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WO2014185256A1 - Procédé de fabrication de substrat de résine conducteur - Google Patents

Procédé de fabrication de substrat de résine conducteur Download PDF

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Publication number
WO2014185256A1
WO2014185256A1 PCT/JP2014/061735 JP2014061735W WO2014185256A1 WO 2014185256 A1 WO2014185256 A1 WO 2014185256A1 JP 2014061735 W JP2014061735 W JP 2014061735W WO 2014185256 A1 WO2014185256 A1 WO 2014185256A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
resin substrate
fine
substrate
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/061735
Other languages
English (en)
Japanese (ja)
Inventor
松村　智之
孝敏 末松
昌紀 後藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to JP2015517018A priority Critical patent/JPWO2014185256A1/ja
Publication of WO2014185256A1 publication Critical patent/WO2014185256A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • H10K71/611—Forming conductive regions or layers, e.g. electrodes using printing deposition, e.g. ink jet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/105—Metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes

Definitions

  • the present invention mainly relates to a method for producing a conductive resin substrate used as an electrode of an organic electronic element such as an organic EL element. More specifically, the present invention relates to a method for manufacturing a low-resistance conductive resin substrate having a fine metal wire pattern with good adhesion to the substrate.
  • a method for producing a conductive substrate having a fine metal wire pattern methods such as a subtractive method and an additive method have been devised and widely used as a highly reliable method.
  • conductive substrates have been used in various electronic devices, and as the performance of the devices has increased, the metal fine line patterns in the conductive substrates have been required to have a considerably higher density. Therefore, even when any of the above methods is used, it has become common to form a desired fine metal line pattern using a photolithography process capable of fine processing.
  • a resist is applied to the entire surface of the substrate and pre-baked, and then irradiated with ultraviolet rays or the like through a photomask, and a resist pattern is formed by development. Thereafter, unnecessary portions are removed by etching using this resist pattern as a mask to form a fine metal wire pattern.
  • the conventional process for forming a fine metal line pattern using photolithography has a problem that most of the metal film and resist material for pattern formation are wasted. There is also a problem that the number of steps of the photoresist process is large and the throughput is lowered.
  • a method for producing a conductive substrate by forming a conductive layer or an insulating layer by various printing methods such as screen printing and inkjet printing using ink containing conductive metal particles has been studied in various fields (for example, , See Patent Document 1). Specifically, a metal nanoparticle dispersed ink composition containing nanoparticles such as silver, gold, and copper is used to print and draw a metal nanoparticle pattern, and then the metal nanoparticles are fired (sintered). This makes it possible to obtain a conductive substrate having a fine metal wire pattern.
  • metal nanoparticle dispersions that enable firing at a low heat treatment temperature have also been studied (see, for example, Patent Document 2). Specifically, by using an organic compound having a low molecular weight and a low boiling point as a protective molecule for silver nanoparticles, firing at a temperature of 100 ° C. or lower is enabled. However, by using an organic compound having a low molecular weight and a low boiling point as a protective molecule, the adhesion to the substrate after firing becomes insufficient. For example, in production in a roll-to-roll process, patterning and firing are performed. When the applied resin substrate with a fine metal wire pattern is wound up by a roll, there may be a problem that the fine metal wire pattern is peeled off due to friction with the back surface of the substrate in contact.
  • the present invention has been made in view of the above-mentioned problems and situations, and a solution to the problem is to provide a method for producing a low-resistance conductive resin substrate having a fine metal wire pattern with excellent adhesion to the substrate. It is. Furthermore, it is providing the manufacturing method of the low resistance conductive resin board
  • substrate which can be used suitably for organic electronic elements, such as an organic electroluminescent element (organic EL element).
  • the present inventor in the course of studying the cause of the above-mentioned problems, (1) Including inorganic compound particles having a refractive index of 1.9 to 3.0 on the transparent resin substrate.
  • the present invention has found that a low-resistance conductive resin substrate having a fine metal wire pattern with excellent adhesion to a substrate can be provided by the method for producing a conductive resin substrate having a step of forming a conductive resin substrate.
  • a method for producing a conductive resin substrate comprising at least the following steps (1) to (3): (1) A step of forming an inorganic particle layer containing inorganic compound particles having a refractive index in the range of 1.9 to 3.0 on a transparent resin substrate (2) A fine line pattern of metal nanoparticles on the inorganic particle layer (3) The step of firing the fine wire pattern of the metal nanoparticles by light irradiation to form the fine metal wire pattern
  • substrate which can be used suitably for organic electronic elements, such as an organic EL element, can be provided.
  • the inorganic particle layer according to the present invention includes inorganic compound particles having a refractive index of 1.9 to 3.0. This not only has an anchoring effect to enhance the adhesion with the fine line pattern of the metal nanoparticles formed on the inorganic particle layer, but also lowers the energy when firing the fine line pattern of the metal nanoparticles by light irradiation. It has been found that there is an effect of enabling low resistance with light irradiation energy. For example, when an inorganic particle layer containing inorganic compound particles having a refractive index of less than 1.9 is used in place of the inorganic particle layer according to the present invention, the conductive resin substrate is obtained as a result of baking by light irradiation with the same energy.
  • the surface resistance was much higher than that of the conductive resin substrate according to the present invention, and the effect of sufficiently reducing the resistance was not obtained. Also, in this case, if the light irradiation energy in firing is increased with the aim of reducing resistance, disconnection due to ablation of the fine metal wire pattern will occur remarkably before sufficient resistance reduction effect is obtained, and sufficient low Resistance could not be achieved.
  • the cause of this is not clear, by adjusting the refractive index of the inorganic compound particles used in the inorganic particle layer to 1.9 or more, the light irradiated during firing is scattered in the inorganic particle layer, resulting in a metal fine line pattern and an inorganic
  • the refractive index of the inorganic compound particles used in the inorganic particle layer to 1.9 or more
  • the light irradiated during firing is scattered in the inorganic particle layer, resulting in a metal fine line pattern and an inorganic
  • the adhesive force at the interface between the metal fine line pattern and the inorganic particle layer is increased, thereby ablating. It is presumed that the inhibitory effect is expressed.
  • the method for producing a conductive resin substrate of the present invention comprises (1) a step of forming an inorganic particle layer containing inorganic compound particles having a refractive index in the range of 1.9 to 3.0 on a transparent resin substrate; A step of forming a fine line pattern of metal nanoparticles on the inorganic particle layer; and (3) a step of firing the fine line pattern of metal nanoparticles by light irradiation to form a fine metal line pattern.
  • This feature is a technical feature common to the inventions according to claims 1 to 3.
  • the average particle size of the inorganic compound particles is in the range of 70 to 300 nm from the viewpoint of reduction in resistance during firing by light irradiation of a fine metal wire pattern, suppression of ablation, and transparency of visible light. It is preferable.
  • the transparent resin substrate is not damaged by thermal deformation, it is preferable to irradiate light with pulsed light.
  • ⁇ representing a numerical range is used in the sense that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
  • the conductive resin substrate manufactured by the manufacturing method of the present invention is configured by sequentially laminating an inorganic particle layer and a fine metal wire pattern on a transparent resin substrate.
  • the inorganic particle layer contains inorganic compound particles having a refractive index of 1.9 to 3.0.
  • the metal fine line pattern includes at least metal nanoparticles.
  • the conductive resin substrate manufactured by the manufacturing method of the present invention when using the conductive resin substrate manufactured by the manufacturing method of the present invention as a transparent electrode of an organic electronic element that requires a surface electrode such as an organic EL element, a conductive polymer is placed on the metal thin wire pattern. A conductive polymer layer containing is provided. Furthermore, in order to prevent moisture and oxygen from diffusing into the element (particularly the organic functional layer) through the transparent resin substrate, it is effective to form a gas barrier layer having a high shielding ability against moisture and oxygen. .
  • the manufacturing method of the conductive resin substrate according to the present invention mainly includes: (1) forming an inorganic particle layer containing inorganic compound particles having a refractive index in the range of 1.9 to 3.0 on the transparent resin substrate; (2) forming a fine pattern of metal nanoparticles on the inorganic particle layer; (3) A step of firing a fine wire pattern of metal nanoparticles by light irradiation to form a fine metal wire pattern; have.
  • each step will be described.
  • the inorganic particle layer according to the present invention contains inorganic compound particles having a refractive index in the range of 1.9 to 3.0.
  • a method for forming such an inorganic particle layer there is used a method in which a coating liquid containing inorganic compound particles having a refractive index in the range of 1.9 to 3.0 is coated on a transparent resin substrate and dried.
  • a coating solution containing inorganic compound particles having a refractive index in the range of 1.9 to 3.0 can be prepared by dispersing the inorganic compound particles in a dispersion medium.
  • the dispersion medium water or a general organic solvent, or a mixed solution of water and an organic solvent is used.
  • the selection of the organic solvent used as the dispersion medium is not particularly limited as long as the dispersibility of the inorganic compound particles and the drying property of the coating film are compatible.
  • general saturated hydrocarbon solvents, aromatic hydrocarbon solvents, ketones, esters, ethers, alcohols, glycols, glycol ethers, amides, sulfoxides, and mixed solvents thereof Can be used.
  • any appropriate method can be selected.
  • various printing methods such as a gravure printing method, a flexographic printing method, an offset printing method, a screen printing method, and an inkjet printing method.
  • Various coating methods such as a roll coating method, a bar coating method, a dip coating method, a spin coating method, a casting method, a die coating method, a blade coating method, a curtain coating method, a spray coating method, and a doctor coating method can be used.
  • a gravure printing method, a flexographic printing method, an offset printing method, a screen printing method, or an inkjet printing method it is preferable to use a gravure printing method, a flexographic printing method, an offset printing method, a screen printing method, or an inkjet printing method.
  • the inorganic particle layer can be formed by depositing a film on the substrate using the above coating method, and then drying by a known heat drying method such as warm air drying or infrared drying, natural drying, or the like.
  • a known heat drying method such as warm air drying or infrared drying, natural drying, or the like.
  • the temperature in the case of heat-drying can be suitably selected according to the board
  • the coating liquid using a dispersion medium containing a hydroxy group in the molecule is used to suppress the heat generation of the film substrate by using infrared light having an emission wavelength in the vicinity of 3 ⁇ m which is the infrared absorption wavelength region of the hydroxy group.
  • a method of drying the coating solution is also effective.
  • alcohol or water is used as a dispersion medium containing a hydroxy group in the molecule.
  • Alcohols include methanol, ethanol, n-propanol, isopropanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether , Ethylene glycol monoisopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethoxymethyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol , Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol, tetraethylene glycol monobutyl ether, propylene glycol, prop
  • the inorganic particle layer is obtained by dispersing inorganic compound particles in a binder material solution (a solvent that does not dissolve inorganic compound particles) as an organic compound, and applying the dispersion onto a transparent resin substrate. It can also be formed.
  • a binder material solution a solvent that does not dissolve inorganic compound particles
  • a binder that can be contained in the inorganic particle layer a resin that is mainly cured by ultraviolet rays or an electron beam, that is, a mixture of a thermoplastic resin and a solvent in an ionizing radiation curable resin or a thermosetting resin can be suitably used.
  • the ionizing radiation curable resin composition can be cured by a normal curing method, that is, irradiation with an electron beam or ultraviolet rays.
  • keV emitted from various electron beam accelerators such as Cockrowalton type, bandegraph type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type.
  • An electron beam having an energy within a range of preferably 30 to 300 keV is used.
  • ultraviolet curing ultraviolet rays emitted from light beams such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used.
  • the ultraviolet irradiation device include a rare gas excimer lamp that emits vacuum ultraviolet rays of 100 to 230 nm. Since the excimer lamp has high light generation efficiency, it can be lit with low power. In addition, since light having a long wavelength that causes a temperature rise is not emitted and energy is emitted at a single wavelength in the ultraviolet region, the temperature rise of the irradiation object due to the irradiation light itself is suppressed.
  • the metal nanoparticle dispersion is patterned on a transparent resin substrate by a printing method.
  • a fine line pattern can be formed by well-known printing methods, such as a gravure printing method, a flexographic printing method, a screen printing method, and an inkjet printing method.
  • a method generally used for electrode pattern formation can be applied to the present invention.
  • Specific examples of the gravure printing method include those described in JP 2009-295980 A, JP 2009-259826 A, JP 2009-96189 A, and JP 2009-90662 A, and the like.
  • Examples of the method described in JP-A-302345 and the method described in JP-A-2012-212784 and JP-A-2008-294391 are examples of the ink jet printing method.
  • Step of forming a fine metal wire pattern by light irradiation The fine metal wire pattern according to the present invention is formed by firing a fine wire pattern of metal nanoparticles by light irradiation.
  • the means for light irradiation is preferably pulsed light irradiation mainly having a wavelength in the visible light region.
  • the pulsed light in the present invention refers to light that emits light within a light emission time range of 1 ⁇ sec to 100 msec.
  • a discharge tube of a flash lamp used for pulsed light irradiation a discharge tube of xenon, helium, neon, argon or the like can be used, but a xenon lamp is preferably used.
  • a preferable spectral band of the flash lamp is in a range of 240 to 2000 nm, and such a band is preferable because the transparent resin substrate is not damaged by thermal irradiation or the like due to irradiation with pulsed light.
  • the light irradiation conditions of the flash lamp are arbitrary, but the total light irradiation energy is preferably in the range of 0.1 to 50 J / cm 2 , and preferably in the range of 0.5 to 10 J / cm 2. More preferred.
  • the light irradiation time is preferably in the range of 10 ⁇ sec to 100 msec, and more preferably in the range of 20 ⁇ sec to 10 msec. Further, the number of times of light irradiation may be one time or a plurality of times, and it is preferably performed within the range of 1 to 1000 times.
  • the irradiation of the flash lamp to the transparent resin substrate is preferably performed from the front side on which the fine line pattern is printed.
  • the transparent resin substrate itself is transparent, it can be irradiated from the back side or from both sides.
  • the pulsed light irradiation may be performed in the air, but can also be performed in an inert gas atmosphere such as nitrogen, argon, helium or the like, if necessary.
  • the substrate temperature at the time of pulsed light irradiation is the heat resistance temperature of the transparent resin substrate, the boiling point (vapor pressure) of the ink dispersion medium containing metal nanoparticles and metal complexes, the type and pressure of the atmospheric gas, the dispersibility of the ink,
  • the temperature may be determined in consideration of thermal behavior such as oxidizability, etc., and is preferably performed within the range of room temperature (25 ° C.) to 200 ° C.
  • the substrate after the fine line pattern is formed may be subjected to heat treatment in advance before performing the pulsed light irradiation.
  • the light irradiation device of the flash lamp is not particularly limited as long as it satisfies the above irradiation energy and irradiation time.
  • the transparent resin substrate according to the present invention has a function of forming and holding a fine metal wire pattern, and a transparent resin substrate or the like in the visible light region can be appropriately selected and used depending on the application.
  • the transparency of the transparent resin substrate can be arbitrarily selected depending on the use, but the higher the transparency, the more applicable to a transparent electrode or the like, which is preferable from the viewpoint of expanding the use.
  • As the transparent resin substrate for example, it is preferable to use a transparent resin plate, a transparent resin film, or the like. Among them, it is more preferable to use a transparent resin film from the viewpoint of productivity and performance such as lightness and flexibility.
  • the total light transmittance of the transparent resin substrate is 70% or more, preferably 80% or more.
  • the total light transmittance can be measured according to JIS K 7375: 2008 “Plastics—How to determine total light transmittance and total light reflectance”.
  • a transparent resin film there is no restriction
  • the transparent resin film include polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, and cyclic olefin.
  • Polyolefin resin films such as polyvinyl resins, vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin films, polysulfone (PSF) resin films, polyether sulfone (PES) resin films, Examples include polycarbonate (PC) resin film, polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, etc. Kill, but as long as it is a resin film transmittance of 80% or more at a wavelength in the visible light range (380 ⁇ 780 nm), can be preferably used as the transparent resin film according to the present invention.
  • PC polycarbonate
  • PC polyamide resin film
  • polyimide resin film acrylic resin film
  • TAC triacetyl cellulose
  • biaxially stretched biaxially oriented polyethylene terephthalate resin film biaxially oriented polyethylene naphthalate resin film, polyethersulfone resin film, polycarbonate resin film, etc. in terms of transparency, heat resistance, ease of handling, strength and cost.
  • a stretched polyester resin film is preferable, and a biaxially stretched polyethylene terephthalate resin film or a biaxially stretched polyethylene naphthalate resin film is more preferable.
  • the inorganic particle layer according to the present invention includes inorganic compound particles having a refractive index of 1.9 to 3.0.
  • the inorganic compound particles having a refractive index in the range of 1.9 to 3.0 include inorganic particles composed of at least one oxide selected from zirconium, titanium, indium, zinc, antimony, cerium, niobium, tungsten, and the like.
  • An oxide particle is mentioned.
  • Specific examples of the inorganic oxide particles include ZrO 2 , TiO 2 , BaTiO 3 , In 2 O 3 , ZnO, Sb 2 O 3 , ITO, CeO 2 , Nb 2 O 5 , WO 3 and the like. Among these, TiO 2 , BaTiO 3 , ZrO 2 , CeO 2 or Nb 2 O 5 is preferable, and TiO 2 is most preferable.
  • the surface treatment material is preferably a different inorganic oxide and / or metal hydroxide, more preferably a metal hydroxide.
  • the coating amount (generally, the coating amount is represented by the mass ratio of the surface treatment material used on the surface of the particles relative to the mass of the particles). ) Is preferably in the range of 0.01 to 99% by mass.
  • the coating amount of the surface treatment material is 0.01% by mass or more, the effect of improving the dispersibility and stability due to the surface treatment can be sufficiently obtained, and when it is within 99% by mass, a high refractive index inorganic It can suppress that the refractive index of a particle layer falls.
  • the inorganic compound particles have a refractive index of 1.9 or more, preferably 1.95 or more, particularly preferably 2.0 or more.
  • the refractive index is 1.9 or more, the effects of the present invention, that is, the effect of suppressing ablation and reducing the resistance in light firing of a fine line pattern, can be obtained.
  • the upper limit of the refractive index of the inorganic compound particles is 3.0 or less. In the material having a refractive index higher than 3.0, the visible light transmittance of the conductive resin substrate according to the present invention is hindered.
  • the transparency of the inorganic particle layer can be arbitrarily selected depending on the application, but the higher the transparency, the more applicable to a transparent electrode or the like, which is preferable from the viewpoint of expanding applications.
  • the total light transmittance of the inorganic particle layer is at least 50% or more, preferably 70% or more.
  • the average particle diameter of the inorganic compound particles is preferably in the range of 70 to 300 nm. If the average particle diameter of the inorganic compound particles is 70 nm or more, the effect of reducing resistance during firing by light irradiation of a fine line pattern is large, and an ablation suppressing effect can be expected. On the other hand, when the average particle size is 300 nm or less, the effect of reducing resistance during firing by light irradiation of a fine line pattern is great, and an ablation suppressing effect can be expected, and the visible light permeability is hardly hindered.
  • the average particle diameter of the inorganic compound particles in the present invention can be easily measured using a commercially available measuring apparatus using a light scattering method. Specifically, Zetasizer 1000 (manufactured by Malvern) is used. Used, the value measured by the laser Doppler method at 25 ° C. and 1 ml of sample diluted solution.
  • the dry layer thickness of the inorganic particle layer is preferably in the range of 100 to 2000 nm. If the dry layer thickness of the inorganic particle layer is 100 nm or more, the fine metal wire pattern can be retained on the transparent resin substrate, and sufficient adhesion can be obtained, and the fine metal wire pattern can be prevented from being thickened. . When the dry layer thickness of the inorganic particle layer is 2000 nm or less, the transparency is not lowered, and it is possible to prevent cracks from occurring during bending.
  • Binder that can be contained in the inorganic particle layer As the binder that can be contained in the inorganic particle layer, known resins can be used without any particular limitation. For example, acrylic ester, methacrylic ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), Polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, Resin such as polyimide and polyetherimide, heat-resistant transparent resin (product name Sila-DEC, manufactured by Chisso Corporation) with silsesquioxane having organic-inorganic hybrid structure, silane containing perfluoroalkyl group In addition to compounds (for example, (heptadecafluoro-1,1,2,2-tetradecyl) tri-phosphat
  • hydrophilic resins can also be used.
  • hydrophilic resin examples include water-soluble resins, water-dispersible resins, colloid-dispersed resins, and mixtures thereof.
  • hydrophilic resin examples include acrylic resins, polyester resins, polyamide resins, polyurethane resins, fluorine resins, etc., for example, polyvinyl alcohol, gelatin, polyethylene oxide, polyvinyl pyrrolidone, casein, starch, agar, carrageenan, polyacrylic.
  • Polymers such as acid, polymethacrylic acid, polyacrylamide, polymethacrylamide, polystyrene sulfonic acid, cellulose, hydroxyl ethyl cellulose, carboxyl methyl cellulose, hydroxyl ethyl cellulose, dextran, dextrin, pullulan, water-soluble polyvinyl butyral can be mentioned, but these Among these, polyvinyl alcohol is preferable.
  • One type of resin used as a binder that can be contained in the inorganic particle layer may be used alone, or two or more types may be mixed and used as necessary.
  • a binder that can be contained in the inorganic particle layer a resin that is mainly cured by ultraviolet rays or an electron beam, that is, a mixture of a thermoplastic resin and a solvent in an ionizing radiation curable resin or a thermosetting resin can also be suitably used.
  • a binder is preferably a polymer having a saturated hydrocarbon or polyether as a main chain, and more preferably a polymer having a saturated hydrocarbon as a main chain.
  • the binder that can be contained in the inorganic particle layer is preferably crosslinked.
  • the polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder, it is preferable to use a monomer having two or more ethylenically unsaturated groups.
  • a compound capable of forming a metal oxide, a metal nitride, or a metal oxynitride by ultraviolet irradiation under a specific atmosphere is particularly preferably used.
  • a compound described in JP-A-8-112879 which can be modified at a relatively low temperature, can be preferably used.
  • polysiloxane having Si—O—Si bond including polysilsesquioxane
  • polysiloxazan containing both of them can be used in combination of two or more.
  • polysiloxanes including polysilsesquioxane
  • polysilazane and polysiloxazan are the same as those described in the gas barrier layer of the transparent substrate described later.
  • the metal fine wire pattern according to the present invention is formed by forming a metal nanoparticle fine wire pattern on an inorganic particle layer and then firing the metal nanoparticle fine wire pattern by light irradiation.
  • a fine line pattern of metal nanoparticles can be obtained by patterning a metal nanoparticle dispersion using a so-called printing method.
  • Metal nanoparticle dispersion The metal nanoparticles used in the metal nanoparticle dispersion are not particularly limited as long as they are excellent in conductivity. For example, metals such as gold, silver, copper, iron, nickel, chromium, and alloys thereof may be used. And it is preferable to contain silver from a viewpoint of stability.
  • the average particle diameter of the metal nanoparticles is preferably in the range of 1 to 100 nm, more preferably in the range of 1 to 50 nm, and particularly preferably in the range of 1 to 30 nm.
  • the average particle size of the metal nanoparticles was determined by observing 200 or more metal nanoparticles that can be observed as a circle, an ellipse, or a substantially circle or ellipse at random from an electron microscope observation of the metal nanoparticles. It is obtained by obtaining the particle size and obtaining the number average value thereof.
  • the particle diameter refers to the minimum distance among the distances between the outer edges of the metal nanoparticles that can be observed as a circle, an ellipse, or a substantially circle or ellipse, between two parallel lines. When measuring the average particle diameter, the ones that clearly represent the side surfaces of the metal nanoparticles are not measured.
  • JP 2010-265543 A JP 2011-68936 A, JP 2012-162767 A, and JP 2012-14496 A.
  • Gazette JP2012-144895, JP2012-52225, JP2008-214591, JP2007-200775, JP2006-193594, JP2012-119132, This is described in detail in Japanese Patent Laid-Open Nos. 2011-153362 and 2009-515023.
  • the metal nanoparticle dispersion contains metal nanoparticles in a dispersion medium such as water, alcohol, or hydrocarbon, but may contain a binder, a dispersant for dispersing the metal, or the like, if necessary.
  • a dispersion medium such as water, alcohol, or hydrocarbon
  • the shape of the fine metal wire pattern according to the present invention is not particularly limited.
  • the pattern shape may be a stripe shape or a mesh shape such as a square lattice or a honeycomb lattice, but the aperture ratio is 80 from the viewpoint of transparency. % Or more is preferable.
  • the aperture ratio means an area ratio in which the fine metal line pattern does not exist per unit area.
  • the aperture ratio of the stripe pattern having a line width of 100 ⁇ m and a line interval of 1 mm is 90%. It is.
  • the line width of the fine line is preferably in the range of 10 to 200 ⁇ m.
  • the line width of the thin wire is 10 ⁇ m or more, desired conductivity is obtained, and if it is 200 ⁇ m or less, sufficient transparency is obtained when used as a transparent electrode.
  • the height of the fine wire is preferably in the range of 0.1 to 5 ⁇ m. If the height of the fine wire is 0.1 ⁇ m or more, desired conductivity is obtained, and if it is 5 ⁇ m or less, the influence of the unevenness on the layer thickness distribution of the organic functional layer is affected when used for an organic electronic device. Can be reduced.
  • the surface specific resistance when the thin metal wire pattern is regarded as one conductive film is preferably 100 ⁇ / ⁇ or less, and is considered to be used as a transparent electrode member suitable for organic electronic elements such as organic EL elements. 10 ⁇ / ⁇ or less is more preferable, and for example, from the viewpoint of increasing the area of an organic EL element or the like, it is particularly preferably 5 ⁇ / ⁇ or less.
  • the surface specific resistance can be measured according to, for example, JIS K 6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.
  • the surface of the metal fine line pattern is preferably smooth.
  • the surface roughness Ra of the metal fine line pattern is preferably 200 nm or less.
  • the value of Ra is the surface roughness specified in JIS B 0601: 1994, and is a value measured as follows in the present invention.
  • the Ra defined in the present invention is a value obtained by measuring Ra on a fine line of a metal fine line pattern, and is obtained by measuring Ra on a straight line having a length of 10 ⁇ m in parallel to the fine line of the metal fine line pattern.
  • the Ra is measured by the following method using a commercially available atomic force microscope (AFM).
  • AFM atomic force microscope
  • An area in which atomic force works by using a Seiko Instruments SPI3800N probe station and SPA400 multifunctional unit as AFM, setting a sample on a horizontal sample stage on a piezo scanner, approaching the sample surface with a cantilever Then, scanning is performed in the XY directions, 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 to 150 ⁇ m and Z 25 ⁇ m 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 30 nm, and is measured in a DFM mode (Dynamic Force Mode).
  • DFM mode Dynamic Force Mode
  • a central portion of 10 ⁇ m ⁇ 10 ⁇ m was measured at a scanning frequency of 0.1 Hz. After the measurement, 10 lines with a length of 10 ⁇ m are drawn at intervals of 0.9 ⁇ m parallel to the thin line, Ra on the line is calculated, and the average value is taken as the value of Ra.
  • the conductive resin substrate according to the present invention is a preferred embodiment in which a conductive polymer layer containing a conductive polymer is formed on a fine metal wire pattern.
  • the term “conductive” refers to a state in which electricity flows, and the sheet resistance measured by a method in accordance with JIS K 7194-1994 “Resistivity Test Method by Conductive Plastic Four-Probe Method” is 1 It means lower than ⁇ 10 8 ⁇ / ⁇ .
  • the conductive polymer is preferably a conductive polymer containing a ⁇ -conjugated conductive polymer and a polyanion since the sheet resistance at the time of film formation is low.
  • the conductive polymer layer may contain a water-soluble organic compound as the second dopant, a resin component as the binder material, and various additives as a coating aid.
  • the dry layer thickness of the conductive polymer layer is preferably in the range of 30 to 2000 nm. It is more preferable that the thickness is 50 nm or more from the viewpoint of conductivity.
  • the conductive resin substrate is used for an organic electronic element, the unevenness difference of the metal fine line pattern is smoothed, and the layer thickness distribution of the organic functional layer is reduced. From the viewpoint of reducing the influence, it is more preferably 60 nm or more. Moreover, from a transparency point, it is more preferable that it is 600 nm or less, and it is still more preferable that it is 300 nm or less.
  • any appropriate method can be selected.
  • a coating method a gravure printing method, a flexographic printing method, an offset printing method, a screen printing method, an inkjet printing method, etc.
  • various coating methods such as roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, curtain coating method, spray coating method, doctor coating method, etc. Can be used.
  • the conductive polymer layer according to the present invention is formed by depositing a liquid containing at least a conductive polymer containing a ⁇ -conjugated conductive polymer and a polyanion on the substrate using the above coating method, followed by hot air drying or It can be formed by drying by a known heat drying method such as infrared drying or natural drying.
  • the temperature for drying by heating can be appropriately selected according to the substrate to be used, but in the case of a resin film substrate, it is preferably carried out at a temperature of 200 ° C. or lower.
  • infrared drying in order to selectively heat the conductive polymer layer, it is preferable to select an infrared wavelength region with less substrate absorption.
  • the substrate is a PET or PEN film
  • near infrared rays 800 to 1500 nm.
  • in order to quickly heat and dry it is also preferable to select an infrared region in the vicinity of 3 ⁇ m where water absorption maximum exists.
  • the conductive polymer according to the present invention includes a ⁇ -conjugated conductive polymer and a polyanion.
  • a conductive polymer can be easily produced by chemically oxidatively polymerizing a precursor monomer that forms a ⁇ -conjugated conductive polymer described later in the presence of an appropriate oxidizing agent, an oxidation catalyst, and a polyanion described later.
  • the ⁇ -conjugated conductive polymer is not particularly limited, and includes polythiophenes (including basic polythiophenes, the same applies hereinafter), polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylene.
  • a chain conductive polymer of vinylenes, polyazulenes, polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphthenes, polythiazyls can be used.
  • polythiophenes and polyanilines are preferable, and polyethylenedioxythiophene is most preferable from the viewpoint of conductivity, transparency, stability, and ease of adsorption to metal nanoparticles.
  • the precursor monomer used to form a ⁇ -conjugated conductive polymer has a ⁇ -conjugated system in the molecule, and even when polymerized by the action of an appropriate oxidizing agent, a ⁇ -conjugated system is formed in the main chain. It is what is done. Examples thereof include pyrroles and derivatives thereof, thiophenes and derivatives thereof, anilines and derivatives thereof, and the like.
  • the polyanion is an acidic polymer in a free acid state, and is a polymer of a monomer having an anion group or a copolymer of a monomer having an anion group and a monomer having no anion group.
  • the free acid may be in the form of a partially neutralized salt.
  • the polyanion includes a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester, and a copolymer thereof. Examples include those containing at least an anionic group.
  • the polyanion is a solubilized polymer that solubilizes the ⁇ -conjugated conductive polymer in a solvent.
  • the anion group of the polyanion functions as a dopant for the ⁇ -conjugated conductive polymer, and improves the conductivity and heat resistance of the ⁇ -conjugated conductive polymer.
  • the anion group of the polyanion may be a functional group capable of causing chemical oxidation doping to the ⁇ -conjugated conductive polymer.
  • a monosubstituted sulfate group A substituted phosphate group, a phosphate group, a carboxy group, a sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group on the ⁇ -conjugated conductive polymer, a sulfo group, a mono-substituted sulfate group, and a carboxy group are more preferable.
  • polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfone. 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 and 2 or more types of copolymers may be sufficient.
  • the polyanion may further have F (fluorine atom) in the compound.
  • F fluorine atom
  • Nafion made by Dupont
  • Flemion made by Asahi Glass Co., Ltd.
  • perfluoro vinyl ether containing a carboxylic acid group
  • the ratio of the ⁇ -conjugated conductive polymer and the polyanion contained in the conductive polymer is preferably in the range of 1: 1 to 20 by mass ratio. From the viewpoints of conductivity and dispersibility, it is more preferably in the range of 1: 2 to 10.
  • Such a conductive polymer is also commercially available, and such a commercially available material can be preferably used in the present invention.
  • a conductive polymer composed of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (abbreviated as PEDOT-PSS) is a Clevios series from Heraeus, and PEDOT-PSS 483095 and 560596 from Aldrich.
  • PEDOT-PSS polystyrene sulfonic acid
  • the 2nd dopant which has the effect which improves the electroconductivity of a conductive polymer can be added to the conductive polymer layer which concerns on this invention.
  • a 2nd dopant There is no restriction
  • 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, glycerin and the like. Among these, ethylene glycol and diethylene glycol are preferable.
  • Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, ⁇ -butyrolactone, and the like.
  • Examples of the ether group-containing compound include diethylene glycol monoethyl ether.
  • Examples of the sulfoxide group-containing compound include dimethyl sulfoxide. These may be used alone or in combination of two or more, but it is preferable to use at least one selected from dimethyl sulfoxide, ethylene glycol, diethylene glycol, and propylene glycol.
  • the conductive polymer layer according to the present invention contains a transparent resin component and an additive in order to ensure film formability and film strength in addition to a conductive polymer containing at least a ⁇ -conjugated conductive polymer and a polyanion. May be.
  • the transparent resin component is not particularly limited as long as it is compatible or mixed and dispersed with the conductive polymer, and may be a thermosetting resin or a thermoplastic resin.
  • polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyimide resins such as polyimide and polyamideimide, polyamide resins such as polyamide 6, polyamide 6,6, polyamide 12 and polyamide 11, polyvinylidene fluoride, Fluorine resin such as polyvinyl fluoride, polytetrafluoroethylene, ethylene tetrafluoroethylene copolymer, polychlorotrifluoroethylene, etc., vinyl resin such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride, epoxy resin, xylene Resin, aramid resin, polyurethane resin, polyurea resin, melamine resin, phenol resin, polyether, acrylic resin and their co-polymer Body, and the like.
  • a water-dispersible binder that can be uniformly dispersed in an aqueous solvent means that the binder is uniformly dispersible in an aqueous solvent and means that the colloidal particles made of the binder are dispersed in the aqueous solvent without agglomeration. .
  • the size (average particle diameter) of the colloidal particles is generally about 0.001 to 1 ⁇ m (1 to 1000 nm). The average particle size of the colloidal particles can be measured with a light scattering photometer.
  • the aqueous solvent includes 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, and a hydrophilic organic solvent.
  • pure water including distilled water and deionized water
  • alcohol solvents such as methanol and ethanol
  • mixed solvents of water and alcohol and the like.
  • the water dispersible binder is preferably transparent.
  • the water-dispersible binder is not particularly limited as long as it is a medium that forms a film, and examples thereof include acrylic resin emulsions, aqueous urethane resins, and aqueous polyester resins.
  • the acrylic resin emulsion is made of vinyl acetate, acrylic acid, a polymer of acrylic acid-styrene, or a copolymer with other monomers.
  • the acid part is composed of a copolymer of an anionic group having a counter salt with a lithium, sodium, potassium, or ammonium salt, and a monomer having a nitrogen atom, and the nitrogen atom has a cationic group in which a hydrochloride or the like is formed.
  • it is anionic.
  • water-based urethane resin examples include water-dispersed urethane resin and ionomer-type water-based urethane resin (anionic).
  • the water-dispersed urethane resin includes a polyether-based urethane resin and a polyester-based urethane resin, preferably a polyester-based urethane resin.
  • the ionomer type water-based urethane resin include polyester-based urethane resins, polyether-based urethane resins, and polycarbonate-based urethane resins, and polyester-based urethane resins and polyether-based urethane resins are preferable.
  • the aqueous polyester resin is synthesized from a polybasic acid component and a polyol component.
  • the polybasic acid component is, for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, adipic acid, succinic acid, sebacic acid, dodecanedioic acid, etc., and these may be used alone. Two or more types may be used in combination, and as the polybasic acid component that can be used particularly preferably, terephthalic acid and isophthalic acid are industrially produced in large quantities and inexpensive. Particularly preferred.
  • Typical examples of the polyol component include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol, bisphenol, and the like. These may be used singly or may be used in combination of two or more.
  • the polyol component that can be particularly suitably used is inexpensive because it is industrially mass-produced, Ethylene glycol, propylene glycol, or neopentyl glycol is particularly preferable because various performances are balanced such as improvement of solvent resistance and weather resistance of the resin coating.
  • the water-dispersible binder can be used alone or in combination.
  • the amount of the water-dispersible binder that can be dispersed in the aqueous solvent is preferably in the range of 50 to 1000% by weight, more preferably 100 to 100%, based on the conductive polymer, from the viewpoint of transparency and conductivity. It is within the range of 900% by mass, and more preferably within the range of 200 to 800% by mass.
  • the water-soluble binder is preferably a water-soluble binder containing a structural unit represented by the following general formula (1).
  • R represents a hydrogen atom or a methyl group.
  • Q represents —C ( ⁇ O) O— or —C ( ⁇ O) NRa—.
  • Ra represents a hydrogen atom or an alkyl group.
  • A represents a substituted or unsubstituted alkylene group or — (CH 2 CHRbO) x CH 2 CHRb—.
  • Rb represents a hydrogen atom or an alkyl group.
  • x represents the average number of repeating units.
  • the water-soluble binder can be easily mixed with the conductive polymer, and also has the same effect as the second dopant described above. By using the water-soluble binder in combination, the conductivity and transparency are not lowered. The thickness of the conductive polymer layer can be increased.
  • the water-soluble binder means a water-soluble binder
  • the water-soluble means that 0.001 g or more of the water-soluble binder is dissolved in 100 g of water at 25 ° C.
  • the dissolution can be measured with a haze meter or a turbidimeter.
  • the water-soluble binder is preferably transparent.
  • the water-soluble binder preferably has a structure including a structural unit represented by the general formula (1).
  • the homopolymer represented by General formula (1) may be sufficient, and the other component may be copolymerized.
  • the structural unit represented by the general formula (1) is preferably contained in an amount of 10 mol% or more, more preferably 30 mol% or more, and more preferably 50 mol% or more. Is more preferable.
  • the water-soluble binder is preferably contained in the conductive polymer-containing layer in the range of 40 to 95% by mass, and more preferably in the range of 50 to 90% by mass.
  • the number average molecular weight of the water-soluble binder is preferably in the range of 3,000 to 2,000,000, more preferably in the range of 4,000 to 500,000, and still more preferably in the range of 5,000 to 100,000.
  • the number average molecular weight and molecular weight distribution of the water-soluble binder can be measured by a generally known gel permeation chromatography (GPC).
  • the solvent to be used is not particularly limited as long as the binder dissolves, and THF (tetrahydrofuran), DMF (dimethylformamide) or CH 2 Cl 2 is preferable, THF or DMF is more preferable, and DMF is further preferable.
  • the measurement temperature is not particularly limited, but 40 ° C. is preferable.
  • the conductive polymer layer may contain inorganic fine particles from the viewpoints of drying property during film formation, film strength, and improvement in light extraction efficiency when used in organic electronic devices such as organic EL devices.
  • a fine particle sol is preferable, and a metal oxide fine particle sol is particularly preferable.
  • the metal oxide fine particles are preferably TiO 2 (titanium dioxide sol) from the viewpoint of stability. Further, among TiO 2 , rutile type is particularly preferable than anatase type, since the catalytic activity is lower, and the weather resistance of the conductive polymer layer and the adjacent layer becomes higher.
  • the particularly preferred primary particle diameter of the titanium dioxide fine particles is in the range of 5 to 15 nm, and most preferably in the range of 6 to 10 nm.
  • Gas barrier layer An organic electronic device such as an organic EL device easily deteriorates in performance when a small amount of moisture or oxygen is present inside the device.
  • a resin substrate is used as the substrate, it is effective to form a gas barrier layer having a high shielding ability against moisture and oxygen in order to prevent moisture and oxygen from diffusing into the element through the resin substrate. is there.
  • membrane by inorganic compounds, such as a silica can be formed by vacuum evaporation or CVD method.
  • a gas barrier layer can be formed by coating and drying a coating solution containing a polysilazane compound and then oxidizing the coating solution by ultraviolet irradiation in a nitrogen atmosphere containing oxygen and water vapor.
  • the polysilazane compound used in the present invention is a polymer having a silicon-nitrogen bond, and is composed of Si—N, Si—H, N—H, etc. SiO 2 , Si 3 N 4 and both intermediate solid solutions SiO x N y etc.
  • the ceramic precursor inorganic polymer When using a resin substrate, as described in JP-A-8-112879, it is preferable that the resin substrate be ceramicized at a relatively low temperature to be modified to silica, and those represented by the following general formula (2) are preferable. Can be used.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.
  • the polysilazane compound represented by the general formula (2) at least one of perhydropolysilazane, in which all of R 1 , R 2 and R 3 are hydrogen atoms, R 1 , R 2 and R 3 is an alkyl group, Examples thereof include organopolysilazanes which are alkenyl groups, cycloalkyl groups, aryl groups, alkylsilyl groups, alkylamino groups, or alkoxy groups, and R 1 , R 2 and R are used from the viewpoint of denseness as a gas barrier film to be obtained. Perhydropolysilazane in which all 3 are hydrogen atoms is particularly preferred.
  • any appropriate method can be selected.
  • a coating method a roll coating method, a bar coating method, a dip coating method, a spin coating method, a casting method, a die coating method, or a blade coating method.
  • various coating methods such as curtain coating, spray coating, and doctor coating
  • various coating methods such as gravure printing, flexographic printing, offset printing, screen printing, and inkjet printing can be used.
  • a gravure printing method a flexographic printing method, an offset printing method, a screen printing method, or an ink jet printing method.
  • the gas barrier layer may be a single layer or may have a laminated structure of two or more layers. When it has a laminated structure, it may be a laminated structure of an inorganic compound, or may be formed as a hybrid film of an inorganic compound and an organic compound. Further, a stress relaxation layer may be sandwiched between the gas barrier layers. Even when a single layer or a plurality of layers are laminated, the thickness of one gas barrier layer is preferably in the range of 30 to 1000 nm, more preferably in the range of 30 to 500 nm, and still more preferably in the range of 90 to 500 nm. Within range. When it is 30 nm or more, the layer layer thickness uniformity is good, and excellent gas barrier performance is obtained. When the thickness is 1000 nm or less, cracks due to bending are rarely abruptly entered, and an increase in internal stress during film formation can be suppressed, and generation of defects can be prevented.
  • water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured by a method according to JIS K 7129: 1992 is 1 preferably ⁇ is 10 -3 g / (m 2 ⁇ 24h) or less, and still more, JIS K 7126: oxygen permeability measured in compliance with the method 1987 is 1 ⁇ 10 -3 ml / (m 2 ⁇ 24 h ⁇ atm) (1 atm is 1.01325 ⁇ 10 5 Pa) and water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) is 1 ⁇ 10 ⁇ 3 It is more preferable that it is g / (m 2 ⁇ 24h) or less.
  • the surface of the substrate can be pretreated with a silane coupling agent or the like in order to improve the adhesion to the substrate.
  • the organic electronic device according to the present invention has a conductive resin substrate and an organic functional layer manufactured by the method of the present invention.
  • a transparent conductive resin substrate formed by the method of the present invention is used as a first electrode portion, an organic functional layer is formed on the first electrode portion, and further disposed opposite to the organic functional layer.
  • the organic functional layer include an organic light emitting layer (also referred to as a light emitting layer), an organic photoelectric conversion layer, a liquid crystal polymer layer, and the like without any particular limitation.
  • the organic functional layer is a thin film and is driven by current. This is particularly effective in the case of an organic light emitting layer and an organic photoelectric conversion layer that are based.
  • the organic electronic element according to the present invention is an organic EL element and an organic photoelectric conversion element will be described.
  • an organic EL device having a light emitting layer as an organic functional layer includes a hole injection layer, a hole in addition to the light emitting layer.
  • a layer that controls light emission such as a transport layer, an electron transport layer, an electron injection layer, a hole blocking layer, or an electron blocking layer, may be used in combination with the light emitting layer.
  • the conductive polymer layer according to the present invention can also function as a hole injection layer, it can also serve as a hole injection layer, but a hole injection layer may be provided independently.
  • the light emitting layer may be a monochromatic light emitting layer having a light emission maximum wavelength in the range of 430 to 480 nm, 510 to 550 nm, and 600 to 640 nm, respectively, and at least three of these light emitting layers are laminated.
  • a white light emitting layer may be used, and a non-light emitting intermediate layer may be provided between the light emitting layers.
  • the organic EL device of the present invention is preferably a white light emitting layer.
  • the light emitting material or doping material that can be used for the light emitting layer includes anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzo Xazoline, 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, ru Ren, distyrylbenzene derivatives,
  • a light emitting material selected from these compounds in a range of 90 to 99.5% by mass and a doping material in a range of 0.5 to 10% by mass.
  • a light emitting layer is produced by a well-known method using said material etc., and methods, such as vapor deposition, application
  • Electrode The conductive resin substrate according to the present invention is used in the first electrode portion or the second electrode portion, and the first electrode portion is a transparent conductive resin substrate and is an anode. It is a preferable aspect.
  • the second electrode part may be a conductive material single layer, but in addition to a conductive material, a resin that holds these may be used in combination.
  • a material having a low work function (4 eV or less) metal referred to as an electron injecting metal
  • an alloy an electrically conductive compound, or a mixture thereof is used.
  • Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this for example, a magnesium / silver mixture from the viewpoint of durability against electron injection and oxidation
  • a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, aluminum and the like are suitable.
  • the second electrode part can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the second electrode portion is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected within the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the light traveling to the second electrode part side is reflected by the second electrode part and returns to the first electrode part side.
  • a metal material as the conductive material of the second electrode portion, this light can be reused, and the light extraction efficiency is further improved.
  • the organic photoelectric conversion element includes a first electrode part, a photoelectric conversion layer having a bulk heterojunction structure (p-type semiconductor layer and n-type semiconductor layer) (hereinafter also referred to as a bulk heterojunction layer), and second. It is preferable to have a structure in which electrode portions are stacked.
  • the conductive resin substrate according to the present invention is used at least on the incident light side. You may have intermediate
  • the photoelectric conversion layer is a layer that converts light energy into electric energy, and constitutes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed. It is preferable.
  • the p-type semiconductor material functions relatively as an electron donor (donor)
  • the n-type semiconductor material functions relatively as an electron acceptor (acceptor).
  • an electron donor and an electron acceptor are “an electron donor that forms a pair of holes and electrons (charge separation state) when electrons are transferred from the electron donor to the electron acceptor when light is absorbed.
  • Body and electron acceptor which does not simply donate or accept electrons like an electrode, but donates or accepts electrons by a photoreaction.
  • Examples of the p-type semiconductor material include various condensed polycyclic aromatic compounds and conjugated compounds.
  • the condensed polycyclic aromatic compound for example, anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, sarkham anthracene, bisanthene, zestrene, heptazelene,
  • Examples thereof include compounds such as pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, and derivatives and precursors thereof.
  • conjugated compound examples include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, tetrathiafulvalene compound, quinone Compounds, cyano compounds such as tetracyanoquinodimethane, fullerenes, and derivatives or mixtures thereof.
  • thiophene hexamers ⁇ -seccithiophene, ⁇ , ⁇ -dihexyl- ⁇ -sexualthiophene, ⁇ , ⁇ -dihexyl- ⁇ -kinkethiophene, ⁇ , ⁇ -bis (3- An oligomer such as butoxypropyl) - ⁇ -sexithiophene can be preferably used.
  • polymer p-type semiconductor examples include polyacetylene, polyparaphenylene, polypyrrole, polyparaphenylene sulfide, polythiophene, polyphenylene vinylene, polycarbazole, polyisothianaphthene, polyheptadiyne, polyquinoline, polyaniline, and the like.
  • SWNT single wall nanotubes
  • merocyanine dyes dyes such as hemicyanine dyes and the like
  • ⁇ such as polysilane and polygermane Conjugated polymers and organic / inorganic hybrid materials described in JP 2000-260999 A can also be used.
  • At least one selected from the group consisting of condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed ring tetracarboxylic acid diimides, metal phthalocyanines, and metal porphyrins is preferable.
  • pentacenes are more preferable. Examples of pentacenes include pentacene derivatives having substituents described in International Publication No. 2003/16599, International Publication No. 2003/28125, US Pat. No. 6690029, Japanese Patent Application Laid-Open No. 2004-107216, The pentacene precursor described in Japanese Patent Application Publication No. 2003/136964 and the like; Amer. Chem. Soc. , Vol127, No14, 4986, and the like, and substituted derivatives thereof and the like.
  • Such compounds include those described in J. Org. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. An acene-based compound substituted with a trialkylsilylethynyl group described in US Pat. No. 9,2706, a pentacene precursor described in US Patent Application Publication No. 2003/136964, etc .; Examples include precursor type compounds (precursors) such as porphyrin precursors. Among these, the latter precursor type can be preferably used.
  • the precursor type is insolubilized after conversion, so when forming a hole transport layer, electron transport layer, hole block layer, electron block layer, etc. on the bulk hetero junction layer by a solution process, the bulk hetero junction layer is This is because the material constituting each of the layers and the material forming the bulk heterojunction layer are not mixed, so that further efficiency improvement and life improvement can be achieved.
  • the chemical structure was changed by a method such as exposing a p-type semiconductor material precursor to a vapor of a compound that causes heat, light, radiation, or a chemical reaction, and converted into a p-type semiconductor material.
  • a compound is preferred. Of these, compounds that cause a chemical structural change by heat are preferred.
  • n-type semiconductor materials include fullerene, octaazaporphyrin, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), naphthalene tetracarboxylic anhydride, naphthalene tetracarboxylic diimide, perylene tetracarboxylic acid
  • n-type semiconductor materials include fullerene, octaazaporphyrin, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), naphthalene tetracarboxylic anhydride, naphthalene tetracarboxylic diimide, perylene tetracarboxylic acid
  • Fullerene-containing polymer compounds include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), etc. Examples thereof include a polymer compound having a skeleton.
  • a polymer compound (derivative) having fullerene C60 as a skeleton is preferable.
  • the fullerene-containing polymers are roughly classified into polymers in which fullerene is pendant from a polymer main chain and polymers in which fullerene is contained in the polymer main chain. Fullerene is contained in the polymer main chain. Are preferred. This is because a polymer containing fullerene in the main chain does not have a branched structure, so that when it is solidified, high-density packing can be achieved, and as a result, high mobility can be obtained. It is estimated that there is not.
  • Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a vapor deposition method and a coating method (including a casting method and a spin coating method).
  • a photoelectric conversion element of this invention may be utilized by a single layer and may be laminated
  • Example 1 ⁇ Preparation of conductive resin substrate ⁇ (1) Preparation of conductive resin substrate original plates (I) to (X) (1.1.1) Preparation of inorganic compound particle dispersion The following particles (i) to (ix) are mixed with ultrapure water. While being cooled at room temperature (25 ° C.), dispersed in an ultrasonic disperser (SMH UH-50) under standard conditions of microchip step (SM-3 MS-3 3 mm ⁇ ) for 10 minutes, 1.0 ⁇ m filter Then, 30 mass% TiO 2 dispersions (I) to (VIII) and ZnO dispersion (IX) were prepared. In addition to this, the following ZrO 2 dispersion (X) was prepared.
  • SSH UH-50 ultrasonic disperser
  • SM-3 MS-3 3 mm ⁇ microchip step
  • Titanium oxide AMT-600 (refractive index 2.52, average particle size 30 nm) (manufactured by Teika)
  • Titanium oxide Super Titania F-2 (refractive index 2.59, average particle size 60 nm) (manufactured by Showa Denko)
  • Titanium oxide MT-700B (refractive index 2.71, average particle size 80 nm) (manufactured by Teica)
  • Titanium oxide Super Titania F-1 (refractive index 2.62, average particle size 90 nm) (manufactured by Showa Denko KK)
  • V) Titanium oxide JA-C (refractive index 2.52, average particle size 180 nm) (manufactured by Teika)
  • Titanium oxide JR-405 (refractive index: 2.71, average particle size: 210 nm) (manufactured by Teica)
  • Vii) Titanium oxide JR-301 (refractive index: 2.71, average particle size: 210 nm)
  • ⁇ ZrO 2 dispersion> Zirconium oxide nano-use ZR-30AL (refractive index 2.4, average particle size 90 nm), solid content concentration 30 mass% aqueous dispersion (manufactured by Nissan Chemical Co., Ltd.)
  • the inorganic compound particle dispersions (I) to (X) prepared above with an applicator were dried layers having a thickness of 0.4 to 0 It was applied to a thickness of 6 ⁇ m and dried using a clean oven at 100 ° C. for 10 minutes to form resin substrates (I) to (X) with inorganic particle layers.
  • the layer thickness of the inorganic particle layer on the substrate was measured by using a high-intensity non-contact three-dimensional surface roughness meter WYKO NT9100 by shaving a part of the inorganic particle layer. The measurement measured the layer thickness in arbitrary 10 places, and calculated
  • a lattice pattern with a right-angle intersection was formed.
  • a desktop robot Shotmaster-300 manufactured by Musashi Engineering Co., Ltd.
  • an ink jet evaluation apparatus EB150 manufactured by Konica Minolta Co., Ltd.
  • the patterned PET film was dried at 80 ° C. for 2 minutes using a clean oven to prepare conductive resin substrate original plates (I) to (X).
  • the thickness of the metal nanoparticle fine line pattern was measured using a high-intensity non-contact three-dimensional surface shape roughness meter WYKO NT9100.
  • conductive resin substrate original plate (RII) In the production of conductive resin substrate original plates (I) to (X), silica particles having a refractive index of 1.45 and an average particle size of 100 nm were used as inorganic compound particles. A conductive resin substrate original plate (RII) was produced in the same manner except that it was used.
  • ⁇ No visual deformation is observed.
  • ⁇ When the conductive resin substrate after firing is placed on the surface plate so that the fine metal wire pattern is on the upper surface, the surface plate and the substrate are partially separated. The distance is less than 3 mm.
  • X When the conductive resin substrate after firing is placed on the surface plate so that the fine metal wire pattern is on the upper surface, the surface plate and the substrate are partially separated, and the distance is 3 mm or more and less than 6 mm.
  • XX When the fired conductive resin substrate is placed on the surface plate so that the fine metal wire pattern is on the upper surface, the surface plate and the substrate are partially separated, and the distance is 6 mm or more
  • the conductive resin substrates (A1) to (D10) having inorganic particle layers containing inorganic compound particles having a refractive index in the range of 1.9 to 3.0 are: Compared to conductive resin substrates (RA1) to (RD3) having an inorganic particle layer containing inorganic compound particles having a refractive index of less than 1.9, the sheet resistance value, ablation suppression and adhesion are excellent. I understand that. Further, as is apparent from Table 3, the conductive resin substrates (E1) to (G10) and (RE1) to (RG10) produced by heating and firing can measure whether the sheet resistance value is not measurable.
  • an inorganic particle layer containing inorganic compound particles having a refractive index in the range of 1.9 to 3.0 is formed on the transparent resin substrate, and a fine pattern of metal nanoparticles is formed on the inorganic particle layer. It was confirmed that firing a fine wire pattern of metal nanoparticles by light irradiation is useful as a method for producing a low-resistance conductive resin substrate having a fine metal wire pattern with excellent adhesion to the substrate.
  • the transparent resin substrate subjected to the dehumidification treatment in the second step was subjected to a modification treatment under the following conditions using the following apparatus.
  • the dew point temperature during the reforming process was -8 ° C.
  • Excimer irradiation equipment MODEL: MECL-M-1-200, wavelength 172 nm, lamp filled gas Xe (Reforming treatment conditions) Excimer light intensity 60 mW / cm 2 (172 nm) 1mm distance between sample and light source Stage heating temperature 70 °C Oxygen concentration in irradiation device 1% Excimer irradiation time 3 seconds
  • a transparent resin substrate having a gas barrier layer was produced as described above.
  • the transparent resin substrate having a gas barrier layer has a water vapor permeability of 1 ⁇ 10 ⁇ 3 g / g at a temperature of 25 ⁇ 0.5 ° C. and a relative humidity of 90 ⁇ 2% RH by a method in accordance with JIS K 7129: 1992. (M 2 ⁇ 24h) or less was confirmed.
  • the conductive resin substrates (BA6) and (BRA2) with the gas barrier layer are the same as the conductive resin substrates (A6) and (RA2) in Example 1. ) was produced.
  • CLEVIOS PH510 PEDOT / PSS aqueous dispersion, manufactured by Heraeus, solid concentration 1.89% by mass
  • 1.60 g Plus Coat Z-561 manufactured by Kyoyo Chemical Industry Co., Ltd., solid content concentration: 25% by mass
  • Conductive resin substrates (CP-A6) and (CP-RA2) are set in a commercially available vacuum deposition apparatus, and the constituent materials of each organic functional layer are arranged in each of the deposition crucibles in the vacuum deposition apparatus. The optimal amount for filling was filled.
  • the evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.
  • the energization crucible containing the following ⁇ -NPD is energized and heated, vapor deposition is performed at a vapor deposition rate of 0.1 nm / second, and hole transport with a layer thickness of 30 nm is performed. A layer was provided.
  • Ir-1 and Ir-14 and the following compound 1-7 were added at a deposition rate of 0.1 nm / second so that the following Ir-1 had a concentration of 13% by mass and the following Ir-14 had a concentration of 3.7% by mass.
  • Co-evaporation was performed to form a green-red phosphorescent light emitting layer having an emission maximum wavelength of 622 nm and a layer thickness of 10 nm.
  • E-66 and compound 1-7 were co-deposited at a deposition rate of 0.1 nm / second so that the following E-66 was 10% by mass, and blue phosphorescence was emitted with a maximum emission wavelength of 471 nm and a layer thickness of 15 nm.
  • a layer was formed.
  • M-1 below is deposited to a thickness of 5 nm to form a hole blocking layer
  • CsF is co-deposited with M-1 so that the layer thickness ratio is 10%
  • electron transport with a thickness of 45 nm is performed.
  • a layer was formed.
  • Al was mask-deposited under a vacuum of 5 ⁇ 10 ⁇ 4 Pa as a material for forming a first electrode portion external extraction terminal and a 50 mm ⁇ 50 mm second electrode portion (cathode).
  • a second electrode portion having a thickness of 100 nm was formed.
  • an adhesive is applied around the second electrode portion except for the end portions so that external lead terminals of the first electrode portion and the second electrode portion can be formed, and Al 2 O 3 is thickened on the polyethylene terephthalate resin film.
  • the adhesive After bonding a flexible sealing member deposited at 300 nm, the adhesive is cured by heat treatment to form a sealing film, and an organic EL element (EL-A6), (EL-RA2) having a light emitting area of 50 mm ⁇ 50 mm was made.
  • EL-A6 organic EL element
  • EL-RA2 organic EL element having a light emitting area of 50 mm ⁇ 50 mm
  • a two-component epoxy compounded resin manufactured by Three Bond Co., Ltd.
  • 2016B and 2103 was blended at a ratio of 100: 3.
  • the present invention can be particularly preferably used for providing a method for producing a low-resistance conductive resin substrate having a fine metal wire pattern with excellent adhesion to the substrate.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

La présente invention aborde le problème consistant à pourvoir à un procédé de fabrication d'un substrat de résine conducteur à faible résistance comportant un motif de fil mince métallique qui présente une excellente adhérence au substrat. Ledit procédé de fabrication d'un substrat de résine conducteur est caractérisé en ce qu'il comprend au moins les étapes suivantes : (1) une étape au cours de laquelle une couche de particules inorganiques contenant des particules de composé inorganique présentant un indice de réfraction situé dans la plage allant de 1,9 à 3,0 inclus est formée sur la partie supérieure d'un substrat de résine transparent ; (2) une étape au cours de laquelle un motif de fil mince constitué de nanoparticules métalliques est formé sur la partie supérieure de la couche de particules inorganiques ; et (3) une étape au cours de laquelle une exposition à la lumière est utilisée en vue de cuire le motif de fil mince de nanoparticules métalliques, formant ainsi un motif de fil mince métallique.
PCT/JP2014/061735 2013-05-17 2014-04-25 Procédé de fabrication de substrat de résine conducteur Ceased WO2014185256A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016143201A1 (fr) * 2015-03-06 2016-09-15 コニカミノルタ株式会社 Électrode transparente, son procédé de fabrication, et élément électroluminescent organique
WO2016147481A1 (fr) * 2015-03-13 2016-09-22 コニカミノルタ株式会社 Électrode transparente, procédé de fabrication d'électrode transparente, et élément électroluminescent organique
WO2017217201A1 (fr) * 2016-06-14 2017-12-21 コニカミノルタ株式会社 Élément électroconducteur transparent et élément électroluminescent organique
KR102111967B1 (ko) * 2018-11-15 2020-05-18 (주)아이테드 투명전극 제조 장치 및 투명전극 제조 방법
EP3711460A1 (fr) * 2017-11-14 2020-09-23 Agfa-Gevaert N.V. Procédé de fabrication d'un motif conducteur
WO2021130292A1 (fr) * 2019-12-23 2021-07-01 Sorbonne Universite Composition d'encre pour la production de micromotifs

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JP2010186642A (ja) * 2009-02-12 2010-08-26 Hitachi Maxell Ltd 透明導電性シート及びその製造方法
US20130095308A1 (en) * 2010-09-17 2013-04-18 Lg Hausys, Ltd. Transparent conductive film having excellent visibility and method of manufacturing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010186642A (ja) * 2009-02-12 2010-08-26 Hitachi Maxell Ltd 透明導電性シート及びその製造方法
US20130095308A1 (en) * 2010-09-17 2013-04-18 Lg Hausys, Ltd. Transparent conductive film having excellent visibility and method of manufacturing the same

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016143201A1 (fr) * 2015-03-06 2016-09-15 コニカミノルタ株式会社 Électrode transparente, son procédé de fabrication, et élément électroluminescent organique
JPWO2016143201A1 (ja) * 2015-03-06 2018-01-18 コニカミノルタ株式会社 透明電極とその製造方法及び有機エレクトロルミネッセンス素子
WO2016147481A1 (fr) * 2015-03-13 2016-09-22 コニカミノルタ株式会社 Électrode transparente, procédé de fabrication d'électrode transparente, et élément électroluminescent organique
JPWO2016147481A1 (ja) * 2015-03-13 2018-01-25 コニカミノルタ株式会社 透明電極、透明電極の製造方法及び有機エレクトロルミネッセンス素子
WO2017217201A1 (fr) * 2016-06-14 2017-12-21 コニカミノルタ株式会社 Élément électroconducteur transparent et élément électroluminescent organique
JPWO2017217201A1 (ja) * 2016-06-14 2019-04-04 コニカミノルタ株式会社 透明導電部材、及び、有機エレクトロルミネッセンス素子
EP3711460A1 (fr) * 2017-11-14 2020-09-23 Agfa-Gevaert N.V. Procédé de fabrication d'un motif conducteur
US11236249B2 (en) 2017-11-14 2022-02-01 Agfa-Gevaert Nv Method of manufacturing a conductive pattern
KR102111967B1 (ko) * 2018-11-15 2020-05-18 (주)아이테드 투명전극 제조 장치 및 투명전극 제조 방법
WO2021130292A1 (fr) * 2019-12-23 2021-07-01 Sorbonne Universite Composition d'encre pour la production de micromotifs

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