CN110637343B - Film with light-transmitting conductive layer, light-adjusting film and light-adjusting device - Google Patents

Film with light-transmitting conductive layer, light-adjusting film and light-adjusting device Download PDF

Info

Publication number
CN110637343B
CN110637343B CN201880030426.8A CN201880030426A CN110637343B CN 110637343 B CN110637343 B CN 110637343B CN 201880030426 A CN201880030426 A CN 201880030426A CN 110637343 B CN110637343 B CN 110637343B
Authority
CN
China
Prior art keywords
conductive layer
light
film
transmitting conductive
transparent conductive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201880030426.8A
Other languages
Chinese (zh)
Other versions
CN110637343A (en
Inventor
藤野望
梨木智刚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority claimed from PCT/JP2018/016721 external-priority patent/WO2018207622A1/en
Publication of CN110637343A publication Critical patent/CN110637343A/en
Application granted granted Critical
Publication of CN110637343B publication Critical patent/CN110637343B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides

Abstract

The film with a light-transmitting conductive layer includes a film base and a light-transmitting conductive layer. The light-transmitting conductive layer and the heated light-transmitting conductive layer obtained by heating the light-transmitting conductive layer at 80 ℃ for 500 hours are both amorphous. The carrier density of the light-transmitting conductive layer was Xa × 1019(/cm3) And the Hall mobility is set to Ya (cm)2V · s) is set to Xc × 10, the carrier density of the heated transparent conductive layer19(/cm3) Hall mobility is set to Yc (cm)2V · s), both of the following formulae (1) and (2) are satisfied. 0.5 ≤ (Xc/Xa) × (Yc/Ya) ≤ 1.5(1) Yc>Ya(2)。

Description

Film with light-transmitting conductive layer, light-adjusting film and light-adjusting device
Technical Field
The invention relates to a film with a light-transmitting conductive layer, a light control film and a light control device.
Background
In recent years, demand for light control devices such as smart windows has been increasing in terms of reduction in air conditioning load, design, and the like. Light control devices are used in various industries as window glass, partitions, interior decoration, and the like of buildings and vehicles.
As the dimming device, for example, there are proposed: a light control glass comprising a light control film and 2 glass plates sandwiching the light control film, wherein the light control film comprises 2 transparent conductive resin substrates and a light control layer sandwiched therebetween (for example, see patent document 1).
The light control glass of patent document 1 can control light by adjusting absorption and scattering of light passing through the light control layer by applying an electric field. In addition, the transparent conductive resin substrate of patent document 1 includes: a transparent resin substrate, and a transparent conductive film formed of ITO on the surface of the transparent resin substrate.
Documents of the prior art
Patent document
Patent document 1: WO2008/075773
Disclosure of Invention
Problems to be solved by the invention
However, the transparent conductive film has either a crystalline structure or an amorphous structure. For example, when a transparent conductive film is formed on a transparent resin substrate by sputtering or the like, an amorphous transparent conductive film is formed. Thereafter, the amorphous transparent conductive film is transformed into a crystal structure by heat.
In general, as the transparent conductive film, a crystalline transparent conductive film having low surface resistance is used.
However, crystalline transparent conductive films have a problem of low crack resistance and scratch resistance. In particular, since the light control film provided in the light control glass is often used as a large-area film, there is a high possibility that cracks or scratches may occur during the process of forming, processing, and transportation. In order to obtain a crystalline transparent conductive film with high productivity, it is necessary to heat an amorphous transparent conductive film at a high temperature (for example, 150 ℃ or higher), and thermal wrinkles due to heating are likely to occur. In particular, a large-area light control film often has poor appearance (design) due to wrinkles of the light control film. Therefore, the demand for an amorphous transparent conductive film is high for a light control film.
However, if the light control film includes an amorphous transparent conductive film, the light control film is exposed to the outside air or sunlight, and thus is naturally transformed into a crystalline transparent conductive film locally or entirely by heat, and the surface resistance is likely to change. As a result, unevenness in surface resistance occurs in the surface of the light control film, and there is a concern that variations in light control may occur.
The present invention provides: a film with a light-transmitting conductive layer having excellent crack resistance, scratch resistance, and thermal stability, a light control film having the same, capable of suppressing variation in light control due to heat, and having excellent appearance, and a light control device.
Means for solving the problems
The present invention (1) comprises a film with a light-transmitting conductive layer, which comprises a film base material and a light-transmitting conductive layer, wherein the light-transmitting conductive layer and the heated light-transmitting conductive layer obtained by heating the light-transmitting conductive layer at 80 ℃ for 500 hours are both amorphous, and the carrier density of the light-transmitting conductive layer is Xa × 1019(/cm3) And the Hall mobility is set to Ya (cm)2V · s) is set to Xc × 10, the carrier density of the heated light-transmissive conductive layer is set to19(/cm3) Hall mobility is set to Yc (cm)2V.s), both of the following formulae (1) and (2) are satisfied,
0.5≤(Xc/Xa)×(Yc/Ya)≤1.5 (1)
Yc>Ya (2)
the invention (2) comprises the film with a light-transmitting conductive layer according to (1), wherein the film base has an elongated shape and has a length in a width direction of 30cm or more.
The invention (3) comprises the film with a light-transmitting conductive layer according to (2), wherein Xc and Yc are measured at a plurality of positions at 3 points in the width direction of the heated light-transmitting conductive layer, respectively, and the standard deviation of Xc is 10X 1019(/cm3) The standard deviation of Yc is 5 (cm)2V · s) or less.
The invention (4) comprises the film with a light-transmitting conductive layer according to any one of (1) to (3), wherein the film base material has a TD direction length of 30cm or more.
The invention (5) comprises the film with a light-transmitting conductive layer according to (4), wherein Xc and Yc are measured at a plurality of positions at 3 points in the TD direction of the heated light-transmitting conductive layer, respectively, and the standard deviation of Xc is 10X 1019(/cm3) The standard deviation of Yc is 5 (cm)2V · s) or less.
The invention (6) comprises the film with a light-transmitting conductive layer according to any one of (1) to (5), wherein the light-transmitting conductive layer contains an indium oxide.
The present invention (7) includes a light control film comprising a 1 st film with a transparent conductive layer, a light control functional layer, and a 2 nd film with a transparent conductive layer in this order, wherein the 1 st film with a transparent conductive layer and/or the 2 nd film with a transparent conductive layer is the film with a transparent conductive layer according to any one of (1) to (6).
The present invention (8) comprises the light control film according to (7), wherein the light control functional layer comprises the following materials: a material exhibiting light modulation by changing at least any one of light transmittance and haze by applying at least any one of an electric field and an electric current.
The present invention (9) includes a light control device comprising the light control film according to (7) or (8) and a transparent protective plate in this order.
ADVANTAGEOUS EFFECTS OF INVENTION
The film with a transparent conductive layer of the present invention is excellent in crack resistance and scratch resistance because the transparent conductive layer and the heated transparent conductive layer are amorphous.
Further, since the carrier density and the hall mobility of the light-transmitting conductive layer and the heated light-transmitting conductive layer satisfy predetermined conditions, the rate of change and/or difference in the surface resistance of the light-transmitting conductive layer due to heat can be suppressed, and therefore, thermal stability is excellent.
The light-controlling film of the present invention is excellent in crack resistance and scratch resistance, and therefore, is excellent in processability and transportability.
The light control film of the present invention is an amorphous light transmitting conductive layer and can be used without a high-temperature heating step, and therefore, even if the light control film is used over a large area, the light control film is excellent in design (appearance).
The light control film of the present invention is excellent in thermal stability, and therefore the light control device of the present invention including the light control film can suppress variation in light control over a long period of time.
Drawings
Fig. 1 is a cross-sectional view showing one embodiment of the film with a light-transmitting conductive layer of the present invention.
Fig. 2A to 2C are plan views of the film with a light-transmitting conductive layer shown in fig. 1, fig. 2A shows the film with a light-transmitting conductive layer before the outline processing, fig. 2B shows the film with a light-transmitting conductive layer having a short side in the TD direction after the outline processing, and fig. 2C shows the film with a light-transmitting conductive layer having a long side in the TD direction after the outline processing.
Fig. 3 is a cross-sectional view of a light control film and a light control device provided with the film with a light-transmissive conductive layer shown in fig. 1.
Detailed Description
In fig. 1, the vertical direction on the paper surface is the vertical direction (thickness direction, 1 st direction), the upper side on the paper surface is the upper side (thickness direction side, 1 st direction side), and the lower side on the paper surface is the lower side (thickness direction side, 1 st direction side).
In fig. 1, 2A, and 2B, the left-right direction on the paper surface is the left-right direction (width direction, short side direction, TD direction, 2 nd direction orthogonal to the 1 st direction).
In fig. 2A and 2B, the vertical direction on the paper surface is the front-back direction (longitudinal direction, MD direction, and 3 rd direction orthogonal to the 1 st direction and the 2 nd direction).
In addition, thick lines shown in fig. 2B and 2C are cutting lines by cutting the film 1 with the light-transmissive conductive layer.
As shown in fig. 1, a film 1 with a light-transmitting conductive layer, which is one embodiment of the film with a light-transmitting conductive layer of the present invention, is formed in a film shape (including a sheet shape) having a predetermined thickness, and has a flat upper surface and a flat lower surface (2 main surfaces) extending in a predetermined direction (front-back direction and left-right direction, i.e., a planar direction) orthogonal to the thickness direction. The film 1 with a translucent conductive layer is not the light control film 4, but is a member such as the light control film 4 (described later, see fig. 3). That is, the film 1 with a light-transmitting conductive layer is a member for producing the light control film 4 and the like, does not include the light control functional layer 5 and the like, and is a commercially available device that is distributed by itself as a member.
Specifically, the film 1 with a light-transmitting conductive layer includes a film base 2 and a light-transmitting conductive layer 3 in this order. That is, the film 1 with a light-transmitting conductive layer includes a film base 2 and a light-transmitting conductive layer 3 disposed on the upper side of the film base 2. Further, the film 1 with a light-transmitting conductive layer is preferably composed of only the film base 2 and the light-transmitting conductive layer 3.
The film base 2 is the lowermost layer of the film 1 with the transparent conductive layer, and is a support material for securing the mechanical strength of the film 1 with the transparent conductive layer.
The film substrate 2 has a film shape (including a sheet shape).
Examples of the material of the film substrate 2 include organic materials, and examples thereof include inorganic materials such as glass, and organic materials are preferable. Since the organic material contains water or an organic gas, crystallinity due to heating of the transparent conductive layer 3 can be suppressed, and amorphousness can be further maintained.
More preferably, the material of the film base 2 is a polymer.
Examples of the polymer include: examples of the resin include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, for example, (meth) acrylic resins (acrylic resins and/or methacrylic resins) such as polymethacrylates, for example, olefin resins such as polyethylene, polypropylene, and cycloolefin polymers, for example, polycarbonate resins, polyether sulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, cellulose resins, polystyrene resins, and norbornene resins. These polymers may be used alone or in combination of 2 or more.
These polymers generally have light-transmitting properties, but materials having light-shielding properties may be used depending on the application.
In the present application, the film base material 2 is defined to have light transmittance when the visible light transmittance is 50% or more and 100% or less, and light blocking property when the visible light transmittance is 0% or more and less than 50%. The method of imparting light-blocking properties is not limited, and for example, light-blocking properties can be adjusted by adding a pigment or dye to a polymer.
The polymer is preferably a polyester resin, and more preferably PET, from the viewpoint of heat resistance, mechanical properties, and the like.
Further, by adjusting the moisture content of the film base 2, the film 1 with a light-transmitting conductive layer having the characteristics described later can be obtained.
Specifically, the moisture content per unit area of the film base 2 is, for example, 10. mu.g/cm2Above, preferably 20. mu.g/cm2Above, more preferably 30. mu.g/cm2Above, and in addition, for example, 200. mu.g/cm2Hereinafter, it is preferably 170. mu.g/cm2The following. When the moisture content of the film base material 2 is within the above range, crystallization is less likely to occur, and a low-resistance amorphous light-transmitting conductive layer 3 can be easily obtained. If the moisture content of the film base 2 is too small, crystallization of the amorphous transparent conductive layer 3 at ambient temperature tends to easily occur, and if the moisture content of the film base 2 is too large, the surface resistance stability of the amorphous transparent conductive layer 3 tends to decrease. Water content (μ g/cm)2) The water content can be calculated as the water content per unit area from the water content determined by JIS K7251-B method (water vaporization method).
A spacer, a protective film, or the like may be provided on the lower surface of the film base 2.
The film base 2 has a thickness of, for example, 2 μm or more, preferably 20 μm or more, more preferably 40 μm or more, and, for example, 300 μm or less, preferably 200 μm or less. The thickness of the thin-film substrate 2 can be measured, for example, using a film thickness meter.
The shape of the film substrate 2 in a plan view is appropriately set according to the use and the object of the film 1 with a light-transmitting conductive layer, and is not particularly limited. As shown in fig. 2A, the film base 2 has, for example, a long, substantially rectangular shape that is long in the front-rear direction and short in the left-right direction. Therefore, the film base 2 has 2 long sides 6 facing each other and 2 short sides 7 connecting both end edges in the left-right direction.
The dimension of the film base 2 in a plan view is appropriately set depending on the use and the object of the film 1 with a light-transmitting conductive layer, and is not particularly limited. The film base 2 has a length (TD length) W of the short side 7 of, for example, 30cm or more, preferably 0.50m or more, more preferably 1.0m or more, still more preferably 1.2m or more, particularly preferably 2m or more, and 10m or less.
The film base material 2 may be wound up to form a long film roll. The number of windings of the long film roll is, for example, 100m or more, preferably 500m or more, more preferably 1000m or more, and, for example, 20000m or less. The long film roll can continuously form the light-transmitting conductive layer 3 in a roll-to-roll manner, and is excellent in productivity.
The transparent conductive layer 3 is a conductive layer that can be patterned by etching in a subsequent step as necessary. As shown in fig. 1, the transparent conductive layer 3 is the uppermost layer of the film 1 with a transparent conductive layer. The light-transmitting conductive layer 3 has a thin film shape (including a sheet shape), and is disposed on the entire upper surface of the film substrate 2 so as to be in contact with the upper surface of the film substrate 2. The light-transmitting conductive layer 3 is amorphous.
Note that the light-transmitting conductive layer 3 is amorphous, for example, as follows: when the material of the light-transmitting conductive layer 3 is ITO (described later), it is immersed in hydrochloric acid (concentration 5 mass%) at 20 ℃ for 15 minutes, washed with water, and dried, and the inter-terminal resistance between about 15mm is measured. In this specification, the light-transmitting conductive layer 3 was judged to be amorphous when the resistance between terminals between 15mm in the light-transmitting conductive layer 3 was 10 k.OMEGA.or more after the film 1 with the light-transmitting conductive layer was immersed in hydrochloric acid (20 ℃ C., concentration: 5% by mass), washed with water and dried.
Examples of the material of the light-transmitting conductive layer 3 include: a metal oxide containing at least 1 metal selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, W. The metal oxide may be further doped with a metal atom shown in the above group, or a metal atom or a semimetal atom not shown in the above group, as necessary.
Examples of the light-transmitting conductive layer 3 include: for example, indium oxides such as indium tin composite oxide (ITO) and indium zinc composite oxide (IZO), and antimony oxides such as antimony tin composite oxide (ATO). The light-transmitting conductive layer 3 contains an indium oxide, and more preferably contains an indium tin composite oxide (ITO), from the viewpoint of reducing surface resistance and ensuring excellent light transmission. That is, the light-transmitting conductive layer 3 is preferably an indium oxide layer, and more preferably an ITO layer. This results in low surface resistance and excellent light transmittance.
When ITO is used as the material of the light-transmitting conductive layer 3, tin oxide (SnO)2) The contents relative to tin oxide and indium oxide (In)2O3) The total amount of (a) is, for example, 0.5% by mass, preferably 3% by mass or more, more preferably 8% by mass or more, further preferably more than 10% by mass, and further, for example, 25% by mass or less, preferably 15% by mass or less, more preferably 13% by mass or less. By setting the content of tin oxide to be equal to or higher than the lower limit, it is possible to achieve a low surface resistance (for example, equal to or lower than 150 Ω/□) of the transparent conductive layer 3 and to more reliably suppress the conversion to a crystalline state. Further, by setting the content of tin oxide to the upper limit or less, the stability of light transmittance and surface resistance can be improved.
The "ITO" In the present specification may contain an additional component other than the above as long as it is a composite oxide containing at least indium (In) and tin (Sn). Examples of the additional component include metal elements other than In and Sn, and specifically include: zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, W, Fe, Pb, Ni, Nb, Cr, Ga, etc.
The light-transmitting conductive layer 3 preferably contains an impurity element. As the impurity elements, there may be mentioned: elements derived from a sputtering gas (for example, Ar element) used in forming the light-transmissive conductive layer 3 are elements derived from water or an organic gas (for example, H element or C element) contained in the film base material 2. By containing these components, the amorphousness of the light-transmitting conductive layer 3 can be further improved.
The thickness of the light-transmitting conductive layer 3 is, for example, 10nm or more, preferably 30nm or more, more preferably more than 30nm, even more preferably 40nm or more, particularly preferably 50nm or more, and is, for example, 200nm or less, preferably 150nm or less, more preferably 100nm or less, even more preferably 80nm or less. The thickness of the light-transmitting conductive layer 3 can be measured by, for example, cross-sectional observation using a transmission electron microscope. When the material of the transparent conductive layer 3 is ITO, the amorphous stability (property of stably maintaining the amorphous property) is generally lower as the thickness of the amorphous transparent conductive layer 3 is larger, and natural crystallization is easily performed. In particular, when the thickness is at a level exceeding 30nm, this tendency is remarkable, and since the light-transmissive conductive layer 3 has the characteristics described below, the amorphous stability is excellent even if the material of the light-transmissive conductive layer 3 is ITO.
The shape and size of the light-transmitting conductive layer 3 in plan view are the same as those of the film base 2 in plan view.
Next, a method for producing the film 1 with a light-transmitting conductive layer will be described.
The film 1 with a light-transmitting conductive layer was obtained as follows: first, a film base 2 is prepared, and then the light-transmissive conductive layer 3 is formed on the surface of the film base 2.
In order to form the light-transmissive conductive layer 3 on the surface of the film base 2, for example, the light-transmissive conductive layer 3 is disposed (laminated) on the upper surface of the film base 2 by a dry method.
Examples of the dry type include: vacuum deposition, sputtering, ion plating, and the like. Sputtering is preferred.
In the sputtering method, a target and the film base material 2 are arranged in a chamber of a vacuum apparatus so as to face each other, and by supplying gas and applying voltage, gas ions are accelerated and irradiated to the target, and a target material is ejected from the target surface and laminated on the surface of the film base material 2.
Examples of the sputtering method include: 2-pole sputtering, ECR (electron cyclotron resonance) sputtering, magnetron sputtering, ion beam sputtering, and the like. Preferably, a magnetron sputtering method is used.
The power source used for the sputtering method may be, for example, any of the following power sources: a Direct Current (DC) power supply, an alternating current intermediate frequency (AC/MF) power supply, a high frequency (RF) power supply, and a high frequency power supply obtained by superimposing a DC power supply.
Examples of the target include the metal oxide constituting the light-transmitting conductive layer 3. For example, when ITO is used as the material of the light-transmissive conductive layer 3, a target formed of ITO is used. Tin oxide (SnO) in a target2) The contents relative to tin oxide and indium oxide (In)2O3) The total amount of (a) is, for example, 0.5% by mass, preferably 3% by mass or more, more preferably 8% by mass or more, and still more preferably more than 10% by mass, and is, for example, 25% by mass or less, preferably 15% by mass or less, and more preferably 13% by mass or less.
The intensity of the horizontal magnetic field on the target surface is, for example, 10mT or more, preferably 20mT or more, and further 200mT or less, preferably 100mT or less, and more preferably 80mT or less, from the viewpoints of the film formation rate, the entry of impurities into the light-transmissive conductive layer 3, and the like. When the horizontal magnetic field strength is in the above range, the plasma density during sputtering can be increased, and the amount of heat applied to the film base material 2 tends to be increased. As a result, impurities (e.g., water) released from the film base 2 easily enter the transparent conductive layer 3, and the light-transmissive conductive layer 3 is likely to be highly amorphous.
The discharge gas pressure during sputtering is, for example, 1.0Pa or less, preferably 0.5Pa or less, and is, for example, 0.01Pa or more, preferably 0.2Pa or more.
By adjusting the temperature of the film base material 2 during sputtering, a film 1 with a light-transmitting conductive layer having the characteristics described later can be obtained.
The temperature of the film base 2 during sputtering is, for example, -30 ℃ or higher, preferably-10 ℃ or higher, and, for example, 180 ℃ or lower, preferably 90 ℃ or lower, more preferably 60 ℃ or lower, further preferably 40 ℃ or lower, and particularly preferably less than 10 ℃.
By setting the upper limit or less, the generation of crystal grains in the transparent conductive layer 3 due to heat during film formation can be suppressed. When the lower limit is set to the above-described lower limit or more, the amount of release of water or organic gas contained in the film base material 2 can be adjusted to an appropriate range, and the light-transmitting conductive layer 3 having a high-quality amorphous film can be easily obtained.
Examples of the gas used in the sputtering method include: such as the use of a non-reactive gas alone, such as a combination of a non-reactive gas and a reactive gas. Examples of the inert gas include Ar gas. Examples of the reactive gas include oxygen gas.
Preferably, a combination of an inert gas and a reactive gas is used.
The ratio of the flow rate of the reactive gas to the flow rate of the inert gas (flow rate of the reactive gas (sccm)/flow rate of the inert gas (sccm)) is, for example, 0.010 to 5. The ratio of the flow rate of the reactive gas to the flow rate of the inert gas is appropriately set depending on the film forming environment such as the gas pressure, the horizontal magnetic field strength of the target surface, and the temperature of the thin film substrate.
In this method, the translucent conductive layer 3 having the characteristics described later can be formed (formed) by adjusting the amount of the reactive gas, particularly the amount of oxygen.
For example, ITO is used as the material of the light-transmitting conductive layer 3. The transparent conductive layer 3 obtained by the sputtering method is generally formed as an amorphous transparent conductive layer 3. At this time, the film quality of the amorphous transparent conductive layer 3 changes according to the amount of oxygen introduced into the amorphous transparent conductive layer 3.
Specifically, when the amount of oxygen introduced into the amorphous transparent conductive layer 3 is less than a proper amount (oxygen deficient state), the amorphous transparent conductive layer is converted into a crystalline state by heating in an air atmosphere.
On the other hand, when the amount of oxygen introduced into the amorphous transparent conductive layer 3 is an appropriate amount, the amorphous structure is maintained even when the layer is heated in an air atmosphere, and the thermal stability is excellent.
On the other hand, when the amount of oxygen introduced into the amorphous transparent conductive layer 3 exceeds a proper amount, the amorphous structure is maintained by heating in an air atmosphere, but the surface resistance after heating is significantly increased, and the thermal stability is poor.
The reason is not limited to any theory, but is presumed as follows. The present invention is not limited to the following theory. When the amount of oxygen contained in the amorphous transparent conductive layer 3 is small (oxygen deficient state), the amorphous transparent conductive layer 3 has a plurality of oxygen deficient portions in the structure, and thus atoms constituting ITO are easily moved by thermal vibration, and an optimum structure is easily obtained. Therefore, by heating in an air atmosphere, an optimum structure (crystalline structure) is obtained while allowing the oxygen-deficient portion to appropriately absorb oxygen. On the other hand, when the amount of oxygen introduced into the amorphous transparent conductive layer 3 is within a proper range, oxygen-deficient portions are less likely to be generated in the amorphous transparent conductive layer 3. That is, the appropriate amount range of oxygen represents a range in which the stoichiometric composition of the amorphous transparent conductive layer 3 is easily obtained. When the amount of oxygen is appropriate, the amorphous transparent conductive layer 3 is less in oxygen-deficient portion even when heated in an atmospheric atmosphere, but is not oxidized and maintains a good amorphous structure. On the other hand, when the oxygen introduction amount contained in the amorphous transparent conductive layer 3 is excessive, oxygen atoms contained in the amorphous transparent conductive layer 3 act as impurities. When the impurity atoms exceed an appropriate content level, they cause neutron scattering, and increase the surface resistance. Therefore, it is presumed that when the amount of oxygen introduced into the amorphous transparent conductive layer 3 is excessive, the amount of oxygen in the transparent conductive layer 3 is further excessive by heating, and the surface resistance increases (thermal stability decreases).
Here, in the roll-to-roll method, when the amorphous light-transmissive conductive layer 3 is formed on the film base material 2 having a large length in the TD direction (for example, 30cm or more), the amount of oxygen supplied at the time of forming the light-transmissive conductive layer 3 is changed in the TD direction of the film base material 2, whereby the light-transmissive conductive layer 3 having the characteristics described later can be obtained. The thin film substrate 2 contains an impurity gas (the aforementioned moisture or organic gas), and the amount of the impurity gas released during sputtering (vacuum deposition) and the amount of the impurity gas entering the transparent conductive layer 3 are not uniform (nonuniform) in the TD direction of the thin film substrate 2. In addition, the amount of oxygen discharged by the vacuum pump is not uniform (non-uniform) in the TD direction with respect to the amount of oxygen introduced.
Therefore, when oxygen is introduced uniformly in the TD direction, a region where oxygen is locally excessive (impurity is excessive) or oxygen is locally insufficient is generated depending on the amount of impurity gas or the amount of waste oxygen in the TD direction, and thus it is difficult to obtain the light-transmitting conductive layer 3 having the characteristics described later. In particular, when the light-transmitting conductive layer 3 is formed by a roll-to-roll method using a long film base material 2 (for example, 300m or more), the amount of impurity gas is likely to vary (non-uniformity) in the TD direction, and the amount of impurity gas varies in the flow (MD direction) of the film base material 2, and thus the light-transmitting conductive layer 3 having the characteristics described below tends to be less likely to be obtained. Therefore, by adjusting the amount of oxygen introduced in the TD direction in accordance with the impurity gas content and oxygen content in the TD direction of the transparent conductive layer 3, the film 1 with a transparent conductive layer having the characteristics described later can be obtained. In the case of obtaining a crystalline light-transmitting conductive layer 3 (not the amorphous light-transmitting conductive layer 3 of the present invention), the amount of oxygen introduced is set to be clearly smaller than the "proper amount" in advance, so that the influence of impurity gas and oxygen amount in the TD direction can be reduced, and the influence of the amount of oxygen introduced in the TD direction is small.
The method for adjusting the oxygen introduction amount in the TD direction is not limited, and for example, the oxygen introduction amount can be appropriately adjusted by dividing the oxygen supply pipe into a plurality of pipes in the TD direction. The number of divisions of the oxygen supply pipe is, for example, 2 or more, preferably 3 or more, and is, for example, 20 or less, preferably 10 or less. By providing the oxygen supply pipe divided into a plurality of parts, the light-transmitting conductive layer 3 having the characteristics described later can be obtained.
The surface resistance of the light-transmitting conductive layer 3 before heating is, for example, 1 Ω/□ or more, preferably 10 Ω/□ or more, and, for example, 250 Ω/□ or less, preferably 200 Ω/□ or less, more preferably 150 Ω/□ or less, and further preferably less than 100 Ω/□. When the surface resistance before heating is not less than the lower limit, deterioration of the optical characteristics of the light-transmissive conductive layer 3 can be suppressed. When the surface resistance before heating is not more than the upper limit, the rate of change and/or difference in surface resistance before and after heating of the transparent conductive layer 3 described later can be prevented from becoming excessively large, and a stable transparent conductive layer 3 can be obtained.
The surface resistance of the heated transparent conductive layer 3 α is the same as the surface resistance of the transparent conductive layer 3.
The rate of change in the surface resistance before and after heating of the transparent conductive layer 3 (the ratio of the surface resistance of the heated transparent conductive layer 3 α to the surface resistance of the transparent conductive layer 3) (that is, the surface resistance of the heated transparent conductive layer 3 α/the surface resistance of the transparent conductive layer 3) is, for example, 0.80 or more, preferably 0.85 or more, more preferably 0.90 or more, and, for example, 1.25 or less, preferably 1.20 or less, more preferably 1.1 or less.
An absolute value of a value obtained by subtracting the surface resistance of the light-transmissive conductive layer 3 from the surface resistance of the heated light-transmissive conductive layer 3 α, and in short, a difference (| [ surface resistance of the heated light-transmissive conductive layer 3 α ] - [ surface resistance of the light-transmissive conductive layer 3 ] |) between the surface resistance of the heated light-transmissive conductive layer 3 α and the surface resistance of the light-transmissive conductive layer 3 are, for example, 40 Ω/□ or less, preferably 30 Ω/□ or less, more preferably 20 Ω/□ or less, still more preferably 15 Ω/□ or less, and, for example, 0 Ω/□ or more, and preferably 0.001 Ω/□ or more. In general, an amorphous light-transmitting conductive layer 3 having a small surface resistance (for example, 250 Ω/□ or less) tends to have a large thickness, and as a result, the amorphous stability deteriorates and the difference in surface resistance between before and after heating tends to increase. However, in the light-transmitting conductive layer 3 of the present invention, the difference in surface resistance before and after heating can be suppressed within the above range by appropriately setting the amount of oxygen, the amount of impurities (for example, the moisture content) in the film, and the film formation process (horizontal magnetic field strength, discharge gas pressure, temperature, and the like of the target surface).
When the difference is equal to or less than the upper limit, it is possible to suppress the change in film quality of the light transmissive conductive layer 3 from becoming excessively large, and to prevent deterioration of the coating property of the light control function layer 5 and/or deterioration of the light control function.
The resistivity of the transparent conductive layer 3 before heating is, for example, 6 × 10-4Omega cm or less, preferably 5.5X 10-4Omega cm or less, more preferably 5X 10-4Omega cm or less, and more preferably 4.8X 10-4Omega cm or less, particularly preferably 4.5X 10-4Omega cm or less, and is, for example, 3X 10-4Omega cm or more, preferably 3.5X 10-4Omega cm or more, more preferably 4.0X 10-4Omega cm or more. When the specific resistance of the transparent conductive layer 3 before heating is not more than the upper limit, the rate of change and/or the difference in surface resistance between before and after heating of the transparent conductive layer 3 can be reduced. When the resistivity is not less than the lower limit, the amorphousness of the transparent conductive layer 3 is easily maintained.
The resistivity of the heated transparent conductive layer 3 α is the same as that of the transparent conductive layer 3, and is preferably equal to or lower than that of the transparent conductive layer 3. Specifically, the ratio of the resistivity of the heated transparent conductive layer 3 α to the resistivity of the transparent conductive layer 3 ([ resistivity of the heated transparent conductive layer 3 α/[ resistivity of the transparent conductive layer 3 ]) is, for example, 1.25 or less, preferably 1.2 or less, more preferably less than 1.2, even more preferably 1.1 or less, particularly preferably 1.0 or less, and most preferably 0.98 or less, and is, for example, 0.5 or more, preferably 0.65 or more, and even more preferably 0.8 or less. When the ratio is within the above range, stable amorphousness is easily obtained.
The heated transparent conductive layer 3 α is obtained by heating the transparent conductive layer 3 at 80 ℃ for 500 hours in an atmospheric environment. The heated transparent conductive layer 3 α is an index of thermal stability of the transparent conductive layer 3. Further, when heating is performed as an accelerated test of long-term thermal stability, the heating conditions may be, for example, 140 ℃ for 1 hour. The heated transparent conductive layer 3 α is amorphous.
The thin film 1 with a translucent conductive layer has the following characteristics based on the hall effect.
[1] Density of carriers (Xa, Xc)
Carrier density of the light-transmitting conductive layer 3 before heating(Xa×1019/cm3) For example, 10X 1019/cm3Above, preferably 20 × 1019/cm3Above, more preferably 30 × 1019/cm3Above, more preferably 35 × 1019/cm3Above, for example, 60 × 1019/cm3Hereinafter, 50 × 10 is preferable19/cm3Hereinafter, more preferably 40 × 1019/cm3The following. As shown in fig. 2A, the carrier density Xa of the transparent conductive layer 3 is determined as follows: the carrier density was measured at a plurality of points P1, P2, and P3 along the direction along the short side 7 (TD direction, short side direction), and was determined as an average value of these. At this time, the number of dots measured was 3. Both ends (2 points of P1 and P3) of the measurement point were located 80mm inward from the position where the end portion of the transparent conductive layer 3 was uniformly formed, and the center point (1 point of P2) was located at the center of the film base 2. In the present application, the phrase "the end portion of the transparent conductive layer 3 is uniformly formed" means the end portion of the region where the thickness of the transparent conductive layer 3 is within ± 10% of the thickness of the transparent conductive layer 3 at the center of the film base 2.
Specifically, when the TD width of the film base material 2 was 1300mm and the transparent conductive layer 3 was uniformly formed over the entire surface, the measurement points were defined as positions where P1 was 80mm, P2 was 650mm, and P3 was 1220 mm.
The term "before heating" means, for example, from after the formation of the transparent conductive layer 3 to before heating to 80 ℃.
Further, even in the case of the film 1 with a transparent conductive layer having an unclear heat history of the transparent conductive layer 3, the film is treated as "before heating" until it is reheated to 80 ℃.
The standard deviation of the carrier density at a plurality of points of 3 points of the length in the direction along the short side 7 of the light-transmitting conductive layer 3 is, for example, 10 × 1019(/cm3) Hereinafter, it is preferably 5 × 1019(/cm3) Hereinafter, 3 × 10 is more preferable19(/cm3) Hereinafter, more preferably 2 × 1019(/cm3) Hereinafter, for example, 0.001 × 1019(/cm3) The above. When the standard deviation is equal to or less than the upper limit, the carrier density Xa in the width direction of the transparent conductive layer 3 can be set uniformly, and therefore, the variation in thermal characteristics in the width direction can be reduced, and the thermal stability can be improved.
On the other hand, the carrier density (Xc × 10) of the heated transparent conductive layer 3 α19/cm3) For example, 10X 1019/cm3Above, preferably 20 × 1019/cm3Above, more preferably 30 × 1019/cm3More than, preferably 32 × 1019/cm3Above, and another example is 70X 1019/cm3Hereinafter, it is preferably 60 × 1019/cm3Hereinafter, 50 × 10 is preferable19/cm3The following. The carrier density Xc of the heated transparent conductive layer 3 α is determined by the same measurement as the carrier density Xa of the transparent conductive layer 3.
The standard deviation of the carrier density at the plurality of points P1, P2, and P3 along the length of the short side 7 of the heated transparent conductive layer 3 α is, for example, 10 × 1019(/cm3) Hereinafter, it is preferably 5 × 1019(/cm3) Hereinafter, 3 × 10 is more preferable19(/cm3) Hereinafter, more preferably 2 × 1019(/cm3) Hereinafter, for example, 0.001 × 1019(/cm3) The above. When the standard deviation is equal to or less than the upper limit, the carrier density Xc in the width direction of the heated transparent conductive layer 3 α can be uniformly set, and therefore, the variation in thermal characteristics in the width direction can be reduced, and the thermal stability can be improved.
From the viewpoint of thermal stability of the light-transmitting conductive layer 3, it is preferable that the standard deviation of the carrier density of the heated light-transmitting conductive layer 3 α be equal to or smaller than the value of the standard deviation of the carrier density of the light-transmitting conductive layer 3. By having the above-described characteristics, the heat stability of the light-transmitting conductive layer 3 is further improved.
[2] Hall mobility (Ya, Yc)
Hall mobility (Ya cm) of the light-transmitting conductive layer 3 before heating2V.s) is, for example10cm2More than V.s, preferably 20cm2More preferably 30cm,/V.s or more2At least V.s, and, for example, 70cm2V.s or less, preferably 50cm2V.s or less, more preferably 40cm2Has a value of/V.s or less. The hall mobility Ya of the light-transmissive conductive layer 3 was determined as an average value of hall mobilities Ya measured at a plurality of points P1, P2, and P3 at 3 points along the direction of the short side 7 (TD direction, short side direction).
The standard deviation of the hall mobility of the plurality of points P1, P2, and P3 of the translucent conductive layer 3 along the length of the short side 7 is, for example, 5cm2Is less than or equal to V.s, preferably 3cm2V.s or less, more preferably 2cm2A value of 1cm or less, more preferably2A value of,/V.s or less, and, for example, 0.001cm2More than V.s. When the standard deviation is equal to or less than the upper limit, the hall mobility Ya in the direction along the short side 7 of the light-transmissive conductive layer 3 can be set uniformly, and therefore, the variation in thermal characteristics in the width direction can be reduced, and thermal stability can be improved.
Hall mobility (Yc cm) of the heated translucent conductive layer 3 α2V.s) is, for example, 10cm2More than V.s, preferably 20cm2More preferably 30cm,/V.s or more2At least V.s, and, for example, 70cm2V.s or less, preferably 50cm2V.s or less, more preferably 45cm2Has a value of/V.s or less. The hall mobility Yc of the heated transparent conductive layer 3 α can be determined by the same measurement as the hall mobility Ya.
The standard deviation of the hall mobilities of the plurality of points P1, P2, and P3 along the length of the short side 7 of the heated translucent conductive layer 3 α is, for example, 5cm2Is less than or equal to V.s, preferably 3cm2V.s or less, more preferably 2cm2A value of 1cm or less, more preferably2A value of,/V.s or less, and, for example, 0.001cm2More than V.s. When the standard deviation is not more than the upper limit, the hall mobility Yc in the width direction of the heated transparent conductive layer 3 α can be set uniformly, and therefore, the width can be reducedThe variation in thermal characteristics in the direction improves thermal stability.
The standard deviation of the hall mobility Yc of the heated light-transmissive conductive layer 3 α is preferably equal to or smaller than the standard deviation of the hall mobility Ya of the light-transmissive conductive layer 3. This further improves the thermal stability of the light-transmitting conductive layer 3.
It should be noted that the hall mobility is based on the hall effect and is a product of the electrical conductivity and the hall coefficient.
Expressions (1) to (4) for the carrier density and the hall mobility of the light-transmitting conductive layer and the heated light-transmitting conductive layer
The carrier density (Xa × 10) of the light-transmitting conductive layer 319/cm3) And carrier density (Xc 10) of the heated light-transmitting conductive layer19/cm3) And the Hall mobility (Ya cm) with the light-transmitting conductive layer 32V.s) and Hall mobility of the heated translucent conductive layer (Ya cm)2V · s) satisfies both the following formula (1) and formula (2).
0.5≤(Xc/Xa)×(Yc/Ya)≤1.5 (1)
Yc>Ya (2)
If the amount is not equal to the above formula (1), the change in surface resistance of the light-transmitting conductive layer 3 due to heating cannot be suppressed, and therefore, the thermal stability is lowered.
Note that (Xc/Xa) is a ratio of the carrier density Xc of the heated transparent conductive layer 3 α to the carrier density Xa of the transparent conductive layer 3, and (Yc/Ya) is a ratio of the hall mobility Yc of the heated transparent conductive layer 3 α to the hall mobility Ya of the transparent conductive layer 3, and if both values are 1 or a value close to 1, the above formula (1) is satisfied. In addition, even if (Xc/Xa) is not close to 1, specifically, significantly larger than 1, as long as (Yc/Ya) is significantly smaller than 1, the above formula (1) is satisfied. Further, the above magnitude relation may be reversed.
(Xc/Xa) × (Yc/Ya) is preferably 0.80 or more, more preferably 0.90 or more, further preferably 0.95 or more, and particularly preferably 1.000 or more. Further, (Xc/Xa) × (Yc/Ya) is preferably 1.3 or less, more preferably 1.2 or less, further preferably 1.15 or less, and particularly preferably 1.10 or less. When (Xc/Xa) × (Yc/Ya) is equal to or higher than the lower limit or equal to or lower than the upper limit, the change in the surface resistance of the light-transmitting conductive layer 3 due to heating can be suppressed, and therefore, the heat stability is excellent.
When formula (2) is satisfied, Yc/Ya exceeds 1.
Yc/Ya exceeds 1.000, and is preferably 1.001 or more, more preferably 1.01 or more, and is, for example, 1.7 or less, preferably 1.5 or less, more preferably 1.3 or less, further preferably 1.2 or less, and particularly preferably 1.1 or less. The light-transmitting conductive layer 3 satisfying the formula (2) easily exhibits good conductivity. On the other hand, when the formula (2) is satisfied, the amorphous transparent conductive layer 3 tends to be crystallized (resistance change) by heating, and the transparent conductive layer 3 satisfies both the formula (1) and the formula (2), and therefore, when Yc/Ya is more than or equal to the lower limit or less than the upper limit, the tolerance of the surface resistance in the width direction (TD direction) of the film base material 2 can be made small. Further, when Yc/Ya is not more than the upper limit, the difference in surface resistance between the transparent conductive layer 3 before and after heating can be reduced.
In addition, Xa, Xc, Ya and Yc preferably satisfy the following formula (3) or the following formula (4).
Xc < Xa and, Yc > Ya (3)
Xc is not less than Xa, and Yc > Ya (4)
When formula (3) is satisfied, Xc/Xa is less than 1, and Yc/Ya exceeds 1. Specifically, Xc/Xa is preferably less than 1.000, more preferably 0.99 or less, and further preferably 0.7 or more, more preferably 0.8 or more, further preferably 0.85 or more, and particularly preferably 0.90 or less. Suitable ranges for Yc/Ya are the same as detailed in formula (2) above. When Xc/Xa is equal to or higher than the lower limit, the tolerance of the surface resistance of the transparent conductive layer 3 can be reduced. When Xc/Xa is equal to or less than the upper limit, the rate of change and/or the difference in surface resistance between the light-transmitting conductive layer 3 before and after heating can be reduced.
When formula (4) is satisfied, Xc/Xa is 1 or more, and Yc/Ya exceeds 1. Specifically, Xc/Xa is preferably 1.000 or more, more preferably 1.01 or more, further preferably 1.02 or more, and is, for example, 1.7 or less, preferably 1.5 or less, more preferably 1.3 or less, further preferably 1.2 or less, and particularly preferably 1.1 or less. Suitable ranges for Yc/Ya are the same as detailed in formula (2) above. When Xc/Xa is equal to or higher than the lower limit, an increase in surface resistance of the light-transmissive conductive layer 3 due to heating is easily suppressed. When Xc/Xa is equal to or less than the upper limit, crystallization of the light-transmitting conductive layer 3 due to heating is easily suppressed.
In this way, a film 1 with a transparent conductive layer (film 1 with a transparent conductive layer before heating) including a film base 2 and a transparent conductive layer 3 was obtained.
The total thickness of the film 1 with a light-transmitting conductive layer is, for example, 2 μm or more, preferably 20 μm or more, and is, for example, 300 μm or less, preferably 200 μm or less.
The film 1 with a transparent conductive layer on which the transparent conductive layer 3 is formed is an industrially applicable device, and the film 1 with a transparent conductive layer on which the heated transparent conductive layer 3 α is formed is a film that is not necessarily an index for measuring the thermal stability of the transparent conductive layer 3 for the purpose of distribution in the market.
The film 1 with a transparent conductive layer can be etched as necessary to pattern the transparent conductive layer 3 into a predetermined shape.
The above-described production method is performed in a roll-to-roll manner, or in a batch manner. Preferably in a roll-to-roll manner.
When the film 1 with a light-transmitting conductive layer is produced by a roll-to-roll method, the direction along the long side 6 is the MD direction (long side direction), and the direction along the short side 7 is the TD direction (short side direction, width direction).
Thereafter, the film 1 with the light-transmitting conductive layer is externally shaped into a desired size according to its use and purpose.
For example, as shown in fig. 2B, the film 1 with the transparent conductive layer is cut, for example, in the MD direction so that the direction along the long side 6 is the MD direction and the direction along the short side 7 is the TD direction, to obtain a plurality of films 1 with the transparent conductive layer. In this case, the length W of the short side 7 (the width direction length, the short side direction length, and the TD direction length) of each of the plurality of films 1 with the light-transmitting conductive layer is, for example, 30cm or more, preferably 0.50m or more, more preferably 1.0m or more, further preferably 1.2m or more, and, for example, 4m or less, preferably 2m or less. When the length W of the short side 7 is equal to or greater than the lower limit, the manufacturing efficiency of the light control film 4 and the light control device 9 described below can be improved, and a large-sized light control film 4 and a large-sized light control device 9 can be manufactured.
On the other hand, as shown in fig. 2C, the film 1 with the transparent conductive layer may be cut, for example, in the MD direction so that the direction along the long side 6 is the TD direction and the direction along the short side 7 is the MD direction, to obtain a plurality of films 1 with the transparent conductive layer. In this case, the length L (length in the longitudinal direction, length in the TD direction) of the long side 6 of each of the plurality of films 1 with the light-transmitting conductive layer is, for example, 30cm or more, preferably 0.50m or more, more preferably 1.0m or more, further preferably 1.2m or more, and, for example, 4m or less, preferably 2m or less. When the length L of the long side 6 is equal to or longer than the lower limit, the film 1 with a light-transmitting conductive layer, which is sufficiently long in the longitudinal direction, can be used for various applications.
For example, in the case where the MD direction and the TD direction are unknown in the manufacturing method (roll-to-roll method) of the light-transmissive conductive film 1 having a predetermined plan view shape, in the present application, the MD direction and the TD direction are determined by measuring the surface resistance of the light-transmissive conductive layer 3 and obtaining the tolerance of the numerical value thereof (the maximum and minimum differences among 3 points) (the measurement position is based on the measurement position described in [1] carrier density (Xa, Xc)). In the measurement of the surface resistance, an arbitrary measurement axis is set to 0 °, the surface resistance is obtained in each of the 4-axis directions of 45 °, 90 °, and 135 °, the direction having the smallest tolerance is defined as the MD direction, and the direction orthogonal to the MD direction is defined as the TD direction.
Next, a method for producing the light control film 4 by using the film 1 with a light-transmitting conductive layer will be described with reference to fig. 3.
As shown in fig. 3, this method includes: the process of manufacturing 2 films 1 with a light-transmitting conductive layer is followed by the process of sandwiching a light-adjusting functional layer 5 between 2 films 1 with a light-transmitting conductive layer.
First, 2 films 1 with a light-transmitting conductive layer were produced.
The 2 films 1 with a light-transmitting conductive layer are the 1 st film 1A with a light-transmitting conductive layer and the 2 nd film 1B with a light-transmitting conductive layer. The film 1A with the 1 st translucent conductive layer and the film 1B with the 2 nd translucent conductive layer have the same configuration.
In the light control film 4, the material of the 1 st film 1A with a transparent conductive layer and the 2 nd film 1B with a transparent conductive layer is preferably a polymer having transparency.
Next, the light control function layer 5 is formed on the upper surface (front surface) of the transparent conductive layer 3 of the film 1A with the transparent conductive layer 1 by, for example, wet process.
For example, a solution containing a liquid crystal composition is applied to the upper surface of the light-transmissive conductive layer 3 in the film 1A with a light-transmissive conductive layer 1. The liquid crystal composition comprises the following materials: a material exhibiting light modulation by changing at least any one of light transmittance and haze by applying at least any one of an electric field and an electric current. The liquid crystal composition may be a known liquid crystal composition contained in a solution, and for example, a liquid crystal dispersion resin described in Japanese patent application laid-open No. 8-194209.
Next, the film 1B with the 2 nd transparent conductive layer was laminated on the film 1B with the 2 nd transparent conductive layer so that the transparent conductive layer 3 of the film 1B with the 2 nd transparent conductive layer was in contact with the surface of the coating film of the liquid crystal composition. Thus, the coating film was sandwiched between 2 films 1 with a transparent conductive layer, i.e., the 1 st film 1A with a transparent conductive layer and the 2 nd film 1B with a transparent conductive layer.
Thereafter, the coating film is subjected to an appropriate treatment (for example, a photo-curing treatment, a heat-drying treatment, or the like) to form the light-controlling functional layer 5. The light control function layer 5 is formed between the translucent conductive layer 3 of the 1 st film 1A with a translucent conductive layer and the translucent conductive layer 3 of the 2 nd film 1B with a translucent conductive layer.
Thus, a light control film 4 comprising a film 1A with a 1 st transparent conductive layer, a light control functional layer 5 and a film 1B with a 2 nd transparent conductive layer in this order was obtained.
The light control film 4 is provided in the light control device 9, for example.
The light control device 9 includes a light control film 4, a transparent protective plate 10, and a power supply 8.
The transparent protective plate 10 is provided on the surface of the film base 2 of each of the 1 st film 1A with a transparent conductive layer and the 2 nd film 1B with a transparent conductive layer. The 2 transparent protective plates 10 are each formed into a plate shape (including a sheet shape) having a predetermined thickness, and have a flat upper surface and a flat lower surface (2 main surfaces) extending in the plane direction. Examples of the material of the transparent protective plate 10 include inorganic materials such as glass.
The power supply 8 is connected to the light-transmitting conductive layer 3 of each of the 1 st film with a light-transmitting conductive layer 1A and the 2 nd film with a light-transmitting conductive layer 1B via a wiring 11. The power supply 8 is configured to be able to apply a variable voltage to the 2 light-transmissive conductive layers 3.
In the light control device 9, a voltage is applied to the 2 light transmissive conductive layers 3 from the power supply 8, thereby generating an electric field in the light control functional layer 5. The electric field is controlled by a power supply 8. Therefore, the dimming function layer 5 blocks or transmits light.
In the film 1 with a transparent conductive layer, since the transparent conductive layer 3 and the heated transparent conductive layer 3 α are both amorphous, they are excellent in crack resistance and scratch resistance.
Further, since the light-transmitting conductive layer 3 and the heated light-transmitting conductive layer 3 α satisfy both the above expressions (1) and (2), a change in the surface resistance of the light-transmitting conductive layer 3 due to heat can be suppressed, and thermal stability is excellent.
As shown in fig. 2A and 2B, when the length W of the short side 7 of the film base 2 is long and 30cm or more, the manufacturing efficiency of the light control film 4 and the light control device 9 can be improved, and a large-sized light control film 4 and a large-sized light control device 9 can be manufactured.
In addition, even when the amorphous state is maintained by heating, the film quality of the conventional amorphous transparent conductive layer 3 varies in the thin film 1 with a transparent conductive layer in the light control device 9, and as a result, variation in surface resistance may occur particularly in the width direction of the film base 2.
Specifically, if the length W of the short side 7, which is the length in the width direction, of the film base 2 is 30cm or more, the standard deviation of Xc and Yc in the width direction tends to increase. That is, variations are liable to occur in Xc and Yc in the width direction.
However, in the film 1 with a light-transmitting conductive layer, since the light-transmitting conductive layer 3 is formed so that the light-transmitting conductive layer 3 and the heated light-transmitting conductive layer 3 α satisfy both the above-described formulas (1) and (2), the standard deviation of Xc and Yc in the width direction is small, that is, the deviation of Xc and Yc in the width direction can be suppressed, and specifically, the standard deviation of Xc can be set to 10 × 1019(/cm3) Hereinafter, the standard deviation of Yc is set to 5 (cm)2V · s) or less. Therefore, the thermal stability in the width direction is more excellent.
As shown in fig. 2C, when the length L of the long side 6 of the film base 2 in the TD direction is 30cm or more, the standard deviation between Xc and Yc in the TD direction tends to increase. That is, the Xc and Yc in the TD direction are liable to be deviated.
However, in the film 1 with a light-transmitting conductive layer, since the light-transmitting conductive layer 3 is formed such that the light-transmitting conductive layer 3 and the heated light-transmitting conductive layer 3 α satisfy the above formula (1), the standard deviation of Xc and Yc in the TD direction, that is, the deviation of Xc and Yc in the TD direction can be suppressed, and specifically, the standard deviation of Xc can be set to 10 × 1019(cm 3) or less, and the standard deviation of Yc is set to 5 (cm)2V · s) or less. Therefore, the thermal stability in the TD direction is more excellent.
When the light-transmitting conductive layer 3 contains an indium oxide, it has low surface resistance and excellent light-transmitting properties.
The light-controlling film 4 shown in fig. 3 is excellent in crack resistance and scratch resistance, and therefore is excellent in processability and transportability.
Further, the light control film 4 is excellent in thermal stability, and therefore the light control device 9 provided with the same can suppress variation in light control for a long time.
Since the light control film 4 can use the amorphous transparent conductive layer 3 without passing through the high-temperature heating step, the light control film 4 has excellent design properties even if used in a large area.
The light control film 4 has excellent thermal stability, and therefore the light control device 9 provided with the same can suppress variations in light control over a long period of time.
In one embodiment, the light control film 4 includes 2 films 1 with a transparent conductive layer shown in fig. 1. That is, the film 1 with a light-transmitting conductive layer shown in fig. 1 is used for all of the films 1 with a light-transmitting conductive layer shown in fig. 3. However, for example, only one of the 2 films 1 with a transparent conductive layer may be the film 1 with a transparent conductive layer shown in fig. 1, and the other film may be a conventional film with a transparent conductive layer.
As shown in fig. 1, in one embodiment, the light-transmissive conductive layer 3 is directly disposed on the surface of the film substrate 2, and for example, although not shown, a functional layer may be provided on the upper surface and/or the lower surface of the film substrate 2.
Examples of the functional layer include: easy adhesion layer, primer layer, hard coat layer, oligomer prevention layer, etc. The easy-adhesion layer is provided to improve adhesion between the film base 2 and the transparent conductive layer 3. The undercoat layer is provided for adjusting the reflectance and the optical hue of the film 1 with a light-transmitting conductive layer. The hard coat layer is provided to improve scratch resistance of the film 1 with a light-transmitting conductive layer. The oligomer prevention layer is provided to suppress oligomer deposition from the film base material 2. The material for these functional layers includes a resin composition and an inorganic oxide, and preferably includes a resin composition. These functional layers may be used alone in 1 kind, or in combination in 2 or more kinds.
Examples
The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples unless the gist thereof is exceeded, and various modifications and changes can be made based on the technical idea of the present invention.
The present invention will be described in more detail below with reference to examples and comparative examples. The present invention is not limited to these examples and comparative examples. In addition, specific numerical values such as the blending ratio (content ratio), the physical property value, and the parameter used in the following description may be replaced with upper limits (defined as "lower" or "less" numerical values) or lower limits (defined as "upper" or "more" numerical values) of the corresponding descriptions such as the blending ratio (content ratio), physical property value, and parameter described in the above "specific embodiment".
Example 1
A polyethylene terephthalate (PET) film having a length of 500m, a width of 1300mm (130cm) and a thickness of 188 μm was prepared as a film base 2. The moisture content of the film base 2 was 75. mu.g/cm2。
The film base material 2 was set in a roll-to-roll sputtering apparatus, and vacuum-evacuated. Thereafter, Ar and O are introduced2On the other hand, the transparent conductive layer 3 made of ITO was manufactured to a thickness of 32nm by a DC magnetron sputtering method in a vacuum atmosphere at a gas pressure of 0.4Pa and at a transport speed of 9 m/min. ITO is amorphous. Thus, a light-transmitting conductive film 1 including a light-transmitting substrate 2 and a light-transmitting conductive layer 3 in this order was produced.
As the target, a sintered body (ITO) of 12 mass% tin oxide and 88 mass% indium oxide was used, and the horizontal magnetic field of the magnet was adjusted to 30 mT.
In the sputtering apparatus, 4 oxygen pipes were disposed in each of the regions obtained by dividing the film base 2 into 4 in the width direction. Then, during sputtering, the oxygen supply amount of the 2 oxygen pipes at the left and right ends was set to 0.94 times the oxygen supply amount of the 2 oxygen pipes at the center. Specifically, in 2 oxygen pipes at both left and right ends, O was added2Ratio of flow rate to Ar flow rate (O)2Ar) was set to 0.030, and in 2 oxygen pipes in the center, O was added2Ratio of flow rate to Ar flow rate (O)2Ar) was set to 0.032.
The temperature of the film base 2 during sputtering was set to 0 ℃.
Example 2
Assuming that the transport speed is 4.5 m/min and the thickness of the transparent conductive layer 3 is 65nm, 2 oxygen gas at the right and left ends are mixedO in the pipe2Ratio of flow rate to Ar flow rate (O)2Ar) was set to 0.030, and O in 2 oxygen pipes in the center portion2Ratio of flow rate to Ar flow rate (O)2Ar) was changed to 0.031, and a film 1 with a light-transmitting conductive layer was produced in the same manner as in example 1.
Example 3
A film 1 with a light-transmitting conductive layer was produced in the same manner as in example 2, except that the oxygen supply amount to the 2 oxygen pipes at the left and right ends was set to 0.92 times the oxygen supply amount to the 2 oxygen pipes at the center. Specifically, O was added to 2 oxygen pipes at both left and right ends2Ratio of flow rate to Ar flow rate (O)2Ar) was set to 0.022, and O in 2 oxygen pipes in the center part was added2Ratio of flow rate to Ar flow rate (O)2Ar) was set to 0.024.
Example 4
A film 1 with a transparent conductive layer was produced in the same manner as in example 2, except that the transport speed of the film substrate 2 in the roll-to-roll sputtering apparatus was set to 1.05 times, and the thickness of the transparent conductive layer 3 was set to 62 nm.
Example 5
A film 1 with a light-transmitting conductive layer was produced in the same manner as in example 2, except that the oxygen supply amount to the 2 oxygen pipes at the left and right ends was set to 0.95 times the oxygen supply amount to the 2 oxygen pipes at the center. Specifically, 2 oxygen pipes at both left and right ends were filled with O2Ratio of flow rate to Ar flow rate (O)2Ar) was set to 0.035, and O in the central 2 oxygen pipes2Ratio of flow rate to Ar flow rate (O)2Ar) was set to 0.037.
Comparative example 1
As the film base material 2, a polyethylene terephthalate (PET) film having a length of 1500m, a width of 1300mm (130cm) and a thickness of 50 μm and provided with a thermosetting resin layer (undercoat layer) (the moisture content of the film base material 2 was 18 μ g/cm)2) As a target, a sintered body (ITO) of tin oxide of 10 mass% and indium oxide of 90 mass% was used. In addition, adding O2Ratio of flow rate to Ar flow rate (O)2and/Ar) was set to 0.011, and the transparent conductive layer 3 formed of ITO was formed to a thickness of 25nm while uniformly introducing the oxygen introduction amount in the TD direction (see fig. 2B). A film 1 with a light-transmitting conductive layer was produced in the same manner as in example 1 except for the above items.
Comparative example 2
As the film substrate 2, polyethylene terephthalate (PET) having a length of 3000m, a width of 1300mm (130cm) and a thickness of 188 μm was used, and O was added2Ratio of flow rate to Ar flow rate (O)2/Ar) was set to 0.033, and a translucent conductive layer 3 made of ITO was formed to a thickness of 65nm while uniformly introducing the oxygen introduction amount in the TD direction (see fig. 2B), and a film 1 with a translucent conductive layer was produced in the same manner as in example 2.
The following measurements were carried out on the light-transmitting conductive films obtained in the examples and comparative examples. The results are shown in Table 1.
[ evaluation ]
(1) Thickness and moisture content of film substrate
The thickness of the film substrate 2 was measured using a film thickness meter (manufactured by Kawasaki corporation, under the device name "Digital gauge DG-205"). The thickness of the light-transmitting conductive layer 3 was measured by observing a cross section thereof using a transmission electron microscope (manufactured by hitachi corporation, under the device name "HF-2000").
The moisture content of the film base 2 was determined by JIS K7251-B method (moisture vaporization method).
(2) Carrier density, Hall mobility and standard deviation of light-transmitting conductive layer
The measurement was carried out using a Hall Effect measurement system (product name "HL 5500 PC" manufactured by Bio-Rad). The carrier density was calculated using the thickness of the transparent conductive layer 3 obtained in (1) above.
Specifically, in each of the examples and comparative examples, the carrier density and the hall mobility were determined at 3 points of an 80mm position (P1), a 650mm position (P2), and a 1220mm position (P3), respectively, in the TD direction of a width 1300 mm. Xa and Ya were obtained as the average values of the above points, and the standard deviation was also obtained.
(3) Carrier density, Hall mobility and standard deviation of heated light-transmitting conductive layer
First, each film 1 with a transparent conductive layer was heated at 80 ℃ for 500 hours to form the transparent conductive layer 3 as a heated transparent conductive layer 3 α.
The carrier density and the hall mobility of each heated light-transmitting conductive layer 3 α were measured by a hall effect measurement system (product name "HL 5500 PC" manufactured by Bio-Rad) in the same manner as in the above (3). The measurement positions of the carrier density and the hall mobility in each example are the same as those in (3) above. Then, Xc and Yc were obtained as the average values of the plurality of points, and the standard deviation was also obtained.
(4) Light-transmitting conductive layer and film quality of heated light-transmitting conductive layer
Each of the light-transmitting conductive layers 3 and each of the heated light-transmitting conductive layers 3 α were immersed in hydrochloric acid (concentration: 5% by mass) for 15 minutes, then washed with water and dried, and the electrical resistance between two terminals of about 15mm of each of the light-transmitting conductive layers 3 was measured. When the inter-terminal resistance between 15mm and 15mm exceeded 10 k.OMEGA.it was judged amorphous, and when it did not exceed 10 k.OMEGA.it was judged crystalline.
(5) Evaluation of rate and difference of surface resistance
The surface resistance in the TD direction (see fig. 2B) of the transparent conductive layer 3 of each film 1 with a transparent conductive layer was obtained by the four-terminal method according to JIS K7194 (1994) (the resistance measurement point of each example and comparative example was the same position as the hall effect measurement point), and the average value of the surface resistance was calculated. That is, first, the average value (Ra) in the TD direction of the surface resistance of the transparent conductive layer 3 of each film 1 with a transparent conductive layer is measured. Next, the average value (Rc) in the TD direction of the surface resistance of the heated transparent conductive layer 3 α after heating at 140 ℃ for 1 hour was measured. The resistance change rate (Rc/Ra) of the surface resistance after heating to the surface resistance before heating was obtained, and evaluation was performed according to the following criteria.
O: a rate of change in surface resistance of 0.8 to 1.25
X: the rate of change of surface resistance is less than 0.8, or exceeds 1.25
At the same time, the difference (| Rc-Ra |) between the surface resistances before and after heating was determined.
(6) Tolerance of surface resistance in width direction (TD direction)
In the same manner as in the "evaluation of the rate of change and difference in surface resistance", the surface resistance in the TD direction of the heated transparent conductive layer 3 α of each film 1 with a transparent conductive layer after heating at 140 ℃ for 1 hour was measured. The maximum resistance (maximum resistance: Rmax) and the minimum resistance (minimum resistance: Rmin) in the TD direction were obtained, and the difference (Rmax-Rmin) therebetween was set as the tolerance of the surface resistance, and evaluated according to the following criteria.
O: the tolerance of the surface resistance is 0 omega/□ or more and 10 omega/□ or less
X: the tolerance of the surface resistance exceeds 10 omega/□
(7) Specific resistance of light-transmitting conductive layer and heated light-transmitting conductive layer
The product of the average value of the surface resistances of the transparent conductive layer 3 (before heating) and the heated transparent conductive layer 3 α (after heating) obtained by the method described in (5) "evaluation of the rate and difference of surface resistance, and the thickness of the transparent conductive layer 3 was obtained, thereby obtaining the respective resistivities of the transparent conductive layer 3 (before heating) and the heated transparent conductive layer 3 α (after heating).
[ Table 1]
Figure GDA0002264407140000271
The present invention is provided as an exemplary embodiment of the present invention, but the present invention is merely exemplary and is not to be construed as limiting. Variations of the present invention that are obvious to those skilled in the art are also included in the scope of the claims of the present application.
Industrial applicability
The film with the light-transmitting conductive layer can be used as a light-adjusting film.
Description of the reference numerals
Film with light-transmitting conductive layer
1A film with a 1 st translucent conductive layer
1B No. 2 film with light-transmitting conductive layer
2 film base Material
3 light-transmitting conductive layer
3 alpha heated light-transmitting conductive layer
4 light modulation film
5 dimming function layer
9 light modulation device
10 transparent protective plate
Carrier density of Xa light-transmitting conductive layer
Hall mobility of Ya light-transmitting conductive layer
Xc is heated to the carrier density of the light-transmissive conductive layer,
hall mobility of Yc heated light-transmitting conductive layer
W width (TD direction length)

Claims (12)

1. A film with a light-transmitting conductive layer, comprising a film base material and a light-transmitting conductive layer,
the light-transmitting conductive layer and the heated light-transmitting conductive layer obtained by heating the light-transmitting conductive layer at 140 ℃ for 1 hour are both amorphous,
the carrier density of the light-transmitting conductive layer is Xa × 1019(/cm3) And the Hall mobility is set to Ya (cm)2/V·s)，
The carrier density of the heated transparent conductive layer is set to Xc x 1019(/cm3) Hall mobility is set to Yc (cm)2At a time of/V.s) of the composition,
satisfying both the following formula (1) and formula (2),
the material of the film substrate is an organic material,
0.5≤(Xc/Xa)×(Yc/Ya)≤1.5 (1)
Yc＞Ya (2)。
2. the film with a light-transmitting conductive layer according to claim 1, wherein the film base material has an elongated shape,
the film base material has a width direction length of 30cm or more.
3. The film with a light-transmitting conductive layer according to claim 2, wherein Xc and Yc are measured at 3 points in the width direction of the heated light-transmitting conductive layer,
the standard deviation of the Xc is 10 x 1019(/cm3) In the following, the following description is given,
the standard deviation of Yc is 5 (cm)2V · s) or less.
4. The film with a light-transmitting conductive layer according to claim 1 or 2, wherein the film substrate has a TD direction length of 30cm or more.
5. The film with a light-transmitting conductive layer according to claim 4, wherein Xc and Yc are measured at positions of 3 points in the TD direction of the heated light-transmitting conductive layer,
the standard deviation of the Xc is 10 x 1019(/cm3) In the following, the following description is given,
the standard deviation of Yc is 5 (cm)2V · s) or less.
6. The film with a light-transmitting conductive layer according to claim 1 or 2, wherein the light-transmitting conductive layer contains an indium oxide.
7. A film with a light-transmitting conductive layer, comprising a film base material and a light-transmitting conductive layer,
the light-transmitting conductive layer and the heated light-transmitting conductive layer obtained by heating the light-transmitting conductive layer at 140 ℃ for 1 hour are both amorphous,
the carrier density of the light-transmitting conductive layer is Xa × 1019(/cm3) And the Hall mobility is set to Ya (cm)2/V·s)，
The carrier density of the heated transparent conductive layer is set to Xc x 1019(/cm3) Hall mobility is set to Yc (cm)2At a time of/V.s) of the composition,
satisfying both the following formula (1) and formula (2),
measuring the surface resistance of the heated light-transmitting conductive layer in the TD direction, determining the maximum resistance and the minimum resistance in the TD direction, and obtaining the surface resistance as the difference between the maximum resistance and the minimum resistance, wherein the tolerance of the surface resistance is more than 0 omega/□ and less than 10 omega/□,
the material of the film substrate is an organic material,
0.5≤(Xc/Xa)×(Yc/Ya)≤1.5 (1)
Yc＞Ya (2)。
8. a light control film comprising a film having a 1 st light-transmitting conductive layer, a light control functional layer and a film having a 2 nd light-transmitting conductive layer in this order,
the film with a light-transmitting conductive layer of claim 1 or 7 is the film with a light-transmitting conductive layer of claim 2.
9. The light control film of claim 8, wherein the light control function layer comprises the following materials: a material exhibiting light modulation by changing at least any one of light transmittance and haze by applying at least any one of an electric field and an electric current.
10. A light control device comprising the light control film according to claim 8 or 9 and a transparent protective plate in this order.
11. The method for producing a film having a light-transmitting conductive layer according to any one of claims 1 to 10,
the method comprises a step of forming the light-transmitting conductive layer on the surface of the film base material by a sputtering method,
the light-transmitting conductive layer and the heated light-transmitting conductive layer obtained by heating the light-transmitting conductive layer at 140 ℃ for 1 hour are both amorphous,
the carrier density of the light-transmitting conductive layer is Xa × 1019(/cm3) And the Hall mobility is set to Ya (cm)2/V·s)，
The carrier density of the heated transparent conductive layer is set to Xc x 1019(/cm3) Hall mobility is set to Yc (cm)2At a time of/V.s) of the composition,
satisfying both the following formula (1) and formula (2),
in the step, the amount of oxygen introduced in the TD direction is adjusted in accordance with the impurity gas content and/or oxygen content of the film base material in the TD direction,
the material of the film substrate is an organic material,
0.5≤(Xc/Xa)×(Yc/Ya)≤1.5 (1)
Yc＞Ya (2)。
12. the method of manufacturing a film with a light-transmitting conductive layer according to claim 11, wherein in the step, oxygen is introduced from an oxygen supply pipe divided into a plurality of parts in the TD direction, and an oxygen introduction amount in the TD direction is adjusted.
CN201880030426.8A 2017-05-09 2018-04-25 Film with light-transmitting conductive layer, light-adjusting film and light-adjusting device Active CN110637343B (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP2017092823 2017-05-09
JP2017-092823 2017-05-09
JP2017-155740 2017-08-10
JP2017155740 2017-08-10
JP2018-026722 2018-02-19
JP2018026722A JP6490262B2 (en) 2017-05-09 2018-02-19 Film with light transmissive conductive layer, light control film and light control device
PCT/JP2018/016721 WO2018207622A1 (en) 2017-05-09 2018-04-25 Film with light-transmitting conductive layer, light control film and light control device

Publications (2)

Publication Number Publication Date
CN110637343A CN110637343A (en) 2019-12-31
CN110637343B true CN110637343B (en) 2021-04-27

Family

ID=65476544

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201880030426.8A Active CN110637343B (en) 2017-05-09 2018-04-25 Film with light-transmitting conductive layer, light-adjusting film and light-adjusting device

Country Status (4)

Country Link
JP (2) JP6490262B2 (en)
KR (1) KR102518569B1 (en)
CN (1) CN110637343B (en)
TW (1) TWI770166B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7378938B2 (en) * 2019-02-22 2023-11-14 日東電工株式会社 Light-transparent conductive film
KR20220155287A (en) * 2020-03-19 2022-11-22 닛토덴코 가부시키가이샤 Transparent conductive layer and transparent conductive sheet
JP2022072099A (en) * 2020-10-29 2022-05-17 日東電工株式会社 Transparent conductive film

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09234816A (en) * 1996-02-29 1997-09-09 Mitsui Toatsu Chem Inc Transparent conductive laminate
CN1168076A (en) * 1995-12-20 1997-12-17 三井东压化学株式会社 Transparent conductive laminate and electroluminescence light-emitting element using same
CN104011806A (en) * 2011-12-27 2014-08-27 积水化学工业株式会社 Light Transmissive Conductive Film And Capacitance-Type Touch Panel Using Same
CN105473756A (en) * 2014-05-20 2016-04-06 日东电工株式会社 Transparent conductive film
JP2016157021A (en) * 2015-02-25 2016-09-01 日東電工株式会社 Transparent conductive film for electric field drive type light control element, light control film, and electric field drive type light control element
CN105929576A (en) * 2016-07-04 2016-09-07 京东方科技集团股份有限公司 Dimming device and control method thereof as well as vehicle-mounted device and control method thereof
CN106133662A (en) * 2014-03-26 2016-11-16 日东电工株式会社 Light-permeable conductive film
WO2017057556A1 (en) * 2015-09-30 2017-04-06 積水化学工業株式会社 Light-transmissive conductive film and manufacturing method for annealed light-transmissive conductive film

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4010587B2 (en) * 1995-12-20 2007-11-21 三井化学株式会社 Transparent conductive laminate and electroluminescence light emitting device using the same
JPWO2004105054A1 (en) * 2003-05-20 2006-07-20 出光興産株式会社 Amorphous transparent conductive film, raw material sputtering target, amorphous transparent electrode substrate, manufacturing method thereof, and color filter for liquid crystal display
US8059331B2 (en) 2006-12-21 2011-11-15 Hitachi Chemical Co., Ltd. Light control film and light control glass
JP4843083B2 (en) * 2009-11-19 2011-12-21 出光興産株式会社 In-Ga-Zn-based oxide sputtering target
JP2015215420A (en) * 2014-05-08 2015-12-03 大日本印刷株式会社 Light control film and light control device
JP6627863B2 (en) * 2015-03-27 2020-01-08 リンテック株式会社 Transparent conductive layer laminating film, method for producing the same, and transparent conductive film
WO2017082229A1 (en) * 2015-11-09 2017-05-18 日東電工株式会社 Optically transparent electroconductive film and light control film

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1168076A (en) * 1995-12-20 1997-12-17 三井东压化学株式会社 Transparent conductive laminate and electroluminescence light-emitting element using same
JPH09234816A (en) * 1996-02-29 1997-09-09 Mitsui Toatsu Chem Inc Transparent conductive laminate
CN104011806A (en) * 2011-12-27 2014-08-27 积水化学工业株式会社 Light Transmissive Conductive Film And Capacitance-Type Touch Panel Using Same
CN106133662A (en) * 2014-03-26 2016-11-16 日东电工株式会社 Light-permeable conductive film
CN105473756A (en) * 2014-05-20 2016-04-06 日东电工株式会社 Transparent conductive film
JP2016157021A (en) * 2015-02-25 2016-09-01 日東電工株式会社 Transparent conductive film for electric field drive type light control element, light control film, and electric field drive type light control element
WO2017057556A1 (en) * 2015-09-30 2017-04-06 積水化学工業株式会社 Light-transmissive conductive film and manufacturing method for annealed light-transmissive conductive film
CN105929576A (en) * 2016-07-04 2016-09-07 京东方科技集团股份有限公司 Dimming device and control method thereof as well as vehicle-mounted device and control method thereof

Also Published As

Publication number Publication date
TWI770166B (en) 2022-07-11
JP6490262B2 (en) 2019-03-27
CN110637343A (en) 2019-12-31
KR102518569B1 (en) 2023-04-05
JP7039506B2 (en) 2022-03-22
KR20200003806A (en) 2020-01-10
JP2019123243A (en) 2019-07-25
TW201907416A (en) 2019-02-16
JP2019029335A (en) 2019-02-21

Similar Documents

Publication Publication Date Title
JP6637565B2 (en) Light transmitting conductive film
US10777709B2 (en) Substrate with transparent electrode and method for producing same
US20140370275A1 (en) Substrate with transparent electrode and method for manufacturing same
CN111391427B (en) Light-transmitting conductive film and light-adjusting film
CN110637343B (en) Film with light-transmitting conductive layer, light-adjusting film and light-adjusting device
KR101809296B1 (en) Transparent electode and electronic device comprising the same
WO2018207622A1 (en) Film with light-transmitting conductive layer, light control film and light control device
KR102032011B1 (en) Conductive laminate and transparent electrode comprising thereof
JP6126395B2 (en) Manufacturing method of substrate with transparent electrode
KR101832521B1 (en) Transparent electode and electronic device comprising the same
CN113168934B (en) Film with light-transmitting conductive layer for touch panel, polarizing film with light-transmitting conductive layer, and touch panel display device
JP7320510B2 (en) SUBSTRATE WITH TRANSPARENT ELECTRODE AND PRODUCTION METHOD THEREOF
WO2020189229A1 (en) Method for manufacturing substrate with transparent electrode attached thereon
KR102136549B1 (en) Method for preparing conductive film
TW202016337A (en) Light-transmitting conductive film and light control film
CN115666928A (en) Light-transmitting conductive sheet, touch sensor, light-adjusting element, photoelectric conversion element, heat ray control member, antenna, electromagnetic wave shielding member, and image display device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant