JP2014229397A - Method for manufacturing electroconductive film, electroconductive film, organic electronic element, and touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an electroconductive film capable not only of inhibiting substrate deformation but also of obtaining a product excellent in terms of transparency and electroconductivity.SOLUTION: The provided method for manufacturing an electroconductive film 1 includes a step of coating, atop a substrate 2, a dispersion obtained by dispersing, within an aqueous solvent, an electroconductive first polymer and an infrared-absorbing second polymer, and a step of forming an electroconductive layer by irradiating the coated dispersion with infrared rays emitted from an infrared heater. The second polymer absorbs, at sites other than dissociative groups, infrared rays having wavelengths of 2.5-3.0 μm. The infrared heater irradiates with infrared rays including components having wavelengths of 2.5-3.0 μm.

Description

  The present invention relates to a method for producing a conductive film 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, as well as a conductive film and an organic material. The present invention relates to an electroluminescence element (hereinafter also referred to as an organic EL element) and a touch panel.

  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 having 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.

  When manufacturing a transparent electrode in place of an ITO transparent electrode, a manufacturing method using a wet coating method is being considered in place of a dry coating method with low productivity such as a vacuum deposition method and a sputtering method which have been conventionally used. For example, as described in Patent Document 1, a dispersion liquid containing a conductive material such as a conductive polymer represented by PEDOT-PSS is directly applied on a transparent substrate, dried by heating, and then a conductive layer. A method for producing a transparent electrode by a wet coating method for forming a film has been developed. When a transparent electrode using this conductive polymer is applied to an organic electronic device (organic EL device, organic solar cell, etc.), moisture remaining in the conductive layer, organic solvent or 2 resulting from insufficient drying The secondary dopant becomes a factor that deteriorates the performance of the organic electronic device, such as generation of dark spots at the time of light emission of the organic EL device and deterioration of the device lifetime.

  On the other hand, along with the increase in area and productivity of organic electronic devices, transparency using a roll-to-roll method using a flexible substrate such as a resin substrate (flexible transparent substrate) Electrode production techniques are desired. In particular, when a conductive polymer transparent electrode using a resin base material is applied to an organic electronic element, due to problems of base material deformation during drying (low heat resistance in the resin base material itself) and performance deterioration of the element described above. A new method for drying a conductive polymer coating film is desired.

  Further, as a drying method other than heat drying, after applying an electrode material paste kneaded with an electrode material, a binder, a conductive agent and a solvent onto a metal sheet such as aluminum or copper, the solvent is dried by far infrared rays of 3.5 μm or more. A method using a near-infrared heater whose region has been cut has been proposed (see, for example, Patent Document 2).

JP 2013-4335 A Japanese Patent No. 4790092

  However, the method described in Patent Document 1 has a problem that the performance of the transparent electrode deteriorates when the conductive layer formed on PET is dried under a heating condition of 110 ° C. for 5 minutes where the base material is not deformed. This is because the solution used for the coating solution is not sufficiently dried, and moisture, secondary dopants and the like remain in the film, causing performance deterioration as a transparent electrode. In addition, when an organic electroluminescence element (organic EL element) is manufactured using these electrodes, there is a problem that a significant performance deterioration such as an increase in electrode surface resistance and a current leakage occurs.

  In addition, the method described in Patent Document 2 focuses on efficiently drying the solvent in the coating film, and does not consider prevention of deformation due to infrared absorption of the base material itself. No mention is made of infrared drying when a transparent resin substrate is used. In addition, when the conductive layer described in Patent Document 1 is dried with an infrared heater in which a far infrared region of 3.5 μm or more is cut, deformation of the substrate is not seen, but drying is insufficient, There existed a problem that a solvent remained and caused the performance deterioration of a transparent electrode and an organic electroluminescent element. Further, Patent Document 2 does not mention the relationship between the binder and the solvent contained in the electrode material paste.

  From the above, in the conductive polymer transparent electrode using the resin base material, a technique capable of removing water, organic solvent and secondary dopant in the conductive layer without damaging the base material is strong. It was desired.

  Moreover, as a coating liquid for forming a conductive layer on a base material in a conventional conductive film, water such as 3,4-polyethylenedioxythiophene polysulfonate (PEDOT / PSS) is used in order to achieve both conductivity and transmittance. Compositions containing a dispersible conductive polymer and a binder resin have been developed.

  As binder resins, hydrophilic binder resins have been studied from the viewpoint of compatibility with water-dispersible conductive polymers. However, since the demand for flexibility is increasing for the base material, using a resin film such as polyethylene terephthalate as the base material, from the viewpoint of avoiding film deformation, compared to the case of using a glass substrate as the base material The drying temperature needs to be low. In addition, the hydroxyl group-containing binder resin known to be compatible with PEDOT / PSS causes a hydroxyl group to undergo a dehydration reaction under acidic conditions and crosslinks between polymer chains. Occur. As a result, the cross-linking reaction proceeds during storage and water is generated, and the conductive film and the device performance using the conductive film may be significantly deteriorated due to the water remaining in the film. In order to solve this problem, in the conventional conductive film, it is necessary to reduce the interaction between the main skeleton of the binder and water.

  A polymer emulsion is known as a binder resin having a small interaction with a solvent such as water. Among the polymer emulsions, polyester emulsions, acrylic emulsions, polyurethane emulsions, etc. are not only introduced with many ester groups and urethane groups, which are hydrophilic sites, in the polymer main chain and side chains, but also in solvents such as water. In order to improve dispersibility, hydrophilic groups such as sulfonic acid, carboxylic acid, hydroxyl group, and ammonium are present. The hydrophilic group in the polymer forms a hydrogen bond with a solvent capable of hydrogen bonding, such as water and a polar solvent, so that it is difficult to release water by low temperature and short heating drying, and the conductive film and the organic electronic device using the conductive film There has been a problem that the performance of the system may deteriorate. In other words, in order to improve the drying property of the conductive film at a low temperature and in a short time, energy is directly applied to a solvent capable of hydrogen bonding, such as water and a polar solvent, and energy is also applied to the binder used in the conductive layer. It is indispensable to impart energy capable of breaking the hydrogen bond between the polymer, particularly the hydrophilic group in the polymer and the solvent capable of hydrogen bonding.

  The present invention has been made in view of the above circumstances, and a method for producing a conductive film, a conductive film, and an organic electronic device that can suppress deformation of the substrate and can provide a product having excellent transparency and conductivity. It is an object to provide a touch panel.

  That is, the said subject which concerns on this invention is solved by the following means.

1. Applying a dispersion liquid in which a first polymer having conductivity and a second polymer having infrared absorptivity are dispersed in an aqueous solvent on a base material, and irradiating the coated dispersion liquid with infrared rays by an infrared heater. Forming a conductive layer by performing, wherein the second polymer absorbs infrared light having a wavelength of 2.5 to 3.0 μm at a site other than the dissociable group, and the infrared heater has a wavelength A method for producing a conductive film, which comprises irradiating an infrared ray of 2.5 to 3.0 μm.

2. The method for producing a conductive film according to 1 above, wherein the infrared heater irradiates infrared rays at a filament temperature of 700 to 3000 ° C.

3. 3. The method for manufacturing a conductive film according to 1 or 2, wherein the infrared heater includes a filter that absorbs infrared rays having a wavelength of 3.5 μm or more.

4). Said 2nd polymer has either a urethane structure, an amide structure, or a silanol structure, The manufacturing method of the electrically conductive film in any one of said 1 to 3 characterized by the above-mentioned.

5. 5. The method for producing a conductive film according to any one of 1 to 4, further comprising a step of forming a conductive layer formed of a metal material on the substrate.

6). A conductive film produced by the method for producing a conductive film according to any one of 1 to 5 above.
Conductive film.

7). An organic electronic device comprising a conductive film manufactured by the method for manufacturing a conductive film according to any one of 1 to 5 as an electrode.

8). A touch panel comprising a conductive film manufactured by the method for manufacturing a conductive film according to any one of 1 to 5 as an electrode.

  According to the present invention, it is possible to obtain a product that suppresses the deformation of the substrate and is excellent in transparency and conductivity.

It is sectional drawing which shows schematic structure of an organic electronic element. It is a top view which illustrates the pattern shape of the metal conductive layer of a transparent electrode. It is sectional drawing which shows schematic structure of a wavelength control infrared heater. It is sectional drawing which shows the modification of the wavelength control infrared heater of FIG. It is sectional drawing which shows schematic structure of an organic EL element. It is a schematic plan view for demonstrating the manufacturing method of an organic EL element. It is a graph which shows the infrared rays transmittance | permeability of a quartz glass filter. It is a graph which shows the infrared spectrum by the presence or absence of a quartz glass filter. It is sectional drawing which shows an example of a touch panel.

  As a result of intensive studies to solve the above-described problems of the prior art, the present inventor has an infrared absorbing property with a wavelength of 2.5 to 3.0 μm in a portion other than the dissociable group as a conductive layer and can be dispersed in an aqueous solvent. Unlike heat-drying, where a coating solution is dried by heat conduction from the film surface by irradiating infrared rays having a wavelength of 2.5 to 3.0 μm using a simple polymer, a solvent capable of hydrogen bonding, such as water and a polar solvent In addition to directly applying energy to the (aqueous solvent), energy can also be directly applied to the polymer. As a result, the present invention is capable of suitably removing the aqueous solvent present in the hydrophilic group portion of the polymer that could not be realized by conventional low-temperature heat drying in which the resin base material such as transparent plastic is not deformed. I came up with an idea.

  The effect of the structure of the present invention is that, in addition to the dissociable group, a polymer dispersible in an aqueous solvent having an infrared absorptivity having a wavelength of 2.5 to 3.0 μm is used, and an infrared ray having a wavelength of 2.5 to 3.0 μm is used. By irradiating and directly applying energy to the polymer, the hydration and adsorption of the solvent capable of hydrogen bonding can be separated from the polymer.

  In heat drying, where the coating liquid is dried by heat conduction from the film surface at a temperature at which the transparent resin substrate does not deform, the water-bonding solvent such as water and polar solvents that are hydrated and adsorbed from the polymer are strictly removed. This is difficult, and as a result, the solvent remains in the film, which degrades the performance of the conductive film, the organic electronic device using the conductive film, and the touch panel. That is, the object of the present invention is to use an infrared solvent having a wavelength of 2.5 to 3.0 μm using a polymer dispersible in an aqueous solvent having an infrared absorptivity having a wavelength of 2.5 to 3.0 μm in addition to the dissociable group. By irradiating and applying energy directly to the polymer, it has been found that the hydration and adsorption of the solvent capable of hydrogen bonding can be separated from the polymer. I came to get.

  According to the configuration of the present invention, both the transparency and conductivity of the conductive film are compatible, the surface roughness is excellent, and the conductivity and transparency are high even after an environmental test under a high temperature and high humidity environment without deformation of the substrate. In addition, by having both good surface roughness and suppressing generation of water derived from the binder resin, a highly stable conductive film, and a long-life organic electronic device and touch panel using the conductive film can be obtained.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.

[Transparent conductive film]
The transparent conductive film has a polymer conductive layer containing at least a conductive polymer and a nonconductive polymer on a transparent resin substrate, and the polymer conductive layer uses the conductive polymer and the nonconductive polymer as an aqueous solvent. It is produced by applying the dispersed dispersion onto a transparent resin substrate and drying it.

  As shown in FIG. 1, the conductive conductive film 1 includes a transparent resin base material 2, a metal conductive layer 4, and a polymer conductive layer 6, and can be used as a transparent electrode.

  The metal conductive layer 4 is a fine line pattern of metal particles formed on the transparent resin substrate 2. The thin line pattern in the metal conductive layer 4 may be formed in a stripe shape as shown in FIGS. 2A to 2C, or may be formed in a mesh shape (mesh shape) as shown in FIG. May be.

  The polymer conductive layer 6 is formed on the transparent resin substrate 2 on which the metal conductive layer 4 is formed. The polymer conductive layer 6 is formed flush and covers the surface of the metal conductive layer 4 and the surface of the transparent resin substrate 2 exposed from between the metal conductive layers 4.

  The transparent conductive film 1 may have a configuration in which the metal conductive layer 4 is omitted. However, the transparent conductive film 1 includes the metal conductive layer 4 as described above, and the polymer conductive layer 6 is laminated on the metal conductive layer 4 to reduce the thickness. It has resistance and uniform sheet resistance.

[Polymer that absorbs infrared light having a wavelength of 2.5 to 3.0 μm at a site other than the dissociable group and can be dispersed in an aqueous solvent]
In the present invention, the non-conductive polymer described above is a polymer that absorbs infrared rays having a wavelength of 2.5 to 3.0 μm at a site other than the dissociable group and can be dispersed in an aqueous solvent. A polymer that absorbs infrared light having a wavelength of 2.5 to 3.0 μm at a site other than the dissociable group and is dispersible in an aqueous solvent is an infrared absorptivity having a wavelength of 2.5 to 3.0 μm at a site other than the dissociable group And does not contain a surfactant, an emulsifier, or the like that assists micelle formation, and can be dispersed in an aqueous solvent as a single polymer.

  In the present invention, “dispersible in an aqueous solvent” means that colloidal particles made of a binder resin are dispersed in the aqueous solvent without agglomeration. The size (average particle diameter) of the colloidal particles is generally about 0.001 to 1 μm (1 to 1000 nm). The size (average particle diameter) of the colloidal particles of the polymer that can be dispersed in the aqueous solvent is preferably 1 to 500 nm, more preferably 5 to 300 nm, and still more preferably the same as the colloidal particles of the conductive polymer compound. Is 5 to 100 nm. When the colloidal particles of the polymer dispersible in the aqueous solvent are large (when larger than 500 nm), the second conductive layer (transparent conductive layer) 13 generated by applying the dispersion to the substrate 11 is used. There exists a possibility that haze and smoothness (surface roughness (Ra)) may deteriorate. Further, when the colloidal particles of the polymer dispersible in the aqueous solvent are extremely small (smaller than 1 nm), the particles are aggregated to reduce the dispersibility of the dispersion liquid. As a result, the second conductive The haze and smoothness (surface roughness (Ra)) of the layer (transparent conductive layer) 13 may be deteriorated. In order to improve the smoothness when the polymer conductive layer 4 is formed, the size of the colloidal particles is more preferably 3 to 300 nm, and further preferably 5 to 100 nm. If the average particle diameter of the particles is less than 5 nm, the dispersion stability due to the aggregation of the particles may deteriorate, resulting in a non-uniform coating surface. As a result, the haze of the coating film is increased and the performance as an optical film may be deteriorated. The size of the colloidal particles can be measured with a light scattering photometer.

  The aqueous solvent is not only pure water (including distilled water and deionized water) but also an aqueous solution containing acid, alkali, salt, etc., a water-containing organic solvent, or a hydrophilic organic solvent. Examples of the aqueous solvent include pure water (including distilled water and deionized water), alcohol solvents such as methanol and ethanol, and mixed solvents of water and alcohol.

  In the present invention, the polymer that absorbs infrared rays having a wavelength of 2.5 to 3.0 μm at a site other than the dissociable group has a site having absorption at 2.5 to 3.0 μm in the polymer. Since the infrared heater used in the present invention has energy at a wavelength of 2.5 to 3.0 μm, the polymer absorbs this energy, so that a polymer dispersible in an aqueous solvent, a conductive polymer compound, etc. An effect of releasing the hydrogen bonding solvent from the material constituting the conductive layer 6 is produced.

  The portion other than the dissociable group that absorbs infrared rays having a wavelength of 2.5 to 3.0 μm is not particularly limited as long as it has infrared absorbing properties having a wavelength of 2.5 to 3.0 μm. Examples include amides, sulfonamides, secondary amines, tertiary amines, 1,3-diketone eoles, and the like. These partial structures may be a monovalent linking group or a divalent linking group, and hydrogen on the nitrogen atom may be substituted with a substituent. Furthermore, examples of the substituent include a silanol group, a hydroxyl lactam group, and an amino group.

  Generally, a polymer dispersible in an aqueous solvent is stably dispersed in an aqueous solvent. Therefore, an anionic substituent such as sulfonic acid or carboxylic acid, a nonionic substituent such as a hydroxyl group, or an ammonium salt structure is contained in the polymer. Contains a dissociative group of a hydrophilic group such as a cationic substituent. These dissociable groups have infrared absorptivity with a wavelength of 2.5 to 3.0 μm, and these dissociable groups of hydrophilic groups are introduced in order to maintain dispersion stability in an aqueous solvent. However, these dissociable groups are hydrophilic and disadvantageous for drying, so the introduction rate is low and the infrared absorption ability cannot be sufficiently exhibited. The polymer that absorbs infrared rays having a wavelength of 2.5 to 3.0 μm according to the present invention absorbs infrared rays having a wavelength of 2.5 to 3.0 μm at a site other than a dissociable group of a hydrophilic group that imparts dispersion stability to an aqueous solvent. A site having a property is contained in the polymer.

  In addition, a dispersion in which a polymer dispersible in an aqueous solvent is covalently bonded to silica particles can also absorb infrared light having a wavelength of 2.5 to 3.0 μm at a site other than the dissociable group and can be dispersed in an aqueous solvent. A kind of polymer. In addition to the dissociable group of the polymer dispersible in the aqueous solvent, such a dispersion works favorably for drying because the silanol group on the silica surface absorbs a wavelength of 2.5 to 3.0 μm.

  The polymer that absorbs infrared rays having a wavelength of 2.5 to 3.0 μm and can be dispersed in an aqueous solvent at a site other than the dissociable group according to the present invention is preferably transparent. Such a polymer is not particularly limited as long as it is a medium capable of forming a film (polymer conductive layer 6). In addition, there is no particular limitation as long as there is no problem in bleed out to the surface of the transparent conductive film 1 and device performance when an organic EL device is laminated, but the polymer dispersion controls the surfactant (emulsifier) and the film forming temperature. It is preferable not to contain a plasticizer or the like.

  The pH of the polymer dispersion that can be dispersed in the aqueous solvent used in the production of the transparent conductive film 1 is compatible with the conductive polymer compound solution that is separately compatible, and the polymer and conductive polymer compound that can be dispersed in the aqueous solvent. From the viewpoint of the conductivity of the mixed liquid (dispersion liquid), it is preferably 0.1 to 11.0, more preferably 3.0 to 9.0, and even more preferably 4.0 to 7.0. It is.

  Examples of dissociable groups used in polymers dispersible in aqueous solvents include anionic groups (sulfonic acid and its salts, carboxylic acid and its salts, phosphoric acid and its salts, etc.), cationic groups (ammonium salts, etc.), etc. Is mentioned. The dissociable group is not particularly limited, but an anionic group is preferable from the viewpoint of compatibility with the conductive polymer solution. The amount of the dissociable group is not particularly limited as long as the polymer dispersible in the aqueous solvent is dispersible in the aqueous solvent, and is preferably as small as possible because the drying load is reduced appropriately in the process. In addition, the counter species used for the anionic group and the cationic group are not particularly limited, but from the viewpoint of performance when the organic EL element including the transparent conductive film 1 and the transparent conductive film 1 is laminated, it is hydrophobic and has a small amount. It is preferable that

  The main skeleton of the polymer dispersible in the aqueous solvent is polyethylene-polyvinyl alcohol (PVA), polyethylene-polyvinyl acetate, polyethylene-polyurethane, polyethylene-polyacrylic acid, polyethylene-polymethacrylic acid, polybutadiene, polybutadiene-polystyrene, polyolefin. Copolymer, polyamide (nylon), polyvinylidene chloride, polyester, polyester-urethane, polyester-acrylate, polyacrylate, polyacrylate copolymer, polymethacrylate, polymethacrylate copolymer, polyacrylate-polyester, polyacrylate-polystyrene , Polyvinyl acetate, polyurethane-polycarbonate, polyurethane-polyether, polyurethane-polyester, polyurethane-poly Acrylates, polyamides, polyacrylic - silica, polyacrylic - polystyrene - silica, silicone, silicone - polyurethane, silicone - polyacrylate, polyvinylidene fluoride - polyacrylates, fluoroolefin - polyvinyl ether. Of these, the main skeleton having no absorption at 2.5 to 3.0 μm can be converted into a polymer having an absorption at 2.5 to 3.0 μm by means of copolymerization, block or grafting. Among these, polyurethane-polycarbonate, polyamide, polyester-urethane, and polyacryl-polystyrene-silica are preferable.

  Commercially available products include Superflex 130 (polyurethane-polyether, manufactured by Daiichi Kogyo Seiyaku), Superflex 210, Superflex 620 (Polyurethane-polyester, manufactured by Daiichi Kogyo Seiyaku), Superflex 126, Superflex 150, Superflex 170, Superflex 300 (polyurethane-polyester-polyether, manufactured by Daiichi Kogyo Seiyaku), Superflex 420, Superflex 460, Superflex 470, Superflex 650 (Polyurethane-polycarbonate, manufactured by Daiichi Kogyo Seiyaku) , Pesresin WAC-14, WAC-17XC (urethane-modified polyester, manufactured by Takamatsu Yushi Co., Ltd.) Mobile 8020, Mobile 8030 (acrylic modified colloidal silica, Japan It can be used styrene-modified colloidal silica, manufactured by Nippon Synthetic Chemical Industry Co.) - manufactured by Synthetic Chemical Industry), Mowinyl 8055A (acrylic. In addition, the polymer dispersible in the aqueous solvent may contain one kind of those described above, or may contain a plurality of kinds.

<Infrared heater>
The infrared heater according to the present invention has an emission spectrum in an absorption band of 2.5 to 3.0 μm of a polymer dispersible in an aqueous solvent, and can irradiate infrared rays having a wavelength of 2.5 to 3.0 μm. Although there will be no limitation if possible, the infrared heater which has a filament temperature of 700-3000 degreeC is preferable. In particular, in order to reduce deformation when a polyester base material such as PET or PEN is used as the transparent resin base material 2, it is necessary to reduce light emission at a wavelength of 3.5 μm or more, and the following means can be mentioned.
(1) Use of an infrared heater that occupies most of the emission spectrum in the near infrared region (2) Use of an infrared heater with a reduced spectrum of 3.5 μm or more

  The infrared heater (1) will be described. Such an infrared heater has a function of generating infrared rays having a maximum wavelength of an emission spectrum in a range of 0.9 to 1.5 μm. By significantly shortening the maximum wavelength of the emission spectrum from the absorption wavelength of about 3.5 μm or more that the transparent resin substrate 2 has, the coating liquid can be dried without deforming the transparent resin substrate 2.

  According to Wien's displacement law, the maximum wavelength of the emitted infrared spectrum correlates with the temperature of the filament. In order to set the maximum wavelength of the emission spectrum, which is a requirement of the infrared heater (1), in the range of 0.9 to 1.5 μm, the filament temperature of the infrared heater is in the range of 3000 ° C. to 1600 ° C.

  In general, an infrared lamp uses a filament temperature of 1200 ° C. or less from the viewpoint of heat resistance of the filament and the tube protecting the filament. On the other hand, it is known in US Pat. No. 7,820,991, etc. that a high filament temperature can be maintained by optimizing the shape of the tube, the shape of the structure supporting the tube, and the cooling function. The present invention can utilize infrared rays generated in these hot filament temperature regions. Details of the infrared heater capable of generating infrared rays within the maximum wavelength range of 0.9 to 1.5 μm of the emission spectrum are described in the aforementioned US Pat. No. 7,820,991.

  When the maximum wavelength of the infrared emission spectrum is 0.9 μm or more, when the organic EL element 10 (see FIG. 5) is manufactured using the transparent conductive film 1 after drying, the possibility that dark spots are generated can be suppressed. In addition, it has been found that the light emission can be made uniform and the light emission lifetime is hardly deteriorated. The reason for this is not clear, but by setting the maximum wavelength of the spectrum to 0.9 μm or more, the filament temperature does not become high and deformation of the transparent resin substrate 2 is suppressed. It is considered that defects generated in the gas barrier layer 3 can be suppressed. The structure and manufacturing method of the organic EL element 10 will be described in Example 3.

  Moreover, when the maximum wavelength is 1.5 μm or less, it is possible to suppress the generation of dark spots, the deterioration of the light emission lifetime, and the like. Although this cause is not clear, it is considered that the conductive polymer layer 6 can be sufficiently dried by setting the maximum wavelength of the spectrum to 1.5 μm or less.

  The infrared heater (wavelength control infrared heater) of (2) will be described. As shown in FIG. 3, the wavelength-controlled infrared heater 20 has a cylindrical appearance, and has a configuration in which the filament 22, the protective tube 24, and the filters 26 and 28 are arranged concentrically in order from the center. ing. The control device 50 controls the filament 22 and controls the cooling mechanism 40 so that the refrigerant flows through the hollow portion between the filters 26 and 28.

  The wavelength control infrared heater 20 has a function of absorbing infrared rays having a wavelength of 3.5 μm or more. “Absorbing infrared rays having a wavelength of 3.5 μm or more” means that in the far infrared region having a wavelength of 3.5 μm or more, the infrared transmittance is 50% or less, preferably 40% or less, more preferably 30%. It means the following.

  Specifically, since the filters 26 and 28 themselves are heated by the filament 22 and become high temperature, the filters 26 and 28 themselves become infrared radiators and emit infrared rays having a longer wavelength than the infrared rays emitted by the filaments 22. However, in the wavelength control infrared heater 20, the refrigerant (for example, cooling air) flows through the hollow portion 30 between the filters 26 and 28, and the cooling function reduces the surface temperature of the filters 26 and 28, Secondary radiation emitted from the filters 26 and 28 can be suppressed. As a result, the wavelength control infrared heater 20 can cut far infrared rays having a wavelength of 3.5 μm or more, which the transparent resin base material 2 has absorptivity. And the coating liquid which is a to-be-dried material is selectively irradiated with infrared rays (near infrared rays) having a wavelength of less than 3.5 μm which is an absorption region of the solvent, thereby applying the coating while suppressing the deformation of the transparent resin substrate 2. The polymer conductive layer 6 can be obtained by drying the liquid.

  Examples of the material of the filters 26 and 28 include quartz glass and borosilicate glass, and quartz glass is preferable from the viewpoint of heat resistance and thermal shock resistance. The thickness and number of the filters 26 and 28 can be appropriately selected and changed according to the necessary infrared spectrum. As described above, the cooling function can be realized by hollowly doubling or multiply laminating wavelength control filters and allowing air to flow through the hollow portion therebetween.

  As described above, the shape of the filters 26 and 28 may cover the entire columnar filament 22 concentrically. As shown in FIG. 4, the three directions of the filament 22 (and the protective tube 24) are reflected on the reflector. The filters 26 and 28 which are covered with 32 and have a flat plate shape on the infrared radiation surface side may be arranged in parallel.

  In the case of a multiple structure in which another filter is arranged in addition to the filters 26 and 28, it is preferable from the viewpoint of cooling efficiency that cooling air is circulated in opposite directions between the hollow portions between the filters. Further, the cooling air on the discharge side may be discharged out of the system, or may be used as part of hot air used in the drying process.

  According to Wien's displacement law, when the filament temperature is raised, the dominant wavelength of the emitted infrared spectrum becomes less than 3.5 μm, which corresponds to the absorption region of the solvent. Is preferably 700 ° C. or higher, and preferably 3000 ° C. or lower from the viewpoint of heat resistance of the filament 22. The wavelength control infrared heater 20 can increase the infrared radiation energy corresponding to the absorption region of these solvents according to the filament temperature. The filament temperature can be appropriately selected and changed depending on the desired coating and drying conditions.

  The surface temperature of the outermost filter 28 disposed on the object to be dried is preferably 200 ° C. or less, and more preferably 150 ° C. or less, from the viewpoint of suppressing secondary radiation due to its own infrared absorption. Such a surface temperature can be adjusted by flowing air into the hollow portion between the filters laminated in a double layer or multiple layers.

  In the infrared irradiation step, that is, the drying step, the drying zone is composed (covered) with a material having high infrared reflectivity, whereby infrared rays that are not absorbed by the material to be dried can be used with high efficiency.

  As shown in FIGS. 3 and 4, the wavelength control infrared heater 20 is connected to a cooling mechanism 40 for circulating (circulating) the refrigerant in the hollow portion 30 so that the refrigerant can be circulated. The control device 50 is electrically connected to 22. In such a system, the control device 50 controls the amount of refrigerant flowing into the hollow portion 30 by the cooling mechanism 40, the heat generation temperature of the filament 22, and the like.

<Conductive polymer compound>
In the present invention, “conductive” refers to a state in which electricity flows, and the sheet resistance measured by a method in accordance with JIS K 7194 “Resistivity Test Method by Conductive Plastic Four-Probe Method” is 1 ×. It means lower than 10 ⁸ Ω / □.

  In the present invention, the conductive polymer compound which is a polymer having conductivity is preferably a conductive polymer compound having a cationic π-conjugated conductive polymer and a polyanion. Such a conductive polymer compound can be easily obtained by chemical oxidative polymerization of a precursor monomer that forms a cationic π-conjugated conductive polymer, which will be described later, in the presence of an appropriate oxidizing agent and an oxidation catalyst, and a polyanion, which will be described later. Can be manufactured.

(Cationic π-conjugated conductive polymer)
In the present invention, the cationic π-conjugated conductive polymer is not particularly limited, and includes polythiophenes (including basic polythiophenes, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, and polyacetylenes. A chain conductive polymer of polyfurans, polyparaphenylene vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, or polythiazyl compounds can be used. As the cationic π-conjugated conductive polymer, polythiophenes or polyanilines are preferable, and polyethylenedioxythiophene is more preferable from the viewpoints of conductivity, transparency, stability, and the like.

(Cationic π-conjugated conductive polymer precursor monomer)
In the present invention, a precursor monomer used for forming a cationic π-conjugated conductive polymer has a π-conjugated system in the molecule, and the main monomer even when polymerized by the action of an appropriate oxidizing agent. A π-conjugated system is formed in the chain. Examples of such precursor monomers 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)
In the present invention, the polyanion used in the conductive polymer compound is substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenylene, substituted or unsubstituted polyimide, substituted or unsubstituted polyamide, substituted or unsubstituted. The polyester and any of these copolymers are preferably composed of a structural unit having an anionic group and a structural unit having no anionic group.

This polyanion is a solubilized polymer that solubilizes a cationic π-conjugated conductive polymer compound in a solvent. The anion group of the polyanion functions as a dopant for the cationic π-conjugated conductive polymer compound, and improves the conductivity and heat resistance of the cationic π-conjugated conductive polymer compound. In addition, the polyanion is used in an excess amount with respect to the cationic π-conjugated conductive polymer compound, so that the dispersibility of the conductive polymer compound particles composed of the cationic π-conjugated conductive polymer compound and the polyanion and It also has a function of improving film forming properties.
The anion group of the polyanion may be a functional group that can cause chemical oxidation doping to the cationic π-conjugated conductive polymer compound. As such an anion group, a mono-substituted sulfate group, a mono-substituted phosphate group, a phosphate group, a carboxy group, a sulfo group and the like are preferable from the viewpoint of ease of production and stability. Further, as the anionic group, a sulfo group, a monosubstituted sulfate group, or a carboxy group is more preferable from the viewpoint of the doping effect of the functional group on the cationic π-conjugated conductive polymer compound.

  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. . Moreover, these homopolymers may be sufficient as a polyanion, and 2 or more types of copolymers may be sufficient as it.

  Further, the polyanion may further have F (fluorine atom) in the compound. Specific examples of such a polyanion include Nafion (manufactured by Dupont) containing a perfluorosulfonic acid group, and Flemion (manufactured by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group.

  Among these, when a compound having a sulfonic acid as a polyanion is used, a conductive polymer-containing layer (second conductive layer 6 in FIG. 1) is formed by coating and drying with an infrared heater, and then further 100 to 120 ° C. Then, after applying a heat drying treatment for 5 minutes or more, irradiation with microwaves, near infrared light, or the like may be performed. In some cases, heat drying may be omitted, and only irradiation with microwaves, near infrared light, or the like may be performed.

  Furthermore, among the compounds having sulfonic acid, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyethyl acrylate sulfonic acid, or polybutyl acrylate sulfonate is preferable.

  The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units from the viewpoint of dispersibility of the conductive polymer compound, and from the viewpoint of solvent solubility and conductivity, it is preferably 50 to 10,000. A range is more preferred.

  Examples of the polyanion production method 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 polymerizable monomer. And the like.

  As a method for producing a polyanion by polymerization of an anionic group-containing polymerizable monomer, 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. Can be mentioned. 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, a polymerizable monomer having no anionic group may be copolymerized with the anionic group-containing polymerizable monomer.

  In addition, when the obtained polymer is a salt of a polyanion, it is preferable to change the acid to a polyanion acid. Examples of methods for transforming polyanion salts into polyanionic acids include ion exchange methods using ion exchange resins, dialysis methods, ultrafiltration methods, etc. Among these, ultrafiltration is used because it is easy to work with. The method is preferred.

  The ratio between the cationic π-conjugated conductive polymer contained in the conductive polymer compound and the polyanion constituting the conductive polymer compound, that is, the weight ratio of the polyanion to the cationic π-conjugated conductive polymer From the viewpoints of properties and dispersibility, 0.5 or more and less than 25 are preferable.

  If the weight ratio of the polyanion to the cationic π-conjugated conductive polymer is less than 25, in addition to improving the conductivity, the amount of water retained by the hydrophilic polyanion or the conductive polymer compound is Thus, the storability of the conductive film and the organic EL element using the conductive film is improved. If the weight ratio is 0.5 or more, the resistance of the conductive polymer compound decreases as the dopant increases, and the effect of the polyanion acting as a protective colloid increases, and the stability of the particles Is improved and the particle size is suppressed. Thus, from the viewpoint of the storage stability of the electroconductivity, particle stability, the conductive film and the organic electroluminescence device using the conductive film, the weight ratio of the polyanion to the cationic π-conjugated conductive polymer is 0.5. More than 25 is preferable.

  Examples of a method for setting the weight ratio of the polyanion to the cationic π-conjugated conductive polymer to a desired value include a method of adjusting the amount of polyanion used during the synthesis of the conductive polymer compound. In this method, if the weight ratio of polyanion is 1.0 or less with respect to the cationic π-conjugated conductive polymer, the conductive polymer compound particles tend to be large. Sometimes other polymer compounds can be used in combination. The polymer compound that can be used in combination is not particularly limited as long as the conductive compound particles are stabilized and the transmittance and conductivity are not deteriorated, but polyacryl such as 2-hydroxyethyl acrylate, or a dissociative group An aqueous dispersion polymer such as a contained self-dispersing polymer is preferred. Also, water in commercially available PEDOT / PSS is removed by drying, azeotropic removal with toluene, or pulverized by a known method such as freeze-drying, then washed with water, PSS is removed, and PSS is removed by ultrafiltration. A method of replacing with water can be used.

As an oxidant used when obtaining a conductive polymer according to the present invention by chemical oxidative polymerization of a precursor monomer that forms a cationic π-conjugated conductive polymer in the presence of a polyanion, for example, J. et al. Am. Soc. 85, 454 (1963), and any oxidizing agent suitable for oxidative polymerization of pyrrole. Such oxidants include, for practical reasons, cheap and easy to handle oxidants such as iron (III) salts (eg FeCl ₃ , Fe (ClO ₄ ) ₃ , organic acids and inorganic acids containing organic residues). Iron (III) salt), hydrogen peroxide, potassium dichromate, alkali persulfate (eg, potassium persulfate, sodium persulfate), ammonium, alkali perborate, potassium permanganate, or copper salts (eg, tetrafluoride). It is preferable to use copper borate). In addition, air or oxygen in the presence of catalytic amounts of metal ions (for example, iron ions, cobalt ions, nickel ions, molybdenum ions, vanadium ions) can be used as an oxidizing agent. Among these, the use of persulfate, iron (III) salts of inorganic acids including organic acids, or iron (III) salts of inorganic acids including organic residues has great application advantages.

  Examples of the iron (III) salt of an inorganic acid containing an organic residue include iron (III) salts of sulfuric acid half esters of alkanols having 1 to 20 carbon atoms (for example, lauryl sulfate), alkyl sulfonic acids having 1 to 20 carbon atoms. (For example, methane, dodecanesulfonic acid), carboxylic acid having 1 to 20 aliphatic carbon atoms (for example, 2-ethylhexylcarboxylic acid), aliphatic perfluorocarboxylic acid (for example, trifluoroacetic acid, perfluorooctanoic acid), aliphatic dicarboxylic acid Acids (eg oxalic acid), in particular aromatic, optionally alkyl substituted sulfonic acids having 1 to 20 carbon atoms (eg Fe (III) salts of benzesenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid) Is mentioned.

  A commercially available material can also be preferably used as such a conductive polymer compound. For example, a conductive polymer (abbreviated as PEDOT-PSS) composed of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid is a Clevios series from Helios, and PEDOT-PSS 483095 and 560596 from Aldrich. , Commercially available 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 as the conductive polymer compound.

  The conductive polymer compound may contain an organic compound as the second dopant. There is no restriction | limiting in particular in the 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 hydroxy group-containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound. Examples of the hydroxy 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.

[Dispersion formed from conductive polymer compound and polymer dispersible in aqueous solvent]
The dispersion containing the conductive polymer compound and the polymer dispersible in the aqueous solvent according to the present invention is a liquid in which the conductive polymer compound and the polymer dispersible in the aqueous solvent are dispersed in the aqueous solvent. . The aqueous solvent is not only pure water (including distilled water and deionized water), but also an aqueous solution containing acid, alkali, salt, etc., a water-containing organic solvent, or a hydrophilic organic solvent. Examples of the aqueous solvent include pure water (including distilled water and deionized water), alcohol solvents such as methanol and ethanol, and mixed solvents of water and alcohol.

  The dispersion according to the present invention is preferably transparent and is not particularly limited as long as it is a medium for forming a film. Further, there is no particular limitation as long as there is no problem in the device performance when the bleed-out to the surface of the transparent conductive film 1 and the organic electronic device are laminated, but the dispersion is not limited to a surfactant (emulsifier) or a structure for assisting micelle formation. It is preferable not to include a plasticizer or the like for controlling the film temperature.

  The pH of the dispersion according to the present invention is not particularly problematic as long as desired conductivity is obtained, but is preferably 0.1 to 7.0, and more preferably 0.3 to 5.0. When the pH of the dispersion is 0.1 or more, more preferably 0.3 or more, the polymer can be suitably prevented from being decomposed during drying. Moreover, if the pH of the dispersion is 7.0 or less, more preferably 5.0 or less, the sheet resistance deterioration of the conductive film due to the reduced function of the dopant is suitably prevented by preventing the neutralization of PEDOT / PSS. be able to.

  In order to control the surface tension of the dispersion according to the present invention, an organic solvent may be added to the dispersion. The organic solvent is not particularly limited as long as a desired surface tension can be obtained, but a monovalent, divalent or polyvalent alcohol solvent is preferable. The boiling point of the organic solvent is preferably 200 ° C. or lower, more preferably 150 ° C. or lower. If the boiling point of the organic solvent is 200 ° C. or lower, more preferably 150 ° C. or lower, the residual solvent in the film can be suitably reduced in short-time drying.

  The size (average particle size) after dispersion treatment of the conductive polymer compound after dispersion treatment and the polymer dispersible in an aqueous solvent contained in the dispersion according to the present invention is preferably 1 to 100 nm, and more Preferably it is 3-80 nm, More preferably, it is 5-50 nm. If the size of the particles in the dispersion is 100 nm or less, the haze and smoothness (surface roughness (Ra)) of the second conductive layer (conductive layer) 13 generated by applying the dispersion to the substrate 11. ) And the performance of the organic electroluminescence device is improved. Further, if the size of the particles in the dispersion is 1 nm or more, the occurrence of aggregation between the particles is suppressed and the dispersibility of the dispersion is improved. As a result, the haze of the second conductive layer (conductive layer) 13 and Smoothness (surface roughness (Ra)) is improved. In order to improve the smoothness during film formation, the size of the particles in the dispersion is more preferably 3 to 80 nm, and further preferably 5 to 50 nm. In addition, even if the average particle size is controlled, if the film forming temperature of the polymer that can be dispersed in the aqueous solvent used is too high, the film shape does not form within the drying temperature, and the particle shape remains and the average roughness of the film surface is reduced. Since the film may deteriorate, it is desirable to control the film forming temperature.

  Examples of a method for setting the average particle size of the dispersion to a desired range include a homogenizer, an ultrasonic disperser (US disperser), a dispersion technique using a ball mill, a reverse osmosis membrane, an ultrafiltration membrane, and a microfiltration membrane. The classification of the used particles can be used. Dispersion techniques using a homogenizer, an ultrasonic disperser (US disperser), a ball mill, etc. all tend to increase particles at high temperatures. Therefore, the temperature during the dispersion operation is preferably -10 ° C to 50 ° C. It is below, More preferably, it is higher than 0 degreeC and less than 30 degreeC. In the case of a dispersion operation by a large shearing force that cuts the polymer, the temperature of the dispersion liquid tends to be high, and the conjugated system of the conductive polymer is broken by heat, which may cause performance deterioration. As a result, when the temperature exceeds 50 ° C., the particle size tends to be small, but the sheet resistance of the second conductive layer (conductive layer) 13 generated by the dispersion may increase. In addition, when an organic solvent is contained in the aqueous solvent, even when the temperature is 0 ° C. or lower (for example, −10 ° C. or higher and 0 ° C. or lower), the dispersion operation can be suitably performed unless the solvent solidifies. It is. Further, since the dispersion is water-rich, the viscosity increases at 0 ° C. or lower, and a load is applied to the stirring. Further, if the temperature is 30 degrees or more, the solvent is evaporated and the dispersion concentration is likely to fluctuate. As a result, the performance of the conductive film 13 may be affected. Classification is not particularly limited as long as a membrane to be used is selected as necessary.

  The polymer particles dispersible in the aqueous solvent and the conductive polymer compound particles in the dispersion according to the present invention are in a state in which the respective particles are dispersed independently, and the particle size of each particle size is It may be a sum, or particles having different compositions may be aggregated. Further, particles having different compositions may be partially mixed during the dispersion operation, or may be completely mixed to form particles.

  The amount (solid content) of the polymer dispersible in the aqueous solvent according to the present invention is preferably 50 to 5000 mass%, more preferably 100 to 3500 mass%, based on the solid content of the conductive polymer compound. Yes, more preferably 200 to 2000% by weight. Here, it is more preferable that the amount of the polymer dispersible in the aqueous solvent is 50 to 5000% by mass with respect to the conductive polymer compound. (The conductive polymer compound absorbs light in the visible light region, so in order to improve the transmittance, it is desirable to reduce the conductive polymer compound as much as possible without reducing the conductivity.) If it exists, it is because the suitable electroconductivity is acquired, without the ratio of a conductive polymer compound becoming small too much. As described above, in order to obtain the effect of improving the transmittance and prevent the decrease in conductivity, the amount of the polymer (for example, polyolefin copolymer) dispersible in the aqueous solvent can be used with respect to the conductive polymer compound. More preferably, it is 100-3500 mass%, and it is further more preferable that it is 200-2000 mass% with respect to a conductive polymer compound.

  The particle size measurement method of the dispersion according to the present invention is not particularly limited, but is preferably a dynamic light scattering method, a laser diffraction method or an image imaging method, and more preferably a dynamic light scattering method. Since the particle diameter of the polymer particles and the conductive polymer compound particles dispersible in the aqueous solvent becomes unstable due to dilution, a concentrated system particle size measuring machine that can measure as it is without diluting the solvent is preferable, Examples of such a thick particle size analyzer include a thick particle size analyzer (manufactured by Otsuka Electronics Co., Ltd.), a zeta sizer nano series (manufactured by Malvern), and the like.

  Fine particles may be added to the dispersion according to the present invention. These fine particles are made of a polymer that can be dispersed in the aqueous solvent constituting the organic compound layer from the viewpoint of reducing the drying load and suppressing the film thickness of the organic compound layer. It is preferably used in replacement. The amount of the fine particles used is preferably 25 to 75% by mass in terms of solid content based on the polymer dispersible in the aqueous solvent, and more preferably 30 to 60% by mass based on the conductive polymer compound. Here, the reason why the amount of the polymer dispersible in the aqueous solvent is preferably 25 to 75% by mass with respect to the conductive polymer is that if it is 25% by mass or more, the drying load reduction effect is sufficient, If it is 75% by mass or less, the film physical properties of the organic compound layer are improved. Thus, in order to obtain a drying load reduction effect and prevent a decrease in film physical properties of the organic compound layer, the amount of the fine particles used is 25 to 75% by mass in terms of solid content with respect to the polymer dispersible in the aqueous solvent. It is more preferable.

(Metal material)
As shown in FIG. 1, a conductive film 1 according to an embodiment of the present invention is a conductive layer (second conductive layer 6 in FIG. 1) containing a conductive polymer compound and a polymer dispersible in an aqueous solvent. In addition, it has a metal material-containing conductive layer (first conductive layer 4 in FIG. 1) formed in a pattern on the substrate 2.

  The metal material is not particularly limited as long as it has conductivity, and may be an alloy in addition to a metal such as gold, silver, copper, iron, nickel, or chromium. In particular, from the viewpoint of ease of pattern formation as described later, the shape of the metal material is preferably metal fine particles or metal nanowires, and the metal material is preferably silver from the viewpoint of conductivity.

  In order to constitute the transparent conductive film 1, the first conductive layer 4 according to the present invention is formed on the transparent substrate 2 so as to exhibit a pattern shape having an opening 2a. The opening part 2a is a part which does not have a metal material on the transparent base material 2, and is a translucent window part. Although there is no restriction | limiting in particular in a pattern shape, For example, it is preferable that they are stripe shape, mesh shape, or random mesh shape. The ratio of the opening 2a to the entire surface of the transparent conductive film 1, that is, the opening ratio, is preferably 80% or more from the viewpoint of transparency. The aperture ratio is the ratio of the portion excluding the light-impermeable conductive part (first conductive layer 4) on the surface of the transparent substrate 2 to the whole. For example, when the light-impermeable conductive portion is striped or meshed, the aperture ratio of the striped pattern having a line width of 100 μm and a line interval of 1 mm is about 90%.

  The line width of the pattern is preferably 10 to 200 μm from the viewpoint of transparency and conductivity. If the line width of the fine line is 10 μm or more, desired conductivity can be obtained, and if the line width of the fine line is 200 μm or less, desired transparency can be obtained. The height of the thin wire is preferably 0.1 to 10 μm. If the height of the fine wire is 0.1 μm or more, desired conductivity is obtained, and if the height of the fine wire is 10 μm or less, current leakage and functional layer thickness distribution in the formation of an organic electronic device Defects are prevented.

  There is no restriction | limiting in particular as a method of forming the stripe-shaped or mesh-shaped 1st conductive layer 4, A conventionally well-known method can be utilized. For example, it can be formed by forming a metal layer on the entire surface of the transparent substrate 2 and applying a known photolithography method to the metal layer. Specifically, a metal layer is formed on the entire surface of the transparent substrate 2 by using one or more physical or chemical forming methods such as printing, vapor deposition, sputtering, and plating, or a metal foil is bonded. After laminating on the transparent substrate 2 with an agent, the first conductive layer 4 processed into a desired stripe shape or mesh shape can be obtained by etching using a known photolithography method. The metal species is not particularly limited as long as it can be energized, and copper, iron, cobalt, gold, silver, and the like can be used. From the viewpoint of conductivity, silver or copper is preferable, and silver is more preferable. It is.

  As another method, a method of printing an ink containing metal fine particles in a desired shape by screen printing, a method of applying a plating catalyst ink in a desired shape by gravure printing or an inkjet method, or a plating process, or A method using silver salt photography technology is mentioned.

  A technique using silver salt photography technology can be implemented with reference to, for example, [0076]-[0112] of Japanese Patent Application Laid-Open No. 2009-140750 and Examples. Further, a method for carrying out a plating process by gravure printing of the catalyst ink can be carried out with reference to, for example, Japanese Patent Application Laid-Open No. 2007-281290.

  In addition, as a random network structure, for example, as described in JP 2005-530005 A, a random network structure of conductive fine particles is spontaneously formed by coating and drying a liquid containing metal fine particles. Techniques for forming can be used. As another method, for example, as described in JP-T-2009-505358, a coating solution (dispersion) containing metal nanowires is applied and dried to form a random network structure of metal nanowires. Techniques to form are available.

  The metal nanowire refers to a fibrous structure having a metal element as a main component. In particular, 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.

As a metal nanowire, in order to form a long conductive path with one metal nanowire, the average length is preferably 3 μm or more, and more preferably 3 to 500 μm. If the length of the metal nanowire is 500 μm or less, one wire spreads well and is arranged without overlapping with other wires. As a result, the film thickness of the first conductive layer 4 is suppressed, and the thinning is achieved. As a result, the transmittance is improved. Moreover, if the length of metal nanowire is 3 micrometers or more, the contact of metal nanowire will increase and desired sheet resistance and transmittance | permeability will be obtained, suppressing the addition amount of metal nanowire. In addition, the relative standard deviation of the length is preferably 40% or less. This is because if the relative standard deviation of the length is 40% or less, the film thickness unevenness of the first conductive layer 4 and the decrease in the sheet resistance uniformity are prevented. 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. Therefore, 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. This is because if the relative standard deviation of the minor axis is 20% or less, the occurrence of unevenness in the film thickness of the first conductive layer 4 is suppressed, and the occurrence of unevenness in luminance of the organic EL element is suppressed. The basis weight of the metal nanowire is preferably 0.02 to 0.5 g / m ² . If the basis weight of the metal nanowire is 0.02 g / m ² or more, a desired sheet resistance is obtained, and if the basis weight is 0.5 g / m ² or less, desired sheet resistance and transmittance are obtained. The weight of the metal nanowire is more preferably 0.03 to 0.2 g / m ² from the viewpoint of sheet resistance and transmittance.

Examples of the metal used for the metal nanowire include copper, iron, cobalt, gold, silver and the like, and silver is preferable from the viewpoint of conductivity. In addition, although a single metal may be used, in order to achieve both conductivity and stability (sulfurization resistance, oxidation resistance, and migration resistance of metal nanowires), the metal as the main component and one or more other types are used. These metals may be included in any proportion.
There is no restriction | limiting in particular in the manufacturing method of metal nanowire, For example, well-known methods, such as a liquid phase method and a gaseous-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, 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. In particular, the method for producing silver nanowires disclosed in the above-mentioned literature can easily produce silver nanowires in an aqueous solution, and the electrical conductivity of silver is the highest among metals, so it is preferably applied to the present invention. can do.

  In addition, the surface specific resistance of the thin wire portion (first conductive layer 4) formed from a metal material is preferably 100Ω / □ or less, and more preferably 20Ω / □ or less from the viewpoint of increasing the area. . The surface specific resistance can be measured based on, for example, JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.

  Moreover, it is preferable that the thin wire | line part (1st conductive layer 4) formed from a metal material is heat-processed in the range which does not damage the transparent base material 2. FIG. As a result, fusion between the metal fine particles and the metal nanowires proceeds, and the fine wire portion formed from the metal material becomes highly conductive.

(Transparent substrate)
The transparent substrate 2 is a plate-like body that can carry the conductive layers 4 and 6, and in order to obtain the transparent conductive film 1, JIS K 7361-1: 1997 (Plastic-Transparent Material Total Light Transmittance Test Preferably, those having a total light transmittance of 80% or more in the visible light wavelength region measured by a method based on (Method) are preferably used.

  As the transparent substrate 2, a material that is excellent in flexibility, has a sufficiently low dielectric loss coefficient, and is a material that absorbs microwaves smaller than the conductive layers 4 and 6 is preferably used. As the transparent base material 2, for example, a resin substrate, a resin film, and the like are preferably used, but it is preferable to use a transparent resin film from the viewpoint of productivity and performance such as lightness and flexibility. The transparent resin film is a film having a total light transmittance of 50% or more measured in a visible light wavelength region measured by a method in accordance with JIS K 7361-1: 1997 (a test method for total light transmittance of plastic-transparent material). Say.

  There is no restriction | limiting in particular in the transparent resin film which can be used preferably, About the material, a shape, a structure, thickness, etc., it can select suitably from well-known things. Examples of such transparent resin films include polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate, and modified polyester, polyethylene (PE) resin films, polypropylene (PP) resin films, polystyrene resin films, and cyclic olefin resins. Polyolefin resin films such as polyvinyl chloride, polyvinyl resin such as polyvinyl chloride, polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate ( PC) resin film, polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, etc. .

  If it is a resin film whose above-mentioned total light transmittance is 80% or more, it is preferably used as a film base material used as the transparent base material 2 of this invention. The film substrate is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film or a polycarbonate film from the viewpoint of transparency, heat resistance, ease of handling, strength and cost. An axially stretched polyethylene terephthalate film or a biaxially stretched polyethylene naphthalate film is more preferred.

  In order to ensure the wettability and adhesiveness of a coating liquid (dispersion), the film base material of the transparent base material 2 used for this invention can give a surface treatment, or can provide 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. 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, an inorganic film, an organic film, or a hybrid film of both of them may be formed on the front or back surface of the film base material. The film substrate on which such a film is formed conforms to JIS K 7129-1992. It is a barrier film having a water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a compliant method of 1 × 10 ⁻³ g / (m ² · 24 h) or less. Further, the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less, water vapor permeability (25 ± 0.5 ° C., relative The humidity (90 ± 2)% RH) is preferably a high barrier film having a value of 1 × 10 ⁻³ g / (m ² · 24 h) or less.

  As a material for forming a barrier film formed on the front surface or back surface of the film base material in order to obtain a high barrier film, any material may be used as long as it has a function of suppressing intrusion of the element such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Furthermore, in order to improve the brittleness of the barrier film, it is more preferable to have a laminated structure of these inorganic layers and layers formed from organic materials. Although there is no restriction | limiting in particular about the lamination order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

(Coating, heating, drying)
The second conductive layer 6 of the present invention is obtained by applying a coating liquid (dispersion liquid) containing the above-described conductive polymer compound and a polymer dispersible in an aqueous solvent onto the transparent substrate 2, heating and drying. It is formed by doing. When the transparent conductive film 1 has a fine line portion formed from a metal material as the first conductive layer 4, the above-described coating liquid is applied onto the transparent substrate 2 on which the fine line portion formed from the metal material is formed. The second conductive layer 6 is formed by heating and drying using an infrared heater. Here, the 2nd conductive layer 6 should just be electrically connected with the metal fine wire part which is the 1st conductive layer 4, and may fully coat | cover the patterned metal fine wire part, or a metal fine wire A part of the part may be covered, or may be in contact with the fine metal wire part.

  In addition to the printing methods such as the gravure printing method, flexographic printing method, and screen printing method, the coating of the coating liquid formed from the conductive polymer compound and the polymer dispersible in the aqueous solvent can be performed by a roll coating method or a bar coating method. Coating method such as 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, inkjet method, etc. Can be used.

  In addition, the transparent conductive film 1 in which the second conductive layer 6 containing a conductive polymer compound and a polymer dispersible in an aqueous solvent is coated or in contact with a part of the thin metal wire portion (first conductive layer 4) is provided. As a manufacturing method, the first conductive layer 4 is formed on the transfer film by the above-described method, and the second conductive layer 6 containing a conductive polymer compound and a polymer dispersible in an aqueous solvent is described later. A method of transferring the laminated layer to the transparent substrate 2 described above is exemplified.

  In addition, as a method for producing the transparent conductive film 1, a conductive polymer compound and a polymer dispersible in an aqueous solvent are contained in the non-conductive portion (opening portion) of the thin metal wire portion by a known method such as an inkjet method. Examples include a method of forming the second conductive layer 6.

  The second conductive layer 6 containing a conductive polymer compound and a polymer dispersible in an aqueous solvent is a conductive polymer in which the weight ratio of the polyanion to the cationic π-conjugated polymer is less than 0.5 to 2.5. It is preferable to include a compound. Thereby, high electroconductivity, high transparency, and strong film | membrane intensity | strength can be obtained.

  By forming the conductive layers 4 and 6 of the present invention having such a structure, a high conductivity that cannot be obtained by a metal or metal oxide fine wire or a conductive polymer layer alone can be obtained. Can be obtained uniformly.

  The dry film thickness of the second conductive layer 6 is preferably 30 to 2000 nm from the viewpoint of surface smoothness and transparency, more preferably 100 nm or more from the viewpoint of conductivity, and the surface of the conductive film 1. From the viewpoint of smoothness, it is more preferably 200 nm or more. The dry film thickness of the second conductive layer 6 is more preferably 1000 nm or less from the viewpoint of transparency.

  The second conductive layer 6 is formed by applying an application liquid (dispersion liquid) containing a conductive polymer compound and a polymer dispersible in an aqueous solvent, and then applying infrared irradiation. Here, in addition to the drying process by infrared irradiation, other drying processes can be performed. Although there is no restriction | limiting in particular as conditions of the drying process used together with infrared irradiation, The heat drying process in the temperature of the range which does not damage the transparent base material 2 and the conductive layers 4 and 6 can be used together, for example, 80-120. Heat drying treatment can be performed at 10 ° C. for 10 seconds to 10 minutes. This heat drying treatment may be performed before or after the drying treatment by infrared irradiation.

  The coating liquid described above contains, as additives, plasticizers, stabilizers (antioxidants, antioxidants, etc.), surfactants, dissolution accelerators, polymerization inhibitors, colorants (dyes, pigments, etc.) and the like. May be. Furthermore, from the viewpoint of improving workability such as coating properties, the coating liquid described above is a solvent (for example, water, alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons). Or other organic solvents).

  In the present invention, Ry and Ra representing the smoothness of the surface of the second conductive layer 6 which is a conductive layer are Ry = maximum height (the difference in height between the top and bottom of the surface) and Ra = arithmetic mean roughness. This is a value according to the surface roughness defined in JIS B601 (1994). In the conductive film 1 according to the present invention, the surface smoothness of the second conductive layer 13 that is a conductive layer is Ry ≦ 50 nm and the second conductive layer 13 that is a conductive layer has a smoothness from the viewpoint of improving conductivity. The surface smoothness is preferably Ra ≦ 10 nm. In the present invention, a commercially available atomic force microscope (AFM) can be used for the measurement of Ry and Ra. For example, it can be measured by the following method.

  Using an SPI 3800N probe station manufactured by Seiko Instruments Inc. and a SPA400 multifunctional unit as the AFM, set a sample cut to a size of about 1 cm square on a horizontal sample table on a piezo scanner, and place the cantilever on the sample surface. When approaching and reaching the region where the atomic force works, 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 Ry is more preferably 50 nm or less, and further preferably 40 nm or less, from the viewpoint of improving conductivity. Similarly, the value of Ra is more preferably 10 nm or less, and further preferably 5 nm or less, from the viewpoint of improving conductivity.

In the present invention, the conductive film 1 preferably has a total light transmittance of 60% or more, more preferably 70% or more, and further preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like. In addition, the electrical resistance value of the second conductive layer 13 which is a conductive layer in the conductive film 1 of the present invention is preferably 1000Ω / □ or less as the surface resistivity from the viewpoint of performance improvement, and is 100Ω / □ or less. More preferably. Furthermore, in order to apply the conductive film 1 to a current-driven optoelectronic device, the surface resistivity is preferably 50Ω / □ or less from the viewpoint of improving the performance when applied to a current-driven optoelectronic device. More preferably, it is 10Ω / □ or less. That is, when the surface resistivity is 10 ³ Ω / □ or less, the conductive film 1 can preferably function as an electrode in various optoelectronic devices. The above-mentioned surface resistivity can be measured in accordance with, for example, JIS K 7194: 1994 (resistivity test method by conductive probe four-probe method) or the like, or using a commercially available surface resistivity meter. It can be easily measured.

There is no restriction | limiting in particular in the thickness of the transparent conductive film 1 which concerns on this invention, Although it can select suitably according to the objective, Generally it is preferable that it is 10 micrometers or less, and transparency and a softness | flexibility are so thin that thickness is thin. It is more preferable because it improves.
<Organic EL device>
An organic EL device according to an embodiment of the present invention includes a transparent conductive film 1 as an electrode, and includes an organic layer including an organic light emitting layer and the transparent conductive film 1. The organic EL element according to the embodiment of the present invention preferably includes the transparent conductive film 1 as an anode, and the organic light-emitting layer and the cathode are arbitrarily selected from materials, configurations, and the like generally used for the organic EL element. Things can be used.

  The element configuration of the organic EL element is as follows: 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, etc. it can.

  In the present invention, the light emitting material or doping material that can be used in the organic light emitting layer includes anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bis. Benzoxazoline, bisstyryl, cyclopentadiene, quinoline metal complex, tris (8-hydroxyquinolinato) aluminum complex, tris (4-methyl-8-quinolinato) aluminum complex, tris (5-phenyl-8-quinolinato) aluminum complex , Aminoquinoline metal complex, benzoquinoline metal complex, tri- (p-terphenyl-4-yl) amine, 1-aryl-2,5-di (2-thienyl) pyrrole derivative, pyran, quinacridone Rubrene, distyrylbenzene derivatives, di still arylene derivatives, various fluorescent dyes, rare earth metal complex, but phosphorescent material and the like, but is not limited thereto. Moreover, it is preferable to contain 90-99.5 mass parts of luminescent materials selected from these compounds, and 0.5-10 mass parts of doping materials. An organic light emitting layer is manufactured by well-known methods, such as vapor deposition, application | coating, transcription | transfer, using the above-mentioned material. The thickness of the organic light emitting layer is preferably 0.5 to 500 nm and more preferably 0.5 to 200 nm from the viewpoint of light emission efficiency.

<< Configuration of Organic EL Element and Manufacturing Method Thereof >>
As shown in FIG. 5, the organic EL element 10 has a transparent electrode 1 composed of a transparent resin substrate 2, a metal conductive layer 4, and a polymer conductive layer 6.
An extraction electrode 12 is formed on the side edge of the transparent resin substrate 2 of the transparent electrode 1.
The extraction electrode 12 is in contact with the metal conductive layer 4 and the polymer conductive layer 6 and is electrically connected to these members. An organic functional layer 14 is formed on the polymer conductive layer 6 of the transparent electrode 1. The organic functional layer 14 includes a hole transport layer, a light emitting layer, a hole block layer, an electron transport layer, and the like. A counter electrode 16 is formed on the organic functional layer 14. The counter electrode 16 is an electrode facing the transparent electrode 1 and has a polarity opposite to that of the transparent electrode 1.

  In the organic EL element 10, the extraction electrode 12 is partly exposed and sealed by the sealing member 18, and the sealing member 18 covers and protects the transparent electrode 1 and the organic functional layer 14.

Then, with reference to FIG. 6, the manufacturing method of the organic EL element 10 is demonstrated.
First, ITO is vapor-deposited on the transparent resin substrate 2, and this is patterned into a predetermined shape by a photolithography method to form the extraction electrode 12 (FIG. 6A). Subsequently, the metal conductive layer 4 is formed by patterning so as to partially overlap the extraction electrode 12 (FIG. 6B). Subsequently, a certain composition composed of a conductive polymer, a non-conductive polymer, etc. is prepared, and the composition is ink-jet printed on the metal conductive layer 4 and dried with a wavelength control infrared heater. The polymer conductive layer 6 is formed, and the metal conductive layer 4 is covered with the polymer conductive layer 6 (FIG. 6C).

Subsequently, an organic functional layer 14 composed of a hole transport layer, a light emitting layer, a hole block layer, an electron transport layer, and the like is formed on the polymer conductive layer 6 (transparent electrode 1) (FIG. 6D). Subsequently, the counter electrode 16 is formed so as to cover the organic functional layer 14 (FIG. 6E), and these members are covered with the sealing member 18 so as to completely cover the transparent electrode 1 and the organic functional layer 14. Sealing is performed (FIG. 6F).
The organic EL element 10 is manufactured by the above process.

  The conductive film 1 according to an embodiment of the present invention has both high conductivity and transparency, and various optoelectronics such as a liquid crystal display element, an organic light emitting element, an inorganic electroluminescent element, electronic paper, an organic solar cell, and an inorganic solar cell. It can be suitably used in the fields of devices, electromagnetic wave shields, touch panels and the like. Among these, it can use especially preferably as an electrically conductive film of the organic EL element and organic thin-film solar cell element by which the smoothness of the electrically conductive film surface is calculated | required severely.

  Moreover, since the organic electronic element (for example, organic EL element) which concerns on this invention can be made to light-emit uniformly, it is preferable to use it for an illumination use, a self-light-emitting display, a backlight for liquid crystals, It can be used for lighting or the like.

  In addition, since the touch panel according to the present invention is flexible and has low resistance, it can be used for curved surface and large area applications, such as ATMs of financial institutions such as banks, vending machines and ticket vending machines. It can be used in a wide variety of fields, mainly for digital information devices such as mobile phones, personal digital assistants (PDAs), digital audio players, portable game machines, copiers, fax machines, car navigation systems, etc. .

  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" and "%" is used in an Example, unless there is particular notice, "mass part" and "mass%" are represented.

Synthesis example 1
<Manufacture of binder resin P-1>
In a 1-liter four-necked flask equipped with a stirrer and a distillation tube, 616.0 g of dimer acid (Tsunodaim 395, manufactured by Tsukino Food Industry Co., Ltd., 94% dimer acid content), 60.1 g of ethylenediamine, 11 of stearic acid .4 g was added, and the temperature was raised to 200 ° C. under a nitrogen atmosphere to carry out the reaction for 30 minutes. Furthermore, reaction time was adjusted so that it might become a desired acid value and an amine value, and polyamide resin P-1 was obtained. The obtained polyamide resin was a dimer acid-based polyamide resin containing 100% by mole of dimer acid in the whole dicarboxylic acid component, and had an acid value of 15.0 mgKOH / g and an amine value of 0.3 mgKOH / g.

Synthesis example 2
Synthesis of Comparative Binder Resin PHEA (Polyacrylic Aqueous Solution): Comparative Compound [Synthesis of Poly-2-hydroxyethyl Acrylate (PHEA)]
In a 300 ml eggplant flask, 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.0 g (43.1 mmol, Fw 116.12), 2,2′-azobis (2-methylisopropionitrile) 0.7 g (4.3 mmol, Fw164.21) and 100 ml of tetrahydrofuran were added, and the mixture was heated to reflux for 8 hours. The solution was then cooled to room temperature and added dropwise into 2.0 L of vigorously stirred methyl ethyl ketone. After stirring the reaction solution for 1 hour, methyl ethyl ketone was decanted and the polymer adhering to the wall surface was washed three times with 100 ml of methyl ethyl ketone. The polymer was dissolved in 100 ml of tetrahydrofuran, transferred to a 200 ml flask, and tetrahydrofuran was distilled off under reduced pressure using a rotary evaporator. Then, by reducing the pressure at 80 ° C. for 3 hours, the remaining THF was distilled off to obtain 4.1 g (yield 82%) of PHEA having a number average molecular weight of 57,800 and a molecular weight distribution of 1.24.

The structure and molecular weight were measured by ¹ H-NMR (400 MHz, manufactured by JEOL Ltd.) and GPC (Waters 2695, manufactured by Waters), respectively. Further, P-14.0 g obtained was dissolved in 16.0 g of pure water to prepare a 20% aqueous solution of PO-A.

<GPC measurement conditions>
Device: Waters 2695 (Separations Module)
Detector: Waters 2414 (Refractive Index Detector)
Column: Shodex Asahipak GF-7M HQ
Eluent: Dimethylformamide (containing 20 mM LiBr)
Flow rate: 1.0 ml / min
Temperature: 40 ° C

Synthesis example 3
Synthesis of Comparative Binder Resin Z (Polymer Dispersion with Visible Absorption): Comparative Compound <Synthesis of Dye OH Form_A>
J. et al. Chem. Soc. , 1957, 4225, 4 g of 4- (2-phenyl-1H-imidazol-4-yl) phenol (Fw 236.27, 21.2 mmol), 4.2 g of N, N-diethylbenzene-1,4-diamine (Fw164.25, 25.4 mmol) was dissolved in 50 ml of ethyl acetate (solution A). Next, a solution in which 29.3 g of potassium carbonate (Fw 138.21, 212 mmol) was dissolved in 50 ml of water (solution B), and a solution in which 11.6 g of ammonium persulfate (Fw 228.20, 50.9 mmol) was dissolved in 20 ml of water (solution C) ) Was prepared. The solution obtained by adding the solution B to the solution A was vigorously stirred, and the solution C was added therein. After stirring for 1 hour, the ethyl acetate layer was washed with water, concentrated and dried, and the resulting solid was column purified with EA / n-heptane to obtain 3.5 g of dye OH-form A (Fw 396.48, yield). 42%).

<Synthesis of Dye Monomer_B>
In an apparatus in a nitrogen atmosphere, 3.0 g of dye OH_A (Fw 396.48, 7.6 mmol), 0.73 g of dehydrated triethylamine (Fw 101.19, 7.2 mmol) and 10 ml of dehydrated ethyl acetate were added, and then an ice bath was used. The internal temperature was adjusted to 5 ° C. or lower. A separately prepared solution consisting of 0.65 g (Fw 90.51, 7.2 mmol) of acryloyl chloride and 5 ml of dehydrated ethyl acetate was added dropwise with a dropping funnel over 10 minutes, and then the internal temperature was raised to room temperature and stirred for 1 hour. did. The obtained ethyl acetate layer was washed with water, 0.1 wt% of hydroquinone was added, and the ethyl acetate was distilled off under reduced pressure using a rotary evaporator. The obtained solid content was subjected to column purification with EA / n-heptane to obtain 1.6 g (Fw 450.53, yield 48%) of the dye monomer_B.

<Polymerization>
In a nitrogen atmosphere apparatus, 1.7 g (Fw 99.13, 17.4 mmol) of dimethylacrylamide, 1.0 g of dye monomer_B (Fw 450.53, 2.2 mmol), 0.014 g of acrylic acid (Fw 72.06, 0.2 mmol) ), 5 ml of degassed methanol was added and stirred for 10 minutes, and then 97.5 mg of AIBN (Fw164.21, mmol) was added thereto and reacted at 60 ° C. for 5 hours. The obtained solution was dropped into 200 ml of vigorously stirred n-heptane, and after stirring for 30 minutes, n-heptane was removed by decantation. After adding 100 ml of n-heptane and stirring for 30 minutes, n-heptane was removed by decantation. The solid content was recovered with acetone and the acetone was removed by rotary evaporator. The obtained solid content was dispersed in distilled water to obtain a binder resin Z (solid content concentration 25%). When the spectral absorption of the acetone solution of the binder resin Z was measured, it was confirmed that the absorption was 0 at 850 nm at λmax of 678 nm.

[Example 1]
<Preparation of base material>
(11) Production of transparent substrate (11.1) Formation of smooth layer UV curing made by JSR Corporation on the surface of 100 μm thick polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) Type organic / inorganic hybrid hard-coating material: OPSTAR Z7501 is applied with a wire bar so that the average film thickness after coating and drying is 4 μm, then dried at 80 ° C. for 3 minutes, and then a high-pressure mercury lamp in an air atmosphere It was used and cured under curing conditions of 1.0 J / cm ² to form a smooth layer.

(11.2) Formation of Gas Barrier Layer Next, a gas barrier layer was formed on the sample substrate provided with the smooth layer under the following conditions.

(11.2.1) Application of Gas Barrier Layer Coating Solution (Average) Film after Drying Perhydropolysilazane (PHPS, AQUAMICA NN320 manufactured by AZ Electronic Materials Co., Ltd.) with a 20% by mass dibutyl ether with a wireless bar Coating was performed so that the thickness was 0.30 μm to obtain a coated sample.

(11.2.2) Drying and dehumidifying treatment <first step; drying treatment>
The obtained coated sample was treated for 1 minute in an atmosphere having a temperature of 85 ° C. and a humidity of 55% RH to obtain a dried sample.

<Second step; dehumidification treatment>
The dried sample was further held for 10 minutes in an atmosphere of a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.) to perform dehumidification.

(11.2.3) Modification Treatment The sample subjected to the dehumidification treatment was subjected to a modification treatment using the following apparatus under the following conditions to form a gas barrier layer. The dew point temperature during the reforming treatment was -8 ° C.

<Modification processing equipment>
Ex. Irradiator MODEL: MECL-M-1-200, wavelength 172 nm, lamp filled gas Xe manufactured by M.D.Com

<Reforming treatment conditions>
Excimer light intensity 60 mW / cm ² (172 nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 1%
Excimer irradiation time 3 seconds

  As described above, the transparent base material 2 (film substrate, transparent resin substrate) for the transparent conductive film 1 having gas barrier properties was produced.

(12) Formation of polymer conductive layer (12.1) Preparation of polymer conductive layer forming composition Transparent conductive polymer Clevios PH750 (1.08% liquid made by Heraeus) and binder resin described in Table 1, After mixing 70 parts by mass of this mixture, 15 parts by mass of dimethyl sulfoxide, and 12 parts by mass of ethylene glycol monobutyl ether, mixing with a solid content ratio of 15:85, water was added to make 100 parts by mass, and the composition for forming a polymer conductive layer A product was prepared.

In Table 1, the abbreviations of the binder resin are as follows.
VE: Poly (methyl vinyl ether) (Tokyo Chemical Co., Ltd. 30% liquid)
PHEA: Poly (2-hydroxyethyl acrylate)
SF420: Superflex 420 (Daiichi Kogyo Seiyaku Co., Ltd. 31.6% solution)
8055A: Mobile 8055A (Nippon Gosei Chemical 44.6% solution)
WAC-14: Pesresin WAC-14 (20% liquid manufactured by Takamatsu Yushi Co., Ltd.)
Polyaniline: Polyaniline M (manufactured by TA Chemical Co., Ltd., 6.0% solution)

(12.2) Application and drying treatment of polymer conductive layer On the transparent substrate 1 for the transparent conductive film 1 having gas barrier properties, the above-described composition for forming a polymer conductive layer was applied by ink jet printing (FIG. 6 (c). )reference).
This was dried under the drying conditions described in Table 1 to form a polymer conductive layer (second conductive layer 6), and without having a metal conductive layer (first conductive layer 4), the polymer conductive layer (first conductive layer 4). “Conductive films TC-101 to TC-133” having two conductive layers 6) were formed.
Inkjet printing was controlled by an inkjet evaluation apparatus EB150 (manufactured by Konica Minolta IJ) using a desktop robot Shotmaster-300 (manufactured by Musashi Engineering) equipped with an ink jet head (manufactured by Konica Minolta IJ).

The drying method in Table 1 is as follows.
HP: Conduction heat transfer drying with hot plate (MH-180CS, manufactured by ASONE Corporation)
IR-1: Radiation heat transfer drying using an infrared heater used in the present invention (IR irradiation apparatus LW-NIR120mit HB-25-250, manufactured by ADPHOS)
IR-2: Radiation heat transfer drying using a wavelength-controlled infrared heater (attached to the IR irradiation device IR-1 are two plate-like quartz glass filters that absorb infrared rays having a wavelength of 3.5 μm or more, and cooling air is passed between the filters. (See Fig. 3)
The HP temperature in Table 1 is the hot plate heating temperature (set temperature).
The filament temperature in Table 1 was measured with a non-contact thermometer (IR-AHS, manufactured by Chino Corporation).
The filter temperature in Table 1 is the surface temperature of the quartz glass filter described above measured with a contact-type thermometer (HFT-60 manufactured by Anritsu Keiki Co., Ltd.), and the flow rate of cooling air is adjusted so that the temperature shown in Table 1 is obtained. It was adjusted.

The infrared transmittance of the quartz glass filter is shown in FIG.
An infrared spectrum with and without the quartz glass filter is shown in FIG.
In FIG. 8, the dotted line portion indicates the spectrum without the filter, and the solid line portion indicates the spectrum with the filter, and the respective spectra from the wavelength of 1 μm to approximately 3 μm are overlapped.

(13) Evaluation of sample The characteristics (drying property, film thickness distribution, and substrate stability) of the sample of the transparent conductive film 1 were evaluated for each sample as follows.

(13.1) Dryability About the dryness of the coating film of a polymer conductive layer (2nd conductive layer 6), the coating-film surface was palpated and the following reference | standard evaluated.
○: There is no stickiness, and it is smooth. Δ: There is stickiness. ×: The coating film is peeled off and the solvent remains. Evaluation criteria: Before forced deterioration, a sample evaluated as ○ passes as the present invention.

(13.2) Substrate stability As a damage evaluation of the transparent substrate 1 by the drying treatment, the substrate deformation was evaluated according to the following criteria.
○: No deformation △: There is a slight warp, but the substrate can be bent freely ×: There is a strong warp, and the substrate does not bend at the warped part Evaluation criteria: Samples rated as ○ before forced deterioration Passed as invention

(13.3) Transparency Based on JIS K 7361-1: 1997, the total light transmittance was measured using HAZE METER NDH5000 manufactured by Tokyo Denshoku Co., Ltd., and evaluated according to the following criteria. In order to use the transparent conductive film 1 as an organic electronic element, it is preferably 80% or more.
○: 80% or more Δ: 75% or more and less than 80% ×: 70% or more and less than 75% Evaluation criteria: A sample evaluated as ○ after forced deterioration passes the present invention.

(13.4) Surface Resistance Based on JIS K 7194: 1994, the surface resistance was measured using a resistivity meter (Loresta GP (MCP-T610 type): manufactured by Dia Instruments Co., Ltd.). The surface resistance is preferably 1000 Ω / □ or less after forced deterioration, and is preferably 30 Ω / □ or less after forced deterioration in order to increase the area of the organic electronic device.
Evaluation criteria: Samples evaluated as 1000 Ω / □ or less after forced deterioration pass the present invention.

(13.5) Surface roughness (Ra)
Using an AFM (Seiko Instruments SPI3800N probe station and SPA400 multifunctional unit) and using a sample cut to a size of about 1 cm square, the surface roughness specified in the above method (JIS B601 (1994)). ).
Evaluation criteria: After forced deterioration, a sample evaluated as Ra ≦ 10 nm passes the present invention.

(14) Summary As shown in Table 1, the TC-121 to 128 and TC-130 to TC133 of the present invention dried using an infrared heater are the conductive films TC-101 to 120 and TC-129 of the comparative examples. On the other hand, all of the drying property of a coating film, base-material stability, transparency, sheet resistance, and surface roughness were excellent.

[Example 2]
<Preparation of base material>
(21) Production of transparent substrate (21.1) Formation of smooth layer UV curing made by JSR Corporation on the surface of 100 μm thick polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) Type organic / inorganic hybrid hard-coating material: OPSTAR Z7501 is applied with a wire bar so that the average film thickness after coating and drying is 4 μm, then dried at 80 ° C. for 3 minutes, and then a high-pressure mercury lamp in an air atmosphere It was used and cured under curing conditions of 1.0 J / cm ² to form a smooth layer.

(21.2) Formation of Gas Barrier Layer Next, a gas barrier layer was formed on the sample substrate provided with the smooth layer under the following conditions.
(21.2.1) Application of Gas Barrier Layer Coating Liquid (Average) Film after Drying Perhydropolysilazane (PHPS, AQUAMICA NN320 manufactured by AZ Electronic Materials Co., Ltd.) with a 20% by mass dibutyl ether with a wireless bar Coating was performed so that the thickness was 0.30 μm to obtain a coated sample.

(21.2.2) Drying and dehumidifying treatment <first step; drying treatment>
The obtained coated sample was treated for 1 minute in an atmosphere having a temperature of 85 ° C. and a humidity of 55% RH to obtain a dried sample.

<Second step; dehumidification treatment>
The dried sample was further held for 10 minutes in an atmosphere of a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.) to perform dehumidification.

(21.2.3) Modification Treatment The sample subjected to the dehumidification treatment was subjected to a modification treatment under the following conditions using the following apparatus to form a gas barrier layer. The dew point temperature during the reforming treatment was -8 ° C.

<Modification processing equipment>
Ex. Irradiator MODEL: MECL-M-1-200, wavelength 172 nm, lamp filled gas Xe manufactured by M.D.Com

<Reforming treatment conditions>
Excimer light intensity 60 mW / cm ² (172 nm)
1mm distance between sample and light source
Stage heating temperature 70 ℃
Oxygen concentration in irradiation device 1%
Excimer irradiation time 3 seconds As described above, the transparent base material 2 (film substrate, transparent resin substrate) for the transparent conductive film 1 having gas barrier properties was produced.

(22) Formation of metal conductive layer A metal conductive layer (first conductive layer 4) is formed on the barrier surface of the transparent base material 2 (see FIG. 6A) for the transparent conductive film 1 having gas barrier properties by the following method. Formed.
On the transparent substrate 2, a silver nano ink (TEC-PR-030: manufactured by Inktec) is printed in a mesh pattern with a width of 50 μm and a pitch of 1 mm using a gravure printing tester K303 MULTICOATER (manufactured by RK Print Coat Instruments Ltd). Then, a metal conductive layer (first conductive layer 4) formed from a metal fine line pattern was formed (see FIG. 6B). The formed product was heat-treated at 120 ° C. for 30 minutes.
When the pattern of the metal conductive layer was measured with a high-intensity non-contact three-dimensional surface shape roughness meter WYKO NT9100 (manufactured by Biko Japan), the pattern width was 60 μm and the average height was 500 nm.

(22) Formation of polymer conductive layer (22.1) Preparation of composition for forming polymer conductive layer Transparent conductive polymer Clevios PH750 (1.08% liquid made by Heraeus) and binder resin described in Table 2 After mixing 70 parts by mass of this mixture, 15 parts by mass of dimethyl sulfoxide, and 12 parts by mass of ethylene glycol monobutyl ether, mixing with a solid content ratio of 15:85, water was added to make 100 parts by mass, and the composition for forming a polymer conductive layer A product was prepared.

In Table 2, the abbreviations of the binder resin are as follows.
VE: Poly (methyl vinyl ether) (Tokyo Chemical Co., Ltd. 30% liquid)
PHEA: Poly (2-hydroxyethyl acrylate)
SF420: Superflex 420 (Daiichi Kogyo Seiyaku Co., Ltd. 31.6% solution)
8055A: Mobile 8055A (Nippon Gosei Chemical 44.6% solution)
WAC-14: Pesresin WAC-14 (20% liquid manufactured by Takamatsu Yushi Co., Ltd.)
Polyaniline: Polyaniline M (manufactured by TA Chemical Co., Ltd., 6.0% solution)

(22.2) Application and Drying Treatment of Polymer Conductive Layer On the transparent base material 2 for the transparent conductive film 1 having gas barrier properties, the above-described polymer conductive layer forming composition was applied by ink jet printing (FIG. 6 ( c)).
This is dried under the drying conditions described in Table 2 to form a polymer conductive layer (second conductive layer 6 in FIG. 1), and a metal conductive layer (first conductive layer 4 in FIG. 1) and polymer conductive layer. The “conductive films TC-201 to TC-238” having (second conductive layer 6) were formed.
Inkjet printing was controlled by an inkjet evaluation apparatus EB150 (manufactured by Konica Minolta IJ) using a desktop robot Shotmaster-300 (manufactured by Musashi Engineering) equipped with an ink jet head (manufactured by Konica Minolta IJ).

The drying methods in Table 2 are as follows.
HP: Conduction heat transfer drying with hot plate (MH-180CS, manufactured by ASONE Corporation)
IR-1: Radiation heat transfer drying using an infrared heater used in the present invention (IR irradiation apparatus LW-NIR120mit HB-25-250, manufactured by ADPHOS)
IR-2: Radiation heat transfer drying using a wavelength-controlled infrared heater (attached to the IR irradiation device IR-1 are two plate-like quartz glass filters that absorb infrared rays having a wavelength of 3.5 μm or more, and cooling air is passed between the filters. (See Fig. 3)
The HP temperature in Table 2 is the heating temperature (set temperature) of the hot plate.
The filament temperature in Table 2 was measured with a non-contact thermometer (IR-AHS manufactured by Chino Corporation).
The filter temperature in Table 2 is the surface temperature of the quartz glass filter described above measured with a contact-type thermometer (HFT-60 manufactured by Anritsu Keiki Co., Ltd.), and the flow rate of cooling air is adjusted so that the temperature shown in Table 2 is obtained. It was adjusted.

The infrared transmittance of the quartz glass filter is shown in FIG.
An infrared spectrum with and without the quartz glass filter is shown in FIG.
In FIG. 8, the dotted line portion indicates the spectrum without the filter, and the solid line portion indicates the spectrum with the filter, and the respective spectra from the wavelength of 1 μm to approximately 3 μm are overlapped.

(23) Evaluation of sample The characteristics (drying property, film thickness distribution, and substrate stability) of the sample of the transparent conductive film 1 were evaluated for each sample as follows.

(23.1) Drying property About the drying property of the coating film of a polymer conductive layer (2nd conductive layer 6 of FIG. 1), the coating-film surface was palpated and the following reference | standard evaluated.
○: There is no stickiness, and it is smooth. Δ: There is stickiness. ×: The coating film is peeled off and the solvent remains. Evaluation criteria: Before forced deterioration, a sample evaluated as ○ passes as the present invention.

(23.2) Substrate stability As a damage evaluation of the transparent substrate 2 due to the drying treatment, the substrate deformation was evaluated according to the following criteria.
○: No deformation △: There is a slight warp, but the substrate can be bent freely ×: There is a strong warp, and the substrate does not bend at the warped part Evaluation criteria: Samples rated as ○ before forced deterioration Passed as invention

(23.3) Transparency Based on JIS K 7361-1: 1997, the total light transmittance was measured using HAZE METER NDH5000 manufactured by Tokyo Denshoku Co., Ltd., and evaluated according to the following criteria. In order to use the sample as an organic electronic device, the total light transmittance is preferably 80% or more.
○: 80% or more Δ: 75% or more and less than 80% ×: 70% or more and less than 75% Evaluation criteria: A sample evaluated as ○ after forced deterioration passes the present invention.

(23.4) Surface Resistance Based on JIS K 7194: 1994, the surface resistance was measured using a resistivity meter (Loresta GP (MCP-T610 type): manufactured by Dia Instruments Co., Ltd.). The surface resistance is preferably 1000 Ω / □ or less after forced deterioration, and is preferably 30 Ω / □ or less after forced deterioration in order to increase the area of the organic electronic device.
Evaluation criteria: Samples evaluated as 1000 Ω / □ or less after forced deterioration pass the present invention.

(23.5) Surface roughness (Ra)
Using an AFM (Seiko Instruments SPI3800N probe station and SPA400 multifunctional unit) and using a sample cut to a size of about 1 cm square, the surface roughness specified in the above method (JIS B601 (1994)). ).
Evaluation criteria: After forced deterioration, a sample evaluated as Ra ≦ 10 nm passes the present invention.

(24) Summary As shown in Table 2, the conductive films TC-221 to TC231 and TC-233 to TC-238 of the present invention dried using an infrared heater are conductive films TC-201 to TC- of the comparative example. In contrast to 220 and TC-232, all of the drying property, substrate stability, transparency, sheet resistance, and surface roughness of the coating film were excellent.

<Example 3>
<Production of organic EL device>
After the transparent conductive film 1 produced in Example 2 was washed with ultrapure water, it was cut into a 30 mm square so that one square tile-shaped pattern with a pattern side length of 20 mm was placed in the center, and used as an anode electrode. The organic EL device was produced respectively. The hole transport layer and subsequent layers were formed by vapor deposition. Using the conductive films TC-201 to TC-238, organic EL elements OEL-301 to OEL-338 were produced, respectively.
Each crucible for vapor deposition in a commercially available vacuum vapor deposition apparatus was filled with a constituent material of each layer in a necessary amount for device production. As the evaporation crucible, a crucible made of a resistance heating material made of molybdenum or tungsten was used.

  First, an organic EL layer 14 formed of a hole transport layer, an organic light emitting layer, a hole blocking layer, and an electron transport layer was sequentially formed.

<Formation of hole transport layer>
After reducing the vacuum to 1 × 10 ⁻⁴ Pa, the vapor deposition crucible containing compound 1 was heated by energization, vapor deposited at a vapor deposition rate of 0.1 nm / second, and a 30 nm thick hole transport layer (organic The lowermost layer of the EL layer 14 was provided (see FIG. 6D).

<Formation of organic light emitting layer>
Next, each light emitting layer was provided in the following procedures. Compound 2, Compound 3 and Compound 5 are deposited on the formed hole transport layer so that Compound 2 is 13.0% by mass, Compound 3 is 3.7% by mass, and Compound 5 is 83.3% by mass. Co-deposited in the same region as the hole transport layer at a speed of 0.1 nm / second to form a green-red phosphorescent organic light-emitting layer (intermediate layer of the organic EL layer 14) having an emission maximum wavelength of 622 nm and a thickness of 10 nm ( (Refer FIG.6 (d)).

Subsequently, 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. The organic light emitting layer (intermediate layer of the organic EL layer 14) emitting blue phosphorescence having a maximum emission wavelength of 471 nm and a thickness of 15 nm was formed (see FIG. 6D).
<Formation of hole blocking layer>
Furthermore, the hole blocking layer (intermediate layer of the organic EL layer 14) was formed by depositing the compound 6 in a thickness of 5 nm in the same region as the formed organic light emitting layer (see FIG. 6D).
<Formation of electron transport layer>
Subsequently, in the same region as the hole-blocking layer 14 formed, CsF was co-evaporated with the compound 6 so as to have a film thickness ratio of 10%, and an electron transport layer (the uppermost layer of the organic EL layer 14) having a thickness of 45 nm was formed. It formed (refer FIG.6 (d)). The organic EL layer 14 is configured by a laminated structure of the hole transport layer, the organic light emitting layer, the hole element layer, and the electron transport layer.

<Formation of cathode electrode>
On the formed electron transport layer 14, the first conductive layer 4 and the second conductive layer 6 of the transparent conductive film 1 are used as anodes, and an anode external lead terminal and Al as a material for forming a 15 mm × 15 mm cathode are 5 × 10 ^−4. Mask evaporation was performed under a vacuum of Pa to form a cathode 16 having a thickness of 100 nm (see FIG. 6E).
Furthermore, an adhesive is applied to the periphery of the cathode 16 except for the ends so that external terminals for the cathode 16 and the anode (the first conductive layer 4 and the second conductive layer 6) can be formed, and polyethylene terephthalate is used as a base material. After bonding a flexible sealing member in which ₂ O ₃ was vapor-deposited at a thickness of 300 nm, the adhesive was cured by heat treatment to form a sealing film 18, and an organic EL element 10 having a light emitting area of 15 mm × 15 mm was produced. (Refer FIG.6 (f)).

(33) Evaluation of organic EL element About the obtained organic EL element 10, the light emission uniformity and lifetime were evaluated as follows.

(33.1) Luminance uniformity The emission uniformity was obtained by applying a direct current voltage to an organic EL element using a source measure unit type 2400 manufactured by KEITHLEY. Regarding 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.
A: Completely uniform light emission, satisfactory O: Almost uniform light emission, no problem Δ: Some light emission unevenness is observed partially, but acceptable X: Light emission unevenness is observed over the entire surface, not acceptable Evaluation criteria: Samples evaluated as ◎ and ○ after the forced deterioration test passed the present invention.

(lifespan)
The obtained organic EL device was continuously emitted at an initial luminance of 5000 cd / m ² , the voltage was fixed, and the time until the luminance was reduced by half was determined. An organic EL element having an anode electrode made of ITO was produced by the same method as described above, the ratio to this was determined, and evaluated according to the following criteria. The lifetime is preferably 100% or more, and more preferably 150% or more.
◎: 150% or more ○: 100% or more and less than 150% △: 80% or more and less than 100% ×: Less than 80% Evaluation criteria: After forced deterioration test, samples evaluated as ◎ and ○ pass as the present invention.

Table 3 shows the evaluation results. In Table 3, “Invention” in the remarks indicates that it corresponds to an example of the present invention, and “Comparison” indicates that it is a comparative example. Further, the conditions for forced deterioration in the third embodiment are the same as those in the first and second embodiments.

  From Table 3, the organic EL elements OEL-301 to OEL-320, OEL-332 of the comparative examples are significantly deteriorated in light emission uniformity and life after heating for 14 days at 80% RH and 90 ° C., which is a forced deterioration test. On the other hand, the organic EL elements OEL-321 to OEL-331, OEL-333 to OEL-338 of the present invention have stable emission uniformity and excellent durability (high lifetime) even after heating. I understand.

<Example 4>
<Production of touch panel>
The touch panel 101 shown in FIG. 9 was assembled by the following method using the conductive films TC-101 to TC-133 and TC-201 to TC238 produced in Examples 1 and 2.

<Assembly method of touch panel>
As illustrated in FIG. 9, the touch panel 101 includes a lower electrode 110, an upper electrode 120, and a thermosetting type dot spacer 130 provided therebetween. The lower electrode 110 is a touch panel glass ITO (sputtering film product), and includes a touch panel glass 111 and a transparent conductive film 112 provided on the touch panel glass 111. The upper electrode 120 includes any one of the conductive films TC-101 to TC-133 and TC-201 to TC238 in the above-described embodiment, and includes a transparent base 121 and a transparent conductive film 122. Then, the transparent conductive film 112 of the lower electrode 110 and the transparent conductive film 122 of the upper electrode 120 are opposed to each other, and a thermosetting type dot spacer 130 is interposed to form a panel with a space of 7 μm. Assembled.

  A resistance measuring machine was attached to the upper electrode 120 and the lower electrode 110 of the assembled touch panel 101, the center of the touch panel 101 was pushed by hand, and the resistance value was measured 1000 times. As a result, compared with the conductive films TC-121 to TC-128, TC-130 to TC-133, TC-221 to TC-231, TC-233 to TC-238 of the present invention, the comparative conductive film TC-201 TC217, TC-229, TC-101 to TC-120, TC-129, TC-201 to TC-220, and TC-232 were confirmed to have a greater decrease in resistance over time.

1 Transparent conductive film (conductive film)
2 Transparent substrate (substrate)
2a Opening 4 First conductive layer 6 Second conductive layer 10 Organic EL element (organic electronic element)
12 Extraction electrode 14 Organic EL layer (hole transport layer, organic light emitting layer, hole blocking layer, electron transport layer)
16 Anode 18 Sealing film 101 Touch panel 110 Lower electrode 111 Glass for touch panel 112 Transparent conductive film 120 Upper electrode 121 Conductive substrate 122 Transparent conductive film 130 Thermosetting type dot spacer

Claims (8)

Applying a dispersion in which a first polymer having conductivity and a second polymer having infrared absorptivity are dispersed in an aqueous solvent on a substrate;
Forming a conductive layer by performing infrared irradiation with an infrared heater on the applied dispersion; and
Including
The second polymer absorbs infrared light having a wavelength of 2.5 to 3.0 μm at a site other than the dissociable group.
The said infrared heater irradiates the infrared rays containing a wavelength of 2.5-3.0 micrometers. The manufacturing method of the electrically conductive film characterized by the above-mentioned. The said infrared heater irradiates infrared rays with the filament temperature of 700-3000 degreeC. The manufacturing method of the electrically conductive film of Claim 1 characterized by the above-mentioned. The said infrared heater is provided with the filter which absorbs infrared rays with a wavelength of 3.5 micrometers or more. The manufacturing method of the electrically conductive film of Claim 1 or Claim 2 characterized by the above-mentioned. The method for producing a conductive film according to any one of claims 1 to 3, wherein the second polymer has any one of a urethane structure, an amide structure, and a silanol structure. The method for producing a conductive film according to any one of claims 1 to 4, further comprising: forming a conductive layer formed of a metal material on the base material. It is manufactured by the manufacturing method of the electrically conductive film as described in any one of Claims 1-5. The electrically conductive film characterized by the above-mentioned. An organic electronic device comprising: a conductive film manufactured by the method for manufacturing a conductive film according to any one of claims 1 to 5 as an electrode. A touch panel comprising: a conductive film manufactured by the method for manufacturing a conductive film according to claim 1 as an electrode.

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