WO2015118904A1 - Film conducteur transparent - Google Patents

Film conducteur transparent Download PDF

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Publication number
WO2015118904A1
WO2015118904A1 PCT/JP2015/050580 JP2015050580W WO2015118904A1 WO 2015118904 A1 WO2015118904 A1 WO 2015118904A1 JP 2015050580 W JP2015050580 W JP 2015050580W WO 2015118904 A1 WO2015118904 A1 WO 2015118904A1
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WO
WIPO (PCT)
Prior art keywords
transparent conductive
layer
refractive index
high refractive
conductive film
Prior art date
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PCT/JP2015/050580
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English (en)
Japanese (ja)
Inventor
弘典 高橋
一成 多田
仁一 粕谷
健一郎 平田
Original Assignee
コニカミノルタ株式会社
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Application filed by コニカミノルタ株式会社 filed Critical コニカミノルタ株式会社
Priority to JP2015560904A priority Critical patent/JP6493225B2/ja
Publication of WO2015118904A1 publication Critical patent/WO2015118904A1/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/13338—Input devices, e.g. touch panels
    • 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
    • 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
    • B32B2307/418—Refractive
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means

Definitions

  • the present invention relates to a transparent conductive film, and more particularly, to a transparent conductive film having good conductivity and transparency and capable of displaying beautiful images without generating rainbow unevenness having angle dependency.
  • transparent conductive films have been used in various devices such as liquid crystal displays, plasma displays, inorganic and organic EL (electroluminescence) displays, touch panels, and solar cells.
  • metals such as gold, silver, platinum, copper, rhodium, palladium, aluminum, and chromium, In 2 O 3 , CdO, CdIn 2 O 4 , Cd 2 SnO 4 , and TiO 2 are used.
  • SnO 2 , ZnO, ITO (indium tin oxide) and other oxide semiconductors are known.
  • a transparent conductive film made of a transparent conductive film or the like is disposed on the image display surface of the display element. Therefore, the transparent conductive film is required to have high light transmittance.
  • a transparent conductive film made of ITO having high light transmittance is often used.
  • a silver deposited film as a transparent conductive film (see, for example, Patent Document 1). Further, in order to increase the light transmittance of the transparent conductor, a silver deposited film is formed of a film having a high refractive index (for example, niobium oxide (Nb 2 O 5 ), IZO (indium / zinc oxide), ICO (indium / cerium oxide). ), And a-GIO (a film made of gallium, indium, and oxygen) are also proposed (see, for example, Patent Documents 2 to 4). Further, it has been proposed to sandwich a vapor deposited silver film with a zinc sulfide film (see, for example, Non-Patent Documents 1 and 2).
  • a high refractive index for example, niobium oxide (Nb 2 O 5 ), IZO (indium / zinc oxide), ICO (indium / cerium oxide).
  • a-GIO a film made of gallium, indium, and oxygen
  • An object of the present invention is to provide a transparent conductive film having good conductivity and transparency, and capable of beautiful image display without occurrence of rainbow unevenness having angle dependency.
  • the present inventor uses a transparent resin support having a small in-plane retardation value Ro for the transparent conductive film in the process of examining the cause of the above-mentioned problems, and contains silver thereon.
  • a transparent resin support having a small in-plane retardation value Ro for the transparent conductive film in the process of examining the cause of the above-mentioned problems, and contains silver thereon.
  • a transparent conductive film having at least one transparent conductive layer and a high refractive index layer on a transparent resin support The in-plane retardation value Ro of the transparent resin support at a measurement wavelength of 589 nm is in the range of 0 to 150 nm,
  • the transparent conductive layer contains silver and has a layer thickness in the range of 3 to 15 nm;
  • the transparent conductive film according to Item 1 or 2 wherein the transparent resin support contains at least one selected from cellulose ester resins, cycloolefin resins, and polycarbonate resins.
  • the transparent conductive layer contains at least one metal selected from gold, copper, nickel, palladium, platinum, zinc, aluminum, manganese, germanium, bismuth, neodymium, and molybdenum. 4.
  • the transparent conductive film according to any one of items up to 3.
  • the high refractive index layer on the support side contains zinc sulfide.
  • the high refractive index layer provided on the side opposite to the support side is composed of indium tin oxide, indium zinc oxide, gallium zinc oxide. Or any one of indium, gallium, and zinc oxide,
  • the transparent conductive film of the present invention is a transparent conductive film having at least one transparent conductive layer and a high refractive index layer on a transparent resin support, and the in-plane retardation Ro of the transparent resin support is 0 to 150 nm. By making it within the range, it is possible to prevent rainbow unevenness having angle dependency.
  • General rainbow unevenness means that in a display image of a transmissive capacitive touch panel, part or all of the members constituting the transparent conductive film have a large retardation value, so that image light having a certain polarization state is generated. This is caused by being converted into a different polarization state for each wavelength and viewing angle when passing through the stacked members of the touch module.
  • FIG. 1 is a schematic diagram for explaining a general rainbow unevenness generation mechanism.
  • a typical configuration of an out-cell type transmissive capacitive touch panel is simplified and schematically shown by focusing on a change in the polarization state of light rays. Showed. Therefore, it does not faithfully reproduce the actual product form and light rays.
  • reference numeral 300 represents an image display element such as a liquid crystal, and a polarizing plate 200 is provided on the outermost surface thereof. Furthermore, the transparent conductive film 100 exists in the upper part.
  • the light emitted from the different pixels A and B travels along the different optical paths in the transparent conductive film as linearly polarized light by the action of the polarizing plate.
  • each light beam traveling in different optical paths is converted into a different polarization state before passing through A 1 and B 1, and then the observer's Reach viewpoint O.
  • ⁇ B1 represents an incident angle from point B
  • ⁇ B2 represents the refraction angle from point B
  • the s-polarized component shows a high reflectivity with respect to the p-polarized component, but as a result, the intensity of the transmitted light is naturally greater for p-polarized light than for s-polarized light, and the ratio is angularly dependent.
  • the amplitude ratios of the p-polarized light component and the s-polarized light component are not already the same.
  • the intensities of the two light beams transmitted from A 1 and B 1 to the viewer side are different, and the viewer visually recognizes the contrast as bright and dark for each part.
  • the refractive index varies depending on the wavelength
  • the reflection intensity ratio for each of the p-s polarization components also varies depending on the wavelength, and the resulting contrast level differs depending on the color.
  • a material having a large refractive index such as ITO was used as a transparent conductive film, and general rainbow unevenness was strongly generated. Therefore, in the case of a material having a refractive index smaller than ITO, such as silver, Although it was predicted that the reflection at the interface would be reduced and its generation would be suppressed, contrary to expectation, rainbow unevenness with angle dependency occurred. It is speculated that the absorption of the transparent conductive layer containing silver and the thinness of the layer may be caused.
  • the inventors of the present invention provide a video display device including a touch panel having a large screen and excellent visibility based on excellent transparent conductivity.
  • a touch panel having a large screen and excellent visibility based on excellent transparent conductivity.
  • the angle-dependent color unevenness is conspicuous on the contrary. I found it to be a serious problem.
  • the present inventors have found out that the angle-dependent color unevenness can be solved under a limited and densely configured condition. That is, by using a support with low retardation and skillfully combining a high refractive index layer and an antisulfuration layer described later with a conductive layer containing silver, industrial practicality and excellent conductivity can be obtained. A transparent conductive film that simultaneously realizes transparency and beautiful image display can be obtained.
  • Schematic diagram explaining the rainbow unevenness generation mechanism Schematic sectional view showing an example of the layer structure of the transparent conductive film of the present invention
  • the schematic diagram which shows an example of the pattern which consists of a conduction
  • the schematic diagram which shows an example of the electrode pattern which consists of a conduction
  • Process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by photolithography Process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by photolithography
  • Process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by photolithography Process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by photolithography
  • Process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by photolithography Process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by photolithography
  • Process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by photolithography Process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by photolithography
  • the transparent conductive film of the present invention is a transparent conductive film having at least one transparent conductive layer and a high refractive index layer on a transparent resin support,
  • the in-plane retardation value Ro of the transparent resin support at a measurement wavelength of 589 nm is in the range of 0 to 150 nm,
  • the transparent conductive layer contains silver and has a layer thickness in the range of 3 to 15 nm;
  • the high refractive index layer is provided on both sides of the transparent conductive layer, and at least one high refractive index layer contains zinc sulfide.
  • the thickness direction retardation value Rt of the transparent resin support is in the range of 0 to 400 nm from the viewpoint of manifesting the effects of the present invention.
  • the transparent resin support contains at least one selected from a cellulose ester resin, a cycloolefin resin and a polycarbonate resin
  • the in-plane retardation value Ro can be within the above range, and the angle dependency This is preferable because an effect of preventing rainbow unevenness can be obtained.
  • the transparent conductive layer contains at least one metal selected from gold, copper, nickel, palladium, platinum, zinc, aluminum, manganese, germanium, bismuth, neodymium and molybdenum.
  • the high refractive index layer on the support side preferably contains zinc sulfide.
  • the high refractive index layer provided on the side opposite to the support side is composed of indium tin oxide, indium zinc oxide, gallium zinc It is preferable to contain either an oxide or indium / gallium / zinc oxide.
  • a layer containing zinc oxide between the transparent conductive layer and the at least one high refractive index layer.
  • FIGS. 1-10 One embodiment of the layer structure of the transparent conductive film of the present invention is shown in FIGS.
  • the transparent conductive film 100 of the present invention includes transparent resin support 1 / first high refractive index layer 2 / transparent conductive layer 3 / second high refractive index layer 4.
  • one of the first high refractive index layer 2 and the second high refractive index layer 4 is a layer containing zinc sulfide (ZnS).
  • ZnS zinc sulfide
  • these layers are layers formed from a thin film.
  • one of the first high refractive index layer 2 and the second high refractive index layer 4 is a layer containing zinc sulfide, and the first high refractive index layer 2 or the second high refractive index layer. 4 and the transparent conductive layer 3 are preferably provided with an anti-sulfurization layer 5 (an anti-sulfurization layer 5a or 5b containing zinc oxide).
  • the metal sulfide is presumed to be produced as follows.
  • the unreacted sulfur component in the first high refractive index layer 2 is transparent. It is blown out into the film forming atmosphere by the metal material (silver) of the conductive layer. Then, the released sulfur component reacts with silver, and silver sulfide is deposited on the high refractive index layer. Moreover, when forming a high refractive index layer and a transparent conductive layer continuously, the sulfur component contained in the film-forming atmosphere of a high refractive index layer remains in the metal layer atmosphere containing the silver of a transparent conductive layer. Then, the sulfur component and silver react to deposit silver sulfide on the high refractive index layer.
  • the silver in the metal film containing silver of the transparent conductive layer is formed by the material of the second high refractive index layer. Played in the film atmosphere. Then, the ejected silver reacts with the sulfur component, and silver sulfide is deposited on the surface of the transparent conductive layer. Furthermore, silver sulfide is generated on the surface of the metal layer containing silver of the transparent conductive layer even when the surface of the transparent conductive layer is in contact with the sulfur component in the film forming atmosphere.
  • the first sulfidation preventing layer 5 a containing zinc oxide may be laminated on the first high refractive index layer 2.
  • the sulfur component in the first high refractive index layer 2 is ejected when the transparent conductive layer 3 is formed.
  • the sulfur component contained in the film formation atmosphere of the first high-refractive index layer 2 is a component of the first antisulfurization layer 5a. Or adsorbed to the constituent components of the first sulfurization prevention layer 5a. Therefore, it becomes difficult for sulfur to be contained in the film-forming atmosphere of the transparent conductive layer 3, and the production of silver sulfide is suppressed.
  • the second sulfidation preventing layer 5 b may be laminated on the transparent conductive layer 3.
  • the transparent conductive layer 3 is protected by the second sulfidation preventing layer 5b, silver in the transparent conductive layer 3 is hardly ejected when the second high refractive index layer 4 is formed.
  • the sulfur component in the film formation atmosphere of the second high refractive index layer 4 is difficult to come into contact with the surface of the transparent conductive layer 3. Therefore, it is difficult to produce silver sulfide on the surface of the transparent conductive layer 3.
  • the transparent conductive layer 3 may be laminated on the entire surface of the transparent resin support 1, and as shown in FIG. It may be patterned into a desired shape.
  • the region a where the transparent conductive layer 3 is laminated is a region where electricity is conducted (hereinafter also referred to as “conduction region”).
  • the region b not including the transparent conductive layer 3 is an insulating region.
  • the pattern composed of the conductive region a and the insulating region b is appropriately selected according to the use of the transparent conductive film 100.
  • the pattern includes a plurality of conductive regions a and line-shaped insulating regions b that divide the conductive regions a. It is possible.
  • the transparent conductive film 100 of the present invention includes layers other than the transparent resin support 1, the first high refractive index layer 2, the transparent conductive layer 3, the second high refractive index layer 4, and the sulfurization prevention layer 5. May be included.
  • an underlayer that can be a growth nucleus when forming the transparent conductive layer 3 may be included between the transparent conductive layer and the first high refractive index layer 2 adjacent to the transparent conductive layer 3.
  • Transparent resin support examples include cellulose ester resins (for example, triacetylcellulose (Zerotac (manufactured by Konica Minolta)), diacetylcellulose, acetylpropionylcellulose, etc.), polycarbonate resins (for example, panlite, Multilon (both made by Teijin)), cycloolefin resin (for example, Zeonoa (made by Nippon Zeon), Arton (made by JSR), Apel (made by Mitsui Chemicals)), acrylic resin (for example, polymethyl methacrylate, acrylite ( (Mitsubishi Rayon Co., Ltd.) and Sumipex (Sumitomo Chemical Co., Ltd.)), and these resins are preferably 50% by mass or more of the transparent resin support. Two or more kinds of these resins may be used.
  • cellulose ester resins for example, triacetylcellulose (Zerotac (manufactured by Konica Minolta)
  • cellulose ester resins cellulose ester resins, cycloolefin resins, and polycarbonate resins are preferable.
  • resins that may be mixed include polyimide, phenol resin, epoxy resin, polyphenylene ether (PPE) resin, polyester resin (for example, polyethylene terephthalate (PET), polyethylene naphthalate), polyether sulfone, ABS / AS resin, One or more resins selected from MBS resin, polystyrene, methacrylic resin, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resin), styrene block copolymer resin, and the like may be included.
  • PPE polyphenylene ether
  • PET polyethylene terephthalate
  • PET polyethylene naphthalate
  • polyether sulfone polyether sulfone
  • ABS / AS resin One or more resins selected from MBS resin, polystyrene, methacrylic resin, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resin), styrene block copolymer resin, and the like may be included.
  • the transparent resin support 1 used in the present invention is a cellulose ester
  • a lower fatty acid ester is preferable, and cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, or the like is used.
  • the cellulose ester used in the present invention preferably has an acyl group substitution degree of 2.85 to 3.00 because the degree of plane orientation can be kept lower, and particularly preferably 2.92 to 3.00.
  • the method for measuring the substitution degree of the acyl group can be measured in accordance with the provisions of ASTM-D817-96.
  • a cellulose ester having a polymerization degree of 250 to 400 is preferably used, and cellulose triacetate is particularly preferably used.
  • the number average molecular weight Mn of the cellulose ester according to the present invention is preferably 70000 to 250,000, since it is excellent in mechanical strength and has an appropriate dope viscosity, and more preferably 80000 to 150,000.
  • a cellulose ester having a ratio Mw / Mn to the weight average molecular weight Mw of 1.0 to 5.0 is preferably used.
  • the in-plane retardation value Ro of the transparent resin support of the present invention at a measurement wavelength of 589 nm is in the range of 0 to 150 nm.
  • Ro is in the range of 0 to 20 nm or 40 to 150 nm.
  • the thickness direction retardation value Rt at a measurement wavelength of 589 nm is preferably in the range of 0 to 400 nm, and particularly preferably, Rt is in the range of 0 to 70 nm or Rt is in the range of 80 to 300 nm.
  • Rt is in the range of 0 to 70 nm or Rt is in the range of 80 to 300 nm.
  • Formula (i) Ro (nx ⁇ ny) ⁇ d
  • Formula (ii) Rt ((nx + ny) / 2 ⁇ nz) ⁇ d
  • Ro is the retardation value in the film plane
  • Rt is the retardation value in the thickness direction
  • nx is the refractive index in the slow axis direction in the film plane
  • ny is the refractive index in the fast axis direction in the film plane
  • (nz represents the refractive index in the thickness direction of the film
  • d represents the thickness (nm) of the film.
  • the in-plane retardation value Ro and the thickness direction retardation value Rt at a measurement wavelength of 589 nm are measured with a phase difference measuring device “KOBRA-21ADH” (Oji Scientific Instruments) in an environment of 23 ° C. and 55% RH. Measured by).
  • the retardation value of the transparent resin support can be controlled by selecting the resin material, the draw ratio during film formation, and the like. Specifically, it can be controlled to an arbitrary value by appropriately selecting the stretching ratio in the longitudinal direction and the transverse direction.
  • the transparent resin support 1 of the present invention preferably has high transparency to visible light, and the average transmittance of light having a wavelength of 450 to 800 nm is preferably 70% or more, more preferably 80% or more. And more preferably 85% or more.
  • the average light transmittance of the transparent resin support 1 is 70% or more, the light transmittance of the transparent conductive film 100 is likely to increase.
  • the average absorptance of light having a wavelength of 450 to 800 nm of the transparent resin support 1 is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less.
  • the average transmittance is measured by making light incident from an angle inclined by 5 ° with respect to the normal line of the surface of the transparent resin support 1.
  • the average absorptance is measured by measuring the average reflectance of the transparent substrate 1 by making light incident from the same angle as the average transmittance.
  • Average absorptance (%) 100 ⁇ (average transmittance + average reflectance) Calculate as Average transmittance and average reflectance are measured with a spectrophotometer.
  • the surface roughness Ra of the transparent resin support is preferably 3.5 nm or less on both surfaces of the transparent resin support, more preferably. Is 3.0 nm or less.
  • the surface roughness Ra of the transparent resin support is 3.5 nm or less on both surfaces of the transparent resin support, the haze value is reduced and a transparent resin support excellent in transparency can be obtained.
  • the surface roughness Ra refers to the arithmetic average roughness in JIS B0601: 2001.
  • the haze value of the transparent resin support 1 of the present invention is preferably 0.01 to 2.5, more preferably 0.1 to 1.2.
  • the haze value of a transparent conductive film is suppressed as the haze value of a support body is 2.5 or less.
  • the haze value is measured with a haze meter “model: NDH 2000” (manufactured by Nippon Denshoku Co., Ltd.).
  • the refractive index of light having a wavelength of 570 nm of the transparent resin support 1 is preferably 1.40 to 1.95, more preferably 1.45 to 1.75, and still more preferably 1.45 to 1.70. It is.
  • the refractive index of the transparent resin support is usually determined by the material of the support.
  • the refractive index of the transparent resin support is measured with an ellipsometer at 23 ° C. and 55% RH.
  • the thickness of the transparent resin support 1 is preferably 1 ⁇ m to 20 mm, more preferably 10 ⁇ m to 2 mm.
  • the thickness of the transparent resin support is 1 ⁇ m or more, the strength of the transparent resin support 1 is increased, and the first high refractive index layer 2 is difficult to be cracked or torn.
  • the thickness of the transparent resin support 1 is 20 mm or less, the flexibility of the transparent conductive film 100 is sufficient.
  • the thickness of the apparatus using the transparent conductive film 100 can be reduced.
  • the apparatus using the transparent conductive film 100 can also be reduced in weight.
  • the high refractive index layer in the present invention refers to a layer having a higher refractive index than that of the transparent resin support 1.
  • the first high refractive index layer 2 is a layer that adjusts the light transmission (optical admittance) of the conductive region a of the transparent conductive film, that is, the region where the transparent conductive layer 3 is formed, and at least the transparent conductive film 100. Formed in the conductive region a.
  • the first high-refractive index layer 2 has a function of protecting the transparent conductive layer from moisture, sulfide, sulfur-containing components, etc. in the atmosphere, so that it is also formed in the insulating region b of the transparent conductive film 100. It is preferable that
  • the first high refractive index layer 2 is a layer that preferably contains zinc sulfide (ZnS). When zinc sulfide is contained in the first high refractive index layer 2, it becomes difficult for moisture to permeate from the transparent resin support 1 side, and corrosion of the transparent conductive layer 3 is suppressed.
  • the first high refractive index layer 2 may contain other dielectric material or oxide semiconductor material together with zinc sulfide.
  • the refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained together with zinc sulfide is preferably 0.1 to 1.1 higher than the refractive index of light having a wavelength of 570 nm of the transparent resin support 1. More preferably, it is larger by 4 to 1.0.
  • the specific refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the first high refractive index layer 2 is preferably larger than 1.5, and is 1.7 to 2.5. More preferably, it is 1.8 to 2.5.
  • the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the optical admittance of the conductive region a of the transparent conductor 100 is sufficiently adjusted by the first high refractive index layer 2.
  • the refractive index of the first high refractive index layer 2 is adjusted by the refractive index of the material included in the first high refractive index layer 2 and the density of the material included in the first high refractive index layer 2.
  • the refractive index is measured with an ellipsometer in an environment of 23 ° C. and 55% RH.
  • the dielectric material or oxide semiconductor material contained in the first high refractive index layer 2 may be an insulating material or a conductive material.
  • the dielectric material or oxide semiconductor material can be a metal oxide. Examples of the metal oxide include SiO 2 , TiO 2 , ITO (indium tin oxide), ZnO, Nb 2 O 5 , ZrO 2 , CeO 2 , Ta 2 O 5 , Ti 3 O 5 , Ti 4 O 7.
  • the first high refractive index layer 2 may contain only one kind of the metal oxide or two or more kinds.
  • SiO 2 is particularly preferable.
  • a method for controlling the composition of ZnS and SiO 2 for example, a sputtering method using a ZnS target containing SiO 2 at an appropriate concentration, or a co-sputtering method using SiO 2 and ZnS targets simultaneously is used. Can be performed.
  • the first high refractive index layer is likely to be amorphous, and the flexibility of the transparent conductive film is likely to be enhanced.
  • the amount of zinc sulfide may be 0.1 to 95% by volume with respect to the total volume of the first high refractive index layer 2. Preferably, it is 50 to 90% by volume or less, and more preferably 60 to 85% by volume or less.
  • the ratio of zinc sulfide is high, the sputtering rate is increased, and the formation rate of the first high refractive index layer 2 is increased.
  • the amorphous nature of the first high refractive index layer 2 is increased, and cracking of the first high refractive index layer 2 is suppressed.
  • the layer thickness of the first high refractive index layer 2 is preferably 15 to 150 nm, more preferably 20 to 80 nm.
  • the layer thickness of the first high refractive index layer 2 is 15 nm or more, the optical admittance of the conductive region a of the transparent conductive film 100 is sufficiently adjusted by the first high refractive index layer 2.
  • the thickness of the first high refractive index layer 2 is 150 nm or less, the light transmittance of the region including the first high refractive index layer 2 is unlikely to decrease.
  • the layer thickness of the first high refractive index layer 2 is measured by an ellipsometer “multi-incidence angle spectroscopic ellipsometer VASE (registered trademark)” (manufactured by JA Woollam).
  • the first high refractive index layer 2 is formed by a general vapor deposition method (also called a deposition method or a vapor deposition method) such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like. It can be a layer formed of From the standpoint that the refractive index (density) of the first high refractive index layer 2 is increased, the first high refractive index layer 2 is preferably a layer formed by an electron beam evaporation method or a sputtering method. In the case of the electron beam evaporation method, it is desirable to have assistance such as IAD (ion assist) in order to increase the film density.
  • IAD ion assist
  • the patterning method is not particularly limited.
  • the first high refractive index layer 2 may be, for example, a layer formed in a pattern by a vapor deposition method by placing a mask or the like having a desired pattern on the deposition surface. It may be a layer patterned by a method.
  • the first sulfidation preventing layer 5a is preferably included.
  • the first sulfurization preventing layer 5a has a function of preventing diffusion of sulfides and sulfur-containing components from the first high refractive index layer.
  • the first sulfidation preventing layer 5a may also be formed in the insulating region b of the transparent conductive film 100.
  • the transparent conductive layer is made transparent from moisture, sulfide, sulfur-containing components, etc. in the atmosphere. Since it has a function of protecting the layer, it is preferably formed also in the insulating region b.
  • the first antisulfurization layer 5a is a layer that preferably contains zinc oxide, and may be a layer that contains a metal oxide, a metal nitride, a metal fluoride, and the like.
  • the first sulfidation preventing layer 5a may contain only one kind or two or more kinds.
  • the metal oxide can react with sulfur or adsorb sulfur.
  • a compound is preferred.
  • the reaction product of the metal oxide and sulfur preferably has high visible light permeability.
  • metal oxides examples include ZnO, TiO 2 , ITO, Nb 2 O 5 , ZrO 2 , CeO 2 , Ta 2 O 5 , Ti 3 O 5 , Ti 4 O 7 , Ti 2 O 3 , TiO, SnO 2 , La 2 Ti 2 O 7 , IZO, AZO, GZO, ATO, ICO, Bi 2 O 3 , a-GIO, Ga 2 O 3 , GeO 2 , SiO 2 , Al 2 O 3 , HfO 2 , SiO, MgO, Y 2 O 3 , WO 3 , etc. are included.
  • metal fluorides examples include LaF 3 , BaF 2 , Na 5 Al 3 F 14 , Na 3 AlF 6 , AlF 3 , MgF 2 , CaF 2 , BaF 2 , CeF 3 , NdF 3 , YF 3 and the like. .
  • metal nitride examples include Si 3 N 4 , AlN, and the like.
  • a layer containing zinc oxide is preferable.
  • the layer thickness of the first sulfidation preventing layer 5a is preferably a layer thickness capable of protecting the surface of the first high refractive index layer 2 from an impact when forming the transparent conductive layer 3 described later.
  • ZnS that can be contained in the first high refractive index layer has a high affinity with the metal contained in the transparent conductive layer 3. Therefore, if the thickness of the first anti-sulfurization layer 5a is very thin and a part of the first high refractive index layer 2 is slightly exposed, a transparent metal film of the transparent conductive layer grows around the exposed part.
  • the transparent conductive layer 3 tends to be dense. That is, the first sulfidation preventing layer 5a is preferably relatively thin, preferably 0.1 to 5.0 nm, and more preferably 0.5 to 2.0 nm.
  • the first antisulfurization layer 5a is a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method or the like.
  • the first antisulfurization layer 5a is a layer patterned into a desired shape
  • the patterning method is not particularly limited.
  • the first sulfidation preventing layer 5a may be a layer formed in a pattern by a vapor deposition method, for example, by placing a mask having a desired pattern on the deposition surface, and may be a known etching method. It may be a layer patterned by.
  • the transparent conductive layer 3 is a film for conducting electricity in the transparent conductive film 100. As described above, the transparent conductive layer 3 may be formed on the entire surface of the transparent resin support 1, or may be patterned into a desired shape.
  • the transparent conductive layer 3 is a layer containing silver and may contain other metals.
  • the metal used together with silver is not particularly limited as long as it is a metal having high transparent conductivity.
  • gold, copper, nickel, palladium, platinum, zinc, aluminum, manganese, germanium, bismuth, neodymium, and molybdenum are preferable.
  • the transparent conductive layer 3 may contain only one kind of these metals or two or more kinds. From the viewpoint of conductivity, the transparent conductive layer is preferably made of an alloy containing 90 atm% or more of silver. When silver is contained at 90 atm% or more, excellent conductivity and high durability can be obtained.
  • the above highly conductive metal when at least one kind of the above highly conductive metal is contained within the above range, predetermined conductivity can be secured even if the thickness of the transparent conductive layer is reduced, and it is contained in the transparent conductive layer.
  • the effect of preventing silver deterioration is obtained and the reliability is improved.
  • the sulfidation resistance of the transparent metal film is enhanced.
  • salt resistance (NaCl) resistance increases.
  • silver and copper are combined, the oxidation resistance increases.
  • the layer thickness of the transparent conductive layer of the present invention is in the range of 3 to 15 nm, preferably in the range of 5 to 13 nm. The desired transparency and plasmon absorption rate can be ensured by this layer thickness.
  • the plasmon absorption rate of the transparent conductive layer 3 is preferably 10% or less (over the entire range) over a wavelength range of 400 to 800 nm, more preferably 7% or less, and even more preferably 5% or less.
  • the transparent conductive layer 3 can be a film formed by any method, but in order to change the average transmittance of the transparent conductive layer, it is formed on a film formed by sputtering or an underlayer described later. It is preferable to use a film.
  • the material collides with the deposition target at high speed, so that a dense and smooth film can be easily obtained, and the light transmittance of the transparent conductive layer 3 is likely to be increased.
  • the transparent conductive layer 3 is a film formed by sputtering, the transparent conductive layer 3 is hardly corroded even in an environment of high temperature and low humidity.
  • the type of the sputtering method is not particularly limited, and may be an ion beam sputtering method, a magnetron sputtering method, a reactive sputtering method, a bipolar sputtering method, a bias sputtering method, a counter sputtering method, or the like.
  • the transparent conductive layer 3 is particularly preferably a film formed by a counter sputtering method. When the transparent conductive layer 3 is a film formed by a counter sputtering method, the transparent conductive layer 3 becomes dense and the surface smoothness is likely to increase. As a result, the surface electrical resistance of the transparent conductive layer 3 becomes lower and the light transmittance is likely to increase.
  • Second anti-sulfur layer> When the second high refractive index layer described later is a zinc sulfide-containing layer, as shown in FIG. 2, the second sulfide containing zinc oxide between the transparent conductive layer 3 and the second high refractive index layer 4 is used. It is preferable that the prevention layer 5b is included.
  • the second sulfidation preventing layer 5b may be formed also in the insulating region b of the transparent conductive film 100, but from the viewpoint of making it difficult to visually recognize the pattern formed of the conductive region a and the insulating region b, only the conductive region a. It is preferable to be formed.
  • the second anti-sulfurization layer 5b is a layer containing zinc oxide, and is a layer containing a metal oxide, a metal nitride, a metal fluoride, and the like. In addition to zinc oxide, only one of these may be contained in the second sulfurization prevention layer 5b, or two or more thereof may be contained.
  • the metal oxide, metal nitride, and metal fluoride may be the same as the metal oxide, metal nitride, and metal fluoride contained in the first high refractive index layer 2 described above. Among these, a layer containing zinc oxide is preferable.
  • the thickness of the second antisulfurization layer 5b is preferably a thickness capable of protecting the surface of the transparent conductive layer 3 from an impact when forming the second high refractive index layer 4 described later.
  • the metal contained in the transparent conductive layer 3 and the ZnS contained in the second high refractive index layer 4 have high affinity. Therefore, if the thickness of the second antisulfurization layer 5b is very thin and a part of the transparent conductive layer 3 is slightly exposed, the transparent conductive layer 3, the second antisulfurization layer 5b, and the second high refractive index layer. Adhesion with 4 tends to increase.
  • the specific layer thickness of the second sulfidation preventing layer 5b is preferably 0.1 to 5.0 nm, and more preferably 0.5 to 2.0 nm.
  • the layer thickness of the second sulfurization preventing layer 5b is measured with an ellipsometer.
  • the second antisulfurization layer 5b may be a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like.
  • a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like.
  • the second antisulfurization layer 5b is a layer patterned into a desired shape
  • the patterning method is not particularly limited.
  • the second antisulfurization layer 5b may be a layer formed in a pattern by a vapor deposition method, for example, by placing a mask having a desired pattern on the deposition surface, and may be a known etching method. It may be a layer patterned by.
  • the second high refractive index layer 4 is a layer for adjusting the light transmittance (optical admittance) of the conductive region a of the transparent conductive film 100, that is, the region where the transparent conductive layer 3 is formed.
  • the conductive film 100 is formed in the conduction region a.
  • the second high-refractive index layer 4 may be formed in the insulating region b of the transparent conductive film 100, but from the viewpoint of making it difficult to visually recognize the pattern composed of the conductive region a and the insulating region b, only the conductive region a. Preferably it is formed. Since the second high refractive index layer 4 makes it difficult for moisture to permeate from the atmosphere side, it has an effect of suppressing the corrosion of the transparent conductive layer 3.
  • the second high refractive index layer 4 is a layer having a refractive index higher than the refractive index of the transparent resin support 1 described above, and one of the first high refractive index layers contains zinc sulfide (ZnS). It is.
  • the second high refractive index layer 4 may include zinc sulfide or other dielectric material or oxide semiconductor material.
  • the refractive index of light having a wavelength of 570 nm of zinc sulfide or other dielectric material or oxide semiconductor material is preferably 0.1 to 1.1 higher than the refractive index of light having a wavelength of 570 nm of the transparent substrate 1. More preferably, it is larger by 1.0.
  • the specific refractive index of light having a wavelength of 570 nm of the dielectric material or the oxide semiconductor material contained in the second high refractive index layer 4 is preferably larger than 1.5 and is 1.7 to 2.5. More preferably, it is 1.8 to 2.5.
  • the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the optical admittance of the conductive region a of the transparent conductive film 100 is sufficiently adjusted by the second high refractive index layer 4.
  • the refractive index of the second high refractive index layer 4 is adjusted by the refractive index of the material included in the second high refractive index layer 4 and the density of the material included in the second high refractive index layer 4.
  • the dielectric material or oxide semiconductor material contained in the second high refractive index layer 4 may be an insulating material or a conductive material.
  • the dielectric material or oxide semiconductor material can be a metal oxide. Examples of the metal oxide include SiO 2 , TiO 2 , ITO (indium tin oxide), ZnO, Nb 2 O 5 , ZrO 2 , CeO 2 , Ta 2 O 5 , Ti 3 O 5 , Ti 4 O 7.
  • the second high refractive index layer 4 may include only one kind of the metal oxide or two or more kinds.
  • ITO indium tin oxide
  • IZO indium tin oxide
  • GZO zinc oxide
  • IGZO indium tin oxide
  • These materials are suitable for patterning and at the same time can provide a protective function for silver.
  • zinc sulfide is particularly preferable as the dielectric material or oxide semiconductor material contained in the second high refractive index layer 4.
  • ZnS zinc sulfide
  • the second high refractive index layer 4 may contain only ZnS or may contain other materials together with ZnS.
  • Materials included with ZnS is a metal oxide or SiO 2 or the like, which may be the dielectric material or an oxide semiconductor material, particularly preferably SiO 2.
  • SiO 2 is contained together with ZnS, the second high refractive index layer is likely to be amorphous, and the flexibility of the transparent conductor is likely to be enhanced.
  • the amount of ZnS is preferably 0.1 to 95% by volume with respect to the total volume of the second high refractive index layer 4.
  • the content is more preferably 50 to 90% by volume or less, and still more preferably 60 to 85% by volume.
  • the ratio of ZnS is high, the sputtering rate increases and the formation rate of the second high refractive index layer 4 increases.
  • the amorphous nature of the second high refractive index layer 4 increases, and cracking of the second high refractive index layer 4 is suppressed.
  • a method for controlling the composition of zinc sulfide and SiO 2 within the above range for example, a sputtering method using a ZnS target containing SiO 2 at an appropriate concentration, or co-sputtering using a SiO 2 and ZnS target simultaneously. This can be done by using the law.
  • the second high refractive index layer is likely to be amorphous, and the flexibility of the transparent conductive film is likely to be enhanced.
  • the ratio of ZnS is high, the sputtering rate increases and the formation rate of the second high refractive index layer 4 increases.
  • the amount of components other than ZnS increases, the amorphousness of the second high refractive index layer 4 increases, and cracking of the second high refractive index layer 4 is suppressed.
  • the layer thickness of the second high refractive index layer 4 is preferably 15 to 150 nm, and more preferably 20 to 80 nm. When the layer thickness of the second high refractive index layer 4 is 15 nm or more, the optical admittance of the conductive region a of the transparent conductor 100 is sufficiently adjusted by the second high refractive index layer 4. On the other hand, if the layer thickness of the second high refractive index layer 4 is 150 nm or less, the light transmittance of the region including the second high refractive index layer 4 is unlikely to decrease. The layer thickness of the second high refractive index layer 4 is measured with an ellipsometer.
  • the formation method of the second high refractive index layer 4 is not particularly limited, and is a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like. It can be. From the viewpoint that the moisture permeability of the second high refractive index layer 4 is lowered, the second high refractive index layer 4 is particularly preferably a film formed by a sputtering method.
  • the patterning method is not particularly limited.
  • the second high refractive index layer 4 may be, for example, a layer formed in a pattern by a vapor deposition method by disposing a mask having a desired pattern on the deposition surface.
  • the layer patterned by the well-known etching method may be sufficient.
  • Hard coat layer> A hard coat layer is provided on at least one surface of the transparent resin support, preferably on the transparent conductive layer side, for the purpose of preventing scratches on the surface of the transparent resin support during the production of the transparent conductive film. It is preferable.
  • the film By providing a hard coat layer on at least one surface of the transparent resin support, the film can be wound, conveyed, and unwound in the production process of the transparent conductive film of the present invention from the time of forming the transparent resin support. It has the effect of preventing the occurrence of scratches due to surface pressure and friction between the film surfaces.
  • the hard coat layer is provided by applying and drying an ultraviolet curable acrylate resin and then curing with an ultraviolet light source.
  • the layer thickness of the hard coat layer is preferably in the range of 0.2 to 5.0 ⁇ m, and if the layer thickness of the hard coat layer is in the above range, a sufficient scratch resistance effect can be obtained. Since generation
  • the hard coat layer can be produced by laminating a SiO 2 thin film by a CVD method, a sputtering method, a vapor deposition method or the like with a layer thickness of 100 nm or less in addition to the application.
  • Anti-blocking layer A blocking prevention layer having a 10-point average roughness Rz of 50 nm or less is provided on the surface of the transparent conductive film of the present invention opposite to the surface provided with the transparent conductive layer of the transparent resin support. preferable.
  • the anti-blocking layer is used to prevent sticking between films when winding and handling the film. This is done by providing an arbitrary roughness on the surface of the film and filling this gap with air. It is possible to prevent sticking between films during unwinding and winding operations.
  • the anti-blocking layer can be provided by applying a coating liquid in which fine particles are mixed with a resin such as an acrylate resin.
  • a resin such as an acrylate resin.
  • resin fine particles can be used as the fine particles.
  • the average particle diameter of the fine particles is preferably within the range of 10 to 300 nm.
  • each thin film layer of a high refractive index layer, an antisulfurization layer and a transparent conductive layer provided on a transparent resin support is formed by a sputtering method or a vapor deposition method. Is preferred.
  • productivity is improved and an effect suitable for mass production is obtained.
  • the value obtained by the present invention is not impaired even by any other thin film manufacturing method such as chemical vapor deposition (CVD).
  • the transparent conductive layer is divided into a plurality of conductive regions a and a line-shaped insulating region that divides the conductive regions a. It is preferable to pattern it into a predetermined shape including b.
  • Examples of the deterioration factor of the transparent conductive layer containing silver include moisture and sulfide contained in the atmosphere. These are taken into the transparent resin support and the hard coat layer, and pass through the hard coat layer to reach the transparent conductive layer. Therefore, the transparent resin support and the hard coat layer alone do not provide sufficient silver protective function for the transparent conductive layer. Therefore, if there is a first high refractive index layer, preferably a first antisulfurization layer, the antisulfurization layer is included. From the viewpoint of preventing the deterioration of the transparent conductive layer, it is preferable to leave it on the transparent resin support without being patterned.
  • a known method can be used as a method of patterning the transparent conductive layer. Specifically, such a patterning method can be performed as follows.
  • the photolithographic method applied to the present invention includes resist coating such as curable resin, preheating, exposure, development (removal of uncured resin), rinsing, etching treatment with an etching solution, and resist stripping.
  • resist coating such as curable resin, preheating, exposure, development (removal of uncured resin), rinsing, etching treatment with an etching solution, and resist stripping.
  • the transparent conductive layer is processed into a desired pattern as shown in FIG.
  • a conventionally known general photolithography method can be used as appropriate.
  • the resist either positive or negative resist can be used.
  • preheating or prebaking can be performed as necessary.
  • a pattern mask having a desired pattern may be disposed, and light having a wavelength suitable for the resist used, generally ultraviolet rays, electron beams, or the like may be irradiated thereon.
  • development is performed with a developer suitable for the resist used.
  • a resist pattern is formed by stopping development with a rinse solution such as water and washing.
  • a rinse solution such as water and washing.
  • the formed resist pattern is pretreated or post-baked as necessary, and then is etched with an etching solution containing an organic solvent to dissolve the intermediate layer in a region not protected by the resist and to form a silver thin film electrode Remove.
  • the photolithography method applied to the present invention is a method generally recognized by those skilled in the art, and the specific application mode is easily selected by those skilled in the art according to the intended purpose. be able to.
  • FIG. 5A to FIG. 5G are process flow diagrams showing an example of forming an electrode pattern on the transparent conductor of the present invention by a photolithography method.
  • a first high refractive index layer 2 As a first step, as shown in FIG. 5A, on the transparent resin support 1, a first high refractive index layer 2, a first antisulfurization layer 5a, a transparent conductive layer 3, a second antisulfurization layer 5b, and a second high A transparent conductive film 100 in which the refractive index layer 4 is laminated in this order is produced.
  • a resist film 6 composed of a photosensitive resin composition or the like is uniformly coated on the transparent conductive film 100.
  • a photosensitive resin composition a negative photosensitive resin composition or a positive photosensitive resin composition can be used.
  • a coating method it is applied on the transparent conductive film 100 by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, hot plate, oven, etc. It can be pre-baked with a heating device. Pre-baking can be performed, for example, using a hot plate or the like in the range of 50 ° C. or higher and 150 ° C. or lower for 30 seconds to 30 minutes.
  • an exposure machine such as a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner or the like is used through a mask 7 made with a predetermined electrode pattern, and 10 to 4000 J / m.
  • the resist film 6A to be removed in the next step is irradiated with light of about 2 (wavelength 365 nm exposure amount conversion).
  • the exposure light source is not limited, and ultraviolet rays, electron beams, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used.
  • the exposed transparent conductive film is immersed in a developing solution to dissolve the resist film 6A in the region irradiated with light.
  • the developing method it is preferable to immerse in the developer for 5 seconds to 10 minutes by a method such as showering, dipping or paddle.
  • a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, tetramethylammonium hydroxide. Examples thereof include aqueous solutions containing one or more quaternary ammonium salts such as side and choline.
  • FIG. 5G the resist film 6 is removed by immersing it in a resist film remover, for example, “N-300” manufactured by Nagase ChemteX Corporation, leaving the first high refractive index layer 2.
  • a transparent conductive film having an electrode pattern can be produced.
  • APC Furuya Metal "Ag alloy" (containing Pd and Cu) 12
  • APC-TR “Ag alloy” made of Furuya Metal (containing Pd and Cu) 13.
  • APC-SR Furuya Metal's “Ag alloy” (containing Pd and Cu) The above three grade alloys have different compositions.
  • Cr metallic chromium 27.
  • ICO Indium / cerium oxide 28.
  • GZO gallium / zinc oxide 30.
  • IGZO Indium / gallium / zinc oxide In the above, n represents a refractive index.
  • ZnS—SiO 2 was RF sputtered at 2 Pa, room temperature, target-side power of 150 W, and formation rate of 3.0 ⁇ / sec (0.3 nm / sec) to form a first high refractive index layer having a layer thickness of 45.0 nm.
  • the target-substrate distance was 90 mm.
  • Ro and Rt were measured with a phase difference measuring device “KOBRA-21ADH” (manufactured by Oji Scientific Instruments) in an environment of 23 ° C. and 55% RH.
  • the ratio (volume ratio) between ZnS and SiO 2 was 75:25 (ZnS: 75% by volume).
  • Transparent conductive layer (Ag) Transparent conductive layer (Ag)
  • APC-TR (“Ag alloy” manufactured by Furuya Metal Co., Ltd.) was sputtered oppositely to form a transparent conductive layer having a layer thickness of 7.5 nm.
  • the target-substrate distance was 90 mm.
  • ZnO—SiO 2 Silicon high refractive index layer
  • ZnS—SiO 2 is RF sputtered by the same method as the first high refractive index layer to form a second high refractive index layer having a layer thickness of 45.0 nm.
  • the volume ratio of ZnS to SiO 2 was 75:25.
  • Transparent conductive films 2 to 28 and 31 to 33 of the present invention were produced in the same manner as the transparent conductive film 1 except that the configurations shown in Tables 1 and 2 were used.
  • ZnS and SiO 2 ratio was carried out by utilizing a co-sputtering method using ZnS and SiO 2 targets simultaneously. The layer thickness of each layer was adjusted by adjusting the sputtering time.
  • the first antisulfurization layer and the second antisulfurization layer were both formed by the same method.
  • TPS3 is used as a transparent resin support, and one electronic heating evaporation source provided in GENER1300, an OPTRAN vacuum evaporation system, and two resistance heating evaporation sources are used in combination, and all layers are vacuumed as follows: It formed by the vapor deposition method.
  • the first high refractive index layer was made of ZnS—SiO 2 , ZnS was co-deposited from a resistance heating evaporation source, and SiO 2 was evaporated from an electron heating evaporation source. At this time, the resistance heating / electron gun current was independently controlled so that the volume ratio of ZnS to SiO 2 was 75:25. The layer thickness was 45.0 nm.
  • ZnO was formed as a first anti-sulfuration layer with a layer thickness of 1.0 nm from an electron heating evaporation source.
  • Ag from the first resistance heating evaporation source and Au from the second resistance heating evaporation source were co-deposited as transparent conductive layers, respectively.
  • the current of each evaporation source was controlled independently so that the ratio of Ag and Au was 98: 2 by weight.
  • the layer thickness was 7.5 nm.
  • ZnO was formed from the electron heating evaporation source with a layer thickness of 1.0 nm as the second sulfurization prevention layer.
  • the second high refractive index layer was made of ZnS—SiO 2 , ZnS was co-deposited from a resistance heating evaporation source, and SiO 2 was evaporated from an electron heating evaporation source. At this time, the resistance heating / electron gun current was independently controlled so that the volume ratio of ZnS to SiO 2 was 75:25. The layer thickness was 45.0 nm, and this was used as the transparent conductive film 29.
  • the transparent conductive film 30 was produced in the same manner as the transparent conductive film 29 as shown in Table 2.
  • Transparent conductive films 101 to 116 of comparative examples were produced in the same manner as the transparent conductive film 1 except that the structure shown in Table 3 was used.
  • the transparent conductive films 112 and 113 were produced by the following method.
  • Toyobo PET (Cosmo Shine A4300 thickness 50 ⁇ m) was used for the transparent resin support.
  • Nb 2 O 5 was formed as a first high refractive index layer with a layer thickness of 27.5 nm.
  • L-430S-FHS manufactured by Anelva Ar 20 sccm, O 2 1 sccm, sputtering pressure 0.5 Pa, room temperature, target side power 150 W, formation rate 1.2 ⁇ / sec (0 Nb 2 O 5 was DC sputtered at .12 nm / sec).
  • the target-substrate distance was 86 mm.
  • Ag was formed as a transparent conductive layer to a layer thickness of 7.3 nm using a sputtering apparatus manufactured by Osaka Vacuum.
  • IZO was formed to a layer thickness of 36.0 nm as the second high refractive index layer. This was designated as transparent conductive film 112.
  • ⁇ Transparent conductive film 113> Using “Zerotack” manufactured by Konica Minolta Co., Ltd., Ro was set to 3 nm by adding a stretching step before drying.
  • the first high refractive index layer was made of ICO and had a layer thickness of 27.0 nm.
  • Cr was formed as a first sulfurization prevention layer with a layer thickness of 0.8 nm, and further, an Ag—Au alloy was prepared as a transparent conductive layer, and an alloy prepared so as to contain Ag and Au at 98 atm% and 2 atm%, respectively.
  • the layer thickness was 9.0 nm.
  • Cr was formed as a second anti-sulfuration layer with a layer thickness of 0.8 nm
  • ICO was formed thereon as a second high refractive index layer with a layer thickness of 27.0 nm.
  • SiO 2 was again formed with a layer thickness of 40.0 nm on the second high refractive index layer.
  • KP801M which is a fluorine-based surface modifying material, was deposited by resistance heating vapor deposition at 190 mA and a forming rate of 10 ⁇ / sec (1 nm / sec) with a Gener 1300 manufactured by Optorun to form a layer thickness of 6.0 nm. This was designated as a transparent conductive film 113.
  • a transparent conductive film comprising a support, a high refractive index layer, an antisulfurization layer and a transparent conductive layer is used.
  • the average transmittance was measured by making light incident from an angle inclined by 5 ° with respect to the normal of the surface of the transparent conductive film on the transparent resin support side.
  • the conductive films 1 to 33 of the present invention provide a transparent conductive film having good conductivity and transparency and capable of displaying beautiful images with no rainbow unevenness having angle dependency. I understand that I can do it.
  • the transparent conductive films 101 to 116 prepared as comparative examples for the effects of the present invention were inferior in various properties as compared with the present invention.
  • the transparent conductive film 101 had insufficient transmittance because the thickness of the conductive layer containing silver was too thick.
  • the transparent conductive film 102 was remarkably inferior in terms of conductivity.
  • the transparent conductive film 103 uses gold for the conductive layer, but due to the refractive index wavelength dispersion property of gold, high transparency in the entire visible range could not be secured, and as a result, the average transmittance was insufficient.
  • the transparent conductive film 107 is inferior in overall transmittance as a result of the absence of the second high refractive index layer having a function of adjusting the optical admittance, so that a portion with a small amount of incident light energy is directed to reflection. It was.
  • the transparent conductive film 108 was not preferable in terms of transmittance because the first high refractive index layer for adjusting the optical admittance was not present, and the conductivity was slightly insufficient. This is because the base when the ZnO as the first anti-sulfurization layer is formed is the surface of the support, which is an exposed organic substance, so that the ZnO thin film explained by the island-like nuclei in the growth mode of the Volmer-Weber As a result of the fact that the microscopic structural characteristics have a strong agglomeration property, it is presumed that the conductive layer formed immediately after that is also affected by this, and the film also has a strong granular interfacial property.
  • the transparent conductive films 109, 110, 112, 114 and 115 also have refractive index wavelength dispersion characteristics specific to various materials such as SiN, TiO 2 , Nb 2 O 5 , ITO and GIO selected instead of ZnS as the high refractive index layer. Therefore, the adjustment of the optical admittance became insufficient and the conductivity was slightly inferior. Regarding this lack of conductivity, the physicochemical properties of the surface on which the conductive layer is formed are different from those of the layer using sulfide, so that the microscopic structure of the conductive layer becomes homogeneous and continuous. Presumed to be missing.
  • the transparent conductive film 116 was inferior in terms of conductivity because the thickness of the conductive layer was too thin.
  • the present invention can be suitably used for a transparent conductive film having good conductivity and transparency and capable of displaying a beautiful image without rainbow unevenness having angle dependency.
  • SYMBOLS 100 Transparent conductive film 200 Polarizing plate 300 Image display element 1 Transparent resin support body 2 1st high refractive index layer 3 Transparent conductive layer 4 2nd high refractive index layer 5a 1st sulfidation prevention layer 5b 2nd sulfation prevention layer 6 Resist film 6A Resist film to be removed 7 Mask 8 Exposure unit EU Transparent electrode unit a Conductive region b Insulating region

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  • Laminated Bodies (AREA)

Abstract

La présente invention a pour objectif de fournir un film conducteur transparent qui présente une bonne conductivité électrique et une excellente transparence et peut afficher de belles images qui ne présentent pas d'irrégularités iridescentes ayant une dépendance angulaire. Un film conducteur transparent selon la présente invention comprend au moins une couche conductrice transparente et une couche à indice de réfraction élevé sur un corps de support de résine transparente. Ce film conducteur transparent est caractérisé en ce que : le corps de support de résine transparente présente une valeur de retard dans le plan (Ro) qui se situe dans la plage allant de 0 à 150 nm à une longueur d'onde de mesure de 589 nm ; la couche conductrice transparente contient de l'argent et présente une épaisseur comprise entre 3 et 15 nm ; et des couches à indice de réfraction élevé sont agencées sur les deux surfaces de la couche conductrice transparente et au moins l'une des couches à indice de réfraction élevé contient du sulfure de zinc.
PCT/JP2015/050580 2014-02-10 2015-01-13 Film conducteur transparent WO2015118904A1 (fr)

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JP2015560904A JP6493225B2 (ja) 2014-02-10 2015-01-13 透明導電性フィルム

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JP2014-023242 2014-02-10
JP2014023242 2014-02-10

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107287851A (zh) * 2016-03-30 2017-10-24 青岛海尔滚筒洗衣机有限公司 带装饰圈的洗衣机门体、洗衣机及洗衣方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09318933A (ja) * 1996-05-28 1997-12-12 Toyobo Co Ltd 電極基板
JP2012230491A (ja) * 2011-04-25 2012-11-22 Nitto Denko Corp タッチパネル用透明導電性フィルムおよび画像表示装置
WO2013118643A1 (fr) * 2012-02-06 2013-08-15 コニカミノルタ株式会社 Film conducteur et panneau tactile l'utilisant
JP2013188876A (ja) * 2012-03-12 2013-09-26 Toppan Printing Co Ltd 透明薄膜積層体及びその製造方法
JP2013225296A (ja) * 2012-03-23 2013-10-31 Fujifilm Corp 導電性部材、それを用いたタッチパネル、表示装置、及び入力装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09318933A (ja) * 1996-05-28 1997-12-12 Toyobo Co Ltd 電極基板
JP2012230491A (ja) * 2011-04-25 2012-11-22 Nitto Denko Corp タッチパネル用透明導電性フィルムおよび画像表示装置
WO2013118643A1 (fr) * 2012-02-06 2013-08-15 コニカミノルタ株式会社 Film conducteur et panneau tactile l'utilisant
JP2013188876A (ja) * 2012-03-12 2013-09-26 Toppan Printing Co Ltd 透明薄膜積層体及びその製造方法
JP2013225296A (ja) * 2012-03-23 2013-10-31 Fujifilm Corp 導電性部材、それを用いたタッチパネル、表示装置、及び入力装置

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107287851A (zh) * 2016-03-30 2017-10-24 青岛海尔滚筒洗衣机有限公司 带装饰圈的洗衣机门体、洗衣机及洗衣方法
CN107287851B (zh) * 2016-03-30 2021-03-02 青岛海尔滚筒洗衣机有限公司 带装饰圈的洗衣机门体、洗衣机及洗衣方法

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JP6493225B2 (ja) 2019-04-03

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