CN107533883B - Light-transmitting conductive film and method for manufacturing annealed light-transmitting conductive film - Google Patents
Light-transmitting conductive film and method for manufacturing annealed light-transmitting conductive film Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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- 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
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- 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
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- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
Abstract
The invention provides a transparent conductive film which can reduce the resistance value even if annealing treatment is carried out in a short time. The light-transmitting conductive film of the present invention comprises a light-transmitting and conductive layer and a base material disposed on one surface side of the conductive layer, wherein the conductive layer is an indium tin oxide amorphous layer, the content of Sn atoms In the conductive layer is 7 wt% or more based on 100 wt% of the total content of In atoms and Sn atoms, and the carrier density of the conductive layer is 4 x 1020/cm3Above, 6 × 1020/cm3The conductive layer has a Hall mobility of 20cm228cm above V.s2Has a value of/V.s or less.
Description
Technical Field
The present invention relates to a light-transmitting conductive film having light-transmitting properties and electrical conductivity. The present invention also relates to a method for manufacturing an annealed transparent conductive film, including a step of annealing the transparent conductive film.
Background
In recent years, touch panel type liquid crystal display devices have been widely used in electronic devices such as smart phones, mobile phones, notebook personal computers, tablet PCs, copiers, and car navigation devices. In such a liquid crystal display device, a transparent conductive film in which a transparent conductive layer is stacked over a substrate is used.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2006-19239
Disclosure of Invention
Technical problem to be solved by the invention
The transparent conductive layer is generally used to improve crystallinity by annealing the entire transparent conductive film. Conventionally, this annealing treatment needs to be performed for a long time, and therefore, there is a problem that the production efficiency of the transparent conductive film is deteriorated and the cost of the transparent conductive film is increased.
On the other hand, when the annealing time is shortened, the resistance value is not easily sufficiently lowered.
The purpose of the present invention is to provide a light-transmitting conductive film that can reduce the resistance value even when annealing is performed in a short time. The present invention also provides a method for manufacturing an annealed transparent conductive film using the transparent conductive film.
Technical solution for solving technical problem
According to a broad aspect of the present invention Provided is a light-transmitting conductive film, which is provided with: the conductive layer is an amorphous layer of indium-tin oxide, the content of Sn atoms In the conductive layer is 7 wt% or more In 100 wt% of the total content of In atoms and Sn atoms In the conductive layer, and the carrier density of the conductive layer is 4 x 1020/cm3Above, 6 × 1020/cm3The conductive layer has a Hall mobility of 20cm228cm above V.s2Has a value of/V.s or less.
In a specific aspect of the transparent conductive film of the present invention, the carrier density of the conductive layer after heating at 150 ℃ for 10 minutes is 7.0 × 1020/cm32.0 × 10 or more21/cm3The Hall mobility of the conductive layer was 20cm after heating at 150 ℃ for 10 minutes230cm above V.s2Has a value of/V.s or less.
In a specific aspect of the transparent conductive film of the present invention, the thickness of the conductive layer is 16nm or more and 19.9nm or less.
According to a broad aspect of the present invention, there is provided a method for manufacturing an annealed transparent conductive film, including a step of annealing the transparent conductive film.
ADVANTAGEOUS EFFECTS OF INVENTION
The light-transmitting conductive film of the present invention comprises a light-transmitting and conductive layer and a base material disposed on one surface side of the conductive layer, wherein the conductive layer is an amorphous layer of indium-tin oxide, the content of Sn atoms In the conductive layer is 7 wt% or more out of 100 wt% of the total content of In atoms and Sn atoms In the conductive layer, and the carrier density of the conductive layer is 4 × 10 20/cm3Above, 6 × 1020/cm3The Hall mobility of the conductive layer is 20cm228cm above V.s2Since the resistance value is not more than V · s, the resistance value can be reduced even if the annealing treatment is performed in a short time.
Drawings
Fig. 1 is a cross-sectional view of a transparent conductive film according to embodiment 1 of the present invention;
fig. 2 is a cross-sectional view of a transparent conductive film according to embodiment 2 of the present invention;
fig. 3 is a cross-sectional view of the transparent conductive film according to embodiment 1 of the present invention, which is subjected to annealing treatment.
Description of the marks
1. 1A … light-transmitting conductive film
1X … annealed transparent conductive film
2. 2A … base Material
2b … No. 2 surface
3 … conductive layer
3X … patterned conductive layer
4 … protective film
11 … substrate film
12 … hard coat layer 1
13 … hard coat 2
14 … base coat
Detailed Description
The present invention will be described in detail below.
The light-transmitting conductive film of the present invention includes a conductive layer and a substrate. The conductive layer has light transmittance and conductivity. The base material is disposed on one surface side of the conductive layer.
In the transparent conductive film of the present invention, the conductive layer is an amorphous layer of indium-tin oxide. In the transparent conductive film of the present invention, the content of Sn atoms is 7 wt% or more based on 100 wt% of the total content of In atoms and Sn atoms In the conductive layer. In the transparent conductive film of the present invention, the carrier density of the conductive layer is 4 × 10 20/cm3Above, 6 × 1020/cm3The following. In the transparent conductive film of the present invention, the hall mobility of the conductive layer is 20cm228cm above V.s2Has a value of/V.s or less.
In the present invention, since the above-described structure is provided, the resistance value can be reduced even if the annealing treatment is performed in a short time. The inventors of the present invention have studied that the transparent conductive film itself before the annealing treatment has a property of reducing the resistance value of the transparent conductive film after the annealing treatment. As a result of the studies of the present inventors, it was found that: in the transparent conductive film before annealing, as long as the conductive layer satisfies the above-described technical means, the resistance value can be reduced even if the annealing is performed in a short time. Further, as a result of the studies by the present inventors, it was found that: even if the annealing treatment is performed in a short time, the conductive layer may satisfy the above-described structure in the transparent conductive film before the annealing treatment in order to obtain an annealed transparent conductive film having a low resistance value. The transparent conductive film of the present invention can be used for obtaining a transparent conductive film subjected to a long-time annealing treatment by performing the long-time annealing treatment. If the annealing treatment is performed for a long time, the resistance value can be further reduced.
From the viewpoint of further reducing the resistance value, the carrier density of the conductive layer before the annealing treatment is preferably 4.5 × 1020/cm3Above, preferably 5.5X 1020/cm3The following.
From the viewpoint of further reducing the resistance value, the hall mobility of the conductive layer before the annealing treatment is preferably 22cm2At least V.s, preferably 26cm2Has a value of/V.s or less.
The substrate preferably comprises a substrate film, preferably a hard coat layer, preferably a primer layer. The transparent conductive film of the present invention preferably includes a protective film, wherein the conductive layer is disposed on a 1 st surface of the base material, and the protective film is disposed on a 2 nd surface of the base material opposite to the 1 st surface.
In addition, since the resistance value of the annealed transparent conductive film can be reduced in the transparent conductive film of the present invention, the display quality can be improved when the annealed transparent conductive film is used for a liquid crystal display device. Therefore, the light-transmitting conductive film subjected to the annealing treatment can be preferably used for a liquid crystal display device, and can be more preferably used for a touch panel.
From the viewpoint of stably achieving a low resistance value, the carrier density of the conductive layer after the annealing treatment (heating at 150 ℃ for 30 minutes) is preferably 7.0 × 10 20/cm3Above, preferably 2.0X 1021/cm3The following. From the viewpoint of stably achieving a low resistance value, the hall mobility of the conductive layer after the annealing treatment (heating at 150 ℃ for 30 minutes) is preferably 20cm2At least V.s, preferably 30cm2Has a value of/V.s or less.
Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.
Fig. 1 is a cross-sectional view of a transparent conductive film according to embodiment 1 of the present invention.
The transparent conductive film 1 shown in fig. 1 is a transparent conductive film before annealing treatment. The transparent conductive film 1 includes a substrate 2, a conductive layer 3, and a protective film 4.
The substrate 2 has a 1 st surface 2a and a 2 nd surface 2 b. The 1 st surface 2a and the 2 nd surface 2b are opposed to each other. A conductive layer 3 is laminated on the 1 st surface 2a of the substrate 2. The 1 st surface 2a is a surface on which the conductive layer 3 is laminated. The base material 2 is a member disposed between the conductive layer 3 and the protective film 4, and is a support member for the conductive layer 3. In this embodiment, the conductive layer 3 is an amorphous layer of indium-tin oxide, the content of Sn atoms is 7 wt% or more In 100 wt% of the total content of In atoms and Sn atoms In the conductive layer 3, and the carrier density of the conductive layer 3 is 4 × 1020/cm3Above, 6 × 1020/cm3The Hall mobility of the conductive layer 3 is 20cm 228cm above V.s2Has a value of/V.s or less.
In the transparent conductive film before the annealing treatment, the conductive layer may be partially provided or may be a patterned conductive layer.
A protective film 4 is laminated on the 2 nd surface 2b of the base material 2. The 2 nd surface 2b is a surface on which the protective film 4 is laminated. By providing the protective film 4, the No. 2 surface 2b of the substrate 2 can be protected.
The substrate 2 has a substrate film 11, a 1 st hard coat layer 12, a 2 nd hard coat layer 13, and a primer layer 14. The base film 11 is made of a material having high light transmittance. A 2 nd hard coat layer 13 and an undercoat layer 14 are sequentially laminated on the surface of the substrate film 11 on the conductive layer 3 side. Primer layer 14 is contiguous with conductive layer 3.
The 1 st hard coat layer 12 is laminated on the surface of the base film 11 on the side of the protective film 4. The 1 st hard coat layer 12 is in contact with the protective film 4.
The conductive layer 3 has high light transmittance and is made of a material having high conductivity.
The protective film may be laminated on the No. 2 surface of the substrate by an adhesive layer. The 2 nd surface of the base material is preferably in contact with the adhesive layer of the protective film.
Fig. 2 is a cross-sectional view of a transparent conductive film according to embodiment 2 of the present invention.
The transparent conductive film 1A shown in fig. 2 is a transparent conductive film before annealing treatment. The transparent conductive film 1A is not provided with the 1 st hard coat layer 12. The light-transmitting conductive film 1A has a substrate 2A in which an undercoat layer 14, a 2 nd hard coat layer 13, and a substrate film 11 are laminated in this order. The transparent conductive film 1A has a protective film 4 directly laminated on the surface of the base film 11 opposite to the conductive layer 3.
In the transparent conductive film of the present invention, the 1 st hard coat layer may not be provided, as in the transparent conductive film 1A. The protective film may be directly laminated on the surface of the base film. In addition, at least 1 layer of the 2 nd hard coat layer and the undercoat layer may not be provided. The conductive layer may be directly laminated on the base film, or the undercoat layer and the conductive layer may be sequentially laminated on the surface of the base film on the conductive layer side. The undercoat layer may be a single layer or a plurality of layers.
Next, a method for producing the transparent conductive film 1 shown in fig. 1 and a method for producing the annealed transparent conductive film 1X shown in fig. 3 will be described.
The light-transmitting conductive film 1 can be produced by the following method, for example.
The 1 st hard coat layer 12 is formed on one surface of the substrate film 11. Specifically, when an ultraviolet curable resin is used as the resin, a photocurable monomer and a photoinitiator are stirred in a diluent to prepare a coating liquid. The obtained coating liquid was applied onto a base film 11, and the resin was cured by irradiation with ultraviolet rays, thereby forming a 1 st hard coat layer 12.
Next, the protective film 4 is formed on the 1 st hard coat layer 12. When a protective film having an adhesive layer provided on a base sheet is used as the protective film 4, the protective film 4 can be formed on the 1 st hard coat layer 12 by bonding the adhesive surface to the surface of the 1 st hard coat layer 12.
Next, the 2 nd hard coat layer 13 is formed on the surface of the base film 11 opposite to the 1 st hard coat layer 12. Specifically, when an ultraviolet curable resin is used as the resin, a photocurable monomer and a photoinitiator are stirred in a diluent to prepare a coating liquid. The obtained coating liquid was applied to the surface of the base film 11 opposite to the 1 st hard coat layer 12 side, and the resin was cured by irradiation with ultraviolet rays to form a 2 nd hard coat layer 13.
Next, undercoat layer 14 is formed on second hard coat layer 13. Specifically, SiO is used2In the case of (2), the undercoat layer 14 may be formed on the 2 nd hard coat layer 13 by evaporation or sputtering.
As described above, the 1 st hard coat layer 12, the 2 nd hard coat layer 13, and the undercoat layer 14 are formed on the base film 11. In the present invention, the 1 st hard coat layer 12, the 2 nd hard coat layer 13, and the undercoat layer 14 may not be provided. In this case, the surface of the substrate film 11 on the conductive layer 3 side is the 1 st surface 2a of the substrate 2, and the surface of the substrate film 11 on the protective film 4 side is the 2 nd surface 2b of the substrate 2.
Next, the conductive layer 3 is formed on the undercoat layer 14, whereby the transparent conductive film 1 can be produced.
The method for forming the conductive layer is not particularly limited. For example, a method of etching a metal film formed by vapor deposition or sputtering, various printing methods such as screen printing or inkjet printing, a known pattern forming method such as photolithography using a resist, or the like can be used. The formed conductive layer can be used to improve crystallinity by annealing treatment described later.
The transparent conductive film 1 is preferably used for obtaining an annealed transparent conductive film 1X shown in fig. 3 by annealing. In order to obtain the annealed transparent conductive film 1X, a step of annealing the transparent conductive film 1 may be performed. When the conductive layer 3 before the annealing treatment is not in a pattern, a resist layer is partially formed on the surface of the conductive layer 3 opposite to the base material film 11 side, and etching treatment is performed, whereby a patterned conductive layer 3X can be formed. Water washing is performed after the etching treatment.
The annealed transparent conductive film 1X has a patterned conductive layer 3X. The patterned conductive layer 3X is partially laminated on the 1 st surface 2a of the base material 2. The annealed transparent conductive film 1X has a portion where the patterned conductive layer 3X is present and a portion where the patterned conductive layer 3X is absent on the 1 st surface 2a of the substrate 2.
The temperature of the annealing treatment is preferably 120 ℃ or higher, more preferably 140 ℃ or higher, preferably 170 ℃ or lower, and more preferably 160 ℃ or lower.
The treatment time of the annealing treatment is preferably 5 minutes or more, more preferably 10 minutes or more, preferably 60 minutes or less, and more preferably 30 minutes or less. In the present invention, the resistance value can be reduced even if the annealing treatment is performed in a short time.
The annealed transparent conductive film 1X may be used as it is by laminating the protective film 4 or may be used by peeling the protective film 4.
Hereinafter, the respective layers constituting the transparent conductive film will be described in detail.
(substrate)
The thickness of the entire substrate is preferably 23 μm or more, more preferably 50 μm or more, preferably 300 μm or less, and more preferably 200 μm or less.
Substrate film:
the substrate film preferably has high light transmittance. Therefore, the material of the base film is not particularly limited, and examples thereof include: polyolefins, polyethersulfones, polysulfones, polycarbonates, cyclic olefin polymers, polyarylates, polyamides, polymethyl methacrylates, polyethylene terephthalates, polybutylene terephthalates, polyethylene naphthalates, cellulose triacetates, cellulose nanofibers, and the like. The material of the substrate film may be used alone or in combination of two or more.
The thickness of the base film is preferably 5 μm or more, more preferably 20 μm or more, preferably 190 μm or less, and more preferably 125 μm or less. When the thickness of the base film is not less than the lower limit and not more than the upper limit, the pattern of the conductive layer can be further hardly recognized.
The light transmittance of the base film is preferably 85% or more, more preferably 90% or more, in the visible light region having a wavelength of 380 to 780 nm.
In addition, the substrate film may contain various stabilizers, ultraviolet absorbers, plasticizers, lubricants, or colorants.
1 st hard coat layer and 2 nd hard coat layer;
the 1 st hard coat layer and the 2 nd hard coat layer are preferably made of a binder resin. The binder resin is preferably a cured resin. As the curable resin, a thermosetting resin, an active energy ray curable resin, or the like can be used. The curable resin is preferably an ultraviolet curable resin from the viewpoint of satisfactory productivity and economy.
Examples of the photocurable monomer for forming the ultraviolet curable resin include: diacrylate compounds such as 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, 1, 4-butanediol dimethacrylate, poly (butylene glycol) diacrylate, tetraethylene glycol dimethacrylate, 1, 3-butanediol diacrylate, triethylene glycol diacrylate, triisopropylene glycol diacrylate, polyethylene glycol diacrylate and bisphenol A dimethacrylate; triacrylate compounds such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol monohydroxy triacrylate and trimethylolpropane triethoxy triacrylate; tetraacrylate compounds such as pentaerythritol tetraacrylate and di-trimethylolpropane tetraacrylate; and pentaacrylate compounds such as dipentaerythritol (monohydroxy) pentaacrylate. As the ultraviolet curable resin, a multifunctional acrylate compound having 5 or more functions can be used. The above multifunctional acrylate compounds may be used alone or in combination of two or more. In addition, a photoinitiator, a photosensitizer, a leveling agent, a diluent, and the like may be added to the above multifunctional acrylate compound.
The 1 st hard coat layer may be composed of a resin portion and a filler. In the case where the 1 st hard coat layer contains a filler, the pattern of the conductive layer can be further less easily recognized. In addition, in the case where the 1 st hard coat layer contains a filler, orange peel may occur, and in the case where a transparent conductive film is used for a liquid crystal display device, display light may not be easily seen. Therefore, from the viewpoint of preventing orange peel from being easily generated, the 1 st hard coat layer preferably contains no filler and is composed of only the resin portion. Alternatively, it is preferable that the average particle size of the filler is smaller than the thickness of the 1 st hard coat layer, and the filler does not protrude on the surface of the 1 st hard coat layer.
The filler is not particularly limited, and examples thereof include: metal oxide particles such as silica, iron oxide, alumina, zinc oxide, titanium oxide, silica, antimony oxide, zirconium oxide, tin oxide, cerium oxide, and indium-tin oxide; and resin particles such as silicone, (meth) acrylate, styrene, and melamine. More specifically, resin particles such as crosslinked polymethyl (meth) acrylate can be used. The above fillers may be used alone or in combination of two or more.
The 1 st hard coat layer and the 2 nd hard coat layer may contain various stabilizers, ultraviolet absorbers, plasticizers, lubricants, or colorants, respectively.
And (3) base coating:
the undercoat layer is, for example, a refractive index adjustment layer. By providing the undercoat layer, the difference in refractive index between the conductive layer and the 2 nd hard coat layer or the base film can be reduced, and therefore, the light transmittance of the light-transmissive conductive film can be further improved.
The material constituting the undercoat layer is not particularly limited as long as it has a refractive index adjusting function, and examples thereof include: SiO 22、MgF2、Al2O3Inorganic materials such as acrylic resin, urethane resin, and trisOrganic materials such as a melamine resin, an alkyd resin, and a siloxane polymer.
The undercoat layer can be formed by a vacuum evaporation method, a sputtering method, an ion spraying method, or a coating method.
(conductive layer)
The conductive layer is formed of a conductive material having light transmittance. As the conductive material, indium-tin oxide (ITO) can be used. The conductive layer is an amorphous layer.
In the present invention, the conductive layer before the annealing treatment is formed so that the carrier density and the hall mobility satisfy the above ranges. The carrier density and the hall mobility can be adjusted according to the type of the introduced gas at the time of forming the conductive layer, the partial pressure thereof, and the amount of on power of the cathode. As an example, in the case of forming a conductive layer by a magnetron sputtering apparatus, a process gas of rare gas such as Ar, Ne, He or the like, or O is used as the process gas 2、H2O、H2The carrier density and the hall mobility are adjusted by mixing and using these gases in combination to have a desired partial pressure.
The thickness of the conductive layer is preferably 12nm or more, more preferably 16nm or more, further preferably 17nm or more, preferably 50nm or less, more preferably 30nm or less, further preferably 19.9nm or less.
When the thickness of the conductive layer is not less than the lower limit, the resistance value of the transparent conductive film can be effectively reduced, and the conductivity can be further improved. When the thickness of the conductive layer is not more than the upper limit, the pattern of the conductive layer can be further made less visible, and the transparent conductive film can be further thinned.
In addition, the light transmittance of the conductive layer is preferably 85% or more, more preferably 90% or more, in the visible light region.
The conductive layer contains In atoms and Sn atoms. The content of Sn atoms In the conductive layer is 7 wt% or more based on 100 wt% of the total content of In atoms and Sn atoms In the conductive layer. When the content of the Sn atom is less than 7 wt%, the carrier density does not increase, and the resistance value is deteriorated. The content of Sn atoms In the conductive layer may be 30 wt% or less, or 20 wt% or less, or 10 wt% or less, based on 100 wt% of the total content of In atoms and Sn atoms.
(protective film)
The protective film is preferably composed of a substrate sheet and an adhesive layer.
The substrate sheet preferably has high light transmittance. The material of the substrate sheet is not particularly limited, and examples thereof include: polyolefins, polyethersulfones, polysulfones, polycarbonates, cyclic olefin polymers, polyarylates, polyamides, polymethyl methacrylates, polyethylene terephthalates, polybutylene terephthalates, polyethylene naphthalates, cellulose triacetates, cellulose nanofibers, and the like.
The pressure-sensitive adhesive layer may be composed of a (meth) acrylic pressure-sensitive adhesive, a rubber pressure-sensitive adhesive, a polyurethane pressure-sensitive adhesive, or an epoxy pressure-sensitive adhesive. The pressure-sensitive adhesive layer is preferably made of a (meth) acrylic pressure-sensitive adhesive from the viewpoint of suppressing an increase in adhesive strength due to heat treatment.
The (meth) acrylic pressure-sensitive adhesive is obtained by adding a crosslinking agent, a tackifier resin, various stabilizers, and the like to a (meth) acrylic polymer as necessary.
The (meth) acrylic acid polymer is not particularly limited, and is preferably a (meth) acrylic acid copolymer obtained by copolymerizing a mixed monomer containing a (meth) acrylate monomer and another copolymerizable polymerizable monomer.
The (meth) acrylate monomer is not particularly limited, but is preferably a (meth) acrylate monomer obtained by esterification of a primary or secondary alkyl alcohol having an alkyl group of 1 to 12 carbon atoms with (meth) acrylic acid, and specifically includes: ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. The (meth) acrylate monomers may be used alone or in combination of two or more.
Examples of the other copolymerizable polymerizable monomers include: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; functional monomers such as isobornyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol dimethacrylate, glycidyl (meth) acrylate, 2-methacryloyloxyethyl isocyanate, (meth) acrylic acid, itaconic acid, maleic anhydride, crotonic acid, maleic acid, and fumaric acid. The other copolymerizable polymerizable monomers may be used alone or in combination of two or more.
The crosslinking agent is not particularly limited, and examples thereof include: isocyanate crosslinking agents, epoxy crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, metal salt crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, amine crosslinking agents, multifunctional acrylate compounds, and the like. The crosslinking agents may be used alone or in combination of two or more.
The adhesion-imparting resin is not particularly limited, and examples thereof include: petroleum resins such as aliphatic copolymers, aromatic copolymers, aliphatic-aromatic copolymers, and alicyclic copolymers; coumarin-indene resins; a terpene-based resin; terpene phenol resins; rosin resins such as polymerized rosin; a phenolic resin; xylene resin, and the like. The adhesion-imparting resin may be a hydrogenated resin. The adhesion-imparting resin may be used alone or in combination of two or more.
The thickness of the protective film is preferably 25 μm or more, more preferably 50 μm or more, preferably 300 μm or less, and more preferably 200 μm or less. When the thickness of the protective film is not less than the lower limit and not more than the upper limit, the pattern of the conductive layer can be further hardly recognized.
The present invention will be described in further detail below based on specific examples. The present invention is not limited to the following examples.
(example 1)
(1) Production of light-transmitting conductive film
On a PET film (thickness 125 μm) as a base film, a conductive layer (indium tin oxide layer) having a thickness of 17.00nm was formed using a DC magnetron sputtering apparatus so that the content of tin atoms was 7 wt% in total 100 wt% of indium atoms and tin atoms, to obtain a light-transmitting conductive film.
(2) Production of annealed transparent conductive film
The conductive layer formed on the PET film was annealed for 10 minutes or 30 minutes using an IR annealer (manufactured by fuji scientific instruments) at a furnace temperature of 150 ℃.
(examples 2 to 8 and comparative examples 1 to 4)
A transparent conductive film and an annealed transparent conductive film were obtained in the same manner as in example 1, except that the hall mobility, carrier density, and thickness of the conductive layer were set as shown in table 1 below. The hall mobility and the carrier density of the conductive layer are adjusted by changing the kind of the introduced gas at the time of forming the conductive layer and the partial pressure amount thereof.
(examples 9 to 16 and comparative examples 5 to 8)
A transparent conductive film and an annealed transparent conductive film were obtained in the same manner as in example 1, except that the content of Sn atoms in the conductive layer, the hall mobility of the conductive layer, the carrier density, and the thickness were set as shown in table 1 below. The hall mobility and the carrier density of the conductive layer are adjusted by changing the type of the introduced gas, the partial pressure amount thereof, and the input power amount of the cathode during formation of the conductive layer.
(evaluation)
(1) Thickness of conductive layer in transparent conductive film before annealing treatment
The thickness of the conductive layer In the transparent conductive film before the annealing treatment was determined by measuring the amount of In per unit area using a fluorescent X-ray analyzer ZSX primus iii + (manufactured by Rigaku).
(2) Carrier density of conductive layer in transparent conductive film before and after annealing treatment
In the light-transmitting conductive film before and after the annealing treatment (after 10 minutes), the carrier density of the conductive layer was measured using a hole-effect measuring apparatus (manufactured by sinken industries). The assay method was the van der Pauw method (DC assay).
(3) Hall mobility of conductive layer in light-transmitting conductive film before and after annealing
In the light-transmitting conductive film before and after the annealing treatment (after 10 minutes), the hall mobility of the conductive layer was measured using a cavitation-effect measuring apparatus (manufactured by sinken industries).
(4) Resistance value in light-transmitting conductive film before annealing treatment and light-transmitting conductive film after annealing treatment
The resistance value of the conductive layer was measured by the 4-terminal method using Loresta-AX MCP-T370 (manufactured by mitsubishi Analytech) for the transparent conductive film before the annealing treatment and for the transparent conductive film after the annealing treatment (after 10 minutes or 30 minutes).
Claims (4)
1. A light-transmitting conductive film comprising:
a conductive layer having light transmittance and conductivity, and
a base material disposed on one surface side of the conductive layer,
the conductive layer is an amorphous layer of indium-tin oxide,
wherein the conductive layer contains Sn atoms In an amount of 7 wt% or more based on 100 wt% of the total content of In atoms and Sn atoms,
the conductive layer has a carrier density of 4 × 1020/cm3Above, 6 × 1020/cm3In the following, the following description is given,
the Hall mobility of the conductive layer is 22cm228cm above V.s2The ratio of the water to the water is less than V.s,
the Hall mobility of the conductive layer was 20cm after heating at 150 ℃ for 10 minutes230cm above V.s2/V·s is less than or equal to.
2. The light-transmitting conductive film according to claim 1, wherein,
the carrier density of the conductive layer after heating at 150 ℃ for 10 minutes was 7.0X 1020/cm32.0 × 10 or more21/cm3The following.
3. The light-transmitting conductive film according to claim 1 or 2, wherein,
the thickness of the conductive layer is 16nm to 19.9 nm.
4. A method for manufacturing a light-transmitting conductive film subjected to annealing treatment, comprising:
a process of annealing the transparent conductive film according to any one of claims 1 to 3.
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| JP6412539B2 (en) * | 2015-11-09 | 2018-10-24 | 日東電工株式会社 | Light transmissive conductive film and light control film |
| JP6490262B2 (en) * | 2017-05-09 | 2019-03-27 | 日東電工株式会社 | Film with light transmissive conductive layer, light control film and light control device |
| WO2018207622A1 (en) * | 2017-05-09 | 2018-11-15 | 日東電工株式会社 | Film with light-transmitting conductive layer, light control film and light control device |
| JP7469043B2 (en) * | 2018-11-07 | 2024-04-16 | 日東電工株式会社 | Film with light-transmitting conductive layer for touch panel, polarizing film with light-transmitting conductive layer, and touch panel display device |
| JP2020096185A (en) * | 2018-12-12 | 2020-06-18 | 日東電工株式会社 | Impedance matching film for radio wave absorber, film with impedance matching film for radio wave absorber, radio wave absorber, and laminate for radio wave absorber |
| JP7198096B2 (en) * | 2019-01-30 | 2022-12-28 | 日東電工株式会社 | transparent conductive film |
| JP7198097B2 (en) * | 2019-01-30 | 2022-12-28 | 日東電工株式会社 | transparent conductive film |
| JP7378937B2 (en) * | 2019-02-22 | 2023-11-14 | 日東電工株式会社 | Light-transparent conductive film |
| JP7378938B2 (en) * | 2019-02-22 | 2023-11-14 | 日東電工株式会社 | Light-transparent conductive film |
| CN115298763A (en) * | 2020-03-19 | 2022-11-04 | 日东电工株式会社 | Transparent conductive film and method for producing transparent conductive film |
| WO2023042844A1 (en) * | 2021-09-17 | 2023-03-23 | 日東電工株式会社 | Transparent electroconductive film |
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