WO2023286602A1 - Stratifié de film conducteur transparent et son procédé de fabrication - Google Patents

Stratifié de film conducteur transparent et son procédé de fabrication Download PDF

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Publication number
WO2023286602A1
WO2023286602A1 PCT/JP2022/025919 JP2022025919W WO2023286602A1 WO 2023286602 A1 WO2023286602 A1 WO 2023286602A1 JP 2022025919 W JP2022025919 W JP 2022025919W WO 2023286602 A1 WO2023286602 A1 WO 2023286602A1
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Prior art keywords
film
transparent conductive
conductive film
layer
transparent
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PCT/JP2022/025919
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English (en)
Japanese (ja)
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繁 山木
周平 米田
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昭和電工株式会社
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    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • 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

Definitions

  • the present invention relates to a transparent conductive film laminate and a method for producing the same, and more particularly to a transparent conductive film laminate useful for suppressing curling that occurs during a heating process, and a method for producing the same.
  • touch panels have come to be mounted on various items around us.
  • the scope of use is expanding, with the development of touch panels for dashboards and center consoles, which used to be limited to only a part of the car navigation system. Since dashboards and center consoles often have curved surfaces, it is required that the touch panels mounted on them also have adaptability to curved surfaces.
  • ITO indium tin oxide
  • ITO indium tin oxide
  • a transparent conductive film using ITO is broken when bent, and the conductivity is remarkably deteriorated.
  • a transparent conductive film containing fine metal wires has been developed. Specific examples include a transparent conductive film using metal nanowires and a transparent conductive film using fine metal wires obtained by subjecting a silver salt emulsion to exposure treatment and then performing development treatment.
  • Amorphous cycloolefin resin is suitable for automotive curved touch panels as a base material for transparent conductive films. This is because the amorphous cycloolefin-based resin has a low retardation, so that visibility is improved when wearing polarized sunglasses while driving a car.
  • a transparent conductive film in which a transparent conductive layer containing fine metal wires is formed on an amorphous cycloolefin resin film is considered promising as a next-generation transparent conductive film.
  • a protective film is attached to the back surface to prevent the substrate from being damaged during transportation.
  • the transparent conductive film laminate tends to curl (warp) during the heating process.
  • problems such as the warped transparent conductive film laminate coming into contact with the upper or lower part of the drying furnace occur, making it difficult to carry out stable and continuous production. Become.
  • Patent Document 1 discloses a laminate in which both the substrate film and the surface protective film (release film) of the transparent conductive film are PET films.
  • a transparent conductive film with an amorphous transparent conductive thin film (ITO film) and a protective film (release film) are adjusted to reduce curling by adjusting the thermal shrinkage rate.
  • ITO film amorphous transparent conductive thin film
  • release film a protective film
  • Patent Document 2 discloses a transparent conductive film having a carrier film having an adhesive layer on at least one surface side of a protective film, and a transparent resin film and a transparent conductive film that are peelably laminated via the adhesive layer.
  • a film wherein the transparent resin film is made of an amorphous cycloolefin-based resin or a polycarbonate-based resin, and the protective film is made of an amorphous resin.
  • Polycarbonate and cycloolefin are used as amorphous resins for forming protective films. leads to an increase in manufacturing cost of the transparent conductive film.
  • the present applicant discloses film laminates in which the transparent resin film, which is the base material of the transparent conductive film, is an amorphous cycloolefin resin in Patent Documents 3 and 4.
  • the thickness of the transparent resin film is limited to a range of 5-25 ⁇ m.
  • the thickness of the transparent conductive film is preferably 25 ⁇ m or less. There is no need to use a thin transparent conductive film. If an excessively thin transparent conductive film is used, the risk of film breakage during the touch panel manufacturing process increases. Therefore, in the case of manufacturing an in-vehicle touch panel that does not need to be carried around and does not require frequent opening and closing operations with a predetermined curved surface shape.
  • the thickness of the transparent resin film is more than 25 ⁇ m with high production yield. In other words, the film laminate disclosed in Patent Document 3 is not suitable for production of a transparent conductive film for manufacturing an in-vehicle touch panel having a curved surface shape.
  • the film laminate disclosed in Patent Document 4 does not have an adhesive layer, and the carrier film (polycarbonate film) is adhered to the transparent conductive film by utilizing the self-adhesiveness of the carrier film (polycarbonate film). Prevents deformation due to curing shrinkage.
  • the self-adhesiveness used in Patent Document 4 is manifested by the excellent smoothness of the surface of the polycarbonate film. In order not to lose it, strict quality control is required, which entails technical difficulties.
  • using a polycarbonate film, which belongs to a relatively expensive category, as a carrier film that is finally discarded leads to an increase in the manufacturing cost of the transparent conductive film.
  • Patent Document 5 discloses a device comprising a substrate, a fine metal wire arranged on the substrate, and an adhesive layer arranged on the fine metal wire, wherein the amount of metal contained in the fine metal wire per unit area is 0.5. 010 g/m 2 or more and 10 g/m 2 or less, the adhesive layer contains a benzotriazole-based compound, and the content of the benzotriazole-based compound is 0.05% by mass or more and 1.5% by mass with respect to the total amount of the adhesive layer.
  • a laminate for a touch panel is disclosed, which has a mass % or less.
  • An object of the present invention is to suppress the curling of the transparent conductive film laminate during the heating process and ensure the yield in subsequent processes when an amorphous cycloolefin resin is used as the base material of the transparent conductive film.
  • An object of the present invention is to provide a transparent conductive film laminate capable of reducing manufacturing costs and a method for manufacturing the same.
  • the present invention has the following embodiments.
  • a transparent conductive film laminate including a transparent conductive film and a carrier film laminated on the transparent conductive film, wherein the transparent conductive film includes thin metal wires on one or both main surfaces of a transparent resin film. and an overcoat layer are laminated in this order, and the transparent resin film is a film of amorphous cycloolefin resin, and the thickness Ts of the transparent resin film is 30 150 ⁇ m, the carrier film is a polyolefin film, only one main surface has adhesiveness, and the transparent conductive film laminate has the transparent conductive film so that the overcoat layer is the outermost layer.
  • a film is detachably laminated on one adhesive main surface of the carrier film, and the ratio (Tc/Ts) of the thickness Tc of the carrier film to the thickness Ts of the transparent resin film is 0.2 ⁇ A transparent conductive film laminate, wherein Tc/Ts ⁇ 0.8.
  • the present invention when an amorphous cycloolefin resin is used for the base material (transparent resin film) of the transparent conductive film, the curling of the transparent conductive film laminate during the heating process is suppressed, and the subsequent process yield is improved. can be ensured and the manufacturing cost can be reduced, and a method for manufacturing the transparent conductive film laminate can be provided.
  • FIG. 3 is a schematic cross-sectional view of a transparent conductive film laminate according to a second embodiment of the invention; It is process drawing of the manufacturing method of the transparent conductive film laminated body which concerns on 1st embodiment. It is process drawing of the modification of the manufacturing method of the transparent conductive film laminated body which concerns on 1st embodiment. It is process drawing of the manufacturing method of the transparent conductive film laminated body which concerns on 2nd embodiment. It is process drawing of the modification of the manufacturing method of the transparent conductive film laminated body which concerns on 2nd embodiment.
  • FIG. 4 is an explanatory diagram of a curl value measuring method according to the embodiment;
  • the transparent conductive film laminate according to this embodiment is a transparent conductive film laminate including a transparent conductive film 10 or 20 and a carrier film 1 laminated on the transparent conductive film 10 or 20 . Only one main surface of the carrier film 1 has adhesiveness.
  • the transparent conductive film 10 is constructed by laminating a transparent conductive layer 3 containing fine metal wires on one main surface of a transparent resin film 2 and an overcoat layer 4 in this order. , a transparent conductive layer 3 containing fine metal wires on both main surfaces of a transparent resin film 2, and an overcoat layer 4 are laminated in this order.
  • the transparent resin film 2 is a film made of an amorphous cycloolefin resin, and has a thickness Ts of 30 to 150 ⁇ m.
  • the transparent conductive A film 10 or 20 is releasably laminated on one main adhesive surface of the carrier film 1 .
  • the carrier film 1 is a polyolefin film, and the ratio (Tc/Ts) of the thickness Tc of the carrier film 1 to the thickness Ts of the transparent resin film 2 is 0.2 ⁇ Tc/Ts ⁇ 0.8. .
  • the transparent conductive film laminate according to the first embodiment is a transparent conductive film laminate including a transparent conductive film 10 and a carrier film 1 laminated on the transparent conductive film 10, as shown in FIG. , the transparent conductive film 10 has a transparent conductive layer 3 containing fine metal wires and an overcoat layer 4 laminated in this order on one main surface of the transparent resin film 2 , and the carrier film 1 Only the main surface has adhesiveness, and the carrier film 1 is detachably laminated on the main surface of the transparent resin film 2 on the other side from the transparent conductive layer 3 on the main surface having adhesiveness.
  • the transparent conductive film laminate according to the second embodiment is a transparent conductive film laminate including a transparent conductive film 20 and a carrier film 1 laminated on the transparent conductive film 20, as shown in FIG.
  • a transparent conductive layer 3 containing thin metal wires and an overcoat layer 4 are laminated in this order on both main surfaces of the transparent resin film 2, and the carrier film 1 is laminated on one side.
  • the carrier film 1 is detachably laminated on the surface of the overcoat layer 4 on one side of the transparent conductive film 20 on the main surface having adhesiveness.
  • an amorphous cycloolefin resin is used as the transparent resin film 2 .
  • the amorphous cycloolefin resin means a (co)polymer containing 50 mol % or more of cycloolefin such as norbornene. Examples thereof include norbornene hydrogenation ring-opening metathesis polymerization type cycloolefin polymers and norbornene/ethylene addition copolymerization type cycloolefin polymers.
  • amorphous cycloolefin polymer resins include, for example, ZEONOR (registered trademark) and ZEONEX (registered trademark) manufactured by Zeon Corporation, ARTON (registered trademark) manufactured by JSR Corporation, and manufactured by Mitsui Chemicals, Inc.
  • APEL registered trademark
  • TOPAS registered trademark manufactured by Polyplastics Co., Ltd.
  • ZEONOR ZF-14, ZF-16, ARTON RX4500, RH4900, and R5000 Specific examples include ZEONOR ZF-14, ZF-16, ARTON RX4500, RH4900, and R5000.
  • Tg glass transition temperature
  • these resin films are preferable because they can withstand heating in subsequent processes such as lead wires and connector portions, and those having a glass transition temperature (Tg) of 130 to 170° C. are more preferable.
  • Tg glass transition temperature
  • the fact that these resin films are amorphous can be confirmed by the fact that no peak based on the crystallization temperature is observed by DSC measurement based on JIS K7121 plastic transition temperature measurement method.
  • the thickness Ts of the transparent resin film 2 is within the range of 30-150 ⁇ m, preferably within the range of 40-125 ⁇ m, and more preferably within the range of 50-100 ⁇ m.
  • the thickness of the transparent resin film 2 is 30 ⁇ m or more, it is easy to handle, and when it is 150 ⁇ m or less, cracks are less likely to occur when a touch panel having a curved surface shape is formed.
  • the transparent conductive layer 3 is formed on the transparent resin film so that the fine metal wires have crossing portions, and has a structure in which light can pass through the openings where the fine metal wires are not formed.
  • metal fine wire means a conductive fiber (metal nanowire) or a lattice pattern (metal mesh) made of metal.
  • a metal nanowire is a metal whose diameter is on the order of nanometers, and is a conductive material having a wire-like shape.
  • a metal mesh is a conductive material having a grid-like pattern of linear metal wires with submicron to micron-order widths.
  • Gold, silver, platinum, copper, nickel, palladium, aluminum, iron, chromium, and alloys thereof can be used as the metal constituting the thin metal wire.
  • Gold, silver, platinum, copper, nickel, and palladium are particularly preferred from the viewpoint of conductivity, and silver is particularly preferred.
  • Metal nanowires can be suitably used as the conductive material that constitutes the metal thin wires. It is preferable that the metal nanowires form a nanostructured network having intersections, and more preferably form a nanostructured network in which at least a part of the intersections are fused. It can be confirmed from the analysis of the electron beam diffraction pattern of a transmission electron microscope (TEM) that the intersections of the metal nanowires are fused.
  • TEM transmission electron microscope
  • the electron beam diffraction patterns of the metal nanowires that are sufficiently distant from the intersections of the metal nanowires and the intersections of the metal nanowires are analyzed, and the crystal structures of the two are different (solvent It can be confirmed from the fact that the crystal structure changes (occurrence of recrystallization) due to heating for drying.
  • a known manufacturing method can be used as a method for manufacturing metal nanowires.
  • silver nanowires can be synthesized by reducing silver nitrate in the presence of poly-N-vinylpyrrolidone using the Poly-ol method (see Chem. Mater., 2002, 14, 4736).
  • Gold nanowires can also be synthesized by reducing chloroauric acid hydrate in the presence of polyvinylpyrrolidone (see J. Am. Chem. Soc., 2007, 129, 1733).
  • WO2008/073143 pamphlet and WO2008/046058 pamphlet regarding large-scale synthesis and purification techniques for silver nanowires and gold nanowires.
  • the average diameter (average diameter) of the metal nanowires is preferably 1 to 500 nm, more preferably 5 to 200 nm, even more preferably 5 to 100 nm, and particularly preferably 10 to 50 nm.
  • the average length of the long axis of the metal nanowires (average length) is preferably 1 to 100 ⁇ m, more preferably 1 to 80 ⁇ m, still more preferably 2 to 70 ⁇ m, and particularly preferably 5 to 50 ⁇ m.
  • the metal nanowires preferably have an average diameter and an average major axis length that satisfy the above ranges, and an average aspect ratio of more than 5, more preferably 10 or more, and further preferably 100 or more. It is preferably 200 or more, and particularly preferably 200 or more.
  • the aspect ratio is a value obtained by a/b when the average diameter of the metal nanowires is approximated by b and the average length of the long axis by a.
  • a and b can be measured using scanning electron microscopy (SEM) and optical microscopy.
  • b average diameter is a measured value obtained by measuring the dimensions of 100 arbitrarily selected silver nanowires using a field emission scanning electron microscope JSM-7000F (manufactured by JEOL Ltd.).
  • a shape measurement laser microscope VK-X200 manufactured by Keyence Corporation is used to measure the dimensions of 100 arbitrarily selected silver nanowires, and the obtained measurement value is determined as the arithmetic mean of
  • Materials for metal nanowires include, for example, at least one selected from the group consisting of gold, silver, platinum, copper, nickel, and palladium, and alloys in which these metals are combined.
  • the fine metal wires can be formed in a shape such as a metal mesh (lattice pattern) on a transparent resin film using a known photolithography technique.
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2015-22397 discloses a method of forming a silver salt emulsion layer containing silver halide, exposing the silver salt emulsion layer, and then developing the layer.
  • the width of the fine metal wire is preferably 0.1 to 300 ⁇ m, more preferably 0.1 to 100 ⁇ m, even more preferably 0.2 to 50 ⁇ m, from the viewpoint of high integration of the fine metal wire.
  • the interval between the metal fine wires is not particularly limited, it is preferably 0.1 to 300 ⁇ m, more preferably 0.1 to 100 ⁇ m, and still more preferably 0.2 to 50 ⁇ m from the viewpoint of high integration of the metal fine wires.
  • the thickness of the metal fine wire is not particularly limited, it is preferably 0.01 to 0.3 ⁇ m, more preferably 0.01 to 0.2 ⁇ m, and further preferably 0.02 to 0.2 ⁇ m from the viewpoint of high integration of the metal fine wire. preferable.
  • the composition for forming the silver salt emulsion layer contains silver halide.
  • the halogen element contained in the silver halide may be any one of chlorine, bromine, iodine and fluorine, and may be combined.
  • silver halide silver halide mainly composed of silver chloride, silver bromide and silver iodide is preferably used, and silver halide mainly composed of silver bromide and silver chloride is more preferably used.
  • the transparent conductive layer 3 may contain a binder resin in addition to the fine metal wires.
  • a binder resin generally, those having transparency and excellent workability can be applied.
  • metal nanowires obtained by the polyol method it is preferable to use a binder resin soluble in alcohol or water from the viewpoint of compatibility with the solvent (polyol) for the production.
  • a binder resin soluble in alcohol or water from the viewpoint of compatibility with the solvent (polyol) for the production.
  • water-soluble cellulosic resins such as poly-N-vinylpyrrolidone, methylcellulose, hydroxyethylcellulose, and carboxymethylcellulose, butyral resins, and poly-N-vinylacetamide (PNVA (registered trademark)
  • PNVA poly-N-vinylacetamide
  • Poly-N-vinylacetamide is a homopolymer of N-vinylacetamide (NVA), but copolymers containing N-vinylacetamide (NVA) as monomer units can also be used.
  • monomers copolymerizable with NVA include N-vinylformamide, N-vinylpyrrolidone, acrylic acid, methacrylic acid, sodium acrylate, sodium methacrylate, acrylamide, acrylonitrile and the like.
  • the polymer preferably contains 70 mol% or more of N-vinylacetamide as a monomer unit, and more preferably contains 80 mol% or more. Preferably, it is more preferably contained in an amount of 90 mol % or more.
  • the weight average molecular weight of the polymer (homopolymer and copolymer) containing N-vinylacetamide as a monomer unit is preferably 30,000 to 4,000,000, more preferably 100,000 to 3,000,000. More preferably, it is 300,000 to 1,500,000.
  • the weight average molecular weight of poly-N-vinylacetamide and N-vinylacetamide copolymer is measured by the following method.
  • a binder resin was dissolved in the following eluent and allowed to stand for 20 hours.
  • the concentration of the binder resin in this solution is 0.05 mass %.
  • gelatin is preferably used as the binder resin.
  • a wet process that is advantageous in terms of manufacturing cost is preferably used.
  • the transparent conductive layer 3 is formed by coating one side of the transparent resin film 2 with a conductive ink (metal nanowire ink) containing the metal nanowires, a binder resin and a solvent as a coating liquid.
  • a conductive ink metal nanowire ink
  • it can be formed by printing on both major surfaces and drying off the solvent.
  • the solvent is not particularly limited as long as the solvent disperses the metal nanowires satisfactorily and dissolves the binder resin but does not dissolve the transparent resin film.
  • Alcohols are saturated monohydric alcohols (methanol, ethanol, normal propanol and isopropanol) having 1 to 3 carbon atoms represented by C n H 2n+1 OH (n is an integer of 1 to 3) [hereinafter simply “carbon atoms It is preferable that at least one type of saturated monohydric alcohol having 1 to 3 carbon atoms is included, and more preferably 40% by mass or more of the total alcohol is saturated monohydric alcohol having 1 to 3 carbon atoms. The use of a saturated monohydric alcohol having 1 to 3 carbon atoms facilitates drying, which is advantageous in terms of the process.
  • Alcohols other than saturated monohydric alcohols having 1 to 3 carbon atoms represented by C n H 2n+1 OH (n is an integer of 1 to 3) can be used in combination.
  • Examples of alcohols other than the saturated monohydric alcohol having 1 to 3 carbon atoms that can be used in combination include ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. is mentioned.
  • the drying rate can be adjusted.
  • the total alcohol content in the mixed solvent is preferably 5 to 90% by mass. When the content of alcohol in the mixed solvent is 5% by mass or more and 90% by mass or less, it is possible to suppress the occurrence of striped patterns (coating spots) during coating.
  • the conductive ink can be produced by stirring and mixing the metal nanowires, the binder resin and the solvent using a rotation or revolution stirrer.
  • the content of the binder resin contained in the conductive ink is preferably in the range of 0.01 to 1.0% by mass.
  • the content of metal nanowires contained in the conductive ink is preferably in the range of 0.01 to 1.0% by mass.
  • the content of the solvent contained in the conductive ink is preferably in the range of 98.0 to 99.98% by mass.
  • a more preferable viscosity of the conductive ink is 1 to 20 mPa ⁇ s, and a further preferable viscosity is 1 to 10 mPa ⁇ s. Viscosity is a value measured at 25° C. with a digital viscometer DV-E (spindle: SC4-18) manufactured by Brookfield.
  • the conductive ink can be printed by, for example, a bar coat printing method, a gravure printing method, an inkjet method, or a slit coating method.
  • the bar coat printing method has good applicability of low-viscosity ink and is excellent in forming a thin film.
  • the bar coat printing method can print even low-viscosity ink containing inorganic or metal particles without clogging.
  • the pattern formed by printing the conductive ink becomes the transparent conductive layer 3 having conductivity by heating and drying the solvent.
  • the thickness of the transparent conductive layer 3 is preferably in the range of 10 nm to 500 nm, more preferably in the range of 10 nm to 300 nm, even more preferably in the range of 15 nm to 200 nm, even more preferably in the range of 20 nm to 100 nm. is particularly preferred.
  • the thickness of the transparent conductive layer 3 is smaller than the thickness of the transparent conductive film 10 or 20 and the carrier film 1, the effect on the curling property is extremely small.
  • the transparent conductive layer 3 is formed by using a silver salt emulsion layer-forming composition containing the silver salt emulsion, a binder resin and a solvent as a coating liquid. It is formed by coating one or both main surfaces of the resin film 2 and performing an exposure and development process.
  • the light source used for exposure is not particularly limited, and includes light such as visible light and ultraviolet rays, and radiation such as X-rays.
  • the method of pattern exposure is not particularly limited, and for example, surface exposure using a photomask or scanning exposure with a laser beam may be used.
  • the shape of the pattern is not particularly limited as long as the fine metal wires are formed to have crossing portions, and is appropriately adjusted according to the pattern of the fine metal wires to be formed, but a lattice pattern is preferable.
  • the method of development processing is not particularly limited, and known methods can be employed. For example, it is possible to use the usual developing techniques used for silver salt photographic films, photographic papers, printing plate-making films, and emulsion masks for photomasks.
  • Development processing can include fixing processing for the purpose of removing and stabilizing silver salts in unexposed areas.
  • a fixing process technique used for silver salt photographic film, photographic paper, printing plate-making film, emulsion mask for photomask, and the like can be used.
  • the metal fine line pattern obtained by rinsing with pure water and drying has a thickness of preferably 0.5 to 5 ⁇ m, more preferably 0.5 to 3 ⁇ m. 0.8 to 1.5 ⁇ m is more preferred.
  • a protective film (overcoat layer) for protecting a transparent conductive film (transparent conductive layer) is a thermosetting film of a curable resin composition (overcoat ink) from the viewpoint of mechanically protecting the transparent conductive film.
  • the cured film is slightly inferior in moldability, it is preferable to use it as a protective film for three-dimensional molding.
  • thermoplastic resin which is excellent in moldability
  • the transparent conductive film laminate is usually used by bonding it to another member, that is, it is mechanically protected by the other member. In that case, high mechanical strength is not required. Therefore, it is preferable that the protective film (overcoat layer 4) constituting the transparent conductive film laminate of one embodiment for three-dimensional molding uses a thermoplastic resin having excellent moldability as a main component.
  • the curable resin composition When a cured film of a curable resin composition is used as the protective film (overcoat layer 4), the curable resin composition includes (A) a polyurethane containing a carboxy group and (B) two groups per molecule. It is preferable to contain the above epoxy compound having an epoxy group and (C) a curing accelerator.
  • a curable resin composition is formed on the transparent conductive film by printing, coating, or the like, and cured to form a protective film. Curing of the curable resin composition can be carried out by, for example, heating and drying the thermosetting resin composition to thermally cure it.
  • (B) epoxy compound having two or more epoxy groups in one molecule may be simply described as "(B) epoxy compound”.
  • the (A) polyurethane containing a carboxyl group preferably has a weight average molecular weight of 1,000 to 100,000, more preferably 2,000 to 70,000, more preferably 3,000 to 50,000. 000 is more preferred.
  • the weight-average molecular weight of a polyurethane containing a carboxyl group is a polystyrene-equivalent value measured by GPC. When the weight-average molecular weight of the carboxy group-containing polyurethane is 1,000 or more, the elongation, flexibility and strength of the coating film after printing are sufficiently exhibited.
  • the weight average molecular weight of the carboxyl group-containing polyurethane is 100,000 or less, the solubility in a solvent is good, and the viscosity of the polyurethane solution after dissolution does not become too high, resulting in excellent handleability.
  • the GPC measurement conditions for the weight average molecular weight of polyurethane containing carboxyl groups are as follows. Apparatus name: HPLC unit HSS-2000 manufactured by JASCO Corporation Column: Shodex column LF-804 Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL/min Detector: RI-2031Plus manufactured by JASCO Corporation Temperature: 40.0°C Sample amount: sample loop 100 ⁇ l Sample concentration: about 0.1% by mass
  • the acid value of the carboxy group-containing polyurethane is preferably 10 to 140 mg-KOH/g, more preferably 15 to 130 mg-KOH/g.
  • the acid value of the carboxy group-containing polyurethane is 10 mg-KOH/g or more, both the curability of the curable resin composition and the solvent resistance of the cured product are good.
  • the acid value of the carboxy group-containing polyurethane is 140 mg-KOH/g or less, the carboxy group-containing polyurethane itself has good solubility in a solvent, and the viscosity of the resin composition can be easily adjusted to a desired viscosity. .
  • problems such as warping of the base film due to excessive hardening of the cured product are less likely to occur.
  • Acid value [B x f x 5.611]/S B: Amount of 0.1N potassium hydroxide-ethanol solution used (ml) f: Factor S of 0.1N potassium hydroxide-ethanol solution: Amount of sample collected (g)
  • Polyurethane containing a carboxy group is, more specifically, a polyurethane synthesized using (a1) a polyisocyanate compound, (a2) a polyol compound, and (a3) a dihydroxy compound having a carboxy group as monomers. be. From the viewpoint of weather resistance and light resistance, it is desirable that each of (a1), (a2) and (a3) does not contain a conjugated functional group such as an aromatic compound. Each monomer will be described in more detail below.
  • (a1) Polyisocyanate compound As the (a1) polyisocyanate compound, a diisocyanate having two isocyanato groups per molecule is usually used. Examples of polyisocyanate compounds include aliphatic polyisocyanates and alicyclic polyisocyanates, and these can be used alone or in combination of two or more. (A) A small amount of polyisocyanate having 3 or more isocyanato groups can be used as long as the carboxy group-containing polyurethane does not gel.
  • aliphatic polyisocyanates examples include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 2 , 2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,2′-diethyl ether diisocyanate, dimer acid diisocyanate and the like.
  • Alicyclic polyisocyanates include, for example, 1,4-cyclohexanediisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 3-isocyanatomethyl-3,5 , 5-trimethylcyclohexyl isocyanate (IPDI, isophorone diisocyanate), bis-(4-isocyanatocyclohexyl) methane (hydrogenated MDI), hydrogenated (1,3- or 1,4-) xylylene diisocyanate, norbornane diisocyanate, etc. mentioned.
  • the content of these in the (a1) polyisocyanate compound (a1) the total amount of the polyisocyanate compound (100 mol%)
  • it is preferably 50 mol % or less, more preferably 30 mol % or less, still more preferably 10 mol % or less.
  • (a2) Polyol compound (a2) Polyol compound (however, (a2) polyol compound does not include (a3) a dihydroxy compound having a carboxyl group described later) usually has a number average molecular weight of 250 to 50,000. Yes, preferably 400 to 10,000, more preferably 500 to 5,000.
  • the number average molecular weight of the polyol compound is a polystyrene-equivalent value measured by GPC under the conditions described above.
  • Examples of (a2) polyol compounds include polycarbonate polyols, polyether polyols, polyester polyols, polylactone polyols, polysilicones with hydroxyl groups on both ends, and C18 (18 carbon atoms) unsaturated fatty acids made from vegetable oils and fats. and a polyol compound having 18 to 72 carbon atoms obtained by hydrogenating a polyvalent carboxylic acid derived from a polymer thereof and converting the carboxylic acid into a hydroxyl group. From the viewpoint of the balance between the water resistance of the protective film, the insulation reliability, and the adhesion to the substrate, the (a2) polyol compound is preferably a polycarbonate polyol.
  • a polycarbonate polyol can be obtained by reacting it with a diol having 3 to 18 carbon atoms, a carbonate ester or phosgene, and is represented by the following structural formula (1), for example.
  • R 3 is a residue of the corresponding diol (HO--R 3 --OH) from which the hydroxyl group has been removed and is an alkanediyl group having 3 to 18 carbon atoms, n 3 is a positive integer, Preferably it is 2-50.
  • the polycarbonate polyol represented by formula (1) is 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1 ,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10 -Decamethylene glycol or 1,2-tetradecanediol can be used as a starting material.
  • the polycarbonate polyol may be a polycarbonate polyol (copolymerized polycarbonate polyol) having multiple types of alkanediyl groups in its skeleton.
  • the use of a copolymerized polycarbonate polyol is often advantageous from the viewpoint of preventing crystallization of (A) polyurethanes containing carboxy groups. Considering solubility in a solvent, it is preferable to use a polycarbonate polyol having a branched skeleton and a hydroxyl group at the end of the branched chain.
  • a dihydroxy compound containing a carboxy group (a3)
  • the dihydroxy compound containing a carboxy group has two selected from a hydroxy group and a hydroxyalkyl group having 1 or 2 carbon atoms, and has a molecular weight of A carboxylic acid or aminocarboxylic acid having a molecular weight of 200 or less is preferable because the cross-linking point can be controlled.
  • Dihydroxy compounds containing a carboxy group include, for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N,N-bishydroxyethylglycine, N,N-bishydroxyethyl Among these, 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are preferred in terms of solubility in solvents.
  • the dihydroxy compound containing a carboxy group can be used alone or in combination of two or more.
  • Polyurethane containing a carboxyl group can be synthesized only from the above three components ((a1), (a2) and (a3)). Furthermore, it can be synthesized by reacting (a4) a monohydroxy compound and/or (a5) a monoisocyanate compound. From the viewpoint of weather resistance and light resistance, (a4) monohydroxy compound and (a5) monoisocyanate compound are preferably compounds containing no aromatic ring or carbon-carbon double bond in the molecule.
  • Polyurethanes containing carboxyl groups can be prepared by using a suitable organic solvent in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate. ) a polyol compound and (a3) a dihydroxy compound having a carboxyl group. It is advantageous to synthesize a polyurethane containing a carboxyl group without a catalyst because it is not necessary to consider contamination with tin or the like in the end.
  • a known urethanization catalyst such as dibutyltin dilaurate.
  • the organic solvent is not particularly limited as long as it has low reactivity with the isocyanate compound.
  • the organic solvent preferably does not contain a basic functional group such as amine and has a boiling point of 50° C. or higher, preferably 80° C. or higher, more preferably 100° C. or higher.
  • solvents examples include toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, acetic acid n-butyl, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N,N-dimethylformamide, N,N-di
  • the organic solvent is propylene.
  • Glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ⁇ -butyrolactone, or combinations thereof are preferred.
  • the order in which the raw materials are added is not particularly limited, but usually (a2) the polyol compound and (a3) the dihydroxy compound having a carboxyl group are first placed in a reaction vessel, dissolved or dispersed in a solvent, and then heated to 20 to 150°C. , more preferably at 60 to 120°C, (a1) the polyisocyanate compound is added dropwise, and then these are reacted at 30 to 160°C, more preferably 50 to 130°C.
  • the molar ratio of raw materials charged is adjusted according to the molecular weight and acid value of the target polyurethane containing carboxyl groups.
  • the molar ratio of (a1) the isocyanato group of the polyisocyanate compound to ((a2) the hydroxyl group of the polyol compound + (a3) the hydroxyl group of the dihydroxy compound having a carboxyl group) is preferably 0.5 to 1.5. :1, more preferably 0.8-1.2:1, more preferably 0.95-1.05:1.
  • the molar ratio of (a2) hydroxyl group of the polyol compound to (a3) hydroxyl group of the dihydroxy compound having a carboxyl group is preferably 1:0.1-30, more preferably 1:0.3-10.
  • Epoxy compounds having two or more epoxy groups in one molecule include, for example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, phenol novolac type Epoxy resins, cresol novolak type epoxy resins, N-glycidyl type epoxy resins, bisphenol A novolak type epoxy resins, chelate type epoxy resins, glyoxal type epoxy resins, amino group-containing epoxy resins, rubber-modified epoxy resins, dicyclopentadiene phenolic type Epoxy resins, silicone-modified epoxy resins, ⁇ -caprolactone-modified epoxy resins, glycidyl group-containing aliphatic epoxy resins, and glycidyl group-containing alicyclic epoxy resins can be mentioned.
  • An epoxy compound having 3 or more epoxy groups in one molecule can be used more preferably.
  • examples of such epoxy compounds include EHPE (registered trademark) 3150 (manufactured by Daicel Corporation), jER604 (manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-4700 (manufactured by DIC Corporation), and EPICLON HP-7200 (manufactured by DIC Corporation). company), pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, and TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.).
  • the (B) epoxy compound may have an aromatic ring in the molecule.
  • the mass of the epoxy compound is preferably 20% by mass or less.
  • the mixing ratio of (A) the carboxy group-containing polyurethane to the (B) epoxy compound is 0.5 to 1.5 in terms of the equivalent ratio of the carboxy group in the polyurethane to the epoxy group of the (B) epoxy compound. It is preferably from 0.7 to 1.3, even more preferably from 0.9 to 1.1.
  • Curing accelerators include, for example, phosphine compounds such as triphenylphosphine and tributylphosphine (manufactured by Hokko Chemical Industry Co., Ltd.), Curesol (registered trademark) (imidazole-based epoxy resin curing agent: manufactured by Shikoku Kasei Kogyo Co., Ltd. ), 2-phenyl-4-methyl-5-hydroxymethylimidazole, U-CAT (registered trademark) SA series (DBU salt: manufactured by San-Apro Co., Ltd.), and Irgacure (registered trademark) 184.
  • phosphine compounds such as triphenylphosphine and tributylphosphine (manufactured by Hokko Chemical Industry Co., Ltd.)
  • Curesol registered trademark
  • imidazole-based epoxy resin curing agent manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • 2-phenyl-4-methyl-5-hydroxymethylimidazole
  • the amount of curing accelerator used if the amount used is too small, the effect of the addition will not be obtained, and if the amount used is too large, the electrical insulation will decrease.
  • Curing aids include, for example, polyfunctional thiol compounds and oxetane compounds.
  • polyfunctional thiol compounds include pentaerythritol tetrakis (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, trimethylolpropane tris (3-mercaptopropionate), and Karenz. (registered trademark) MT series (manufactured by Showa Denko KK) and the like.
  • oxetane compound examples include Aron Oxetane (registered trademark) series (manufactured by Toagosei Co., Ltd.), ETERNACOLL (registered trademark) OXBP and OXMA (manufactured by Ube Industries, Ltd.).
  • the amount of the curing aid used is preferably 0 per 100 parts by mass of the epoxy compound (B) because the effect of the addition can be obtained and the handling property can be maintained by avoiding an excessive increase in the curing speed. .1 to 10 parts by mass, more preferably 0.5 to 6 parts by mass.
  • the curable resin composition preferably contains 95.0% by mass or more and 99.9% by mass or less of the solvent (D), more preferably 96% by mass or more and 99.7% by mass or less, and 97% by mass or more and 99% by mass. It is more preferable to contain 0.5% by mass or less.
  • D As the solvent, a solvent that does not attack the transparent conductive film or the transparent substrate can be used.
  • A The solvent used for synthesizing the carboxy group-containing polyurethane can be used as it is, or other solvents can be used to adjust the solubility or printability of the polyurethane.
  • the solvent used for synthesizing the carboxy group-containing polyurethane may be distilled off before and after adding the new solvent to replace the solvent.
  • the boiling point of the solvent is preferably 80°C to 300°C, more preferably 80°C to 250°C. If the boiling point of the solvent is 80° C. or higher, it is possible to suppress coating unevenness caused by excessively quick drying.
  • the boiling point of the solvent is 300° C. or less, the heat treatment time required for drying and curing can be shortened, and productivity during industrial production can be improved.
  • solvents examples include propylene glycol monomethyl ether acetate (boiling point 146°C), ⁇ -butyrolactone (boiling point 204°C), diethylene glycol monoethyl ether acetate (boiling point 218°C), and tripropylene glycol dimethyl ether (boiling point 243°C) for polyurethane synthesis.
  • ether solvents such as propylene glycol dimethyl ether (boiling point 97° C.) and diethylene glycol dimethyl ether (boiling point 162° C.), isopropyl alcohol (boiling point 82° C.), t-butyl alcohol (boiling point 82° C.), 1-hexanol ( boiling point 157°C), propylene glycol monomethyl ether (boiling point 120°C), diethylene glycol monomethyl ether (boiling point 194°C), diethylene glycol monoethyl ether (boiling point 196°C), diethylene glycol monobutyl ether (boiling point 230°C), triethylene glycol (boiling point 276°C) ), a solvent containing a hydroxyl group such as ethyl lactate (boiling point 154° C.), methyl ethyl ketone (boiling point 80° C.), and eth
  • solvents can be used alone or in combination of two or more.
  • the solubility of the polyurethane, epoxy compound, etc. to be used should be taken into consideration so that aggregation and precipitation do not occur.
  • a solvent having a boiling point of more than 100°C having a hydroxy group, or a solvent having a boiling point of 100°C or less from the viewpoint of the drying property of the ink.
  • Solvents that attack the transparent conductive film or transparent substrate when used alone can be used as a mixed solvent with another solvent so long as they have a composition that does not attack the transparent conductive film or transparent resin film.
  • the curable resin composition comprises (A) a polyurethane containing a carboxyl group, (B) an epoxy compound, (C) a curing accelerator, and (D) a solvent, and (D) in the curable resin composition. It can be produced by blending such that the content of the solvent is 95.0% by mass or more and 99.9% by mass or less, and stirring so that these components are uniform.
  • the solid content concentration in the curable resin composition varies depending on the desired film thickness and printing method, but is preferably 0.1 to 10% by mass, more preferably 0.5% to 5% by mass. preferable.
  • the solid content concentration is in the range of 0.1 to 10% by mass, the film thickness does not become excessively thick when the curable resin composition is applied on the transparent conductive film, and the electrical connection with the transparent conductive film is maintained.
  • sufficient weather resistance and light resistance can be imparted to the protective film.
  • the protective film solid content in the curable resin composition (A) a polyurethane containing a carboxy group, (B) an epoxy compound, and (C) curing in a curing accelerator
  • the ratio of the aromatic ring-containing compound defined by the following formula contained in (residue) is preferably suppressed to 15% by mass or less.
  • (C) curing residue in the curing accelerator used herein means that all or part of the curing accelerator (C) may disappear (decompose, volatilize, etc.) depending on the curing conditions, so it is protected under the curing conditions. It means the (C) curing accelerator remaining in the film.
  • (C) curing accelerator remaining in the protective film after curing cannot be accurately quantified, it is calculated based on the charged amount assuming that it does not disappear due to curing conditions, and the ratio of the aromatic ring-containing compound is It is preferable to use (C) the curing accelerator within the range of 15% by mass or less.
  • the protective film When a resin composition containing a thermoplastic resin having excellent molding processability as a main component is used as the protective film (overcoat layer 4), 94% by mass or more of the resin component constituting the protective film is derived from the thermoplastic resin. is preferred. 6 mass % or less of the resin component constituting the protective film may be derived from the curable resin (compound). If the amount of the curable resin (compound) of the resin component in the resin composition is in the range of 6% by mass or less, the function as a protective film can be improved without significantly deteriorating the three-dimensional moldability. However, three-dimensional moldability is best when the resin composition does not contain a curable resin (compound).
  • the protective film can be formed by applying a resin composition in which a resin is dissolved in a solvent onto the transparent conductive film.
  • a resin composition having a Applicable resin compositions include, for example, ethyl cellulose or a resin composition containing (A) a polyurethane containing a carboxyl group, which is a thermoplastic resin component in the curable resin composition described above, as a main component.
  • a resin composition containing a polyurethane containing a carboxy group is a thermoplastic resin component in the above-mentioned curable resin composition (A) a polyurethane containing a carboxy group as a main component (containing 94% by mass or more of the resin component).
  • thermoplastic resin used for forming the protective film, such as a polyurethane containing a carboxyl group, protects
  • the thermosetting resin used to form the protective film which accounts for 94% by mass or more of the resin component of the film, such as an epoxy resin (compound) having two or more epoxy groups in one molecule, and a curing accelerator (curing (including auxiliaries) corresponds to 6% by mass or less of the resin component of the protective film.
  • an epoxy resin having two or more epoxy groups in one molecule is more than 0% by mass and 6% by mass or less in the resin component.
  • the blending ratio of the epoxy resin (compound) and the carboxy group-containing polyurethane is determined by the molar ratio (Ep/COOH) of the epoxy group (Ep) of the epoxy resin to the carboxy group (COOH) of the carboxy group-containing polyurethane. It is preferably more than 0 and 0.02 or less.
  • curable resin composition or resin composition containing a thermoplastic resin as a main component for example, by printing such as bar coat printing method, gravure printing method, ink jet method, slit coating method, etc., thin metal wires are formed.
  • a curable resin composition or a resin composition containing a thermoplastic resin as a main component is applied on a substrate on which a transparent conductive layer is formed, and the solvent is dried and removed. Then, the curable resin is cured to form a protective film (overcoat layer 4).
  • the thickness of the resulting protective film is preferably more than 30 nm and 1 ⁇ m or less.
  • the thickness of the protective film is more than 50 nm and 500 nm or less, and more preferably more than 100 nm and 200 nm or less.
  • the thickness of the protective film is 1 ⁇ m or less, it becomes easy to conduct with the wiring in the post-process.
  • the thickness of the protective film is more than 30 nm, the effect of protecting the transparent conductive layer is sufficiently exhibited.
  • the thickness of the protective film (overcoat layer 4) is approximately 1 ⁇ m or less, which is smaller than the thicknesses of the transparent conductive film and the carrier film, so that the effect on the curling property is extremely small.
  • This carrier film 1 forms a transparent conductive film laminate together with the transparent conductive film 10 or 20 laminated so as to be peelable.
  • the carrier film 1 may be a polyolefin film as a base film with an adhesive layer of polyolefin resin on one side, or may be a laminate of a polyolefin film having adhesiveness and a polyolefin film having no adhesiveness.
  • a polyolefin film is used for the carrier film 1.
  • Polyolefins include, for example, polyethylene, polypropylene, or mixtures thereof.
  • polyethylene includes homopolymers of ethylene and copolymers of ethylene and other olefins.
  • Polypropylene also includes homopolymers of propylene and copolymers of propylene with other olefins.
  • Examples of the other olefins include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, and decene. Among these, ethylene, propylene and butene are preferred.
  • the blending ratio of the other olefin in the copolymer of ethylene or propylene and the other olefin is preferably 40% by mass or less based on the total mass of ethylene or propylene as a monomer and the other olefin, 30% by mass or less is more preferable, and 20% by mass or less is particularly preferable.
  • polyethylene examples include high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (L-LDPE).
  • HDPE high-density polyethylene
  • LDPE low-density polyethylene
  • L-LDPE linear low-density polyethylene
  • the polyolefin film preferably contains at least polypropylene. Specifically, it preferably contains at least one selected from the group consisting of propylene homopolymers and copolymers of propylene and other olefins.
  • copolymers of propylene and other olefins examples include copolymers of propylene and ethylene, copolymers of propylene and butene, and copolymers of propylene, ethylene and butene. These copolymers may be random copolymers or block copolymers.
  • the blending ratio of other olefins in the copolymer is preferably 40% by mass or less, preferably 30% by mass or less, and 20% by mass or less, based on the total mass of propylene as a monomer and other olefins. Especially preferred.
  • the polyolefin film can contain a mixture of polypropylene and polyethylene.
  • the content of polypropylene in the mixture of polypropylene and polyethylene is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more, based on the total mass of polypropylene and polyethylene.
  • the content ratio is preferably 97% by mass or less.
  • the content of polyethylene in the mixture of polypropylene and polyethylene is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less, based on the total mass of polypropylene and polyethylene.
  • the content ratio is preferably 3% by mass or more.
  • the polyolefin film in the present embodiment may be a mixture containing, in addition to the above polyolefin, a copolymer of an olefin and a compound having a vinyl group other than the above olefin.
  • a copolymer of an olefin and a compound having a vinyl group other than the above olefin.
  • substituents e.g., vinyl acetate
  • cyclic (aromatic ring , alicyclic) structure eg, styrene, hydrogenated styrene.
  • the adhesive force can be further increased.
  • the polyolefin film in this embodiment may have a polyolefin single-layer structure or may have a multi-layer polyolefin structure.
  • each layer is composed of the above polyolefin, and the composition may be the same or different.
  • Examples of the multilayer lamination structure include a two-layer lamination structure of A layer/B layer, a three-layer lamination structure of A layer/B layer/A layer or A layer/B layer/C layer.
  • the A layer, the B layer, and the C layer mean different compositions.
  • a layer with high adhesion e.g., a layer containing an olefin elastomer
  • a layer with high surface smoothness is used on one main surface (layer A), and the other main surface (layer B in the case of a two-layer laminate structure)
  • a layer with low adhesion e.g., a layer that does not contain an olefin elastomer
  • a layer with low surface smoothness for the layer C in the case of a three-layer laminate structure blocking when wound with a roll is suppressed. easier to do.
  • a commercially available polyolefin film can be used.
  • Toraytec registered trademark
  • FSA registered trademark
  • SANITECT registered trademark
  • Specific model numbers include, for example, Tretec N711, Tretec A521, FSA010M, FSA020M, FSA030M, and PAC-3-70.
  • the thickness Tc of the carrier film 1 is 0.2 times or more and 0.8 times or less the thickness Ts of the transparent resin film 2, that is, 0.2 ⁇ Tc/Ts ⁇ 0.8, preferably 0.2 ⁇ Tc. /Ts ⁇ 0.6. Within this range, the curl generated when the transparent conductive film laminate is heated can be reduced, the curl after standing to cool is relatively small, and the carrier film can be replaced and flattened easily. , there is no problem in manufacturing during the production of the transparent conductive film laminate and in the post-process using the transparent conductive film laminate.
  • the thickness Tc of the carrier film 1 is preferably 25 ⁇ m or more in terms of workability and availability.
  • the transparent conductive film laminate is a transparent conductive film laminate including a transparent conductive film 10 or 20 and a carrier film 1 laminated on the transparent conductive film 10 or 20.
  • the carrier film 1 has one main surface only has stickiness.
  • a transparent conductive layer 3 containing fine metal wires, an overcoat layer 4 are laminated in this order.
  • One main surface having adhesiveness is detachably laminated to the coat layer 4 (FIGS. 1 and 2).
  • the transparent resin film 2 and the transparent conductive layer 3 are adjacent, and the transparent conductive layer 3 and the overcoat layer 4 are adjacent.
  • the transparent conductive film laminate having the above structure was cut into a size of 10 cm ⁇ 10 cm, and the curl value immediately after heating at 80 ° C. for 30 minutes was 0 to 5 mm, and the curl value after standing to cool for 30 minutes was 0 to 0. 20 mm is preferred. This makes it possible to control the amount and direction of curling during and after the heating process such as drying, so that the transparent conductive film laminate can be easily transported.
  • the method for manufacturing the transparent conductive film laminate (FIG. 1) comprises the steps of: laminating a carrier film 1 on one main surface of a transparent resin film 2; and forming a transparent conductive layer 3 and an overcoat layer 4 in this order on the main surface opposite (the other side) to the laminated side.
  • the transparent resin film 2 on which the first carrier film 1 is detachably laminated is placed on the side on which the carrier film 1 is laminated.
  • FIGS. 3A to 3D show process diagrams of the method for manufacturing the transparent conductive film laminate according to the first embodiment
  • FIGS. 4A to 4D show the first embodiment. Process drawing of the modification of the manufacturing method of the transparent conductive film laminated body concerning a form is shown.
  • the transparent conductive film laminate is a transparent resin film in which a transparent resin film 2 is detachably laminated on the main surface of a carrier film 1 having adhesiveness.
  • a laminate is formed (FIGS. 3(a) and 3(b)), and a transparent conductive layer 3 is formed on the main surface of the transparent resin film 2 opposite (the other side) to the main surface on which the carrier film 1 is laminated. (FIG. 3(c)) and then forming an overcoat layer 4 on the transparent conductive layer 3 (FIG. 3(d)).
  • the transparent resin film 2 and the transparent conductive layer 3 are adjacent, and the transparent conductive layer 3 and the overcoat layer 4 are adjacent.
  • the transparent conductive film laminate has adhesiveness between the transparent conductive film 10 and the carrier film 1. It can also be manufactured by a process of laminating the main surfaces of. As shown in FIGS. 4A to 4C, the step of preparing the transparent conductive film 10 is to form a transparent conductive layer 3 on one main surface of the transparent resin film 2 (FIG. 4A). , (b)), and then an overcoat layer 4 is formed on the transparent conductive layer 3 (FIG. 4(c)). Next, as shown in FIG.
  • a step of releasably laminating the main surface is carried out to manufacture a transparent conductive film laminate.
  • FIGS. 5A to 5I show process diagrams of the method for manufacturing a transparent conductive film laminate according to the second embodiment
  • FIGS. 6A to 6G show the second embodiment. Process drawing of the modification of the manufacturing method of the transparent conductive film laminated body concerning a form is shown.
  • the transparent conductive film laminate is laminated with the first carrier film 1A of the transparent resin film 2 in which the first carrier film 1A is detachably laminated.
  • a transparent conductive layer 3 and an overcoat layer 4 were sequentially formed on the main surface opposite (the other side) to the side where the layer is formed (FIGS. 5(a) to 5(d)).
  • the carrier film 1B is detachably laminated (FIG. 5(e)), and then the first carrier film 1A laminated on the transparent resin film 2 is detached (FIGS. 5(f), (g), FIG. 5 ( Fig.
  • the transparent conductive layer 3 is placed on the main surface of the transparent resin film 2 opposite (the other side) to the main surface on which the transparent conductive layer 3 is laminated. It can be manufactured by the step of sequentially forming the coat layer 4 (FIGS. 5(h) and (i)).
  • the transparent resin film 2 and the two transparent conductive layers 3, 3 respectively formed on both main surfaces thereof are adjacent to each other, and the two transparent conductive layers 3, 3 and the transparent resin film 2
  • the overcoat layers 4, 4 respectively formed on the main surfaces of the two transparent conductive layers 3, 3 on the side opposite to (the other side of) the side on which the is laminated are adjacent to each other.
  • the transparent conductive film laminate is obtained by preparing the transparent conductive film 20 and then laminating the transparent conductive film 20 and the carrier film 1 in a detachable manner. It can also be manufactured in a process.
  • the step of preparing the transparent conductive film 20 includes sequentially forming the transparent conductive layer 3 and the overcoat layer 4 on one main surface of the transparent resin film 2, as shown in FIGS. 6(a)-(c)), then the transparent conductive layer 3 and the overcoat layer 4 are sequentially formed on the other main surface of the transparent resin film 2 (FIGS. 6(d)-(c)). f)).
  • a step of detachably laminating the carrier film 1 on the surface of the overcoat layer 4 on one side of the transparent conductive film 20 is carried out to produce a transparent conductive film laminate. be.
  • the Young's modulus (modulus of longitudinal elasticity) was measured using a precision universal It was measured using a testing machine.
  • the experimental conditions and Young's modulus calculation method were set with reference to JIS K7161. The measurement was performed under heating at 80°C so as to match the manufacturing conditions of the transparent conductive film, but when the polyethylene film was measured under heating at 80°C, the flexibility became too low and the Young's modulus could not be calculated. I didn't. Therefore, the polyethylene film was tested at room temperature (25° C.).
  • the Young's modulus of the polyolefin film is smaller than that of the amorphous cycloolefin polymer film. That is, the polyolefin film was shown to be more flexible and softer than the amorphous cycloolefin polymer film.
  • the Young's modulus of the PET film is greater than that of the amorphous cycloolefin polymer film. That is, it was shown that the PET film is less flexible and stiffer than the amorphous cycloolefin polymer film.
  • ⁇ Production of silver nanowire ink> 5 g of a water/ethanol mixed solvent dispersion of silver nanowires synthesized by the above polyol method (silver nanowire concentration 3% by mass, water/ethanol 41/56 [mass ratio]), 6.4 g of water, 20 g of methanol (Fujifilm Sum Ko Junyaku Co., Ltd.), 39 g of ethanol (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 25 g of propylene glycol monomethyl ether (PGME, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 3 g of propylene glycol (PG, manufactured by Asahi Glass Co., Ltd.), PNVA (registered trademark) aqueous solution (manufactured by Showa Denko K.K., solid content concentration 10% by mass, weight average molecular weight 900,000) was mixed with 1.8 g and mixed with a mix rotor VMR-5R (man
  • 100 g of silver nanowire ink was prepared by stirring in an air atmosphere (rotational speed: 100 rpm).
  • the temperature of the reaction solution was lowered to 70° C., and 59.69 g of Desmodur (registered trademark)-W (bis-(4-isocyanatocyclohexyl)methane), manufactured by Sumika Covestrourethane Co., Ltd., was added as a polyisocyanate through a dropping funnel. was added dropwise over 30 minutes. After completion of the dropwise addition, the temperature was raised to 120°C and the reaction was carried out at 120°C for 6 hours. After confirming by IR that the isocyanate had almost disappeared, 0.5 g of isobutanol was added and the reaction was further carried out at 120°C for 6 hours. went.
  • the weight average molecular weight of the resulting carboxy group-containing polyurethane determined by GPC was 32,300, and the acid value of the resin solution was 35.8 mgKOH/g.
  • Overcoat ink 1 10.0 g of the (A) polyurethane solution containing a carboxy group obtained above (content of carboxy group-containing polyurethane: 45% by mass) was weighed into a plastic container, and (D) 1-hexanol (COH) 85 was added as a solvent. 3 g of ethyl acetate (EA) and 85.2 g of ethyl acetate (EA) were added, and the mixture was stirred for 12 hours at room temperature in an air atmosphere (rotational speed: 100 rpm) using a mix rotor VMR-5R (manufactured by AS ONE Corporation).
  • overcoat ink 2 7.1 g of the (A) carboxyl group-containing polyurethane solution obtained above (carboxyl group-containing polyurethane content: 45% by mass), 46.5 g of 1-hexanol (C6OH) and 46.5 g of ethyl acetate (EA) as solvents. 5 g was added, and the mixture was stirred with a mix rotor VMR-5R (manufactured by AS ONE Co., Ltd.) for 12 hours at room temperature in an air atmosphere (rotational speed: 100 rpm). Uniformity was visually confirmed, and overcoat ink 2 was obtained.
  • the non-volatile (solid) concentration (content of polyurethane containing carboxy groups) of Overcoat Ink 2 calculated from the mass before and after solvent drying was 3% by mass.
  • overcoat ink 3 10.0 g of the (A) polyurethane solution containing a carboxy group obtained above (content of carboxy group-containing polyurethane: 45% by mass) was weighed into a plastic container, and (D) 1-hexanol (COH) 74 was used as a solvent. .6 g and 74.6 g of ethyl acetate (EA) were added, and the mixture was stirred for 12 hours at room temperature in an air atmosphere with a mix rotor VMR-5R (manufactured by AS ONE Corporation) (rotational speed: 100 rpm).
  • EA ethyl acetate
  • the nonvolatile content (solid content) concentration (total amount of polyurethane containing carboxy group, epoxy compound, and curing accelerator) of overcoat ink 3 calculated from the mass before and after solvent drying was 3% by mass.
  • the molar ratio (Ep/COOH) of the epoxy group (Ep) of the epoxy resin to the carboxy group (COOH) of the carboxy group-containing polyurethane in the overcoat ink 3 was 0.02.
  • overcoat ink 4 The carboxy group-containing polyurethane solution blended in overcoat ink 2 was changed to 30.0 g of Ethocel (registered trademark) STD 100 cps (ethyl cellulose manufactured by Dow Chemical (U.S.)) solution (ethanol solution with a solid concentration of 10% by mass), Overcoat ink 4 was obtained in the same manner as overcoat ink 2, except that 35.0 g of 1-hexanol (C6OH) and 35.0 g of ethyl acetate (EA) were added as solvents.
  • Example 1 ⁇ Formation of transparent conductive layer (silver nanowire layer)> Using an A4 size corona discharge surface treatment apparatus (manufactured by Wedge Co., Ltd.) A4SW-FLNW type, an A4 size amorphous cycloolefin polymer film ZF14-100 (manufactured by Nippon Zeon Co., Ltd., thickness Ts of 100 ⁇ m, used as a transparent resin film, A glass transition temperature of 136° C. [catalog value]) was subjected to corona discharge treatment (conveyance speed: 3 m/min, number of treatments: 2 times, output: 0.3 kW).
  • A4 size corona discharge surface treatment apparatus manufactured by Wedge Co., Ltd.
  • A4SW-FLNW type an A4 size amorphous cycloolefin polymer film ZF14-100 (manufactured by Nippon Zeon Co., Ltd., thickness Ts of 100 ⁇ m, used as
  • the wet film thickness A silver nanowire ink was applied to the entire surface of the film (surface treated with corona discharge) so that the thickness of the film was 22 ⁇ m (coating speed: 500 mm/sec). After that, it was dried with hot air at 80° C.
  • a thermostat HISPEC HS350 manufactured by Kusumoto Kasei Co., Ltd.
  • the film thickness of the silver nanowire layer was measured using a film thickness measurement system F20-UV (manufactured by Filmetrics Co., Ltd.) based on optical interferometry. The average value obtained by measuring three points at different measurement points was used as the film thickness. The spectrum from 450 nm to 800 nm was used for analysis.
  • This measurement system can directly measure the film thickness (T cn ) of the silver nanowire layer formed on the transparent substrate. As a result, it was 80 nm.
  • overcoat ink 1 was applied to the entire surface so that the wet film thickness was 5 ⁇ m (coating speed: 333 mm/sec). After that, hot air drying (thermal curing) was performed at 80° C.
  • HISPEC HS350 manufactured by Kusumoto Kasei Co., Ltd.
  • the film thickness of the overcoat layer was measured using a film thickness measurement system F20-UV (manufactured by Filmetrics Co., Ltd.) based on the optical interferometry, as in the case of the film thickness of the silver nanowire layer.
  • the average value obtained by measuring three points at different measurement points was used as the film thickness.
  • the spectrum from 450 nm to 800 nm was used for analysis.
  • the total thickness (T cn + T p ) can be directly measured, the film thickness (T p ) of the overcoat layer can be obtained by subtracting the previously measured film thickness (T cn ) of the silver nanowire layer from this measured value.
  • the film thickness (T p ) of the overcoat layer was 90 nm.
  • a transparent conductive film laminate having a transparent conductive layer on one main surface of a transparent resin film On the side of the transparent resin film on which the transparent conductive layer (silver nanowire layer) of the transparent resin film constituting the transparent conductive film with the overcoat layer formed is not formed, a PE-based adhesive film Tretec A521 (processed by Toray Film Co., Ltd.) is used as a carrier film. (manufactured by Co., Ltd., thickness Tc: 25 ⁇ m). The main surface of the sticky side was press-bonded and laminated to form a transparent conductive film laminate.
  • Example 2 Amorphous cycloolefin polymer film ZF14-050 (manufactured by Nippon Zeon Co., Ltd., thickness Ts: 50 ⁇ m, glass transition temperature: 136° C. [catalog value]) was used as the transparent resin film, and Tretec N711 (a PE adhesive film) was used as the carrier film.
  • a transparent conductive film laminate was formed under the same conditions as in Example 1, except that Toray Advanced Film Co., Ltd. (thickness Tc: 30 ⁇ m) was used.
  • Example 3 Transparent under the same conditions as in Example 2, except that an amorphous cycloolefin polymer film ZF16-040 (manufactured by Nippon Zeon Co., Ltd., thickness Ts: 40 ⁇ m, glass transition temperature: 163° C. [catalog value]) was used as the transparent resin film.
  • a conductive film laminate was formed.
  • Example 4 A transparent conductive film laminate was formed under the same conditions as in Example 3, except that a PP adhesive film FSA010M (manufactured by Futamura Chemical Co., Ltd., thickness Tc: 30 ⁇ m) was used as the carrier film.
  • a PP adhesive film FSA010M manufactured by Futamura Chemical Co., Ltd., thickness Tc: 30 ⁇ m
  • Example 5 A4 size amorphous cycloolefin polymer film ZF14-100 (manufactured by Nippon Zeon Co., Ltd., thickness Ts: 100 ⁇ m, glass transition temperature: 136° C. [catalog value]) as a transparent resin film was coated on one main surface with a carrier film as a carrier film. The sticky main surface of Toretec A521 PE-based adhesive film (manufactured by Toray Advanced Film Co., Ltd., thickness Tc: 25 ⁇ m) was pressed and laminated.
  • Example 1 Subsequently, on the main surface of the transparent resin film opposite to the side on which the carrier film is laminated, using the silver nanowire ink and overcoat ink used in Example 1, under the same conditions, a transparent conductive film was formed. A layer (silver nanowire layer) and an overcoat layer were sequentially formed to form a transparent conductive film laminate having the same structure as in Example 1.
  • Example 6 A transparent conductive film laminate was formed under the same conditions as in Example 1, except that a PE-based self-adhesive film PAC-3-70 (manufactured by San A Kaken Co., Ltd., thickness Tc: 70 ⁇ m) was used as the carrier film.
  • a PE-based self-adhesive film PAC-3-70 manufactured by San A Kaken Co., Ltd., thickness Tc: 70 ⁇ m
  • Example 7 A transparent conductive film laminate was formed under the same conditions as in Example 1, except that overcoat ink 2 was used as the overcoat ink.
  • Example 8 A transparent conductive film laminate was formed under the same conditions as in Example 1, except that Overcoat Ink 3 was used as the overcoat ink.
  • Example 9 A transparent conductive film laminate was formed under the same conditions as in Example 1, except that Overcoat Ink 4 was used as the overcoat ink.
  • Example 10 ⁇ Preparation of Transparent Conductive Film Laminate Having Transparent Conductive Layers on Both Main Surfaces of Transparent Resin Film> Under the same conditions as in Example 1, both main surfaces of an amorphous cycloolefin polymer film ZF14-100 (manufactured by Nippon Zeon Co., Ltd., thickness Ts: 100 ⁇ m, glass transition temperature: 136° C. [catalog value]) as a transparent resin film. Corona treated. Subsequently, a transparent conductive layer (silver nanowire layer) and an overcoat layer were formed on one main surface (first surface) under the same conditions as in Example 1.
  • an amorphous cycloolefin polymer film ZF14-100 manufactured by Nippon Zeon Co., Ltd., thickness Ts: 100 ⁇ m, glass transition temperature: 136° C. [catalog value]
  • a transparent conductive layer (silver nanowire layer) and an overcoat layer were formed under the same conditions as in Example 1 on the other main surface (second surface) on which the transparent conductive layer was not formed, and a transparent resin film was formed.
  • a transparent conductive film having transparent conductive layers (silver nanowire layers) on both main surfaces was obtained.
  • the main surface having adhesiveness of PE-based adhesive film Tretec A521 manufactured by Toray Advanced Film Co., Ltd., thickness Tc is 25 ⁇ m) as a carrier film is crimped, They were laminated to form a transparent conductive film laminate.
  • Example 11 Under the same conditions as in Example 1, both main surfaces of an amorphous cycloolefin polymer film ZF14-100 (manufactured by Nippon Zeon Co., Ltd., thickness Ts: 100 ⁇ m, glass transition temperature: 136° C. [catalog value]) as a transparent resin film. Corona treated. Subsequently, on one main surface (second surface), the main surface having adhesiveness of PE-based adhesive film Tretec A521 (manufactured by Toray Advanced Film Co., Ltd., thickness Tc is 25 ⁇ m) as a carrier film is crimped, Laminated.
  • PE-based adhesive film Tretec A521 manufactured by Toray Advanced Film Co., Ltd., thickness Tc is 25 ⁇ m
  • the silver nanowire ink and overcoat ink used in Example 1 were applied under the same conditions. Then, a first transparent conductive layer (silver nanowire layer) and a first overcoat layer were sequentially formed to form a transparent conductive film laminate having the same structure as in Example 1. Subsequently, on the first overcoat layer, the adhesive main surface of a PE-based adhesive film Toretec A521 (manufactured by Toray Advanced Film Co., Ltd., thickness Tc: 25 ⁇ m) as a carrier film is crimped and laminated.
  • a PE-based adhesive film Toretec A521 manufactured by Toray Advanced Film Co., Ltd., thickness Tc: 25 ⁇ m
  • the carrier film that had been press-bonded and laminated on one main surface (second surface) of the transparent resin film was peeled off. After that, on one main surface (second surface) of the exposed transparent resin film, using the silver nanowire ink and overcoat ink used in Example 1, under the same conditions, a second transparent conductive layer (silver nanowire layer) and a second overcoat layer were sequentially formed to form a transparent conductive film laminate having the same structure as in Example 10.
  • Example 12 A transparent conductive film laminate was formed under the same conditions as in Example 11, except that overcoat ink 2 was used as the overcoat ink.
  • Example 13 A transparent conductive film laminate was formed under the same conditions as in Example 11, except that Overcoat Ink 3 was used as the overcoat ink.
  • Example 14 A transparent conductive film laminate was formed under the same conditions as in Example 11, except that Overcoat Ink 4 was used as the overcoat ink.
  • Comparative example 1 Transparent conductive film under the same conditions as in Example 1 except that T2-50 (manufactured by Sanei Kaken Co., Ltd., thickness Tc is 50 ⁇ m) of PET film having an acrylic pressure-sensitive adhesive layer (thickness of about 10 ⁇ m) was used as the carrier film. A laminate was formed.
  • Comparative example 2 Transparent conductive film under the same conditions as in Example 2 except that T2-50 (manufactured by Sanei Kaken Co., Ltd., thickness Tc is 50 ⁇ m) of PET film having an acrylic pressure-sensitive adhesive layer (thickness of about 10 ⁇ m) was used as the carrier film. A laminate was formed.
  • Comparative example 3 A transparent conductive film laminate was prepared under the same conditions as in Comparative Example 2 except that a PET film EXR911 (manufactured by Sanei Kaken Co., Ltd., thickness Tc of 125 ⁇ m) having an acrylic pressure-sensitive adhesive layer (thickness of about 10 ⁇ m) was used as the carrier film. formed.
  • a PET film EXR911 manufactured by Sanei Kaken Co., Ltd., thickness Tc of 125 ⁇ m
  • an acrylic pressure-sensitive adhesive layer thickness of about 10 ⁇ m
  • Comparative example 4 Amorphous cycloolefin polymer film ZF14-023 (manufactured by Nippon Zeon, thickness Ts: 23 ⁇ m, glass transition temperature: 136° C. [catalog value]) was used as the transparent resin film, and PE adhesive film Tretec N711 (Toray Film Co., Ltd.) was used as the carrier film.
  • a transparent conductive film laminate was formed under the same conditions as in Example 1, except that the film (manufactured by Kako Co., Ltd., having a thickness Tc of 30 ⁇ m) was used.
  • Comparative example 5 A transparent conductive film laminate was formed under the same conditions as in Comparative Example 4, except that Overcoat Ink 2 was used as the overcoat ink.
  • Comparative example 6 A transparent conductive film laminate was formed under the same conditions as in Example 4, except that Overcoat Ink 3 was used as the overcoat ink.
  • Comparative example 7 A transparent conductive film laminate was formed under the same conditions as in Example 4, except that Overcoat Ink 4 was used as the overcoat ink.
  • Comparative example 8 A transparent conductive film laminate was formed under the same conditions as in Comparative Example 2, except that a PE adhesive film PAC-3-50THK (manufactured by San A Kaken Co., Ltd., thickness Tc: 50 ⁇ m) was used as the carrier film.
  • a PE adhesive film PAC-3-50THK manufactured by San A Kaken Co., Ltd., thickness Tc: 50 ⁇ m
  • the uneven shape of the transparent conductive film laminate was observed through the glass window.
  • the test piece was placed on a horizontal surface with the overcoat layer facing up, and the curl value was quickly measured with a ruler. This was taken as the curl value during heating. Further, it was allowed to cool at room temperature for 30 minutes, and the curl value was measured with a ruler. This was taken as the curl value after standing to cool.
  • FIGS. 7(a) and (b) show explanatory diagrams of the method of measuring the curl value.
  • FIG. 7A shows the case where the transparent conductive film laminate curls convexly
  • FIG. 7B shows the case where the transparent conductive film laminate curls concavely.
  • the height hmax of the highest point of the transparent conductive film laminate from the horizontal plane Hs on which the transparent conductive film laminate is placed was measured and used as the curl value.
  • the material of the carrier film is polyolefin, and the ratio of the thickness Ts of the amorphous cycloolefin polymer film to the thickness Tc of the carrier film (Tc/Ts) is 0.2.
  • Tc/Ts the ratio of the thickness Ts of the amorphous cycloolefin polymer film to the thickness Tc of the carrier film
  • Example 1 After standing to cool, the thermal shrinkage rate of polyolefin is greater than that of amorphous cycloolefin polymer. It was confirmed that the transparent conductive film laminate can be reattached to a carrier film, and that the transparent conductive film laminate becomes flat after the reattachment. In Example 1 and Examples 7 to 9 in which only the overcoat layer was changed, the curl values during heating and after standing to cool were the same. It is presumed that the curling was hardly affected because the thickness of the overcoat layer was small relative to the thickness of the entire transparent conductive film laminate.
  • Example 10 to 14 Even when the transparent resin film has transparent conductive layers on both sides (Examples 10 to 14), deformation can be suppressed in the same way as when the transparent resin film has a transparent conductive layer on one side (Examples 1 to 9).
  • Example 1 and 5 and in Examples 10 and 11 the same evaluation results were obtained because the structures of the obtained transparent conductive film laminates were the same although the manufacturing processes were different.
  • Example 11 and Examples 12 to 14 in which only the overcoat layer was changed the curl values during heating and after standing to cool were the same. It is presumed that the curling was hardly affected because the thickness of the overcoat layer was small relative to the thickness of the entire transparent conductive film laminate.
  • Comparative Example 1 in which the material of the carrier film is PET, the deformation during heating was so large that it interfered with roll conveyance. This is probably because the carrier film (PET) could not follow the thermal expansion of the transparent resin film (amorphous cycloolefin polymer) because PET is more rigid than polyolefin. Even if the material of the carrier film was polyolefin, when Tc/Ts exceeded 0.8 (Comparative Examples 4 to 8), the deformation during heating became so large that it interfered with roll transport.

Landscapes

  • Laminated Bodies (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

La présente invention vise à procurer un stratifié de film conducteur transparent et son procédé de fabrication, ce par quoi, lorsqu'une résine à base de cyclooléfine amorphe est utilisée dans un matériau de base d'un film conducteur transparent, le gondolage d'un stratifié de film conducteur transparent pendant un processus de chauffage est supprimé, le rendement d'un processus ultérieur peut être assuré, et les coûts de fabrication peuvent être réduits. La solution selon l'invention porte sur un stratifié de film conducteur transparent contenant un film conducteur transparent 10 et un film de support 1 stratifié sur celui-ci. Le film conducteur transparent 10 est obtenu par stratification d'une couche conductrice transparente 3, qui contient un fil métallique fin, et d'une couche de finition 4, dans cet ordre, sur une surface principale d'un film de résine transparent 2 comprenant une résine à base de cyclooléfine amorphe (épaisseur Ts = 30 à 150 µm). Le film de support 1 comprend un film de polyoléfine, et une seule surface principale du film de support 1 est adhésive. Le film conducteur transparent 10 est stratifié de manière amovible sur la surface principale adhésive du film de support 1 de telle sorte que la couche de finition 4 devient la couche la plus externe. Le rapport (Tc/Ts) entre l'épaisseur Tc du film de support 1 et l'épaisseur Ts du film de résine transparent 2 satisfait à 0,2 ≦ Tc/Ts ≦ 0,8.
PCT/JP2022/025919 2021-07-15 2022-06-29 Stratifié de film conducteur transparent et son procédé de fabrication WO2023286602A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020088112A (ja) * 2018-11-22 2020-06-04 日東電工株式会社 導電性フィルムの製造方法
WO2021075424A1 (fr) * 2019-10-18 2021-04-22 昭和電工株式会社 Stratifié à film transparent électriquement conducteur et son procédé de traitement

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020088112A (ja) * 2018-11-22 2020-06-04 日東電工株式会社 導電性フィルムの製造方法
WO2021075424A1 (fr) * 2019-10-18 2021-04-22 昭和電工株式会社 Stratifié à film transparent électriquement conducteur et son procédé de traitement

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