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WO2023074664A1 - Film électroconducteur transparent - Google Patents

Film électroconducteur transparent Download PDF

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Publication number
WO2023074664A1
WO2023074664A1 PCT/JP2022/039656 JP2022039656W WO2023074664A1 WO 2023074664 A1 WO2023074664 A1 WO 2023074664A1 JP 2022039656 W JP2022039656 W JP 2022039656W WO 2023074664 A1 WO2023074664 A1 WO 2023074664A1
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Prior art keywords
transparent conductive
conductive film
conductive layer
thiol
metal nanowires
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English (en)
Japanese (ja)
Inventor
純一 長瀬
佑輔 茂手木
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to KR1020247009284A priority Critical patent/KR20240087709A/ko
Priority to CN202280071784.XA priority patent/CN118160051A/zh
Publication of WO2023074664A1 publication Critical patent/WO2023074664A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • 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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • the present invention relates to transparent conductive films.
  • a transparent conductive film in which a metal oxide layer such as an indium-tin composite oxide layer (ITO layer) is formed on a transparent resin film has been widely used as a transparent conductive film used for touch sensor electrodes and the like.
  • ITO layer indium-tin composite oxide layer
  • a transparent conductive film having a conductive layer containing metal nanowires has been proposed as a transparent conductive film with excellent flexibility.
  • a transparent conductive film there is a problem that the metal nanowires deteriorate and the resistance increases under high humidity.
  • a possible solution to this problem is to protect the conductive layer composed of metal nanowires with a polymer matrix.
  • the present invention was made to solve the above problems, and the purpose thereof is to provide a transparent conductive film that has a conductive layer containing metal nanowires and has excellent humidification reliability.
  • a transparent conductive film of the present invention comprises a transparent substrate and a transparent conductive layer disposed on at least one side of the transparent substrate, the transparent conductive layer comprising metal nanowires and a polymer matrix, the polymer matrix contains thiol-based compounds.
  • the thiol-based compound is a thiol-based compound having a dithiolane skeleton.
  • the thiol-based compound is ⁇ -lipoic acid.
  • the content of the thiol-based compound having a dithiolane skeleton is 0.1 to 5 parts by weight with respect to 100 parts by weight of the polymer constituting the polymer matrix.
  • the metal nanowires have a fused network structure.
  • the transparent conductive layer further contains a silane coupling agent. In one embodiment, the transparent conductive layer has a visible light transmittance of 80% or more. In one embodiment, the transparent conductive layer has a sheet resistivity of 200 ⁇ / ⁇ or less.
  • FIG. 1 is a schematic cross-sectional view of a transparent conductive film according to one embodiment of the invention.
  • FIG. 1 is a schematic cross-sectional view of a transparent conductive film according to one embodiment of the present invention.
  • the transparent conductive film 100 comprises a transparent substrate 10 and a transparent conductive layer 20 arranged on at least one side of the transparent substrate 10 .
  • Transparent conductive layer 20 includes metal nanowires 21 and polymer matrix 22 .
  • transparent conductive layer 20 is configured such that metal nanowires 21 reside in a polymer matrix 22 .
  • the polymer matrix contains a thiol-based compound.
  • the polymer matrix-added thiol-based compound constituting the transparent conductive layer binds to the metal nanowires so as to form a protective film on the surface, and as a result, the deterioration of the metal nanowires is prevented. Conceivable.
  • the transparent conductive film of the present invention that exhibits such effects can maintain preferable conductivity without deteriorating the metal nanowires even under high humidity. Such an effect becomes more pronounced by appropriately selecting the thiol-based compound, as will be described later.
  • a transparent conductive film with excellent flexibility and high environmental durability can be obtained. can.
  • the thickness of the transparent conductive film is preferably 10 ⁇ m to 500 ⁇ m, more preferably 15 ⁇ m to 300 ⁇ m, and even more preferably 20 ⁇ m to 200 ⁇ m.
  • the visible light transmittance of the transparent conductive film is preferably 80% or higher, more preferably 85% or higher, and particularly preferably 90% or higher. Within such a range, for example, a transparent conductive film suitable for use as a transparent electrode can be obtained.
  • the sheet resistance value of the transparent conductive film is preferably 200 ⁇ / ⁇ or less, more preferably 150 ⁇ / ⁇ or less, and still more preferably 100 ⁇ / ⁇ or less.
  • the sheet resistance value of the transparent conductive film is preferably as small as possible, but the lower limit is, for example, 1 ⁇ / ⁇ (preferably 0.5 ⁇ / ⁇ , more preferably 0.1 ⁇ / ⁇ ).
  • the transparent conductive layer comprises metal nanowires and a polymer matrix.
  • a transparent conductive layer containing metal nanowires By forming a transparent conductive layer containing metal nanowires, it is possible to obtain a transparent conductive film having excellent flexibility and light transmittance. Metal nanowires are protected by a polymer matrix. As a result, corrosion of the metal nanowires is prevented, and a transparent conductive film with superior durability can be obtained.
  • the polymer matrix contains a thiol-based compound.
  • the thickness of the transparent conductive layer is preferably 10 nm to 1000 nm, more preferably 20 nm to 500 nm.
  • the visible light transmittance of the transparent conductive layer is preferably 80% or higher, more preferably 85% or higher, even more preferably 90% or higher, and particularly preferably 95% or higher.
  • the sheet resistance value of the transparent conductive layer is preferably 200 ⁇ / ⁇ or less, more preferably 150 ⁇ / ⁇ or less, and even more preferably 100 ⁇ / ⁇ or less.
  • the sheet resistance value of the transparent conductive film is preferably as small as possible, but the lower limit is, for example, 1 ⁇ / ⁇ (preferably 0.5 ⁇ / ⁇ , more preferably 0.1 ⁇ / ⁇ ).
  • a metal nanowire is a conductive substance that is made of metal, has a needle-like or thread-like shape, and has a nanometer-sized diameter.
  • the metal nanowires may be straight or curved.
  • a transparent conductive layer composed of metal nanowires is used, the metal nanowires form a mesh, so that even a small amount of metal nanowires can form a good electrical conduction path.
  • a conductive film can be obtained.
  • the metal nanowires are mesh-like, openings are formed in the gaps of the meshes, and a transparent conductive film with high light transmittance can be obtained.
  • the ratio of the thickness d to the length L of the metal nanowires is preferably 10 to 100,000, more preferably 50 to 100,000, and particularly preferably 100 to 10,000.
  • the metal nanowires having a large aspect ratio are used in this manner, the metal nanowires can cross each other satisfactorily, and a small amount of metal nanowires can exhibit high conductivity. As a result, a transparent conductive film with high light transmittance can be obtained.
  • the “thickness of the metal nanowire” means the diameter when the cross section of the metal nanowire is circular, the minor axis when the metal nanowire is elliptical, and the polygonal In some cases it means the longest diagonal.
  • the thickness and length of metal nanowires can be confirmed with a scanning electron microscope or a transmission electron microscope.
  • the thickness of the metal nanowires is preferably less than 500 nm, more preferably less than 200 nm, particularly preferably 10 nm to 100 nm, and most preferably 10 nm to 50 nm. Within such a range, a transparent conductive layer with high light transmittance can be formed.
  • the length of the metal nanowires is preferably 1 ⁇ m to 1000 ⁇ m, more preferably 10 ⁇ m to 500 ⁇ m, and particularly preferably 10 ⁇ m to 100 ⁇ m. Within such a range, a transparent conductive film with high conductivity can be obtained.
  • metals constituting the metal nanowires can be any appropriate metal as the metal constituting the metal nanowires as long as it is a conductive metal.
  • metals forming the metal nanowires include silver, gold, copper, and nickel. Also, materials obtained by subjecting these metals to plating (for example, gold plating) may be used. Silver, copper or gold is preferred, and silver is more preferred, from the viewpoint of conductivity.
  • any appropriate method can be adopted as the method for producing the metal nanowires. Examples include a method of reducing silver nitrate in a solution, a method of applying voltage or current from the tip of a probe to the surface of a precursor, pulling out metal nanowires at the tip of the probe, and forming the metal nanowires continuously. .
  • silver nanowires can be synthesized by liquid phase reduction of a silver salt such as silver nitrate in the presence of a polyol such as ethylene glycol and polyvinylpyrrolidone. Uniformly sized silver nanowires are described, for example, in Xia, Y.; et al. , Chem. Mater. (2002), 14, 4736-4745, Xia, Y.; et al. , Nano letters (2003) 3(7), 955-960, mass production is possible.
  • the transparent conductive layer containing the metal nanowires can be formed by applying a dispersion of the metal nanowires in a solvent onto the transparent substrate and then drying the coating layer.
  • the solvent examples include water, alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, aromatic solvents, and the like. From the viewpoint of reducing environmental load, it is preferable to use water.
  • the dispersion concentration of the metal nanowires in the metal nanowire dispersion liquid is preferably 0.1% by weight to 1% by weight. Within such a range, a transparent conductive layer having excellent conductivity and light transmittance can be formed.
  • the metal nanowire dispersion liquid may further contain any appropriate additive depending on the purpose.
  • the additive include a corrosion inhibitor that prevents corrosion of metal nanowires, a surfactant that prevents aggregation of metal nanowires, and the like.
  • the type, number and amount of additives used can be appropriately set according to the purpose.
  • any appropriate method can be adopted as a method for applying the metal nanowire dispersion.
  • coating methods include spray coating, bar coating, roll coating, die coating, inkjet coating, screen coating, dip coating, letterpress printing, intaglio printing, and gravure printing.
  • Any appropriate drying method (for example, natural drying, air drying, heat drying) may be employed as a drying method for the coating layer.
  • the drying temperature is typically 50° C. to 200° C.
  • the drying time is typically 1 minute to 10 minutes.
  • the content of metal nanowires in the transparent conductive layer is preferably 30 wt% to 90 wt%, more preferably 45 wt% to 80 wt%, relative to the total weight of the transparent conductive layer. Within such a range, a transparent conductive film having excellent conductivity and light transmittance can be obtained.
  • the density of the transparent conductive layer is preferably 1.3 g/cm 3 to 10.5 g/cm 3 , more preferably 1.5 g/cm 3 to 3.0 g/cm 3 . 3 . Within such a range, a transparent conductive film having excellent conductivity and light transmittance can be obtained.
  • the transparent conductive layer is patterned. Any appropriate patterning method may be employed depending on the form of the transparent conductive layer.
  • the shape of the pattern of the transparent conductive layer may be any appropriate shape depending on the application. For example, patterns described in JP-A-2011-511357, JP-A-2010-164938, JP-A-2008-310550, JP-A-2003-511799, and JP-A-2010-541109 can be mentioned.
  • the transparent conductive layer After the transparent conductive layer is formed on the transparent substrate, it can be patterned using any appropriate method depending on the form of the transparent conductive layer.
  • the metal nanowires in the transparent conductive layer have a fused network structure.
  • the metal nanowires having the fused network structure are in a state where the metal nanowires are fused to each other at the contact points.
  • the transparent conductive layer containing the metal nanowires having the fused network structure can be formed, for example, by adding an additive for promoting fusion to the metal nanowire dispersion.
  • the additive include metal halides (e.g., LiCl, CsCl, NaF, NaCl, NaBr, NaI, KCl, MgCl 2 , CaCl 2 , AlCl 3 , AgF, etc.), inorganic acids (e.g., nitric acid, nitrous acid , sulfuric acid, etc.), organic acids (e.g., oxalic acid, citric acid, formic acid, acetic acid, lactic acid, propionic acid, butyric acid, acrylic acid, pyruvic acid, trichloroacetic acid, trifluoroacetic acid, hexanoic acid, octanoic acid, decanoic acid, dodecane (lauric) acid, tetradecane (myristic) acid,
  • the transparent conductive layer containing the metal nanowires having the fused network structure is subjected to heat treatment and/or pressure treatment after applying the metal nanowire dispersion containing the additive. can be formed.
  • the temperature of the heat treatment is, for example, 50.degree. C. to 200.degree.
  • the transparent conductive layer containing the metal nanowires having the fused network structure may be formed by exposing the coating layer of the metal nanowire dispersion to an acid halide vapor.
  • Acid halide vapors include vapors such as HCl, HBr, HI, or mixtures thereof.
  • a metal nanowire having a fused network structure and a method for producing the same are described, for example, in Japanese Patent Publication No. 2015-530693. The description of the publication is incorporated herein by reference.
  • polymer matrix Any appropriate polymer can be used as the polymer that constitutes the polymer matrix.
  • the polymer include acrylic polymers; polyester polymers such as polyethylene terephthalate; aromatic polymers such as polystyrene, polyvinyltoluene, polyvinylxylene, polyimide, polyamide, and polyamideimide; polyurethane polymers; epoxy polymers; Polymer; acrylonitrile-butadiene-styrene copolymer (ABS); cellulose; silicon-based polymer; polyvinyl chloride; Preferably, polyfunctional compounds such as pentaerythritol triacrylate (PETA), neopentyl glycol diacrylate (NPGDA), dipentaerythritol hexaacrylate (DPHA), dipentaerythritol pentaacrylate (DPPA), trimethylolpropane triacrylate (TMPTA), etc.
  • a curable resin composed of acrylate preferably an ultraviolet cur
  • the polymer matrix can be formed by forming a layer of metal nanowires on a transparent substrate, applying a polymer solution on the layer, and then drying or curing the applied layer. This operation forms a transparent conductive layer with metal nanowires in a polymer matrix.
  • the polymer solution contains a polymer that constitutes the polymer matrix or a precursor of the polymer (a monomer that constitutes the polymer).
  • the polymer solution may contain a solvent.
  • the solvent contained in the polymer solution include alcohol-based solvents, ketone-based solvents, tetrahydrofuran, hydrocarbon-based solvents, aromatic solvents, and the like.
  • the solvent is volatile.
  • the boiling point of the solvent is preferably 200° C. or lower, more preferably 150° C. or lower, and still more preferably 100° C. or lower.
  • R is an aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 30 carbon atoms, preferably an aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms is.
  • R may be linear or branched.
  • R may also contain double and/or triple bonds at any suitable position.
  • R may also have any suitable substituents.
  • Substituents include, for example, SH groups, hydroxyl groups, NH2 groups, alkyl ester groups, carboxyl groups, allyl groups, and halogen groups.
  • R may have a substituent containing elements such as N, S, O, Si, and P.
  • thiol compounds include ⁇ -thioglycerol, aminoethanethiol, thioglycolic acid, methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, thio 2-ethylhexyl glycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, ethylene glycol thioglycolate, neopentyl glycol thioglycolate, pentaerythritol thioglycolate etc.
  • a thiol-based compound having a dithiolane skeleton (preferably a 1,2-dithiolane skeleton) is used.
  • a thiol-based compound having a dithiolane skeleton is characterized in that it hardly reacts with the compound constituting the polymer matrix. Therefore, it is possible to form a conductive layer that does not impair the protective function of the polymer matrix and has excellent adhesion to the transparent substrate.
  • a thiol-based compound having a dithiolane skeleton has two bonding points, and thus can densely coat the metal nanowires.
  • Such a thiol-based compound can contribute to the improvement of moisture resistance even when the amount added is small. If the amount of the thiol-based compound added is small, the protective function of the polymer matrix is not hindered, and a conductive layer having excellent adhesion to the transparent substrate can be formed.
  • Examples of thiol compounds having a dithiolane skeleton include ⁇ -lipoic acid, 5-(1,2-dithiolan-3-yl)pentanamide, 4-Methyl-1,2-dithiolane-4-carboxamid, and the like. .
  • ⁇ -lipoic acid is preferred.
  • ⁇ -lipoic acid is used, the above effect becomes remarkable, and a transparent conductive film having excellent durability can be obtained due to the effects of ⁇ -lipoic acid such as radical trapping and anti-oxidation.
  • an alkylthiol is used as the thiol-based compound.
  • alkylthiols include alkylthiols such as methanethiol, ethanethiol, propanethiol, n-octanethiol, n-dodecanethiol, hexadecanethiol and n-octadecanethiol.
  • the content of the thiol compound is preferably 0.04 parts by weight to 10 parts by weight, more preferably 0.1 parts by weight to 8 parts by weight, with respect to 100 parts by weight of the polymer constituting the polymer matrix, More preferably, it ranges from 0.12 parts by weight to 5 parts by weight. Within such a range, a transparent conductive film having excellent moisture resistance can be obtained.
  • the content of the thiol-based compound having a dithiolane skeleton is preferably It is 0.1 to 5 parts by weight, more preferably 0.15 to 3 parts by weight.
  • the content of the thiol-based compound having a dithiolane skeleton is within such a range, a transparent conductive film can be obtained that is remarkably excellent in electrical conductivity as well as moisture resistance. If the content of the thiol-based compound having a dithiolane skeleton is too high, the thiol-based compound may react with the metal nanowires, resulting in a decrease in electrical conductivity.
  • the transparent conductive layer (substantially polymer matrix) further comprises a coupling agent.
  • a silane coupling agent is preferably used as the coupling agent.
  • a coupling agent acts to reduce moisture resistance (humidification reliability), but according to the present invention, the combined use of a thiol compound and a coupling agent prevents metal nanowires from deteriorating. It is possible to obtain a transparent conductive film having excellent adhesion between the transparent substrate and the transparent conductive layer while maintaining humidification reliability.
  • the present invention is advantageous in that the inclusion of a thiol compound enhances the effectiveness of the coupling agent.
  • An amino-based silane coupling agent can be preferably used as the silane coupling agent. Also, an amino-based silane coupling agent and an acryl-based silane coupling agent may be used in combination.
  • amino-based silane coupling agents include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -amino ethyl)- ⁇ -aminopropyltriethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane, ⁇ -phenylaminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3- dimethyl-butylidene)propylamine.
  • amino-based silane coupling agents are commercially available.
  • Specific examples of commercially available products include KBE-9103, KBM-575, and KBM-6123 manufactured by Shin-Etsu Chemical Co., Ltd., and A-1102, A-1122, and A-1170 manufactured by Momentive Performance Materials Japan. be done.
  • Preferred is 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine.
  • An acrylic silane coupling agent is typically a silane coupling agent having a (meth)acrylic group in its skeleton.
  • acrylic silane coupling agents include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxymethyl trimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane.
  • acrylic silane coupling agents are commercially available.
  • Specific examples of commercially available products include KBM-502 and KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd. Preferred is 3-acryloxypropyltrimethoxysilane or 3-methacryloxypropylmethyldimethoxysilane.
  • the content of the coupling agent (preferably a silane coupling agent) is preferably 0.001 to 20 parts by weight, more preferably 0.02 parts by weight, relative to 100 parts by weight of the polymer constituting the polymer matrix. parts by weight to 10 parts by weight. Within such a range, a transparent conductive film having excellent adhesion between the transparent substrate and the transparent conductive layer can be obtained.
  • the thickness of the transparent substrate is preferably 8 ⁇ m to 500 ⁇ m, more preferably 10 ⁇ m to 250 ⁇ m, still more preferably 10 ⁇ m to 150 ⁇ m, and particularly preferably 15 ⁇ m to 100 ⁇ m.
  • the total light transmittance of the transparent substrate is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. Within such a range, a transparent conductive film suitable as a transparent conductive film provided in a touch panel or the like can be obtained.
  • any appropriate resin can be used as the resin constituting the transparent substrate as long as the effects of the present invention can be obtained.
  • the resin constituting the transparent substrate include cycloolefin-based resins, polyimide-based resins, polyvinylidene chloride-based resins, polyvinyl chloride-based resins, polyethylene terephthalate-based resins, and polyethylene naphthalate-based resins.
  • Preferred are cycloolefin resins.
  • polynorbornene can be preferably used as the cycloolefin-based resin.
  • Polynorbornene refers to a (co)polymer obtained by using a norbornene-based monomer having a norbornene ring as part or all of the starting material (monomer).
  • the glass transition temperature of the resin constituting the transparent substrate is preferably 50°C to 200°C, more preferably 60°C to 180°C, still more preferably 70°C to 160°C.
  • a transparent substrate having a glass transition temperature within such a range can prevent deterioration during formation of a transparent conductive layer.
  • the transparent base material may further contain any appropriate additive as necessary.
  • additives include plasticizers, heat stabilizers, light stabilizers, lubricants, antioxidants, UV absorbers, flame retardants, colorants, antistatic agents, compatibilizers, cross-linking agents, and thickeners. etc.
  • the type and amount of additive used can be appropriately set according to the purpose.
  • any appropriate molding method is used, and examples include compression molding, transfer molding, injection molding, extrusion molding, blow molding, powder molding, and FRP molding. , and solvent casting method.
  • the extrusion molding method or the solvent casting method is preferably used. This is because the smoothness of the resulting transparent base material can be enhanced and good optical uniformity can be obtained. Molding conditions can be appropriately set according to the composition, type, etc. of the resin used.
  • Various surface treatments may be applied to the transparent substrate as necessary. Any appropriate method is adopted for the surface treatment depending on the purpose. Examples include low-pressure plasma treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment.
  • the transparent substrate is surface-treated to make the transparent substrate surface hydrophilic.
  • Silver nanowire dispersion liquid I was prepared by dispersing the silver nanowires (concentration: 0.2% by weight) and pentaethylene glycol dodecyl ether (concentration: 0.1% by weight) in pure water.
  • Example 1 A commercially available long cycloolefin (norbornene) resin film (manufactured by Nippon Zeon Co., Ltd., product name “Zeonor ZF16”, thickness 40 ⁇ m) was used as a substrate.
  • the silver nanowire dispersion liquid I was applied to this base material and dried.
  • materials for forming the overcoat layer 80 parts by weight of "Unidic ELS-888" (trade name, manufactured by DIC Corporation) and 20 parts by weight of "Unidic RS28-605" (trade name, manufactured by DIC Corporation) were used.
  • a resin composition A was prepared by blending.
  • This resin composition A was applied to the conductive layer and irradiated with ultraviolet rays at an exposure amount of 230 mJ/cm 2 to form a polymer matrix and obtain a transparent conductive film.
  • the surface resistance of the transparent conductive film was 50 ⁇ , and the thickness of the transparent conductive layer was 60 nm.
  • Example 2 A transparent conductive film was obtained in the same manner as in Example 1, except that the amount of ⁇ -lipoic acid added was 3 parts by weight with respect to 100 parts by weight of the resin composition A. The obtained transparent conductive film was subjected to the above evaluation. Table 1 shows the results.
  • Example 3 A transparent conductive film was obtained in the same manner as in Example 1, except that 0.15 parts by weight of decanethiol was used instead of 0.15 parts by weight of ⁇ -lipoic acid. The obtained transparent conductive film was subjected to the above evaluation. Table 1 shows the results.
  • Example 4 A transparent conductive film was obtained in the same manner as in Example 3, except that the amount of decanethiol added was 3 parts by weight. The obtained transparent conductive film was subjected to the above evaluation. Table 1 shows the results.
  • Example 5 A transparent conductive film was obtained in the same manner as in Example 1, except that 0.15 parts by weight of perfluorodecanethiol was used instead of 0.15 parts by weight of ⁇ -lipoic acid. The obtained transparent conductive film was subjected to the above evaluation. Table 1 shows the results.
  • Example 6 A transparent conductive film was obtained in the same manner as in Example 5, except that the amount of perfluorodecanethiol added was 3 parts by weight. The obtained transparent conductive film was subjected to the above evaluation. Table 1 shows the results.
  • Example 1 A transparent conductive film was obtained in the same manner as in Example 1, except that neither the thiol compound nor the silane coupling agent was added. The obtained transparent conductive film was subjected to the above evaluation. Table 1 shows the results.
  • Example 2 A transparent conductive film was obtained in the same manner as in Example 1, except that no thiol compound was added. The obtained transparent conductive film was subjected to the above evaluation. Table 1 shows the results.
  • Example 3 A transparent conductive film was obtained in the same manner as in Example 1, except that no thiol compound was added and the thickness of the transparent conductive layer was set to 90 nm. The obtained transparent conductive film was subjected to the above evaluation. Table 1 shows the results.
  • the transparent conductive layer has excellent adhesion to the transparent substrate of the transparent conductive layer and has little change in resistance and haze even under humidified conditions, even though it contains metal nanowires.
  • a conductive film that is, a transparent conductive film having excellent humidification reliability can be obtained.

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  • Engineering & Computer Science (AREA)
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  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Human Computer Interaction (AREA)
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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
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Abstract

L'invention concerne un film électroconducteur transparent qui est pourvu d'une couche électroconductrice contenant des nanofils métalliques, et présente une excellente fiabilité d'humidification.　Ce film électroconducteur transparent est pourvu d'un matériau de base transparent et d'une couche électroconductrice transparente disposée sur au moins un côté du matériau de base transparent. La couche électroconductrice transparente contient des nanofils métalliques et une matrice polymère. La matrice polymère contient un composé à base de thiol. Dans un mode de réalisation, le composé à base de thiol a un squelette dithiolane.
PCT/JP2022/039656 2021-10-29 2022-10-25 Film électroconducteur transparent Ceased WO2023074664A1 (fr)

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CN202280071784.XA CN118160051A (zh) 2021-10-29 2022-10-25 透明导电性膜

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JP2021177523A JP2023066744A (ja) 2021-10-29 2021-10-29 透明導電性フィルム

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Publication number Priority date Publication date Assignee Title
WO2025004503A1 (fr) * 2023-06-28 2025-01-02 日東電工株式会社 Film conducteur transparent

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003049123A1 (fr) * 2001-12-05 2003-06-12 Asahi Glass Company, Limited Film conducteur, procede de fabrication correspondant et substrat comprenant ce film
JP2009505358A (ja) * 2005-08-12 2009-02-05 カンブリオス テクノロジーズ コーポレイション ナノワイヤに基づく透明導電体
JP2015037061A (ja) * 2013-08-15 2015-02-23 王子ホールディングス株式会社 導電性シートの製造方法、導電性シート、および、タッチパネル
JP2015530693A (ja) * 2012-06-22 2015-10-15 シー３ナノ・インコーポレイテッドＣ３Ｎａｎｏ Ｉｎｃ． 金属ナノ構造化網目構造および透明導電性の材料
JP2016017114A (ja) * 2014-07-07 2016-02-01 信越ポリマー株式会社 導電性高分子溶液およびその製造方法ならびに塗膜

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003049123A1 (fr) * 2001-12-05 2003-06-12 Asahi Glass Company, Limited Film conducteur, procede de fabrication correspondant et substrat comprenant ce film
JP2009505358A (ja) * 2005-08-12 2009-02-05 カンブリオス テクノロジーズ コーポレイション ナノワイヤに基づく透明導電体
JP2015530693A (ja) * 2012-06-22 2015-10-15 シー３ナノ・インコーポレイテッドＣ３Ｎａｎｏ Ｉｎｃ． 金属ナノ構造化網目構造および透明導電性の材料
JP2015037061A (ja) * 2013-08-15 2015-02-23 王子ホールディングス株式会社 導電性シートの製造方法、導電性シート、および、タッチパネル
JP2016017114A (ja) * 2014-07-07 2016-02-01 信越ポリマー株式会社 導電性高分子溶液およびその製造方法ならびに塗膜

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KR20240087709A (ko) 2024-06-19

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