CN111148626A - Transparent conductive film - Google Patents

Transparent conductive film Download PDF

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Publication number
CN111148626A
CN111148626A CN201880062416.2A CN201880062416A CN111148626A CN 111148626 A CN111148626 A CN 111148626A CN 201880062416 A CN201880062416 A CN 201880062416A CN 111148626 A CN111148626 A CN 111148626A
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China
Prior art keywords
transparent conductive
layer
conductive film
optical adjustment
transparent
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CN201880062416.2A
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Chinese (zh)
Inventor
松本圭祐
加藤久登
岩松祥平
安藤豪彦
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Nitto Denko Corp
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Nitto Denko Corp
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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

The transparent conductive film comprises a transparent resin substrate, an optical adjustment layer and a transparent conductive layer in this order, wherein the hardness of the optical adjustment layer is 0.5GPa or more according to JIS Z2255, and the surface roughness Ra of the transparent conductive layer is 40nm or less.

Description

Transparent conductive film
Technical Field
The present invention relates to a transparent conductive film, and more particularly, to a transparent conductive film suitable for optical applications.
Background
Conventionally, a transparent conductive film formed with a transparent conductive layer containing indium tin composite oxide (ITO) or the like has been used for optical applications such as touch panels.
For example, a transparent conductive film having a transparent resin film and a transparent conductive film with an optical adjustment layer therebetween is disclosed (for example, see patent document 1). In the transparent conductive film of patent document 1, when the transparent conductive film is etched into a specific pattern, the difference in reflectance between the pattern and the non-pattern is suppressed to be small by the optical adjustment layer, and the appearance is improved.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-62609
Disclosure of Invention
Problems to be solved by the invention
However, with the recent increase in the use of touch panels, there has been a demand for moisture and heat durability such that the performance of a transparent conductive film is not easily reduced when the touch panel is used in a high-temperature and high-humidity environment. Specifically, it is required that cracks (chipping of the film surface) do not occur even when the film is left for a long period of time in an environment of 85 ℃ and 85% RH.
Therefore, in the transparent conductive film of patent document 1, it is studied to increase the wet heat durability by hardening the optical adjustment layer.
However, if the optical adjustment layer is hardened, it is easily embrittled. Therefore, when the transparent conductive thin film is bent during production or use, cracks may occur, resulting in poor bendability.
The invention provides a transparent conductive film with good humidity and heat durability and bending resistance.
Means for solving the problems
The present invention [1] is a transparent conductive film comprising a transparent resin substrate, an optical adjustment layer and a transparent conductive layer in this order, wherein the optical adjustment layer has a hardness of 0.5GPa or more according to JIS Z2255, and the transparent conductive layer has a surface roughness Ra of 40nm or less.
The invention [2] is the transparent conductive film according to [1], wherein the surface roughness Ra of the transparent conductive layer is 10nm or more.
The invention [3] comprises the transparent conductive film according to [1] or [2], wherein the thickness of the optical adjustment layer is 10nm or more and 100nm or less.
The invention [4] comprises the transparent conductive film according to any one of [1] to [3], wherein the optical adjustment layer is formed of a resin composition containing an epoxy resin having a weight average molecular weight of 1500 or more.
The invention [5] is the transparent conductive film according to any one of [1] to [4], wherein the transparent conductive layer does not crack when the transparent conductive film is bent 180 degrees along a round bar having a diameter of 16 mm.
ADVANTAGEOUS EFFECTS OF INVENTION
The transparent conductive film of the present invention comprises a transparent resin substrate, an optical adjustment layer, and a transparent conductive layer in this order, and the hardness of the optical adjustment layer is 0.5GPa or more, and therefore, the transparent conductive film is excellent in moisture-heat durability. Further, the transparent conductive layer has excellent bending resistance because the surface roughness Ra of the transparent conductive layer is 40nm or less.
Drawings
Fig. 1 is a cross-sectional view of one embodiment of the transparent conductive film of the present invention.
Fig. 2 is a cross-sectional view of the transparent conductive thin film shown in fig. 1 after patterning.
FIG. 3 is a schematic view showing a transparent conductive film subjected to a moist heat durability test.
Fig. 4 is a schematic view showing a bending resistance test performed on the transparent conductive film.
Detailed Description
An embodiment of the transparent conductive film of the present invention will be described with reference to fig. 1.
In fig. 1, the vertical direction on the paper surface is the vertical direction (thickness direction, first direction), the upper side on the paper surface is the upper side (one side in the thickness direction, one side in the first direction), and the lower side on the paper surface is the lower side (the other side in the thickness direction, the other side in the first direction). The horizontal direction and the depth direction of the paper surface are plane directions orthogonal to the vertical direction. Specifically, the arrows in the direction of the figures are used.
1. Transparent conductive film
The transparent conductive film 1 has a film shape (including a sheet shape) having a specific thickness, extends in a specific direction (surface direction) orthogonal to the thickness direction, and has a flat upper surface and a flat lower surface. The transparent conductive film 1 is, for example, a member such as a touch panel substrate provided in an image display device, that is, is not an image display device. That is, the transparent conductive film 1 is a member used for manufacturing an image display device or the like, does not include an image display element such as an LCD module, and includes a hard coat layer 2, a transparent resin substrate 3, an optical adjustment layer 4, and a transparent conductive layer 5, which will be described later, and is distributed as a single member, and is an industrially applicable device.
Specifically, as shown in fig. 1, the transparent conductive film 1 includes a hard coat layer 2, a transparent resin substrate 3, an optical adjustment layer 4, and a transparent conductive layer 5 in this order. More specifically, the transparent conductive film 1 includes a transparent resin substrate 3, a hard coat layer 2 disposed on a lower surface (the other surface in the thickness direction) of the transparent resin substrate 3, an optical adjustment layer 4 disposed on an upper surface (one surface in the thickness direction) of the transparent resin substrate 3, and a transparent conductive layer 5 disposed on an upper surface of the optical adjustment layer 4. The transparent conductive film 1 preferably includes a hard coat layer 2, a transparent resin substrate 3, an optical adjustment layer 4, and a transparent conductive layer 5.
2. Hard coating
The hard coat layer (cured resin layer) 2 is a scratch protective layer for preventing the surface of the transparent conductive film 1 (i.e., the upper surface of the transparent conductive layer 5) from being scratched, for example, when a plurality of transparent conductive films 1 are stacked. Further, an anti-blocking layer for imparting blocking resistance to the transparent conductive film 1 may be formed.
The hard coat layer 2 is the lowermost layer of the transparent conductive film 1 and has a film shape. The hard coat layer 2 is disposed on the entire lower surface of the transparent resin substrate 3 so as to be in contact with the lower surface of the transparent resin substrate 3.
The hard coat layer 2 is formed of, for example, a hard coat composition. The hard coat composition contains a resin.
Examples of the resin include a curable resin and a thermoplastic resin (for example, a polyolefin resin), and a curable resin is preferably used.
Examples of the curable resin include active energy ray-curable resins which are cured by irradiation with active energy rays (specifically, ultraviolet rays, electron beams, and the like), thermosetting resins which are cured by heating, and active energy ray-curable resins are preferable.
Examples of the active energy ray-curable resin include polymers having a functional group having a polymerizable carbon-carbon double bond in the molecule. Examples of such a functional group include a vinyl group, a (meth) acryloyl group (a methacryloyl group and/or an acryloyl group), and the like.
Specific examples of the active energy ray-curable resin include (meth) acrylic ultraviolet-curable resins such as urethane acrylate and epoxy acrylate.
Examples of the curable resin other than the active energy ray-curable resin include urethane resins, melamine resins, alkyd resins, siloxane polymers, and organosilane condensates.
These resins may be used alone or in combination of two or more.
The hard coat composition preferably further contains particles in addition to the resin. Thereby, the hard coat layer 2 can be made into an anti-blocking layer having blocking resistance.
Examples of the particles include inorganic particles and organic particles. Examples of the inorganic particles include silica particles, metal oxide particles containing zirconium oxide, titanium oxide, zinc oxide, tin oxide, and the like, and carbonate particles such as calcium carbonate, and the like. Examples of the organic particles include crosslinked acrylic resin particles. The particles may be used alone or in combination of two or more.
The mode particle diameter of the particles is, for example, 0.5 μm or more, preferably 1.0 μm or more, and is, for example, 2.5 μm or less, preferably 1.5 μm or less. In the present specification, the mode particle diameter refers to a particle diameter indicating the maximum value of the particle distribution, and can be obtained by, for example, measurement under specific conditions (sheath fluid: ethyl acetate, measurement mode: HPF measurement, measurement mode: total count) using a flow particle image analyzer (product name "FPTA-3000S" manufactured by Sysmex corporation). As a measurement sample, a sample obtained by diluting the particles with ethyl acetate to 1.0 wt% and uniformly dispersing the particles using an ultrasonic cleaner was used.
The content ratio of the particles is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, with respect to 100 parts by mass of the resin.
The hard coat composition may further contain known additives such as a leveling agent, a thixotropic agent, and an antistatic agent.
From the viewpoint of scratch resistance, the thickness of the hard coat layer 2 is, for example, 0.5 μm or more, preferably 1 μm or more, and is, for example, 10 μm or less, preferably 3 μm or less.
The thickness of the hard coating may be calculated based on, for example, the wavelength of the interference spectrum observed using an instantaneous multi-channel photosystem.
3. Transparent resin base material
The transparent resin substrate 3 is a transparent substrate for ensuring the mechanical strength of the transparent conductive film 1. That is, the transparent resin substrate 3 supports the transparent conductive layer 5 together with the optical adjustment layer 4.
The transparent resin substrate 3 has a film shape (including a sheet shape). The transparent resin substrate 3 is disposed on the entire upper surface of the hard coat layer 2 so as to be in contact with the upper surface of the hard coat layer 2. More specifically, the transparent resin substrate 3 is disposed between the hard coat layer 2 and the optical adjustment layer 4 so as to be in contact with the upper surface of the hard coat layer 2 and the lower surface of the optical adjustment layer 4.
The transparent resin substrate 3 is, for example, a transparent polymer film. Examples of the material of the transparent resin substrate 3 include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, (meth) acrylic resins such as polymethacrylate (acrylic resins and/or methacrylic resins), olefin resins such as polyethylene, polypropylene, and cycloolefin polymer (COP), polycarbonate resins, polyether sulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, cellulose resins, polystyrene resins, and norbornene resins. The transparent resin substrate 3 may be used alone or in combination of two or more.
From the viewpoint of transparency, moisture and heat durability, mechanical strength, and the like, a polyester resin may be preferably used, and PET may be more preferably used.
The total light transmittance (JIS K7375-.
The thickness of the transparent resin substrate 3 is, for example, 2 μm or more, preferably 20 μm or more, and further, for example, 300 μm or less, preferably 150 μm or less, from the viewpoints of mechanical strength, scratch resistance, dot characteristics when the transparent conductive film 1 is formed into a film for a touch panel, and the like. The thickness of the transparent resin substrate 3 can be measured using, for example, a Microgauge-type thickness gauge.
The surface roughness Ra of the upper surface of the transparent resin substrate 3 is, for example, 1nm or more, preferably 10nm or more, for example, less than 1 μm, preferably 0.5 μm or less. By setting the surface roughness of the transparent resin substrate 3 to the above range, the surface roughness of the transparent conductive layer 5 can be set to an appropriate range.
4. Optical adjustment layer
The optical adjustment layer 4 is a layer for adjusting optical properties (for example, refractive index) of the transparent conductive film 1 in order to suppress the observation of wiring patterns in the transparent conductive layer 5 and ensure excellent transparency of the transparent conductive film 1.
The optical adjustment layer 4 has a film shape (including a sheet shape) and is disposed on the entire upper surface of the transparent resin substrate 3 so as to be in contact with the upper surface of the transparent resin substrate 3. More specifically, the optical adjustment layer 4 is disposed between the transparent resin substrate 3 and the transparent conductive layer 5 so as to be in contact with the upper surface of the transparent resin substrate 3 and the lower surface of the transparent conductive layer 5.
The optical adjustment layer 4 is formed of an optical adjustment composition.
(1) The optical adjustment composition may be a composition in which the hardness of the optical adjustment layer 4 described later is 0.5GPa or more, and from the viewpoint of the hardness of the optical adjustment layer 4, a resin composition containing an epoxy resin having a weight average molecular weight of 1500 or more (hereinafter referred to as a high molecular weight epoxy resin) (hereinafter referred to as a high molecular weight epoxy resin composition) is preferably used.
As the high molecular weight epoxy resin, an epoxy polymer having a saturated hydrocarbon ring can be preferably cited. Examples of the saturated hydrocarbon ring include a cyclohexane ring and a norbornene ring, and preferred examples thereof include a cyclohexane ring.
Examples of the epoxy polymer having a saturated hydrocarbon ring include a polymer of an epoxy monomer having a saturated hydrocarbon ring, a copolymer of an epoxy monomer having a saturated hydrocarbon ring and another monomer copolymerizable with the epoxy monomer, and the like.
Examples of the epoxy monomer having a saturated hydrocarbon ring include 3, 4-epoxycyclohexanecarboxylic acid 3, 4-epoxycyclohexylmethyl ester, hydrogenated bisphenol A diglycidyl ether, and the like. These monomers may be used alone or in combination of two or more.
Examples of the other monomer include epoxy monomers having an aromatic hydrocarbon ring such as bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, naphthalene diglycidyl ether, biphenyl diglycidyl ether, and triglycidyl isocyanurate.
The high molecular weight epoxy resin is preferably rubber modified. That is, a rubber-modified epoxy resin can be preferably used.
Examples of the rubber to be modified include polybutadiene (e.g., 1, 2-polybutadiene and 1, 4-polybutadiene), styrene-butadiene rubber, butyl rubber, polyisobutylene rubber, chloroprene rubber, nitrile rubber, and acrylic rubber. Polybutadiene can be preferably cited.
The high molecular weight epoxy resin has a weight average molecular weight of 1500 or more, preferably 1800 or more, and for example 10000 or less, preferably 5000 or less. The weight average molecular weight was measured by Gel Permeation Chromatography (GPC) and determined by a standard polystyrene conversion value.
The content of the high molecular weight epoxy resin in the high molecular weight epoxy resin composition is, for example, 20 mass% or more, preferably 40 mass% or more, and, for example, 80 mass% or less.
From the viewpoint of hardness, the high molecular weight epoxy resin composition preferably further contains a curing agent.
Examples of the curing agent include antimony-based curing agents such as antimony trioxide, benzylmethyl-p-methoxycarbonyloxyphenylsulfonium hexafluoroantimonate and hexafluoroantimonate, and p-methylthiophenol and naphthol-based compounds. These curing agents may be used alone or in combination of two or more.
The high molecular weight epoxy resin composition may contain other resins such as a low molecular weight (weight average molecular weight less than 1500) epoxy resin as long as the high molecular weight epoxy resin is used as a main component (component having the largest content ratio).
When the high molecular weight epoxy resin composition (optical adjustment composition) contains the curing agent, the content of the curing agent is, for example, 0.005 parts by mass or more, preferably 0.01 parts by mass or more, and is, for example, 0.5 parts by mass or less, preferably 0.1 parts by mass or less, relative to 100 parts by mass of the high molecular weight epoxy resin.
(2) Examples of the optical adjustment composition for adjusting the hardness of the optical adjustment layer 4 to 0.5GPa or more include, in addition to the high molecular weight epoxy resin composition, a resin composition containing a polymer having an aromatic ring (e.g., benzene ring, naphthalene ring), and the like.
Examples of the resin composition containing a polymer having an aromatic ring include a polyphenylene ether composition, an acrylic composition, and a polysiloxane composition.
The polyphenylene ether composition contains polyphenylene ether.
As such polyphenylene ether, for example, a polymer having a phenylene ether unit (e.g., 2, 6-dimethyl-1, 4-phenylene ether unit, 2,3, 6-trimethyl-1, 4-phenylene ether unit) is cited. The polyphenylene ether may have a glycidyl ether skeleton as a terminal of the main chain or a side chain.
The acrylic composition contains a polymer (acrylic polymer) of a monomer component containing, as a main component, a (meth) acrylate and a monomer having an aromatic ring copolymerizable with the (meth) acrylate.
The (meth) acrylate is a methacrylate and/or an acrylate, and specific examples thereof include alkyl (meth) acrylates having a linear or branched alkyl moiety having 1 to 14 carbon atoms (preferably 1 to 4 carbon atoms) such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate.
Examples of the monomer having an aromatic ring include alkenyl aromatic monomers such as styrene, α -methylstyrene, vinyltoluene, and divinylbenzene.
The polysiloxane composition contains polysiloxane having an aromatic ring in a side chain.
Examples of such a polysiloxane include a hydrosilylation reaction product of a siloxane having a silylhydride group and an aromatic hydrocarbon compound having an alkenyl group.
Examples of the siloxane having a hydrosilyl group include a polysiloxane having a methylhydrogensiloxane unit and a dimethylsiloxane unit, a polysiloxane having a methylhydrogensiloxane unit and a methylphenylsiloxane unit, and the like.
Examples of the aromatic hydrocarbon compound having an alkenyl group include divinylbenzene and the like.
From the viewpoint of heat resistance and expansion resistance, the resin composition containing a polymer having an aromatic ring may contain an isocyanate compound in addition to the above components. Examples of the isocyanate compound include hexamethylene diisocyanate, toluene diisocyanate, bis (4-isocyanatophenyl) methane, 2-bis (4-isocyanatophenyl) propane, allyl isocyanate, trimethylolpropane adducts and isocyanurates thereof.
The optical adjustment composition may further contain particles in addition to the above components. The particles can be suitably selected depending on the refractive index required for the optical adjustment layer 4, and examples thereof include inorganic particles and organic particles. Examples of the inorganic particles include silica particles, metal oxide particles containing zirconium oxide, titanium oxide, zinc oxide, and the like, and carbonate particles such as calcium carbonate, and the like. Examples of the organic particles include crosslinked acrylic resin particles.
The gelation time of the optical adjustment composition when heated to 90 ℃ is, for example, 30 seconds or more, preferably 50 seconds or more, and is, for example, 100 seconds or less, preferably 80 seconds or less. By setting the gelation time within the above range, the processing speed can be increased. The gelation time can be determined by, for example, disposing the optical conditioning composition on a plate having a surface temperature of 90 ℃ using a gelation tester, and measuring the time until the optical conditioning composition is cured.
The hardness of the optical adjustment layer 4 is 0.5GPa or more. Preferably 0.6GPa or more, for example 1.0GPa or less, preferably 0.8GPa or less. By setting the hardness of the optical adjustment layer 4 to be not less than the lower limit, the transparent conductive film 1 is excellent in moisture and heat resistance. In particular, even when left standing for a long period of time in a high-humidity high-temperature environment, the occurrence of cracks can be suppressed, and a large increase in the surface resistance value after standing can be further suppressed.
The hardness of the optical adjustment layer 4 is, for example, the hardness of the optical adjustment layer 4 when the optical adjustment layer 4 having a thickness of 30nm is disposed on a PET film having a thickness of 50 μm, and can be measured according to JIS Z2255 (2003, ultra-micro load hardness test method).
The refractive index of the optical adjustment layer 4 is, for example, 1.20 or more, preferably 1.40 or more, and is, for example, 1.70 or less, preferably 1.60 or less. By setting the refractive index of the optical adjustment layer 4 in the above range, the wiring pattern can be further suppressed from being observed.
The thickness of the optical adjustment layer 4 is, for example, 1nm or more, preferably 10nm or more, and is, for example, 200nm or less, preferably 100nm or less. By setting the thickness of the optical adjustment layer 4 to the above range, the surface roughness of the transparent conductive layer 5 can be set to an appropriate range more reliably. The thickness of the optical adjustment layer 4 can be measured using, for example, an instantaneous multi-channel photometric system.
5. Transparent conductive layer
The transparent conductive layer 5 is a conductive layer for forming a wiring pattern and forming a transparent pattern portion 7 by a subsequent process.
The transparent conductive layer 5 is the uppermost layer of the transparent conductive film 1 and has a thin film shape (including a sheet shape). The transparent conductive layer 5 is disposed on the entire upper surface of the optical adjustment layer 4 so as to be in contact with the upper surface of the optical adjustment layer 4.
Examples of the material of the transparent conductive layer 5 include metal oxides containing at least 1 metal selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W. The metal oxide may be further doped with the metal atoms shown in the above group as necessary.
Examples of the material of the transparent conductive layer 5 include indium-containing oxides such as Indium Tin Oxide (ITO) and antimony-containing oxides such as Antimony Tin Oxide (ATO), and indium-containing oxides are preferably used, and ITO is more preferably used.
As material for the transparent conductive layer 5When ITO is used, the material is preferably selected from tin oxide and indium oxide (In)2O3) Total amount of tin oxide (SnO)2) The content is, for example, 0.5% by mass or more, preferably 3% by mass or more, and is, for example, 15% by mass or less, preferably 13% by mass or less. By setting the content of tin oxide to the lower limit or more, the durability of the ITO layer can be further improved. By setting the content of tin oxide to the upper limit or less, crystal transformation of the ITO layer is easily achieved, and the transparency and stability of surface resistance can be improved.
As long as the "ITO" In the present specification is a composite oxide containing at least indium (In) and tin (Sn), it may contain an additional component other than indium (In). Examples of the additional component include metal elements other than In and Sn, and specifically include Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, W, Fe, Pb, Ni, Nb, Cr, Ga, and the like.
The refractive index of the transparent conductive layer 5 is, for example, 1.85 or more, preferably 1.95 or more, and is, for example, 2.20 or less, preferably 2.10 or less.
The thickness of the transparent conductive layer 5 is, for example, 10nm or more, preferably 15nm or more, and is, for example, 30nm or less, preferably 25nm or less. The thickness of the transparent conductive layer 5 can be measured using, for example, an instantaneous multi-channel photometric system.
The ratio of the thickness of the transparent conductive layer 5 to the thickness of the optical adjustment layer 4 (transparent conductive layer 5/optical adjustment layer 4) is, for example, 0.1 or more, preferably 0.5 or more, and is, for example, 1.2 or less, preferably 0.8 or less.
The transparent conductive layer 5 may be either crystalline or amorphous, or may be a mixture of crystalline and amorphous. The transparent conductive layer 5 is preferably formed of a crystal, more specifically, a crystalline ITO layer. This can improve the transparency of the transparent conductive layer 5, and can further reduce the surface resistance of the transparent conductive layer 5.
In the case where the transparent conductive layer 5 is a crystalline film, for example, it can be determined as follows: when the transparent conductive layer 5 is an ITO layer, it is immersed in hydrochloric acid (concentration: 5 mass%) at 20 ℃ for 15 minutes, then washed with water and dried, and the resistance between terminals between 15mm or so is measured. In this specification, the ITO layer was judged to be crystalline when the resistance between terminals of 15mm was 10 kOmega or less after immersion/washing/drying in hydrochloric acid (20 ℃ C.; concentration: 5% by mass).
6. Method for producing transparent conductive film
Next, a method for producing the transparent conductive thin film 1 will be described.
For producing the transparent conductive film 1, for example, the hard coat layer 2 is provided on the other surface of the transparent resin substrate 3, and the optical adjustment layer 4 and the transparent conductive layer 5 are provided in this order on one surface of the transparent resin substrate 3. That is, the hard coat layer 2 is provided on the lower surface of the transparent resin substrate 3, the optical adjustment layer 4 is provided on the upper surface of the transparent resin substrate 3, and the transparent conductive layer 5 is provided on the upper surface of the optical adjustment layer 4. The details are as follows.
First, a known or commercially available transparent resin substrate 3 is prepared.
Then, from the viewpoint of adhesion between the transparent resin substrate 3 and the hard coat layer 2 or the optical adjustment layer 4, the lower surface or the upper surface of the transparent resin substrate 3 may be subjected to etching treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, or oxidation, or undercoating treatment, as necessary. The transparent resin substrate 3 may be cleaned or dedusted by solvent cleaning, ultrasonic cleaning, or the like.
Next, the hard coat layer 2 is provided on the lower surface of the transparent resin substrate 3. For example, the hard coat layer 2 is formed on the lower surface of the transparent resin substrate 3 by wet-coating the hard coat composition on the lower surface of the transparent resin substrate 3.
Specifically, for example, a diluted solution (varnish) obtained by diluting the hard coat composition with a solvent is prepared, and then the diluted solution is applied to the lower surface of the transparent resin substrate 3 and dried.
Examples of the solvent include an organic solvent and an aqueous solvent (specifically, water), and preferred examples thereof include an organic solvent. Examples of the organic solvent include alcohol compounds such as methanol, ethanol, and isopropanol; ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester compounds such as ethyl acetate and butyl acetate; ether compounds such as propylene glycol monomethyl ether; for example, aromatic compounds such as toluene and xylene. These solvents may be used alone or in combination of two or more.
The solid content concentration in the diluted solution is, for example, 1 mass% or more, preferably 10 mass% or more, and is, for example, 30 mass% or less, preferably 20 mass% or less.
The coating method can be appropriately selected depending on the diluent and the transparent resin substrate 3. Examples thereof include a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, a wire bar coating method, a gravure coating method, and an extrusion coating method.
The drying temperature is, for example, 50 ℃ or higher, preferably 70 ℃ or higher, for example 200 ℃ or lower, preferably 100 ℃ or lower.
The drying time is, for example, 0.5 minutes or more, preferably 1 minute or more, for example 60 minutes or less, preferably 20 minutes or less.
In this case, the hard coat composition is preferably applied so that the thickness of the dried coating film is smaller than the diameter of the particles contained therein.
Then, when the hard coat composition contains an active energy ray-curable resin, the active energy ray-curable resin is cured by irradiating the diluted solution with an active energy ray after drying.
In the case where the hard coating composition contains a thermosetting resin, the drying step allows the thermosetting resin to be thermally cured while the solvent is dried.
Next, the optical adjustment layer 4 is provided on the upper surface of the transparent resin base material 3. For example, the optical adjustment layer 4 is formed on the upper surface of the transparent resin substrate 3 by wet-coating the optical adjustment composition on the upper surface of the transparent resin substrate 3.
Specifically, for example, a diluted solution (varnish) obtained by diluting the optical adjustment composition with a solvent is prepared, and then the diluted solution is applied to the upper surface of the transparent resin substrate 3 and dried.
Examples of conditions for preparing, coating, and drying the optical adjustment composition include the same conditions as those for preparing, coating, and drying the hard coat composition.
When the optical adjustment composition contains an active energy ray-curable resin, the active energy ray-curable resin is cured by irradiating the diluted solution with an active energy ray after drying.
In the case where the optical adjustment composition contains a thermosetting resin, the drying step allows the thermosetting resin to be thermally cured while the solvent is dried.
Next, the transparent conductive layer 5 is provided on the upper surface of the optical adjustment layer 4. For example, the transparent conductive layer 5 is formed on the upper surface of the optical adjustment layer 4 by a dry method.
Examples of the dry method include a vacuum deposition method, a sputtering method, and an ion plating method. Sputtering is preferably used. The transparent conductive layer 5 can be formed as a thin film by this method.
In the case of the sputtering method, the target material may be the above inorganic material constituting the transparent conductive layer 5, and ITO is preferably used. The tin oxide concentration of the ITO is, for example, 0.5 mass% or more, preferably 3 mass% or more, and is, for example, 15 mass% or less, preferably 13 mass% or less, from the viewpoint of durability, crystallization, and the like of the ITO layer.
Examples of the sputtering gas include inert gases such as Ar. Further, reactive gases such as oxygen may be used in combination as necessary. When the reactive gases are used in combination, the flow ratio of the reactive gases is not particularly limited, and is, for example, 0.1 to 5% by flow with respect to the total flow ratio of the sputtering gas and the reactive gases.
Sputtering is carried out under vacuum. Specifically, from the viewpoint of suppressing a decrease in sputtering rate, discharge stability, and the like, the gas pressure during sputtering is, for example, 1Pa or less, preferably 0.7Pa or less.
The power source used for the sputtering method may be any one of a DC power source, an AC power source, an MF power source, and an RF power source, for example, or a combination thereof.
In order to form the transparent conductive layer 5 having a desired thickness, sputtering may be performed a plurality of times by appropriately setting a target, sputtering conditions, and the like.
Thereby, the transparent conductive film 1 can be obtained.
Next, crystal conversion treatment is performed on the transparent conductive layer 5 of the transparent conductive film 1 as necessary.
Specifically, the transparent conductive film 1 is subjected to heat treatment in the air.
The heat treatment can be performed using, for example, an infrared heater, a dryer (oven), or the like.
The heating temperature is, for example, 100 ℃ or higher, preferably 120 ℃ or higher, and is, for example, 200 ℃ or lower, preferably 160 ℃ or lower. By setting the heating temperature within the above range, thermal damage to the transparent resin substrate 3 and impurities generated from the transparent resin substrate 3 can be suppressed, and crystal transformation can be reliably performed.
The heating time is appropriately determined depending on the heating temperature, and is, for example, 10 minutes or more, preferably 30 minutes or more, and is, for example, 5 hours or less, preferably 3 hours or less.
This makes it possible to obtain a transparent conductive film 1 having a crystallized transparent conductive layer 5.
The total thickness of the transparent conductive film 1 thus obtained is, for example, 2 μm or more, preferably 20 μm or more, and is, for example, 300 μm or less, preferably 150 μm or less.
The surface roughness Ra of the transparent conductive layer 5 in the transparent conductive film 1 (i.e., the upper surface of the transparent conductive film 1) is 40nm or less, preferably 20nm or less. By setting the surface roughness Ra to the upper limit or less, the bending resistance is excellent.
The surface roughness Ra of the transparent conductive layer 5 is, for example, 1nm or more, preferably 8nm or more, and more preferably 10nm or more. When the surface roughness Ra is not less than the lower limit, damage of the transparent conductive layer 5 due to contact with a guide roller can be suppressed in the roll-to-roll process, and the conveyance performance by roll-to-roll can be improved.
The surface roughness Ra is an arithmetic average roughness Ra, which is measured using an atomic force microscope. The surface roughness Ra of the transparent conductive film 1 does not substantially change before and after crystallization of the transparent conductive layer 5.
The transparent conductive layer 5 may be patterned into a stripe pattern or the like as shown in fig. 2 by a known etching method before or after the crystal conversion treatment, if necessary.
In the etching, for example, a covering portion (masking tape or the like) is disposed on the transparent conductive layer 5 so as to correspond to the non-pattern portion 6 and the pattern portion 7, and the transparent conductive layer 5 (non-pattern portion 6) exposed from the covering portion is etched using an etching solution. Examples of the etching solution include acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, phosphoric acid, and mixed acids thereof. Then, the covering portion is removed from the upper surface of the transparent conductive layer 5 by, for example, peeling or the like.
In the above-described manufacturing method, the hard coat layer 2, the optical adjustment layer 4, and the transparent conductive layer 5 may be formed in this order on the transparent resin substrate 3 while conveying the transparent resin substrate 3 by a roll-to-roll method, or a part or all of these layers may be formed by a batch method (a single-sheet method). From the viewpoint of productivity, it is preferable to form each layer on the transparent resin substrate 3 while conveying the transparent resin substrate 3 by a roll-to-roll method.
7. Effect of action
The transparent conductive film 1 comprises a transparent resin substrate 3, an optical adjustment layer 4, and a transparent conductive layer 5 in this order, and the hardness of the optical adjustment layer 4 is 0.5GPa or more. Therefore, even when used under a high-temperature and high-humidity environment, the transparent conductive film 1 can be inhibited from deteriorating in performance and has excellent moisture and heat durability. Specifically, the occurrence of cracks in the transparent conductive layer 5 can be suppressed even when the film is left for a long period of time in an environment of 85 ℃ and 85% RH.
In the transparent conductive film 1, the surface roughness Ra of the transparent conductive layer 5 is 40nm or less. Therefore, even if the transparent conductive film 1 is bent, the occurrence of cracks in the transparent conductive layer 5 can be suppressed, and the bending resistance is excellent. Specifically, when the transparent conductive film 1 is bent 180 degrees along a round bar having a diameter of 16mm (preferably 12mm), the occurrence of cracks in the transparent conductive layer 5 can be suppressed.
It is presumed that this is based on the following mechanism. When the surface roughness of the transparent conductive thin film 1 is large, variation in thickness becomes large, and variation occurs in film stress applied during bending.
Therefore, cracks are likely to occur in the portions where the film stress is large. In addition, generally, the thicker the thickness, the more likely the film is to crack. When the surface roughness of the transparent conductive thin film 1 is large, a region having a large thickness increases, and the probability of occurrence of cracks increases.
In contrast, in the present invention, the variation in thickness is reduced by setting the surface roughness Ra to the upper limit or less. Therefore, the variation of the film stress is reduced or the region where the thickness becomes locally large is reduced. Therefore, it is presumed that cracks due to bending can be suppressed.
In the transparent conductive film 1, the surface roughness Ra of the transparent conductive layer 5 is preferably 10nm or more. In this case, the conveyance property (windup property) in the roll-to-roll process is excellent.
Specifically, in the roll-to-roll process, after a transparent conductive layer is formed on the upper surface of the optical adjustment layer, the obtained transparent conductive film is guided (induced) to a winding roll using a guide roll, and finally wound into a roll shape. In this case, since the guide roller is disposed in contact with the transparent conductive layer, if the transparent conductive layer is excessively smooth, the transparent conductive layer may excessively adhere to the surface of the guide roller, and the transparent conductive layer may be peeled off from the optical adjustment layer, thereby causing a defect of breakage. This problem is particularly likely to occur under the condition that the slidability of the transparent conductive film 1 cannot be improved by ejecting air to the guide roller, specifically, under the condition that the transparent conductive layer is formed under vacuum by sputtering or the like.
In contrast, in the transparent conductive film 1 of the present invention, the surface roughness Ra of the transparent conductive layer 5 is preferably 10nm or more, whereby the adhesion between the guide roller and the transparent conductive layer 5 can be reduced. Therefore, the transparent conductive layer 5 is prevented from being damaged by the guide roller, and the transparent conductive film 1 can be smoothly conveyed and wound.
For example, an optical device includes a transparent conductive film 1. Examples of the optical device include an image display device. When an image display device (specifically, an image display device having an image display element such as an LCD module) includes the transparent conductive film 1, the transparent conductive film 1 is used as, for example, a substrate for a touch panel. Examples of the form of the touch panel include various forms such as an optical form, an ultrasonic form, a capacitance form, and a resistance film form, and particularly, the touch panel is suitably used for a capacitance form.
8. Modification example
In the embodiment shown in fig. 1, the transparent conductive film 1 includes the hard coat layer 2 disposed on the lower surface of the transparent resin substrate 3, and for example, although not shown, the transparent conductive film 1 may not include the hard coat layer 2. That is, the lowermost layer of the transparent conductive film 1 may be the transparent resin substrate 3.
From the viewpoint of scratch and blocking resistance, the transparent conductive film 1 is preferably provided with a hard coat layer 2.
In the embodiment shown in fig. 1, the transparent conductive film 1 may not have another functional layer such as a hard coat layer or an optical adjustment layer on the upper side of the transparent resin substrate 3, and may have 1 or 2 or more functional layers, for example, although not shown.
Examples
The present invention will be described more specifically below with reference to examples and comparative examples. The present invention is not limited to the examples and comparative examples at all. Specific numerical values of the blending ratio (content ratio), physical property value, parameter, and the like used in the following description may be replaced with upper limit values (defined as "lower" or "lower" numerical values) or lower limit values (defined as "upper" or "lower" numerical values) described in the above-described "embodiment" in accordance with the corresponding blending ratio (content ratio), physical property value, parameter, and the like.
Example 1
The transparent conductive film was produced as follows through a roll-to-roll process.
As the transparent resin substrate, a polyethylene terephthalate film (PET, thickness 50 μm, Mitsubishi resin, Ltd., surface roughness Ra of the upper surface 0.3 μm) was prepared.
A diluted solution of a hard coat composition containing a plurality of particles (crosslinked acrylic resin, monodisperse particles) having a diameter (mode particle diameter) of 1.45 μm, a binder resin (product name "unicic" manufactured by DIC corporation, urethane acrylate resin), and a solvent (butyl acetate) was applied to the lower surface of the PET film using a gravure coater, dried, and then irradiated with ultraviolet rays using a high-pressure mercury lamp. Thereby forming a hard coat layer having a thickness of 1.5 μm.
Next, 10 parts by mass of a rubber-modified epoxy resin ("アデカフィルテラ BUR-12A", manufactured by ADEKA K.K., epoxy polymer having a weight-average molecular weight of 2000 and a cyclohexane ring) and 0.001 part by mass of an antimony-based curing agent ("アデカフィルテラ BUR-12B", manufactured by ADEKA K.K.) were mixed to prepare an optical adjustment composition. The gelation time of the optical adjustment composition at 90 ℃ was 60 seconds.
To the optical adjustment composition, 90 parts by mass of methyl isobutyl ketone was mixed to prepare a varnish of the optical adjustment composition. The varnish of the optical adjustment composition was coated on the upper surface of the PET film and dried. Thus, an optical adjustment layer having a thickness of 30nm was formed. The refractive index of the optical adjustment layer was 1.53.
Next, an ITO layer (transparent conductive layer) having a thickness of 20nm was formed on the upper surface of the optical adjustment layer by sputtering. Specifically, an ITO target of a sintered body containing 90 mass% of indium oxide and 10 mass% of tin oxide was sputtered in a vacuum atmosphere in which 98% of argon gas and 2% of oxygen gas were introduced and the gas pressure was 0.4 Pa. Then, the ITO layer was crystallized by heating for 140 minutes and 90 minutes. The refractive index of the ITO layer was 2.00.
In this manner, the transparent conductive film of example 1 was produced.
Examples 2 to 3
A transparent conductive film was produced in the same manner as in example 1 except that transparent resin substrates having different surface roughnesses were prepared, and the surface roughness Ra of the transparent conductive layer side of the transparent conductive film was adjusted to table 1.
Comparative example 1
A transparent conductive film was produced in the same manner as in example 1 except that transparent resin substrates having different surface roughnesses were prepared, and the surface roughness Ra of the transparent conductive layer side of the transparent conductive film was adjusted so as to be Ra in table 1.
Comparative examples 2 to 4
A transparent conductive film was produced in the same manner as in example 1 except that the following optical adjustment composition and transparent resin base materials having different surface roughness were prepared, and the surface roughness Ra of the transparent conductive layer side of the transparent conductive film was adjusted so as to be Ra of table 1.
Optical adjustment composition: the optical adjustment composition is prepared by mixing a methoxylated methylolmelamine resin, a polyester having isophthalic acid units, a maleate ester, and a silicone.
The respective configurations and evaluations of the transparent conductive film were measured as follows.
(1) Thickness of
The PET film was measured using a Microgauge (product of MITUTOYO).
The hard coat layer, the optical adjustment layer, and the transparent conductive layer were calculated based on the waveform of the interference spectrum using an instantaneous multi-channel photometry system ("MCPD 2000", available from great ottoman electronic co.
(2) Refractive index
The refractive index of each layer was measured by a predetermined measurement method shown in a refractive index meter (manufactured by ATAGO corporation) by using an abbe refractometer and allowing measurement light to enter a measurement surface under a condition of 25 ℃.
(3) Hardness of optical adjustment layer
The hardness of the optical adjustment layer was measured in accordance with JIS Z2255 (2003, ultra micro load hardness test method).
Specifically, samples for measuring hardness were prepared, each having an optical adjustment layer with a thickness of 30nm as described in examples or comparative examples provided on the upper surface of a PET film with a thickness of 50 μm. The ultra-micro load Hardness (HTL) was measured by pressing an indenter to the upper surface of the optical adjustment layer of these samples. The results are shown in Table 1.
The device comprises the following steps: Nano-Inducer (Triboindenter, product of Hysitron inc.)
Using a pressure head: verkovich (triangular cone shape)
The using method comprises the following steps: single press
Measuring temperature: 25 deg.C
Pressing depth: 20nm
(4) Surface roughness
The arithmetic average roughness Ra of the surface of the ITO layer of the transparent conductive thin film was measured using an atomic force microscope (Nonoscope IV, manufactured by Digital Instruments inc.).
(5) Damp and hot durability test
In the transparent conductive films of examples and comparative examples, masking tapes having a width of 2mm were attached to the upper surface of the ITO layer at intervals of 10mm, and then the ITO layer of the portion to which the masking tape was not attached was etched to pattern a striped ITO layer (having a width of 10mm) (see fig. 3). The masking tape was peeled off, and the transparent conductive film 1 was further heated at 150 ℃ for 30 minutes.
Next, a glass plate 9 is disposed on the ITO layer 5 of the transparent conductive film 1 via an adhesive 8 (see fig. 3). The transparent conductive film with the glass plate was put into a high temperature and humidity apparatus ("LHL-113", manufactured by ESPEC corporation), and left to stand at 85 ℃ and 85% RH for 240 hours (high temperature and humidity test). Then, the adhesive 8 and the glass plate 9 are peeled off.
The surface of the transparent conductive film after the test was observed at a magnification of 10 times with a laser microscope, the case where cracks were clearly observed was evaluated as x, and the case where cracks were hardly observed was evaluated as ○, and the results are shown in table 1.
(6) Bending resistance test
Round bar tests were performed (round bars 16mm or 12mm in diameter). Specifically, the transparent conductive films 1 of the examples and comparative examples were cut to have a length of 150mm × a width of 10mm, the transparent conductive films 1 were arranged so that the ITO layer 5 was in contact with the round bar 10, and the transparent conductive films 1 were bent 180 degrees so as to follow the round bar 10 (see fig. 4). The ITO layer surface of the curved transparent conductive film 1 was observed at a magnification of 10 times with a laser microscope.
The case where cracks were observed in the bent portion in the case where the round bar had both diameters of 16mm and 12mm was evaluated as x, the case where no cracks were observed in the bent portion when the round bar having a diameter of 16mm was used, but cracks were observed when the round bar having a diameter of 12mm was used was evaluated as △, the case where cracks were not observed in the case where the round bar had both diameters of 16mm and 12mm was evaluated as ○, and the results are shown in table 1.
(7) Transportability
In the production of a transparent conductive film, an ITO layer is formed by sputtering under vacuum, and then a guide roller is brought into contact with the surface of the ITO layer under the vacuum, the transparent conductive film is guided to a winding roller, and the transparent conductive film is wound into a roll shape. The surface of the ITO layer of the transparent conductive film was observed with the naked eye.
The case where peeling of the ITO layer was observed over a large area was evaluated as X, the case where peeling of the ITO layer was locally observed was evaluated as △, and the case where peeling of the ITO layer was not observed was evaluated as ○. the results are shown in Table 1.
[ Table 1]
[ TABLE 1]
Figure BDA0002425483290000201
The present invention is provided as an exemplary embodiment of the present invention, but is merely an example and is not to be construed as limiting. Variations of the invention that are obvious to those skilled in the art are intended to be encompassed by the following claims.
Industrial applicability
The transparent conductive film of the present invention is applicable to various industrial products, and can be suitably used for, for example, a substrate for a touch panel provided in an image display device.
Description of the reference numerals
1 transparent conductive film
3 transparent resin base Material
4 optical adjustment layer
5 transparent conductive layer

Claims (5)

1. A transparent conductive film comprising a transparent resin substrate, an optical adjustment layer and a transparent conductive layer in this order,
the hardness of the optical adjustment layer is 0.5GPa or more according to JIS Z2255,
the surface roughness Ra of the transparent conductive layer is less than 40 nm.
2. The transparent conductive film according to claim 1, wherein the surface roughness Ra of the transparent conductive layer is 10nm or more.
3. The transparent conductive film according to claim 1, wherein the thickness of the optical adjustment layer is 10nm or more and 100nm or less.
4. The transparent conductive film according to claim 1, wherein the optical adjustment layer is formed of a resin composition containing an epoxy resin having a weight average molecular weight of 1500 or more.
5. The transparent conductive film according to claim 1, wherein the transparent conductive layer does not crack when the transparent conductive film is bent 180 degrees along a round bar having a diameter of 16 mm.
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