent electrodes TC-101 to 114 are superior to the transparent electrodes TC-115 to TC-118 in terms of smoothness, conductivity and light transmission, and in a high temperature and high humidity environment. It can be seen that there is little deterioration in smoothness, conductivity, and light transmittance, and the stability is excellent.
  • Example 2 Production of organic EL devices >> The prepared transparent electrode substrate was washed with ultrapure water, cut into a 30 mm square so that one square tile-shaped transparent pattern with a pattern side length of 20 mm was placed in the center, and used for the anode electrode, respectively. A device was fabricated. The hole transport layer and subsequent layers were formed by vapor deposition. Organic EL elements OEL-201 to OEL-218 were produced using transparent electrodes TC-101 to TC-118, respectively.
  • Each of the deposition crucibles in a commercially available vacuum deposition apparatus was filled with a constituent material for each layer in a necessary amount for device fabrication.
  • the evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.
  • an organic EL layer including a hole transport layer, an organic light emitting layer, a hole blocking layer, and an electron transport layer was sequentially formed.
  • each light emitting layer was provided in the following procedures.
  • Compound 2 is 13.0% by mass, Compound 3 is 3.7% by mass, and Compound 5 is 83.3% by mass.
  • Co-evaporation was performed in the same region as the hole transport layer at a rate of 0.1 nm / second to form a green-red phosphorescent organic light emitting layer having a maximum emission wavelength of 622 nm and a thickness of 10 nm.
  • compound 4 and compound 5 are deposited in the same region as the organic light-emitting layer emitting green-red phosphorescence at a deposition rate of 0.1 nm / second so that compound 4 is 10.0% by mass and compound 5 is 90.0% by mass.
  • Co-evaporation was performed to form a blue phosphorescent organic light emitting layer having an emission maximum wavelength of 471 nm and a thickness of 15 nm.
  • a hole blocking layer was formed by depositing compound 6 in a thickness of 5 nm on the same region as the formed organic light emitting layer.
  • CsF was co-evaporated with compound 6 so as to have a film thickness ratio of 10% to form an electron transport layer having a thickness of 45 nm.
  • a transparent electrode is used as an anode, an anode external takeout terminal and Al as a 15 mm ⁇ 15 mm cathode forming material are mask-deposited under a vacuum of 5 ⁇ 10 ⁇ 4 Pa, and a 100 nm thick anode Formed.
  • a flexible seal in which an adhesive is applied around the anode except for the end portion, and polyethylene terephthalate is used as a base material and Al 2 O 3 is deposited in a thickness of 300 nm so that external terminals for the cathode and anode can be formed.
  • the adhesive was cured by heat treatment to form a sealing film, and an organic EL device having a light emitting area of 15 mm ⁇ 15 mm was produced.
  • emission uniformity For light emission uniformity, a KEITHLEY source measure unit 2400 type was used to apply a DC voltage to the organic EL element to emit light. With respect to the organic EL elements OEL-201 to OEL-218 that emitted light at 1000 cd / m 2 , each light emission luminance unevenness was observed with a 50 ⁇ microscope. Further, the organic EL elements OEL-201 to OEL-218 were heated in an oven at 60% RH and 80 ° C. for 2 hours, and then conditioned again in the environment of 23 ⁇ 3 ° C. and 55 ⁇ 3% RH for 1 hour or more. Thereafter, the emission uniformity was observed in the same manner.
  • the comparative organic EL elements OEL-215 to OEL-218 are significantly deteriorated in light emission uniformity after heating at 80 ° C. for 30 minutes, whereas the organic EL elements OEL-201 to OEL-214 of the present invention It can be seen that the light emission uniformity is stable even after heating and has excellent durability.

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  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Non-Insulated Conductors (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne une électrode transparente qui réalise un élément EL organique qui possède une excellente transparence, conductivité et résistance de film et qui présente une faible détérioration de sa transparence, conductivité et résistance de film même dans un environnement à haute température et à forte humidité, qui présente une excellente stabilité et uniformité d'émission lumineuse et qui possède une très bonne durée de vie d'émission lumineuse avec une faible détérioration de l'uniformité d'émission lumineuse. Pour que l'élément EL organique qui emploie l'électrode possède une très bonne durée de vie avec une grande uniformité d'émission lumineuse et une faible détérioration de l'uniformité d'émission lumineuse, dans un film conducteur transparent comprenant une première couche conductrice constituée d'un matériau métallique façonnée en motif sur un substrat et une deuxième couche conductrice contenant un polymère conducteur, la deuxième couche conductrice contient une résine de liage incluant des unités structurelles comprenant un groupe d'hydroxyde et des unités structurelles ne comprenant pas un groupe d'hydroxyde mais comprenant une liaison d'ester ou d'amide.
PCT/JP2011/065034 2010-07-29 2011-06-30 Film conducteur transparent et élément électroluminescent organique Ceased WO2012014621A1 (fr)

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JP2013020869A (ja) * 2011-07-13 2013-01-31 Konica Minolta Holdings Inc 透明導電膜、その形成方法および有機エレクトロルミネッセンス素子
WO2014147134A1 (fr) 2013-03-20 2014-09-25 Basf Se Complexes de carbène d'azabenzimidazole formant des amplificateurs d'efficacité dans des oled
WO2014177518A1 (fr) 2013-04-29 2014-11-06 Basf Se Complexes de métal de transition avec des ligands carbène et leur utilisation dans des delo
WO2015000955A1 (fr) 2013-07-02 2015-01-08 Basf Se Complexes de métal et de carbène de type diazabenzimidazole monosubstitué destinés à être utilisés dans des diodes électroluminescentes organiques
WO2015063046A1 (fr) 2013-10-31 2015-05-07 Basf Se Azadibenzothiophènes pour applications électroniques
WO2016016791A1 (fr) 2014-07-28 2016-02-04 Idemitsu Kosan Co., Ltd (Ikc) Benzimidazolo[1,2-a] benzimidazoles 2,9-fonctionnalisé utilisés comme hôtes pour diodes électroluminescentes organiques (oled)
EP2982676A1 (fr) 2014-08-07 2016-02-10 Idemitsu Kosan Co., Ltd. Benzimidazo [2,1-B] benzoxazoles pour applications électroniques
EP2993215A1 (fr) 2014-09-04 2016-03-09 Idemitsu Kosan Co., Ltd. Azabenzimidazo[2,1-a]benzimidazoles pour applications électroniques
EP3015469A1 (fr) 2014-10-30 2016-05-04 Idemitsu Kosan Co., Ltd. 5-((benz)imidazol-2-yl)benzimidazo[1,2-a]benzimidazoles pour des applications électroniques
WO2016079667A1 (fr) 2014-11-17 2016-05-26 Idemitsu Kosan Co., Ltd. Dérivés d'indole pour des applications électroniques
WO2016079169A1 (fr) 2014-11-18 2016-05-26 Basf Se Complexes de pt-carbène ou de pd-carbène destinés à être utilisés dans des diodes électroluminescentes organiques
EP3034506A1 (fr) 2014-12-15 2016-06-22 Idemitsu Kosan Co., Ltd Dérivés de carbazole 4-fonctionnalisés pour applications électroniques
EP3034507A1 (fr) 2014-12-15 2016-06-22 Idemitsu Kosan Co., Ltd Dibenzothiophènes et dibenzofurannes 1-functionalisés pour diodes électroluminescentes organiques (OLED)
EP3053918A1 (fr) 2015-02-06 2016-08-10 Idemitsu Kosan Co., Ltd Benzimidazoles substitués par un 2-carbazole pour des applications électroniques
EP3054498A1 (fr) 2015-02-06 2016-08-10 Idemitsu Kosan Co., Ltd. Bisimidazodiazocines
EP3061759A1 (fr) 2015-02-24 2016-08-31 Idemitsu Kosan Co., Ltd Dibenzofuranes à substituant nitrile
EP3070144A1 (fr) 2015-03-17 2016-09-21 Idemitsu Kosan Co., Ltd. Composés cycliques à sept chaînons
EP3072943A1 (fr) 2015-03-26 2016-09-28 Idemitsu Kosan Co., Ltd. Benzonitriles de dibenzofurane/carbazole-substitué
EP3075737A1 (fr) 2015-03-31 2016-10-05 Idemitsu Kosan Co., Ltd Benzimidazolo [1,2-a] benzimidazole portant des groupes heteroarylnitril aryl- ou pour diodes électroluminescentes organiques
WO2016193243A1 (fr) 2015-06-03 2016-12-08 Udc Ireland Limited Dispositifs oled très efficaces à temps de déclin très courts
EP3150604A1 (fr) 2015-10-01 2017-04-05 Idemitsu Kosan Co., Ltd. Groupes benzimidazolo [1,2-a] benzimidazoles portant des benzimidazolo [1,2-a] benzimidazolyles, groupes carbazolyles, groupes benzofuranes ou benzothiophènes pour diodes électroluminescentes organiques
EP3150606A1 (fr) 2015-10-01 2017-04-05 Idemitsu Kosan Co., Ltd. Benzimidazolo[1,2-a]benzimidazoles avec des groupements benzofurane ou benzothiophène pour des diodes émittant de la lumière
WO2017056053A1 (fr) 2015-10-01 2017-04-06 Idemitsu Kosan Co., Ltd. Groupes benzimidazolo[1,2-a]benzimidazolyle, groupes carbazolyle, groupes benzofuranne ou groupes benzothiophène portant un composé benzimidazolo[1,2-a] benzimidazole pour diodes électroluminescentes organiques
WO2017056055A1 (fr) 2015-10-01 2017-04-06 Idemitsu Kosan Co., Ltd. Benzimidazolo[1,2-a]benzimidazole portant des groupes triazine pour diodes électroluminescentes organiques
JP2017510994A (ja) * 2013-12-19 2017-04-13 フラウンホーファー−ゲゼルシャフト・ツール・フェルデルング・デル・アンゲヴァンテン・フォルシュング・アインゲトラーゲネル・フェライン 機能性有機層を含む透明ナノワイヤー電極
WO2017078182A1 (fr) 2015-11-04 2017-05-11 Idemitsu Kosan Co., Ltd. Hétéroaryles fusionnés à un benzimidazole
WO2017093958A1 (fr) 2015-12-04 2017-06-08 Idemitsu Kosan Co., Ltd. Dérivés benzimidazolo[1,2-a]benzimidazole pour des diodes électroluminescentes organiques
EP3184534A1 (fr) 2015-12-21 2017-06-28 UDC Ireland Limited Complexes de métaux de transition comportant des ligands tripodes et leur utilisation dans des delo
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EP3239161A1 (fr) 2013-07-31 2017-11-01 UDC Ireland Limited Complexes de carbène-métal diazabenzimidazole luminescent
US9862739B2 (en) 2014-03-31 2018-01-09 Udc Ireland Limited Metal complexes, comprising carbene ligands having an O-substituted non-cyclometalated aryl group and their use in organic light emitting diodes
EP3318566A1 (fr) 2012-09-20 2018-05-09 UDC Ireland Limited Aza-dibenzofuranes pour applications électroniques
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EP3466954A1 (fr) 2017-10-04 2019-04-10 Idemitsu Kosan Co., Ltd. Phénylquinazolines condensées et pontées avec un hétéroatome
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JP2013020869A (ja) * 2011-07-13 2013-01-31 Konica Minolta Holdings Inc 透明導電膜、その形成方法および有機エレクトロルミネッセンス素子
EP3318566A1 (fr) 2012-09-20 2018-05-09 UDC Ireland Limited Aza-dibenzofuranes pour applications électroniques
US10249827B2 (en) 2012-09-20 2019-04-02 Udc Ireland Limited Azadibenzofurans for electronic applications
WO2014147134A1 (fr) 2013-03-20 2014-09-25 Basf Se Complexes de carbène d'azabenzimidazole formant des amplificateurs d'efficacité dans des oled
WO2014177518A1 (fr) 2013-04-29 2014-11-06 Basf Se Complexes de métal de transition avec des ligands carbène et leur utilisation dans des delo
WO2015000955A1 (fr) 2013-07-02 2015-01-08 Basf Se Complexes de métal et de carbène de type diazabenzimidazole monosubstitué destinés à être utilisés dans des diodes électroluminescentes organiques
EP3266789A1 (fr) 2013-07-02 2018-01-10 UDC Ireland Limited Complexes métalliques contenant des ligands diazabenzimidazole-carbéniques monosubstitués destinés à être utilisés dans des diodes électroluminescentes organiques
EP3608329A1 (fr) 2013-07-02 2020-02-12 UDC Ireland Limited Complexes métalliques contenant des ligands diazabenzimidazole-carbéniques monosubstitués destinés à être utilisés dans des diodes électroluminescentes organiques
EP3239161A1 (fr) 2013-07-31 2017-11-01 UDC Ireland Limited Complexes de carbène-métal diazabenzimidazole luminescent
WO2015063046A1 (fr) 2013-10-31 2015-05-07 Basf Se Azadibenzothiophènes pour applications électroniques
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US10109387B2 (en) 2013-12-19 2018-10-23 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Transparent nanowire electrode comprising a functional organic layer
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EP3466954A1 (fr) 2017-10-04 2019-04-10 Idemitsu Kosan Co., Ltd. Phénylquinazolines condensées et pontées avec un hétéroatome

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