WO2018180961A1 - Stratifié conducteur transparent et son procédé de procuction - Google Patents

Stratifié conducteur transparent et son procédé de procuction Download PDF

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Publication number
WO2018180961A1
WO2018180961A1 PCT/JP2018/011632 JP2018011632W WO2018180961A1 WO 2018180961 A1 WO2018180961 A1 WO 2018180961A1 JP 2018011632 W JP2018011632 W JP 2018011632W WO 2018180961 A1 WO2018180961 A1 WO 2018180961A1
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layer
transparent conductive
conductive laminate
transparent
auxiliary electrode
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PCT/JP2018/011632
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English (en)
Japanese (ja)
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務 原
豪志 武藤
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リンテック株式会社
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Publication of WO2018180961A1 publication Critical patent/WO2018180961A1/fr

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    • 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
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • 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
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • 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
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • 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
    • 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
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a transparent conductive laminate and a method for producing the same.
  • the transparent conductive layer has a resistance value lower than that of the transparent conductive layer as an auxiliary electrode layer
  • a structure provided with a pattern layer of fine metal wires or metal paste is used, and a transparent resin layer may be disposed between the fine wires or between the pattern layers.
  • Patent Document 1 discloses a flexibility obtained by applying a coating liquid containing transparent conductive particles and a dispersion medium on a transparent base sheet and laminating a transparent conductive film from the viewpoint of making the electronic device flexible.
  • a transparent conductive sheet is disclosed.
  • Patent Document 2 discloses that the transparent conductive layer is formed of indium-tin oxide (ITO) or the like by a dry film forming method from the viewpoint of demanding high transparency and low resistance. .
  • ITO indium-tin oxide
  • Patent Document 1 Although it has flexibility because it uses a transparent substrate sheet, it has a configuration in which conductivity is expressed in a transparent conductive film formed by applying a coating liquid containing transparent conductive particles and a dispersion medium. For this reason, there is no disclosure of a transparent conductive film formed by a dry film formation method.
  • Patent Document 2 discloses that the transparent conductive layer is formed on the surface composed of the auxiliary electrode layer and the transparent resin layer by a dry film forming method, but the present inventors have further studied. As a result, due to the strong stress of the film formed by the dry film formation method in addition to the temperature rise during film formation, irregularities occur on the surface of the transparent conductive layer, resulting in a decrease in optical properties, for example, a large haze value. It came to discover that there is a problem of increasing.
  • an object of the present invention is to provide a transparent conductive laminate having excellent optical characteristics and flexibility at the same time.
  • the present inventors have determined that the elastic modulus of the opening portion of the auxiliary electrode layer or the embedded resin layer provided above the opening portion and the auxiliary electrode layer has a specific value. By controlling to the range, it was found that while having flexibility, an increase in haze of the transparent conductive layer formed by the dry film forming method can be suppressed, and the present invention was completed. That is, the present invention provides the following (1) to (13).
  • (1) A transparent conductive laminate comprising at least an embedded resin layer, an auxiliary electrode layer, and a transparent conductive layer on a transparent substrate, wherein the transparent conductive layer is made of a metal oxide, and the embedded resin layer
  • a solar cell element or organic electroluminescence element comprising the transparent conductive laminate according to any one of (1) to (10) above.
  • the manufacturing method of a transparent conductive laminated body including the process of forming the said embedded resin layer on an electrode layer and an opening part, and the process of forming the said transparent conductive layer.
  • the transparent conductive laminate of the present invention is a transparent conductive laminate comprising at least an embedded resin layer, an auxiliary electrode layer, and a transparent conductive layer on a transparent substrate, and the transparent conductive layer is made of a metal oxide.
  • the elastic modulus at 25 ° C. of the embedded resin layer is 3000 to 8000 MPa, and the elastic modulus at 70 ° C. is 1000 to 7000 MPa. By controlling the elastic modulus at 25 ° C. and 70 ° C.
  • a “transparent conductive laminate” and a “transparent conductive laminate” are used separately.
  • the “transparent conductive laminate” means a laminate that does not include a transparent conductive layer in the configuration of the “transparent conductive laminate” of the present invention. The configuration of the transparent conductive laminate of the present invention will be described with reference to the drawings.
  • FIG. 1 is a cross-sectional view showing an example of the configuration of the transparent conductive laminate of the present invention.
  • the transparent conductive laminate 1 ⁇ / b> A has a configuration in which an embedded resin layer 3, an auxiliary electrode 4, and a transparent conductive layer 5 are laminated on a transparent substrate 2.
  • the auxiliary electrode layer 4 has an opening 9 between adjacent auxiliary electrode layers 4, and the embedded resin layer 3 exists on the opening 9 and the auxiliary electrode layer 4.
  • FIG. 2 is a cross-sectional view showing another example of the configuration of the transparent conductive laminate of the present invention.
  • the transparent conductive laminate 1B has a structure in which a transparent gas barrier layer 7, an adhesion layer 8, an embedded resin layer 3, an auxiliary electrode 4 and a transparent conductive layer 5 are laminated on a transparent substrate 2 with a primer layer 6 interposed therebetween. is there.
  • the auxiliary electrode layer 4 has an opening 9 between adjacent auxiliary electrode layers 4, and the embedded resin layer 3 exists on the opening 9 and the auxiliary electrode layer 4. In the above, the embedded resin layer 3 may exist only in the opening 9.
  • the transparent substrate used in the present invention is not particularly limited, and may be appropriately selected according to the device to be used. For example, it is not particularly limited as long as it has flexibility and high transmittance in the visible light range. , Flexible glass, resin film and the like.
  • Resin film materials include polyimide, polyamide, polyamideimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cyclohexane
  • Examples include olefin copolymers, cycloolefin polymers, aromatic polymers, polyurethane polymers, and the like.
  • polyester examples include polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), and polyarylate.
  • cycloolefin polymer examples include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof.
  • a cycloolefin polymer industrially, Apel (manufactured by Mitsui Chemicals, ethylene-cycloolefin copolymer), Arton (manufactured by JSR, norbornene copolymer), Zeonore (manufactured by Nippon Zeon Co., Ltd., norbornene copolymer) Polymer) and the like.
  • Apel manufactured by Mitsui Chemicals, ethylene-cycloolefin copolymer
  • Arton manufactured by JSR, norbornene copolymer
  • Zeonore manufactured by Nippon Zeon Co., Ltd., norbornene copolymer
  • Polymer polyethylene terephthalate
  • PEN polyethylene naphthalate
  • a cycloolefin polymer and a cycloolefin copolymer are particularly preferable.
  • polyimide is particularly preferable.
  • the thickness of the transparent substrate is preferably 1 to 1000 ⁇ m, more preferably 5 to 250 ⁇ m, and still more preferably 10 to 200 ⁇ m. If it is this range, the mechanical strength as a base material and transparency can be ensured.
  • the auxiliary electrode layer used for this invention is provided in order to reduce the sheet resistance value of the transparent conductive layer of the transparent conductive laminated body of this invention. Moreover, in order to suppress the fall of the light transmittance of a transparent conductive layer, it patterns and provides an opening part normally.
  • the material of the auxiliary electrode layer is not particularly limited, but patterning is preferably performed using a method such as photolithography.
  • the material of the auxiliary electrode layer is gold, silver, copper, aluminum, magnesium, nickel, platinum, single metal such as palladium, palladium, silver-palladium, silver-copper, silver-magnesium, aluminum-silicon, aluminum-silver Binary or ternary aluminum alloys such as aluminum-copper and aluminum-titanium-palladium.
  • silver, copper, aluminum, and an aluminum alloy are preferable from the viewpoint of specific resistance, and copper and aluminum alloy are more preferable from the viewpoint of cost, etching property, and corrosion resistance.
  • a conductive paste containing a conductive material can be used as a material for the auxiliary electrode layer.
  • the conductive paste is not particularly limited.
  • a conductive paste in which conductive fine particles such as metal fine particles, carbon and ruthenium oxide, and conductive carbon materials such as metal nanowires and carbon nanotubes are dispersed in a solvent is used.
  • a binder component may be included, and two or more kinds of conductive pastes may be mixed and used.
  • An auxiliary electrode layer is obtained by printing and baking or curing this conductive paste.
  • the material of the metal fine particles is not particularly limited, and examples thereof include materials composed of the single metals and alloys described above. From the viewpoint of conductivity, silver, copper, aluminum and the like are preferable. From the viewpoint of corrosion resistance and chemical resistance, platinum, rhodium, ruthenium, palladium and the like are preferable, and one or more of these metals may be included. Moreover, you may use the composite fine particle like the copper particle which coat
  • the conductive carbon material is inferior to metal in terms of conductivity, but is low in price and excellent in corrosion resistance and chemical resistance.
  • the conductive carbon material is not particularly limited, and examples thereof include acetylene black, ketjen black, oil furnace black, conductive single-walled carbon nanotubes, conductive multi-walled carbon nanotubes, and graphene powder.
  • ruthenium oxide (RuO 2 ) fine particles are more expensive than the conductive carbon material, but can be used as an auxiliary electrode layer because they are conductive materials having excellent corrosion resistance.
  • the auxiliary electrode layer may be a single layer or a multilayer structure.
  • the multilayer structure may be a multilayer structure in which layers made of the same kind of material are laminated, or a multilayer structure in which layers made of at least two kinds of materials are laminated.
  • the multilayer structure is more preferably a two-layer structure in which layers of different materials are stacked.
  • the formed auxiliary electrode layer may be subjected to chemical treatment.
  • a blackening treatment to an auxiliary electrode layer mainly made of copper for the purpose of preventing reflection can be mentioned.
  • the contrast can be improved when the transparent conductive laminate of the present invention is used in a display device or a lighting device.
  • the pattern of the auxiliary electrode layer used in the present invention is not particularly limited, and is a lattice, honeycomb, comb, strip (stripe), linear, curved, wavy (sine curve, etc.), polygonal shape. And the like, a circular mesh shape, an elliptical mesh shape, and an indeterminate shape. Among these, a lattice shape, a honeycomb shape, or a comb shape is preferable.
  • the thickness of the auxiliary electrode layer is preferably 10 nm to 20 ⁇ m, more preferably 100 nm to 15 ⁇ m, still more preferably 1 ⁇ m to 10 ⁇ m.
  • the aperture ratio of the opening portion of the auxiliary electrode layer pattern (the portion where the auxiliary electrode layer is not formed) is preferably 80% or more and less than 100%, more preferably, from the viewpoint of transparency (light transmittance). Is 85% or more and less than 99%, more preferably 90% or more and less than 98%.
  • the aperture ratio is the ratio of the total area of the openings to the area of the entire region where the pattern of the auxiliary electrode layer including the openings is formed.
  • the line width of the auxiliary electrode layer is preferably from 0.1 to 100 ⁇ m, more preferably from 1 to 80 ⁇ m, still more preferably from 5 to 60 ⁇ m. If the line width is within this range, the aperture ratio is wide, the transmittance can be secured, and a stable low-resistance transparent conductive laminate can be obtained, which is preferable.
  • the embedded resin layer used in the present invention suppresses the occurrence of unevenness on the surface of the transparent conductive layer of the transparent conductive laminate due to the temperature rise during the formation of the transparent conductive layer and the stress relaxation of the film, and the transferability of the auxiliary electrode layer. Used to improve and develop flexibility.
  • the embedded resin layer has an elastic modulus at 25 ° C. of 3000 to 8000 MPa and an elastic modulus at 70 ° C. of 1000 to 7000 MPa.
  • the elastic modulus at 25 ° C. is less than 3000 MPa, the transferability of the auxiliary electrode layer is inferior, so that a transparent conductive laminate using a transfer process cannot be formed. Flexibility falls that the elastic modulus in 25 degreeC is over 8000 Mpa. Further, if the elastic modulus at 70 ° C. is less than 1000 MPa, unevenness is likely to occur on the surface of the embedded resin layer due to thermal shrinkage derived from thermal history during dry film formation and film stress of the transparent conductive layer, and haze In addition to the rise, the transparent conductive layer is easily cracked.
  • the elastic modulus at 70 ° C. exceeds 7000 MPa, stress relaxation of the transparent conductive layer after film formation cannot be sufficiently suppressed, and the transparent conductive layer may be peeled off.
  • the elastic modulus at 25 ° C. is preferably 3300 to 7900 MPa, more preferably 3500 to 7500 MPa, still more preferably 3600 to 7300 MPa.
  • the elastic modulus at 70 ° C. is preferably 1100 to 6700 MPa, more preferably 1200 to 6500 MPa, and still more preferably 1300 to 6400 MPa.
  • the transferability of the auxiliary electrode layer is improved, and at the same time, stress relaxation of the transparent conductive layer after film formation can be suppressed, and haze increases. This leads to suppression, and a transparent conductive laminate having excellent optical properties is obtained.
  • the glass transition temperature of the embedded resin layer is preferably 90 ° C. or higher, more preferably 110 ° C. or higher, and further preferably 130 ° C. or higher. When the glass transition temperature of the embedded resin layer is within this range, the elastic modulus at 70 ° C. can be maintained within the above-described range.
  • the thickness of the embedded resin layer is preferably 0.1 to 100 ⁇ m, more preferably 1 to 80 ⁇ m, and still more preferably 5 to 60 ⁇ m. When the thickness of the embedded resin layer is within this range and the elastic modulus is within the range of the present invention, stress relaxation of the transparent conductive layer after film formation can be suppressed, and the auxiliary electrode layer can be embedded. .
  • the embedded resin layer used in the present invention is not particularly limited as long as the above-described elastic modulus is within the range of the present invention.
  • the embedded resin layer is made of a transparent resin composition containing inorganic fine particles. It may be. Moreover, it does not need to contain inorganic fine particles.
  • the following energy ray-sensitive composition is cured.
  • the energy beam sensitive composition includes (i) an energy beam curable compound, (ii) inorganic fine particles, and (iii) a photopolymerization initiator. By irradiating the energy ray sensitive composition with energy rays, it can be crosslinked and cured.
  • the composition contains additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, an infrared absorber, an antistatic agent, a leveling agent, and an antifoaming agent as long as the effects of the present invention are not impaired. be able to.
  • the term “energy beam” means an electromagnetic wave such as an ultraviolet ray or an electron beam or a charged particle beam having energy quanta.
  • (I) Energy ray curable compound As the energy ray curable compound, a polyfunctional (meth) acrylate monomer and / or a (meth) acrylate prepolymer is preferable, and a polyfunctional (meth) acrylate monomer is more preferable.
  • (meth) acrylate means both acrylate and methacrylate, and the same applies to other similar terms.
  • multifunctional (meth) acrylate monomers examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol diene.
  • Examples of (meth) acrylate-based prepolymers include polyester (meth) acrylate-based prepolymers, epoxy (meth) acrylate-based prepolymers, urethane (meth) acrylate-based prepolymers, polyol (meth) acrylate-based prepolymers, and the like. It is done.
  • the polyester (meth) acrylate-based prepolymer can be obtained, for example, by esterifying a hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid. it can.
  • the epoxy acrylate prepolymer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it.
  • the urethane acrylate prepolymer can be obtained, for example, by esterifying a polyurethane oligomer having hydroxyl groups at both ends obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid.
  • the polyol acrylate prepolymer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. These prepolymers may be used alone or in combination of two or more, and may be used in combination with the polyfunctional (meth) acrylate monomer.
  • the inorganic fine particles used in the present invention are not particularly limited, but damage the basic characteristics of the transparent conductive laminate, such as a decrease in total light transmittance (increase in haze) of the transparent conductive laminate.
  • the silica fine particles, titanium oxide fine particles, alumina fine particles, and calcium carbonate fine particles are exemplified.
  • the surface was modified with an organic compound having a polymerizable unsaturated group capable of reacting with the energy ray curable compound.
  • Silica fine particles are preferred.
  • Silica fine particles whose surface is modified with an organic compound having a polymerizable unsaturated group are prepared by reacting a silanol group on the surface of the silica fine particle with a polymerizable unsaturated group-containing organic compound having a functional group capable of reacting with the silanol group. Can be obtained.
  • the organic compound having a polymerizable unsaturated group that modifies the surface of the inorganic fine particles is included as a constituent of (ii) the inorganic fine particles, and the above-mentioned (i) energy ray-curable compound and Are distinguished.
  • polymerizable unsaturated group-containing organic compound having a functional group capable of reacting with the silanol group for example, a compound represented by the following general formula (1) is preferable.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a halogen atom or a group represented by the following formula.
  • organic compounds examples include (meth) acrylic acid chloride, (meth) acrylic acid 2-isocyanate ethyl, (meth) acrylic acid glycidyl, (meth) acrylic acid 2,3-iminopropyl, (meth) (Meth) acrylic acid and derivatives thereof such as 2-hydroxyethyl acrylate, (meth) acrylic acid, (meth) acryloyloxypropyltrimethoxysilane and the like may be mentioned, and these may be used alone or in combination of two or more.
  • the content of the inorganic fine particles in the entire volume of the embedded resin layer containing the inorganic fine particles is preferably 20 to 70% by volume, more preferably 30 to 65% by volume, and further preferably 30 to 60% by volume.
  • the content of the inorganic fine particles is within this range, for example, the elastic modulus at 70 ° C. of the embedded resin layer can be controlled to a high value. Moreover, heat resistance can be improved.
  • the inorganic fine particles silica fine particles are preferable.
  • the energy ray-sensitive composition contains a photopolymerization initiator.
  • the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylamino
  • photopolymerization initiators may be used alone or in combination of two or more.
  • Commercially available products such as Irgacure 127, Irgacure 184, Irgacure 819, Darocur 1173 and the like can be used as appropriate.
  • Examples of commercially available energy ray-sensitive compositions containing the above (i) energy ray-curable compound, (ii) silica fine particles, and (iii) a photopolymerization initiator include, for example, “Opster Z7530”, “Opster Z7524”, “OPSTAR TU4086” (product name, all manufactured by JSR Corporation), and the like.
  • an embedded resin layer may be formed using an energy ray sensitive composition
  • an energy ray sensitive composition comprising (ii) an energy ray curable compound and (iii) a photopolymerization initiator that does not contain silica fine particles.
  • the energy ray curable compound is preferably a urethane acrylate compound.
  • 2 mol or more of hydroxyl group is contained per 1 mol of a compound having 2 or more NCO groups in one molecule.
  • examples thereof include compounds having one or more (meth) acrylic groups in one molecule, obtained by reacting acrylic monomers.
  • hydroxyl group-containing acrylic monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono
  • examples include hydroxyl group-containing (meth) acrylates such as (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate.
  • the compound having two or more NCO groups in one molecule is preferably an oligomer having a molecular weight of about 500 to 50,000 obtained by reacting a polyisocyanate compound such as diisocyanate and a polyol compound such as diol.
  • polyisocyanate compound examples include aliphatic polyisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, and aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and phenylene diisocyanate.
  • polyol compound examples include glycols such as ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, and 1,4-cyclohexanedimethanol; trivalent or higher polyols such as glycerin and pentaerythritol; polyethylene glycol, polypropylene Polyether-type diols such as glycol, polytetramethylene glycol, polyhexamethylene glycol; the above diols react with dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid Polyester-type diols obtained in this manner.
  • glycols such as ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, and 1,4-cyclohexanedimethanol
  • UV curable urethane acrylate resin manufactured by Nippon Synthetic Chemical Co., Ltd., UT5746, solid content 80% by mass, ethyl acetate solution
  • the photopolymerization initiator include compounds that generate radicals when irradiated with light.
  • examples of such photopolymerization initiators include alkylphenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and oxime ester photopolymerization initiators. Of these, acylphosphine oxide photoreaction initiators are preferred from the viewpoint of easy adjustment of the elastic modulus.
  • the content of the photopolymerization initiator is preferably 0.2 to 5 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the (i) energy beam curable compound. When the content of the photopolymerization initiator is in this range, the weather resistance is good and the curability is sufficient.
  • the energy ray sensitive composition may contain an ultraviolet absorber as necessary.
  • the UV absorber include benzotriazole UV absorbers, hindered amine UV absorbers, benzophenone UV absorbers, and triazine UV absorbers. These ultraviolet absorbers may be used alone or in combination of two or more. Among these, a radical polymerizable ultraviolet absorber having a radical polymerizable double bond in the molecule is preferable.
  • the content when the ultraviolet absorber is contained is preferably 0.1 with respect to a total of 100 parts by mass of (i) active energy ray-curable compound, (ii) silica fine particles, and (iii) photopolymerization initiator. The amount is 2 to 10 parts by mass, more preferably 0.5 to 7 parts by mass.
  • the energy ray-sensitive composition may contain a light stabilizer as necessary.
  • light stabilizers include hindered amine light stabilizers, benzophenone light stabilizers, and benzotriazole light stabilizers. These light stabilizers may be used alone or in combination of two or more.
  • the content when the light stabilizer is contained is preferably 0.2 with respect to a total of 100 parts by mass of (i) energy ray-curable compound, (ii) silica fine particles, and (iii) photopolymerization initiator. -10 parts by mass, more preferably 0.5-7 parts by mass.
  • a polymerization inhibitor, a viscosity modifier, surfactant, an antifoamer, an organometallic coupling agent, a silane coupling agent etc. can be added as needed.
  • the transparent conductive layer used in the present invention is made of a metal oxide.
  • Metal oxides include indium-tin oxide (ITO), indium-zinc oxide (IZO), aluminum-zinc oxide (AZO), gallium-zinc oxide (GZO), indium-gallium-zinc oxide (IGZO), niobium oxide, titanium oxide, tin oxide, and the like. These can be used alone or in combination. Among these, ITO and IZO are particularly preferable from the viewpoints of transmittance, sheet resistance, and stability.
  • the film thickness of the transparent conductive layer is preferably 5 to 200 nm, more preferably 10 to 100 nm, and further preferably 20 to 50 nm.
  • the total light transmittance of the transparent conductive layer is preferably 70% or more, more preferably 80% or more, more preferably 90% or more, as measured in accordance with JIS K7361-1. Is more preferable.
  • the turbidity of the transparent conductive layer is preferably 10% or less, more preferably 5% or less.
  • the sheet resistance value of the transparent conductive layer is preferably 1000 ⁇ / ⁇ or less, more preferably 500 ⁇ / ⁇ or less, and still more preferably 100 ⁇ / ⁇ or less.
  • a dry film forming method is preferable from the viewpoint of obtaining high transmittance and low sheet resistance.
  • resistance vapor deposition, electron beam deposition, molecular beam epitaxy, ion beam, ion plating, sputtering, etc. physical vapor deposition (hereinafter also referred to as “PVD”), thermal CVD,
  • PVD physical vapor deposition
  • CVD chemical vapor deposition method
  • plasma CVD method a plasma CVD method
  • photo CVD method an epitaxial CVD method
  • an atomic layer CVD method or the like.
  • a sputtering method is preferable because a low sheet resistance value, high-precision film thickness control, a predetermined composition ratio is easily obtained, and quality stability is high. After the film is formed by the above method, a more excellent sheet resistance value can be obtained by performing a heat treatment within a range that does not affect other laminated bodies as necessary.
  • the dry film forming method referred to here is generally called a dry process method by treating the surface of a material using a gas phase or a molten state.
  • the transparent conductive laminate of the present invention preferably further comprises an adhesion layer on the surface of the embedded resin layer opposite to the transparent conductive layer, and is interposed between the embedded resin layer and a transparent gas barrier layer described later. More preferably, the adhesive layer is included. As described above, the adhesion layer is used to improve adhesion between the embedded resin layer and the transparent gas barrier layer, for example, and to improve flexibility of the transparent conductive laminate.
  • the elastic modulus at 25 ° C. of the adhesive layer is preferably 100 to 3000 MPa, more preferably 200 to 2400 MPa, and still more preferably 400 to 2200 MPa.
  • the elastic modulus of the adhesive layer at 25 ° C. is in the above range, the adhesiveness is improved and the flexibility is further improved by interposing directly between the transparent gas barrier layer and the embedded resin layer.
  • the glass transition temperature of the adhesion layer is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 60 ° C. or higher.
  • the glass transition temperature of the adhesion layer is lower than the glass transition temperature of the embedded resin layer to be combined, and if it is within this range, the adhesion and flexibility are improved.
  • the thickness of the adhesion layer is preferably 1 to 120 ⁇ m, more preferably 3 to 100 ⁇ m, and still more preferably 4 to 80 ⁇ m. When the thickness of the embedded resin layer is in the above-described range and the thickness of the adhesion layer is in this range, the flexibility of the transparent conductive laminate is improved.
  • the adhesion layer used in the present invention is not particularly limited as long as the above-described elastic modulus is within the range of the present invention, and is preferably made of a transparent resin composition in the same manner as the embedded resin layer.
  • a transparent resin composition in the same manner as the embedded resin layer.
  • an energy beam curable compound, a thermoplastic resin, etc. are mentioned.
  • Examples of the energy ray curable compound include the same compounds as those used for the embedded resin layer described above.
  • thermoplastic resin examples include polyolefin resins such as polyethylene, polypropylene, polybutene, (meth) acrylic resins, polyvinyl chloride resins, polystyrene resins, polyvinylidene chloride resins, ethylene-vinyl acetate copolymer ken. , Polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, acetal resin, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester resin such as polybutylene naphthalate (PBN), nylon 6, polyamide resins such as nylon 66, and the like.
  • polyolefin resins such as polyethylene, polypropylene, polybutene, (meth) acrylic resins, polyvinyl chloride resins, polystyrene resins, polyvinylidene chloride resins, ethylene-vinyl acetate copolymer ken.
  • the said resin may be used individually by 1 type, and may be used in combination of 2 or more type.
  • polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyvinylidene chloride are preferable.
  • Examples of commercially available energy ray curable compounds include UV curable acrylic resins (Toyo Ink, UA-A1, solid content 100% by mass), UV curable acrylic resins (Toa Gosei Co., Ltd., UVX6125, solids). 100% by weight) and the like, and Irgacure 819 (manufactured by BASF) as a photopolymerization initiator. Similar to the above-described embedded resin layer, an adhesive layer having a predetermined elastic modulus can be obtained by adjusting the amount of a photopolymerization initiator or the like.
  • the content of the photopolymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass with respect to 100 parts by mass of the energy ray curable compound. When the content of the photopolymerization initiator is within this range, curability is sufficient.
  • a polymerization inhibitor, a viscosity modifier, surfactant, an antifoamer, an organometallic coupling agent, etc. can be added as needed.
  • the transparent conductive laminate of the present invention preferably further includes a transparent gas barrier layer on the transparent substrate.
  • the transparent gas barrier layer used in the present invention suppresses the permeation of water vapor in the atmosphere that has passed through the transparent substrate 2 in FIG. 2, for example, and as a result, the water vapor of the embedded resin layer 3, the auxiliary electrode layer 4, etc. Has a function to prevent transmission.
  • the transparent conductive laminate of the present invention By keeping the water vapor transmission rate in such a range and maintaining the water vapor transmission rate of other layers such as the auxiliary electrode layer and the embedded resin layer at a predetermined value, for example, the transparent conductive laminate of the present invention An increase in sheet resistance can be suppressed without the transparent conductive layer being deteriorated by moisture. Further, when used as a translucent electrode of an electronic device, it is possible to suppress deterioration over time of the active layer and the like inside the device, leading to a longer life of the device.
  • a layer containing a metal oxide As a transparent gas barrier layer, a layer containing a metal oxide; a layer obtained by subjecting a layer containing a polymer compound (hereinafter sometimes referred to as “polymer layer”) to a modification treatment such as ion implantation; Can be mentioned.
  • a method for forming the layer containing the metal oxide the above-described method for forming a transparent conductive layer can be used.
  • a lower sheet resistance value can be obtained by performing heat treatment within a range that does not affect other laminated bodies as necessary.
  • metal oxide materials include metals such as silicon, aluminum, magnesium, zinc, and tin; inorganic materials such as silicon oxide, silicon monoxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, tin oxide, and zinc tin oxide Oxides; inorganic nitrides such as silicon nitride, aluminum nitride and titanium nitride; inorganic carbides; inorganic sulfides; inorganic oxynitrides such as silicon oxynitride; inorganic oxide carbides; inorganic nitride carbides; inorganic oxynitride carbides . These can be used alone or in combination of two or more.
  • membrane which uses an inorganic oxide, an inorganic nitride, or a metal as a raw material from a gas-barrier viewpoint is preferable.
  • a silicon oxynitride layer made of a layer containing metal oxide or a layer containing a polysilazane compound and having oxygen, nitrogen, and silicon as main constituent atoms formed by a modification treatment has interlayer adhesion, From the viewpoint of having gas barrier properties and bending resistance, it is preferably used.
  • Polymer compounds used for the polymer layer include silicon-containing polymer compounds such as polyorganosiloxane and polysilazane compounds, polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester Etc. These polymer compounds can be used alone or in combination of two or more. Among these, a silicon-containing polymer compound is preferable as the polymer compound because of its superior gas barrier properties. Examples of silicon-containing polymer compounds include polysilazane compounds, polycarbosilane compounds, polysilane compounds, and polyorganosiloxane compounds. Among these, a polysilazane compound is preferable from the viewpoint of forming a transparent gas barrier layer having excellent gas barrier properties.
  • the transparent gas barrier layer can be formed, for example, by subjecting the polysilazane compound-containing layer to plasma ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, heat treatment, and the like.
  • ions implanted by the plasma ion implantation process include hydrogen, nitrogen, oxygen, argon, helium, neon, xenon, and krypton.
  • a specific processing method of the plasma ion implantation processing a method of injecting ions present in plasma generated using an external electric field into a polysilazane compound-containing layer, or a gas barrier without using an external electric field.
  • the plasma treatment is a method for modifying a layer containing a silicon-containing polymer by exposing the polysilazane compound-containing layer to plasma.
  • plasma treatment can be performed according to the method described in Japanese Patent Application Laid-Open No. 2012-106421.
  • the ultraviolet irradiation treatment is a method for modifying a layer containing a silicon-containing polymer by irradiating a polysilazane compound-containing layer with ultraviolet rays.
  • the ultraviolet modification treatment can be performed according to the method described in JP2013-226757A.
  • the ion implantation treatment is preferable because it can efficiently modify the inside of the polysilazane compound-containing layer without roughening the surface and form a gas barrier layer having more excellent gas barrier properties.
  • the method for laminating the transparent gas barrier layer is not particularly limited, but the laminating method is preferable because it can be easily produced.
  • the transparent gas barrier layer may be a single layer or a laminate of two or more layers. Further, when two or more layers are laminated, they may be the same or different.
  • the film thickness of the transparent gas barrier layer is preferably 20 nm to 50 ⁇ m, more preferably 30 nm to 1 ⁇ m, still more preferably 40 to 500 nm. When the film thickness of the transparent gas barrier layer is within this range, excellent gas barrier properties and adhesiveness can be obtained, and flexibility and coating strength can be compatible.
  • a primer layer When forming a transparent gas barrier layer on a transparent substrate, a primer layer may be used to improve the adhesion between the transparent substrate and the transparent gas barrier layer.
  • the primer layer for example, an acrylic-based, polyester-based, polyurethane-based, or rubber-based primer layer can be appropriately used.
  • the thickness of the primer layer is usually 0.1 to 10 ⁇ m, preferably 0.5 to 5 ⁇ m.
  • the thickness of the primer layer is in the above range, by covering the unevenness of the transparent substrate, defects derived from the transparent substrate are reduced, the gas barrier performance of the transparent gas barrier layer is improved, and the transparent substrate Adhesion between the transparent gas barrier layers is improved, and the surface can be smoothly peeled off from the transfer substrate side in a surface smoothness transfer step of the transfer substrate surface described later.
  • the haze of the transparent conductive laminate of the present invention is preferably 2.5% or less, more preferably 2.0% or less.
  • the increase rate of haze before and after dry film formation is preferably 1.40 or less, more preferably 1.25. Hereinafter, it is more preferably 1.10 or less.
  • the sheet resistance value on the transparent conductive layer side of the transparent conductive laminate of the present invention is preferably 10 ⁇ / ⁇ or less, more preferably 5 ⁇ / ⁇ or less, and further preferably 1 ⁇ / ⁇ or less. When the sheet resistance value is within this range, a transparent conductive laminate having excellent electrical characteristics can be obtained.
  • the thickness of the transparent conductive laminate is preferably 10 to 300 ⁇ m, more preferably 10 to 200 ⁇ m, and still more preferably 20 to 150 ⁇ m. If it is this range, when a transparent conductive layer is laminated
  • the total light transmittance (T 0 ) of the opening of the transparent conductive laminate is preferably 80% to 96%, more preferably 90 to 96%, and still more preferably 92% to 96%.
  • the total light transmittance (T) of the transparent conductive laminate including the auxiliary electrode layer is preferably 80% to 95%, more preferably 83% to 95%, and still more preferably 85% to 95%. is there.
  • the ratio T / T 0 of the total light transmittance (T) of the transparent conductive laminate including the auxiliary electrode layer to the total light transmittance (T 0 ) of the opening of the transparent conductive laminate is due to an increase in surface resistivity, etc. If electrical characteristics are not impaired, the closer to 1, the better. 0.93 to 0.99 is preferable, 0.96 to 0.99 is more preferable, and 0.97 to 0.99 is even more preferable. is there.
  • the auxiliary electrode layer is printed in the same pattern, it means that the closer the line width of the auxiliary electrode layer is, the closer it is to 1.
  • the transparent conductive laminate of the present invention has excellent optical properties and flexibility. Further, the sheet resistance value is small, and the transferability of the auxiliary electrode layer is excellent. Therefore, it is preferable to apply to a solar cell element or an organic electroluminescence element that requires a large area.
  • the method for producing a transparent conductive laminate of the present invention comprises at least an embedded resin layer, an auxiliary electrode layer, and a transparent conductive layer on a transparent substrate, the transparent conductive layer comprising a metal oxide,
  • a method for producing a transparent conductive laminate wherein the elastic modulus at 25 ° C. of the resin layer is 3000 to 8000 MPa and the elastic modulus at 70 ° C. is 1000 to 7000 MPa, the step of forming the auxiliary electrode layer, Including a step of forming the embedded resin layer in the opening of the auxiliary electrode layer, or on the auxiliary electrode layer and in the opening, and a step of forming the transparent conductive layer.
  • the auxiliary electrode layer forming step is a step of forming a pattern made of the above-described auxiliary electrode layer material on a transfer substrate described later.
  • a method of forming the auxiliary electrode layer after providing an auxiliary electrode layer on which a pattern is not formed on a transfer substrate, a known physical treatment or chemical treatment mainly using a photolithography method, or a combination thereof.
  • the pattern of the auxiliary electrode layer is formed directly by a method of processing into a predetermined pattern shape, or by a screen printing method, a rotary screen printing method, a screen offset printing method, an inkjet method, an offset printing method, a gravure offset printing method, etc. And the like.
  • a PVD method physical vapor deposition method
  • a vacuum deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, an ALD method (atomic layer deposition method).
  • CVD chemical vapor deposition
  • various coatings such as dip coating, spin coating, spray coating, gravure coating, die coating, and doctor blade, and electrodeposition.
  • a wet process, a silver salt method, etc. are mentioned, and it is suitably selected according to the material of the auxiliary electrode layer.
  • the embedded resin layer forming step is a step of laminating an embedded resin layer on the opening of the auxiliary electrode layer or on the opening and the auxiliary electrode layer, as one aspect.
  • Another aspect is a step of laminating an embedded resin layer on the adhesion layer or the transparent gas barrier layer.
  • Examples of the method for forming the embedded resin layer include a dip coating method, a spin coating method, a spray coating method, a gravure coating method, a die coating method, a doctor blade method, and a Meyer bar coating method.
  • Examples of the method of irradiating energy radiation include ultraviolet rays and electron beams.
  • the ultraviolet rays are obtained with a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, etc., and the light quantity is usually 100 to 500 mJ / cm 2 , while the electron beam is obtained with an electron beam accelerator or the like, and the irradiation dose is usually 150 to 350 kV.
  • ultraviolet rays are particularly preferable.
  • a cured film can be obtained, without adding a photoinitiator.
  • the transparent conductive layer forming step is a step of forming a transparent conductive layer on the surface side composed of the auxiliary electrode layer and the embedded resin layer.
  • the method for forming the transparent conductive layer is as described above.
  • the production of the transparent conductive laminate of the present invention preferably further includes an adhesion layer forming step.
  • An adhesion layer formation process is a process of forming an adhesion layer on an embedding resin layer as one mode.
  • the adhesion layer is formed on the transparent gas barrier layer.
  • the method for forming the adhesion layer is the same as the method for forming the embedded resin layer described above.
  • the production of the transparent conductive laminate of the present invention preferably further includes a transparent gas barrier layer forming step.
  • the transparent gas barrier layer forming step is a step of forming a transparent gas barrier layer on the transparent substrate via the primer layer described above.
  • the method for forming and laminating the transparent gas barrier layer is as described above.
  • the production of the transparent conductive laminate of the present invention preferably further includes a transfer substrate forming step.
  • the transfer substrate forming step is a step of forming a release layer on the support of the transfer substrate.
  • the support material is not particularly limited, and examples thereof include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polypropylene and polymethylpentene, polycarbonate films, and polyvinyl acetate films. Among them, a polyester film is preferable, and a biaxially stretched polyethylene terephthalate film is particularly preferable.
  • the thickness of the support is preferably 10 to 500 ⁇ m, more preferably 20 to 300 ⁇ m, still more preferably 30 to 100 ⁇ m. If it is this range, since mechanical strength can be ensured, it is preferable.
  • the release layer used in the present invention may or may not be appropriately provided depending on the support to be used. However, in the case of providing, the layer obtained by curing the silicone resin composition or the ultraviolet curable release composition (hereinafter referred to as “cured”). It is sometimes referred to as a “layer”).
  • the silicone resin composition is not particularly limited, and examples thereof include an addition reaction type silicone resin composition containing a photosensitizer.
  • the addition reaction type silicone resin composition is obtained by adding a catalyst (for example, a platinum-based catalyst) and a photosensitizer to a main agent composed of an addition reaction type silicone resin and a crosslinking agent, and, if necessary, an addition reaction inhibitor. Further, a release adjusting agent, an adhesion improving agent and the like may be added.
  • a well-known ultraviolet curable peeling composition may be sufficient and a commercial item can be used. Specific examples include a silicone-based, fluorine-based, alkyl pendant-based, and long-chain alkyl-based ultraviolet curable release composition. If necessary, the above-described addition reaction inhibitor, peeling regulator, adhesion improver, and the like may be added. Moreover, it is preferable that the ultraviolet curable releasable composition segregates silicon on the surface.
  • a coating liquid comprising a silicone resin composition or an ultraviolet curable release composition and the above-described additive component used as desired is applied onto the substrate, for example, gravure coating. It can be applied by the method, bar coating method, spray coating method, spin coating method or the like.
  • an appropriate organic solvent may be added for the purpose of adjusting the viscosity of the coating solution.
  • an organic solvent There is no restriction
  • the transfer process of the transfer substrate surface is a process of peeling the transfer substrate, and the surface composed of the auxiliary electrode layer and the embedded resin layer.
  • the peeling method of the surface which consists of a transfer base material, an auxiliary electrode layer, and a transparent resin layer does not have a restriction
  • the surface composed of the auxiliary electrode layer and the embedded resin layer can be made excellent in smoothness, increase in haze, etc. can be suppressed, and as a result, the optical characteristics of the transparent conductive laminate can be improved. It leads to improvement.
  • a step of laminating different laminates by a laminating method or the like may be included.
  • a laminate comprising a transfer substrate / auxiliary electrode layer and a laminate comprising an embedded resin layer / transparent gas barrier layer / primer layer / transparent substrate are laminated to form a transfer substrate / auxiliary electrode.
  • a laminate comprising a layer / embedded resin layer / transparent gas barrier layer / primer layer / transparent substrate may be used.
  • a laminate comprising a transfer substrate / auxiliary electrode layer / embedded resin layer and a laminate comprising a transparent gas barrier layer / primer layer / transparent substrate are laminated to form a transfer substrate / auxiliary electrode layer.
  • a laminate comprising: / embedded resin layer / transparent gas barrier layer / primer layer / transparent substrate may be used.
  • a laminate comprising a transfer substrate / auxiliary electrode layer / embedded resin layer / adhesion layer and a laminate comprising a transparent gas barrier layer / primer layer / transparent substrate are laminated, or a transfer substrate / A laminate comprising an auxiliary electrode layer / embedded resin layer and a laminate comprising an adhesion layer / transparent gas barrier layer / primer layer / transparent substrate are laminated to form a transfer substrate / auxiliary electrode layer / embedded resin layer / It is good also as a laminated body containing the adhesion layer which consists of adhesion layer / transparent gas barrier layer / primer layer / transparent substrate.
  • the transfer substrate is then peeled off from the transfer substrate / auxiliary electrode interface side to form a transparent conductive laminate, and the surface comprising the auxiliary electrode layer and the embedded resin layer of the transparent conductive laminate
  • the transparent conductive laminate of the present invention can be produced.
  • the elastic modulus may be measured as described in the examples, or after the transparent conductive laminate was prepared, the transparent conductive laminate was cut obliquely with, for example, a diamond knife, and the measurement location was exposed and then exposed. Measurements may be made so that the indenter of the dynamic ultra-micro hardness tester is in vertical contact with the measurement location, or other layers stacked on the measurement location may be removed by etching, etc. You may measure after exposing.
  • C Haze Haze was measured according to JIS K 7136 using a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd., HAZE METER NDH5000).
  • zipping is “when the auxiliary electrode layer on the transfer substrate is transferred from the transfer substrate to the embedded resin layer side, the auxiliary electrode layer of the transfer substrate does not peel smoothly, and the sound is crispy. It means a phenomenon that repeats peeling or stopping while standing. When transferring, zipping may occur, and the auxiliary electrode layer may not be peeled off from the transfer substrate, and a portion that is not transferred may occur.
  • (G) Dry-type film-forming property The haze before and after dry-type film formation was measured when a transparent conductive layer was formed to a thickness of 50 nm on the surface composed of the auxiliary electrode layer and the embedded resin layer by the dry-type film formation method. Then, the dry film-forming property was evaluated.
  • the dry film forming resistance refers to fluctuations in the haze value due to dry film formation.
  • ⁇ When haze rise is 10% or less ⁇ : When haze rise is more than 10% and 50% or less x: When haze rise is more than 50% (h) Flexibility Repeated bending tester (YUASA) Using the Koki Co., Ltd.), the sheet resistance value ⁇ before and after bending 100 times so that the transparent conductive layer of the transparent conductive laminate is convex so that the bent portion is 50 mm ⁇ is measured, and the following standard The flexibility was evaluated according to the following.
  • Adhesive tape (cello tape (registered trademark) manufactured by Nichiban Co., Ltd.) is pasted on the transparent conductive layer surface that is cross-cut into a grid shape, and in accordance with the cross-cut tape method of JIS K5600-5-6 (cross-cut method) (Registered Trademark) A peel test was performed, and the adhesion of the transparent conductive layer, the embedded resin layer, and the adhesion layer was evaluated according to the following criteria. In addition, about adhesiveness, it determined by the following reference
  • Example 1 The following UV curable acrylic resin solution A was applied on a slide glass having a thickness of 1 mm with an applicator, dried at 90 ° C. for 2 minutes, and then release sheet B [polyethylene terephthalate film subjected to silicone release treatment] (SP manufactured by Lintec Corporation, SP -PET 381031, thickness 38 ⁇ m), and using a conveyor type UV irradiation device (manufactured by Heraeus, high-pressure mercury lamp), the integrated light is irradiated from the coated surface so that the integrated light amount is 250 mJ / cm 2. Obtained.
  • the film thickness after curing was 50 ⁇ m.
  • UV curable acrylic resin solution A A solution obtained by adding 1.5 parts by mass of a photoinitiator (Irgacure 819, manufactured by BASF) to 100 parts by mass of UV curable acrylic resin (manufactured by Nippon Synthetic Chemical Co., Ltd., UT5746, solid content 80% by mass, ethyl acetate solution) .
  • Embed UV curable acrylic resin composition A on alkali-free glass (Corning, EagleXG, 100 mm square, 0.7 mm thickness) so that the film thickness after curing is 25 ⁇ m under the same coating and curing conditions as described above.
  • the resin layer A was formed and haze Ha0 was measured.
  • Table 1 An ITO layer, which is a transparent conductive layer, was formed by sputtering on the embedded resin layer A thus formed under the following conditions, and haze H a1 after the film formation was measured.
  • a metal paste (conductive composition) for printing an auxiliary electrode layer made of a thin silver wire As a metal paste (conductive composition) for printing an auxiliary electrode layer made of a thin silver wire, a silver paste (manufactured by Mitsuboshi Belting Co., Ltd., trade name: low-temperature fired conductive paste MDot (registered trademark)) was used, and the line width was 30 ⁇ m, Using a screen plate (printing area 100 mm square) having a honeycomb structure with a pitch of 1200 ⁇ m, an auxiliary electrode layer is formed on a transfer substrate by printing with a screen printing machine (manufactured by Micro Tech, model name: MT-320TV). did. After printing, temporary drying was performed at 70 ° C. for 1 minute, followed by baking at 150 ° C.
  • a screen printing machine manufactured by Micro Tech, model name: MT-320TV
  • the transfer substrate used here was PET A4100 (100 ⁇ m thickness) manufactured by Toyobo Co., Ltd., and the untreated surface was used as the electrode printing surface.
  • the obtained electrode had a width of 40 ⁇ m and a height of 7 ⁇ m.
  • the UV curable acrylic resin composition A was applied to the transparent gas barrier layer side surface of the transparent substrate having the transparent gas barrier layer described later with an applicator and dried at 90 ° C. for 2 minutes.
  • transfer substrate / auxiliary electrode layer / embedded resin layer A / gas barrier layer / primer layer / A laminate A of transparent substrates was obtained.
  • the laminated body A is irradiated with a conveyor-type UV irradiator (manufactured by Heraeus, high-pressure mercury lamp) from the transparent substrate side having the transparent gas barrier layer so that the accumulated light amount becomes 250 mJ / cm 2.
  • the embedded resin layer A was cured (thickness of the embedded resin layer A after curing: 25 ⁇ m).
  • the transfer base material is peeled off from the interface side consisting of the embedded resin layer A and the auxiliary electrode layer, so that the auxiliary electrode layer and the embedded resin layer having openings through the transparent gas barrier layer on the transparent base material.
  • a transparent conductive laminate A in which a composite layer composed of A was laminated was prepared, and the elastic modulus and haze H b0 of the embedded resin layer A at 25 ° C. and 70 ° C. were measured with a dynamic ultra-small surface hardness meter. .
  • the transparent conductive layer was formed to a thickness of 50 nm in the same manner as the transparent conductive layer formation conditions described above to form a transparent conductive laminate, and the haze H b1 , sheet resistance value ⁇ , water vapor transmission rate ( WVTR) was measured.
  • a perhydropolysilazane-containing liquid manufactured by AZ Electronic Materials, trade name: AZNL110A-20
  • a perhydropolysilazane layer having a thickness of 200 nm was formed.
  • argon (Ar) was plasma ion-implanted into the obtained perhydropolysilazane layer under the following conditions to form a perhydropolysilazane layer (hereinafter referred to as “inorganic layer A”) in which plasma ions were implanted.
  • inorganic layer B two silicon oxynitride layers (inorganic layer B) were repeatedly formed on the inorganic layer A in the same manner as the inorganic layer A except that the thickness of the perhydropolysilazane layer was 150 nm, and a transparent gas barrier layer was laminated.
  • RF power source Model number “RF56000”, JEOL high voltage pulse power source: “PV-3-HSHV-0835”, Kurita Manufacturing Co., Ltd.
  • Example 2 A transparent conductive laminate B was prepared in the same manner as in Example 1 except that the embedded resin layer B was formed using the following UV curable acrylic resin solution B, and embedded using a dynamic ultra-small surface hardness meter. The elastic modulus at 25 ° C. and 70 ° C. of the resin layer B and the haze H b0 of the transparent conductive laminate B were measured. Next, the transparent conductive layer was laminated to obtain a transparent conductive laminate, and haze H b1 , sheet resistance value ⁇ , and water vapor transmission rate (WVTR) were measured. Further, as in Example 1, the glass transition temperature Tg of the embedded resin layer B was measured.
  • a photoinitiator Irgacure 819, manufactured by BASF
  • Example 1 A transparent conductive laminate C was produced in the same manner as in Example 1 except that the embedded resin layer C was formed using the following UV curable acrylic resin solution C. Although the elastic modulus at 25 ° C. and 70 ° C. of the embedded resin layer C was measured, haze H b0 , haze H b1, etc. of the transparent conductive laminate C were not measured due to poor transferability. Further, in the same manner as in Example 1, the glass transition temperature Tg of the embedded resin layer C was measured.
  • UV curable acrylic resin solution C 50 parts of UV curable acrylic resin (UA-A1 manufactured by Toyo Ink Co., Ltd.) for 100 parts by mass of UV curable acrylic resin (manufactured by Nippon Synthetic Chemical, UT5746, solid content 80% by mass, ethyl acetate solution), light A solution obtained by adding 1.5 parts by mass of an initiator (Irgacure 819, manufactured by BASF).
  • UV curable acrylic resin U-A1 manufactured by Toyo Ink Co., Ltd.
  • UV curable acrylic resin manufactured by Nippon Synthetic Chemical, UT5746, solid content 80% by mass, ethyl acetate solution
  • an initiator Irgacure 819, manufactured by BASF
  • Example 2 A transparent conductive laminate D was produced in the same manner as in Example 1 except that the embedded resin layer D was formed using the following UV curable acrylic resin solution D. Although the elastic modulus at 25 ° C. and 70 ° C. of the embedded resin layer D was measured, the haze H b0 , haze H b1, etc. of the transparent conductive laminate D were not measured because of poor transferability. Further, in the same manner as in Example 1, the glass transition temperature Tg of the embedded resin layer D was measured.
  • UV curable acrylic resin solution D A solution comprising a UV curable acrylic resin (UA-A1 manufactured by Toyo Ink Co., Ltd.).
  • Example 3 The following adhesion layer coating liquid A was applied onto a slide glass having a thickness of 1 mm with an applicator, dried at 90 ° C. for 2 minutes, and then release sheet B [polyethylene terephthalate film subjected to silicone release treatment] (SP-PET 381031 manufactured by Lintec Corporation). , And a thickness of 38 ⁇ m) was applied and irradiated from the coated surface using a conveyor-type UV irradiation device (manufactured by Heraeus, high-pressure mercury lamp) so that the integrated light amount was 250 mJ / cm 2 , thereby obtaining an adhesion layer A.
  • the film thickness after curing was 50 ⁇ m.
  • Adhesion layer coating solution A A coating solution comprising a UV curable acrylic resin (manufactured by Toyo Ink, UA-A1, solid content: 100% by mass).
  • a transfer substrate with an auxiliary electrode layer was prepared in the same manner as in Example 1.
  • the UV curable acrylic resin solution A is applied to the auxiliary electrode layer side of the transfer substrate with an applicator and dried at 90 ° C. for 2 minutes, and the transfer substrate / auxiliary electrode layer / embedded resin layer A (uncured) A laminate B was formed.
  • an adhesion layer A (UV curable acrylic resin (UA-A1 manufactured by Toyo Ink Co., Ltd.)) was applied with an applicator to the transparent gas barrier layer side of the transparent substrate having the transparent gas barrier layer formed in the same manner as in Example 1. Then, irradiation is performed from the adhesion layer A side by a conveyor type UV irradiator (manufactured by Heraeus, high-pressure mercury lamp) so that the integrated light amount is 250 mJ / cm 2, and the adhesion layer A / transparent gas barrier layer / primer layer / transparent substrate A laminate C (thickness of the adhesion layer A after curing: 5 ⁇ m) was formed.
  • the elastic modulus at 25 ° C.
  • the embedded resin layer A of the laminate B and the adhesion layer A of the laminate C are bonded with a laminator, and integrated from the transparent resin substrate side by a conveyor type UV irradiator (manufactured by Heraeus, high-pressure mercury lamp). Irradiation was performed so that the amount of light was 250 mJ / cm 2 to cure the embedded resin layer A in the laminate B (thickness of the embedded resin layer A after curing: 25 ⁇ m).
  • a transparent conductive laminate E in which a composite layer composed of the embedded resin layer A is laminated is manufactured, and the elastic modulus at 25 ° C. and 70 ° C. of the embedded resin layer A and haze H are measured by a dynamic ultra-small surface hardness meter. c0 was measured. Furthermore, a transparent conductive layer was formed to a thickness of 50 nm in the same manner as in Example 1 to obtain a transparent conductive laminate, and haze H c1 , sheet resistance value ⁇ , and water vapor transmission rate (WVTR) were evaluated.
  • Example 4 A transparent conductive laminate F was produced in the same manner as in Example 1 except that the film thickness of the adhesion layer A was changed to 25 ⁇ m, and the haze H c0 of the transparent conductive laminate F was evaluated. Next, the transparent conductive layer was laminated to obtain a transparent conductive laminate, and haze H b1 , sheet resistance value ⁇ , and water vapor transmission rate (WVTR) were measured.
  • Example 5 A transparent conductive laminate G was produced in the same manner as in Example 1 except that the thickness of the adhesion layer A was changed to 50 ⁇ m, and the haze H c0 of the transparent conductive laminate G was evaluated. Next, the transparent conductive layer was laminated to obtain a transparent conductive laminate, and haze H b1 , sheet resistance value ⁇ , and water vapor transmission rate (WVTR) were measured.
  • Example 6 A transparent conductive laminate H was produced in the same manner as in Example 1 except that the film thickness of the adhesion layer A was changed to 75 ⁇ m, and the haze H c0 of the transparent conductive laminate H was evaluated. Next, the transparent conductive layer was laminated to obtain a transparent conductive laminate, and haze H b1 , sheet resistance value ⁇ , and water vapor transmission rate (WVTR) were measured.
  • Example 7 the embedded resin layer A is changed to an embedded resin layer E made of the following UV curable acrylic resin solution E, and coating is performed with a die coater so that the thickness directly above the transfer substrate is 1 ⁇ m (after curing). Then, while drying at 70 ° C. for 30 seconds, the adhesion layer A is changed to the adhesion layer B composed of the following adhesion layer coating liquid B, and coated and cured to a thickness of 10 ⁇ m (after curing) with a bar coater, Further, except that the embedded resin layer E and the adhesion layer B were bonded, a transparent conductive laminate I was prepared in the same manner as in Example 3, and the embedded resin layer E 25 was measured with a dynamic ultra-small surface hardness meter.
  • the elastic modulus at ° C. and 70 ° C. and the haze H c0 of the transparent conductive laminate I were measured.
  • adherence layer B after hardening before bonding was measured with the dynamic ultra fine surface hardness meter similarly to Example 3.
  • the transparent conductive layer was laminated to obtain a transparent conductive laminate, and haze H b1 , sheet resistance value ⁇ , and water vapor transmission rate (WVTR) were measured.
  • an embedded resin layer E was produced on a slide glass having a thickness of 1 mm using a UV curable acrylic resin solution E (film thickness after curing; 50 ⁇ m), and the glass transition temperature Tg. was measured.
  • the adhesion layer B was produced on the 1 mm-thick slide glass by the same method as Example 3 using the adhesion layer coating liquid B (film thickness after curing: 50 ⁇ m), and the glass transition temperature Tg was measured.
  • UV curable acrylic resin solution E A solution prepared by adding a UV curable acrylic resin containing inorganic fine particles (manufactured by JSR, Opstar Z7530, solid content 73 mass%, methyl ethyl ketone solution) as a diluent solvent to adjust the solid content to 30 wt%.
  • Adhesion layer coating solution B 1 part by weight of photoinitiator (BASF, Irgacure 819) and 100 parts by weight of silane coupling agent (Shin-Etsu Chemical Co., Ltd.) with respect to 100 parts by weight of UV curable acrylic resin (Toa Gosei Co., Ltd., UVX6125, solid content 100% by weight) , KBM903) to which 1 part by mass is added.
  • photoinitiator BASF, Irgacure 819
  • silane coupling agent Shin-Etsu Chemical Co., Ltd.
  • Example 8 A transparent conductive laminate J was prepared in the same manner as in Example 3 except that the thickness of the adhesion layer A after curing was 100 ⁇ m, and the haze H c0 of the transparent conductive laminate J was evaluated. Next, the transparent conductive layer was laminated to obtain a transparent conductive laminate, and haze H b1 , sheet resistance value ⁇ , and water vapor transmission rate (WVTR) were measured.
  • the transparent conductive laminate of the present invention has excellent optical properties and flexibility at the same time, and further has a small sheet resistance value, such as flexible solar cell elements and organic electroluminescence elements that require a large area. It can also be used for devices.
  • 1A, 1B transparent conductive laminate 2: transparent substrate 3: embedded resin layer 4: auxiliary electrode layer 5: transparent conductive layer 6: primer layer 7: transparent gas barrier layer 8: adhesion layer 9: opening

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Abstract

La présente invention concerne : un stratifié conducteur transparent présentant simultanément d'excellentes propriétés optiques et une excellente flexibilité, et pourvu, sur un matériau de base transparent, d'au moins une couche de résine intégrée, d'une couche d'électrode auxiliaire et d'une couche conductrice transparente, la couche conductrice transparente comprenant un oxyde métallique, et la couche de résine intégrée ayant un module d'élasticité allant de 3000 à 8000 MPa à 25 °C et allant de 1000 à 7000 MPa à 70 °C ; et un procédé de production du stratifié conducteur transparent.
PCT/JP2018/011632 2017-03-31 2018-03-23 Stratifié conducteur transparent et son procédé de procuction WO2018180961A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024105901A1 (fr) * 2022-11-14 2024-05-23 パナソニックＩｐマネジメント株式会社 Substrat conducteur
WO2024106117A1 (fr) * 2022-11-14 2024-05-23 パナソニックＩｐマネジメント株式会社 Substrat conducteur

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JPH0279308A (ja) * 1988-09-14 1990-03-19 Seiko Epson Corp 電極形成方法
WO2005041217A1 (fr) * 2003-10-28 2005-05-06 Sumitomo Metal Mining Co., Ltd. Corps conducteur transparent multicouche, procede de fabrication et dispositif utilisant un corps conducteur transparent multicouche
JP2005332705A (ja) * 2004-05-20 2005-12-02 Fujimori Kogyo Co Ltd 透明電極基板とその製造方法及びこの基板を用いた色素増感型太陽電池
JP2009146640A (ja) * 2007-12-12 2009-07-02 Konica Minolta Holdings Inc 導電性材料の製造方法、透明導電膜、有機エレクトロルミネッセンス素子
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024105901A1 (fr) * 2022-11-14 2024-05-23 パナソニックＩｐマネジメント株式会社 Substrat conducteur
WO2024106117A1 (fr) * 2022-11-14 2024-05-23 パナソニックＩｐマネジメント株式会社 Substrat conducteur

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