WO2017170757A1

WO2017170757A1 - Electrochromic dimming member, light-transmissive conductive film, and electrochromic dimming element

Info

Publication number: WO2017170757A1
Application number: PCT/JP2017/013038
Authority: WO
Inventors: 秀行米澤; 望藤野; 健太渡辺; 智剛梨木
Original assignee: 日東電工株式会社
Priority date: 2016-04-01
Filing date: 2017-03-29
Publication date: 2017-10-05
Also published as: ES2959787T3

Abstract

This electrochromic dimming member is provided with, in order: a transparent base material; a light-transmissive conductive layer; and an electrochromic dimming layer. The light-transmissive conductive layer is provided with, in order: a first indium-based conductive oxide layer; a metal layer; and a second indium-based conductive oxide layer.

Description

Electrochromic light control member, light transmissive conductive film, and electrochromic light control device

The present invention relates to an electrochromic light control member, a light-transmitting conductive film, and an electrochromic light control device, and more specifically, an electrochromic light control member, a light-transmitting conductive film for use therein, and an electrochromic light control device including the same It relates to an element.

Conventionally, a current-driven dimmer using an electrochromic material whose light transmission amount, color, and the like change by an electrochemical redox reaction is known.

For example, an electrochromic element that includes a working electrode sheet, a counter electrode sheet, an electrochromic compound, and an electrolyte, and the working electrode sheet includes a glass sheet and a transparent conductive oxide film has been proposed (see, for example, Patent Document 1). In the electrochromic element of Patent Document 1, a single layer made of a crystalline ITO film is used as the transparent conductive oxide film.

Japanese Patent Application Laid-Open No. 2015-172666

However, in the electrochromic device, from the viewpoint of improving the responsiveness of the electrochromic compound and saving energy, the surface resistance value of the electrode substrate such as the working electrode sheet is required to be reduced (low resistance). As a method for reducing resistance, a method of increasing the thickness of the ITO film is studied.

However, if the thickness of the ITO film is increased, cracks are likely to occur when the electrode substrate is bent. Since the electrochromic element is current-driven, if a crack occurs in the electrode substrate, the redox function of the electrochromic compound at the crack is inhibited, resulting in a problem that the dimming function is significantly reduced. Specifically, for example, the uniformity at the time of coloring or decoloring is lowered, and color unevenness may occur.

An object of the present invention is to provide an electrochromic light control member, a light-transmitting conductive film, and an electrochromic light control device that are excellent in low resistance and bending resistance.

This invention [1] is equipped with a transparent base material, a transparent conductive layer, and an electrochromic light control layer in order, and the transparent conductive layer includes a first indium conductive oxide layer, a metal layer, And an electrochromic light control member comprising a second indium-based conductive oxide layer in order.

This invention [2] contains the electrochromic light control member as described in [1] whose surface resistance value of the said transparent conductive layer is 50 ohms / square or less.

This invention [3] contains the electrochromic light control member as described in [1] or [2] whose near-infrared average transmissivity in the said light transmissive conductive layer in 800 nm or more and 1500 nm or less is 80% or less. Yes.

According to the present invention [4], the electrochromic tone according to any one of [1] to [3], wherein the light-transmitting conductive layer has an average near-infrared reflectance at 800 nm to 1500 nm of 10% or more. Includes a light member.

According to the present invention [5], the light-transmitting conductive layer has a ratio (R ₁ / R ₀ ) between the initial surface resistance value R ₀ and the surface resistance value R ₁ after bending the light-transmitting conductive layer. The electrochromic light control member according to any one of [1] to [4], which is 1.05 or less.

In the present invention [6], the transparent base material includes the electrochromic light control member according to any one of [1] to [5], which is a flexible film.

According to the present invention [7], any one of the first indium conductive oxide layer and the second indium conductive oxide layer is an amorphous film. The electrochromic light control member described in the item is included.

The present invention [8] is a light transmissive conductive film for use in the electrochromic light control member according to any one of [1] to [7], comprising a transparent substrate and a light transmissive conductive layer The light-transmitting conductive layer includes a first indium-based conductive oxide layer, a metal layer, and a second indium-based conductive oxide layer in order from the transparent substrate. Includes film.

The present invention [9] is provided on the surface opposite to the electrochromic light control layer with respect to the electrochromic light control member according to any one of [1] to [7] and the transparent substrate. And an electrochromic light control device including the electrode substrate.

According to the electrochromic light control member, the light transmissive conductive film and the electrochromic light control element of the present invention, since the light transmissive conductive layer is excellent in low resistance, the electrochromic light control layer is excellent in responsiveness and energy saving. In addition, since the light-transmitting conductive layer is excellent in bending resistance, the occurrence of cracks can be suppressed even when the light-transmitting conductive film is bent in the process of manufacturing or handling. Reduction can be suppressed.

FIG. 1 shows a cross-sectional view of one embodiment of the electrochromic light control member of the present invention. FIG. 2 shows a cross-sectional view of one embodiment of the light-transmitting conductive film of the present invention constituting the electrochromic light control member shown in FIG. FIG. 3: shows sectional drawing of one Embodiment of the electrochromic light control element of this invention provided with the electrochromic light control member shown in FIG. FIG. 4 is a modification of the electrochromic light control member, and shows a cross-sectional view of the electrochromic light control member in which the first indium-based conductive oxide layer is directly disposed on the upper surface of the transparent substrate. FIG. 5 is a modification of the electrochromic light control member, and shows a cross-sectional view of the electrochromic light control member in which the inorganic layer is interposed between the protective layer and the first indium-based conductive oxide layer. FIG. 6 shows a schematic perspective view of a test for measuring the bending resistance of a light-transmitting conductive film.

In FIG. 1, the vertical direction of the paper is the vertical direction (thickness direction, first direction), the upper side of the paper is the upper side (one side in the thickness direction, the first direction), and the lower side of the paper is the lower side (thickness direction). The other side, the other side in the first direction). In FIG. 1, the left-right direction on the paper surface is the left-right direction (width direction, second direction orthogonal to the first direction), the left side on the paper surface is the left side (second side in the second direction), and the right side on the paper surface is the right side (the other side in the second direction). ). In FIG. 1, the paper thickness direction is the front-rear direction (a third direction orthogonal to the first direction and the second direction), the front side of the paper is the front side (the third direction one side), and the back side of the paper surface is the rear side (the third direction). The other side). Specifically, it conforms to the direction arrow in each figure.

1. Electrochromic light control member An electrochromic light control member (hereinafter also referred to as EC light control member) has a film shape (including a sheet shape) having a predetermined thickness, and a predetermined direction (front-rear direction) orthogonal to the thickness direction. And it extends in the left-right direction, that is, the surface direction, and has a flat upper surface and a flat lower surface (two main surfaces). The EC light control member is, for example, a component such as a light control panel provided in the light control device, that is, not the light control device. That is, the EC dimming member is a component for producing a dimming device and the like, and does not include a light source such as an LED or an external power source, and is a device that can be distributed and used industrially.

Specifically, as shown in FIG. 1, the EC light control member 1 includes, in order, a transparent substrate 2, a protective layer 3, a light-transmissive conductive layer 4, and an electrochromic light control layer 5 (hereinafter referred to as EC). And a light control layer.). That is, the EC light control member 1 includes a transparent base material 2, a protective layer 3 disposed above the transparent base material 2, a light transmissive conductive layer 4 disposed above the protective layer 3, and a light transmissive property. And an EC light control layer 5 disposed on the upper side of the conductive layer 4. Preferably, the EC light control member 1 includes only the transparent base material 2, the protective layer 3, the light transmissive conductive layer 4, and the EC light control layer 5. Hereinafter, each layer will be described in detail.

2. Transparent base material The transparent base material 2 is a part of the electrode substrate of the EC light control member 1, is the lowermost layer of the EC light control member 1, and is a support material that ensures the mechanical strength of the EC light control member 1. . The transparent substrate 2 supports the light transmissive conductive layer 4 and the EC light control layer 5 together with the protective layer 3.

The transparent substrate 2 is made of, for example, a polymer film.

The polymer film has transparency and flexibility. Examples of the material of the polymer film include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, for example, (meth) acrylic resins (acrylic resin and / or methacrylic resin) such as polymethacrylate, Olefin resins such as polyethylene, polypropylene, cycloolefin polymer (COP), for example, polycarbonate resin (PC), polyether sulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, cellulose resin, polystyrene resin, norbornene resin Etc. These polymer films can be used alone or in combination of two or more. From the viewpoints of transparency, flexibility, heat resistance, mechanical properties, etc., polyester resins, olefin resins, and PC are preferable, and PET, COP, and PC are more preferable.

The thickness of the transparent substrate 2 is, for example, 2 μm or more, preferably 20 μm or more, and for example, 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less, and further preferably 80 μm or less. By setting the thickness of the transparent base material 2 within the above range, the bending resistance, and thus the color uniformity of the EC light control layer 5 can be further improved.

3. Protective layer The protective layer 3 is a part of the electrode substrate of the EC light control member 1 and makes it difficult to cause scratches on the upper surfaces of the light-transmissive conductive layer 4 and the EC light control layer 5 (that is, excellent scratch resistance). A scratch-protecting layer. The protective layer 3 is an optical adjustment layer that adjusts the optical physical properties of the EC light control member 1 in order to suppress visual recognition of the pattern when the light transmissive conductive layer 4 is formed in a pattern shape such as a wiring pattern. But there is.

The protective layer 3 has a film shape (including a sheet shape), and is disposed on the entire upper surface of the transparent substrate 2 so as to be in contact with the upper surface of the transparent substrate 2.

The protective layer 3 is formed from a resin composition.

Resin composition contains, for example, resin, particles and the like. The resin composition preferably contains a resin, and more preferably consists only of a resin.

Examples of the resin include a curable resin, a thermoplastic resin (for example, a polyolefin resin), and preferably a curable resin.

Examples of the curable resin include an active energy ray-curable resin that is cured by irradiation with active energy rays (specifically, ultraviolet rays, electron beams, etc.), for example, a thermosetting resin that is cured by heating, and the like. Preferably, an active energy ray curable resin is used.

Examples of the active energy ray-curable resin include a polymer having a functional group having a polymerizable carbon-carbon double bond in the molecule. Examples of such a functional group include a vinyl group and a (meth) acryloyl group (methacryloyl group and / or acryloyl group).

Examples of the active energy ray-curable resin include (meth) acrylic resin (acrylic resin and / or methacrylic resin) containing a functional group in the side chain.

These resins can be used alone or in combination of two or more.

Examples of the particles include inorganic particles and organic particles. Examples of the inorganic particles include silica particles, for example, metal oxide particles made of zirconium oxide, titanium oxide, and the like, for example, carbonate particles such as calcium carbonate. Examples of the organic particles include crosslinked acrylic resin particles.

The thickness of the protective layer 3 is, for example, 0.1 μm or more, preferably 1 μm or more, and for example, 10 μm or less, preferably 5 μm or less. The thickness of the protective layer 3 is measured by, for example, cross-sectional observation with a transmission electron microscope (TEM).

4). Light-transmissive conductive layer The light-transmissive conductive layer 4 is a part of the electrode substrate of the EC light control member 1, and is a conductive layer that supplies current from an external power source (not shown) to the EC light control layer 5. is there. The light transmissive conductive layer 4 is also a transparent conductive layer.

As shown in FIG. 1, the light transmissive conductive layer 4 has a film shape (including a sheet shape), and is disposed on the entire upper surface of the protective layer 3 so as to be in contact with the upper surface of the protective layer 3. ing.

The light-transmitting conductive layer 4 includes, in order from the transparent substrate 2 side, a first indium-based conductive oxide layer 6 (hereinafter also abbreviated as a first oxide layer), a metal layer 7, and a second indium-based layer. And a conductive oxide layer 8 (hereinafter also abbreviated as a second oxide layer). That is, the light-transmissive conductive layer 4 is formed on the first oxide layer 6 disposed on the protective layer 3, the metal layer 7 disposed on the first oxide layer 6, and the metal layer 7. And a second oxide layer 8 to be disposed. The light transmissive conductive layer 4 is preferably composed of only the first oxide layer 6, the metal layer 7, and the second oxide layer 8.

The surface resistance value of the light-transmitting conductive layer 4 (initial surface resistance value R ₀ and surface resistance value R ₁ after bending) is, for example, 50Ω / □ or less, preferably 30Ω / □ or less, more preferably 20Ω. / Ω or less, more preferably 15Ω / □ or less, for example, 0.1Ω / □ or more, preferably 1Ω / □ or more, more preferably 5Ω / □ or more.

The ratio (R ₁ / R ₀ ) between the initial surface resistance value R ₀ of the light transmissive conductive layer 4 and the surface resistance value R ₁ after the light transmissive conductive layer 4 is bent is, for example, 1.05 or less. Preferably, it is 1.02 or less, More preferably, it is 1.00 or less, for example, 0.95 or more. By setting the ratio in the above range, the bending resistance is excellent and an increase in the surface resistance value due to bending can be suppressed.

As shown in FIG. 6, the light-transmitting conductive layer 4 after bending is disposed on a mandrel having a diameter of 5 mm, with the light-transmitting conductive film 9 described later being placed outside. The light-transmitting conductive layer 4 of the light-transmitting conductive film 9 is bent when a load of 50 g / mm is applied downward with respect to the width of the light-transmitting conductive film 9.

The surface resistance value of the light transmissive conductive layer 4 is measured, for example, on the surface of the light transmissive conductive layer 4 of the light transmissive conductive film 9 in accordance with the four-probe method of JIS K7194 (1994). Is obtained.

The specific resistance of the light-transmitting conductive layer 4 is, for example, 2.5 × 10 ⁻⁴ Ω · cm or less, preferably 2.0 × 10 ⁻⁴ Ω · cm or less, more preferably 1.1 × 10 ^{− 4} Ω · cm or less, for example, 0.01 × 10 ⁻⁴ Ω · cm or more, preferably 0.1 × 10 ⁻⁴ Ω · cm or more, more preferably 0.5 × 10 ^−4. Ω · cm or more.

The specific resistance of the light transmissive conductive layer 4 depends on the thickness of the light transmissive conductive layer 4 (total thickness of the first oxide layer, the metal layer 7 and the second oxide layer 8) and the surface of the light transmissive conductive layer 4. It is calculated using the resistance value.

The thickness of the light-transmissive conductive layer 4, that is, the total thickness of the first oxide layer 6, the metal layer 7, and the second oxide layer 8 is, for example, 20 nm or more, preferably 40 nm or more, more preferably 60 nm or more. More preferably, it is 80 nm or more, and for example, 150 nm or less, preferably 120 nm or less, more preferably 100 nm or less.

5). First Indium-Based Conductive Oxide Layer The first oxide layer 6 is a conductive layer that imparts conductivity to the light-transmissive conductive layer 4 together with a metal layer 7 and a second oxide layer 8 described later. The first oxide layer 6, together with the second oxide layer 8 to be described later, suppresses the visible light reflectance of the metal layer 7 and optical adjustment for improving the visible light transmittance of the light-transmissive conductive layer 4. It is also a layer.

The first oxide layer 6 is the lowermost layer in the light transmissive conductive layer 4 and has a film shape (including a sheet shape). The first oxide layer 6 is in contact with the entire upper surface of the protective layer 3 and in contact with the upper surface of the protective layer 3. To be arranged.

The first oxide layer 6 contains indium oxide (In ₂ O ₃ ). The first oxide layer 6 includes, for example, at least one metal selected from the group consisting of Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W. It may be doped with atoms.

The conductive oxide (indium conductive oxide) forming the first oxide layer 6 may contain only indium (In) as a metal element, and (half) other than indium (In) It may contain a metal element. Preferably, the main metal element is indium (In). A conductive oxide whose main metal element is indium has excellent barrier properties.

The conductive oxide can further improve conductivity, transparency, and bending resistance by containing one or more (semi) metal elements as impurity elements. The ratio of the number of impurity metal elements contained in the first oxide layer 6 to the number of atoms of the main metal element In (number of atoms of the impurity metal element / number of In atoms) is, for example, less than 0.50, preferably Is 0.40 or less, more preferably 0.30 or less, and still more preferably 0.20 or less. For example, 0.01 or more, preferably 0.05 or more, more preferably 0.00. 10 or more. Thereby, it is excellent in transparency and bending resistance.

The conductive oxide forming the first oxide layer 6 is preferably indium tin composite oxide (ITO), indium gallium composite oxide (IGO), or indium gallium zinc composite from the viewpoint of low resistance and transparency. An oxide (IGZO) etc. are mentioned, More preferably, ITO is mentioned.

The content of tin oxide (SnO ₂ ) contained in ITO is, for example, 0.5% by mass or more, preferably 3% by mass or more with respect to the total amount of tin oxide and indium oxide (In ₂ O ₃ ). More preferably, it is 6% by mass or more, more preferably 8% by mass or more, particularly preferably 10% by mass or more, and for example, 35% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 13% by mass or less. The content of indium oxide (In ₂ O ₃ ) is the remainder of the content of tin oxide (SnO ₂ ). By setting the content of tin oxide (SnO ₂ ) contained in ITO within a suitable range, it is easy to suppress film quality change over time of the ITO film.

The conductive oxide of the first oxide layer 6 may be either crystalline or amorphous, but is preferably amorphous from the viewpoint of uniform formation of the metal layer 7. That is, the first oxide layer 6 is preferably an amorphous film, more preferably an amorphous ITO film.

In the present invention, in a planar TEM image at a magnification of 25,000 times, when the area ratio occupied by crystal grains is 80% or less (preferably 0% or more and 50% or less), it is assumed to be amorphous and 80% If it is over, it is assumed to be crystalline.

The content ratio of ITO in the first oxide layer 6 is, for example, 95% by mass or more, preferably 98% by mass or more, more preferably 99% by mass or more, and for example, 100% by mass or less.

The thickness T1 of the first oxide layer 6 is, for example, 5 nm or more, preferably 20 nm or more, more preferably 30 nm or more, and for example, 60 nm or less, preferably 50 nm or less. If the thickness of the 1st oxide layer 6 is the said range, it will be easy to adjust the visible light transmittance | permeability of the transparent conductive layer 4 to a high level. The thickness of the first oxide layer 6 is measured, for example, by cross-sectional observation with a transmission electron microscope (TEM).

6). Metal Layer The metal layer 7 is a conductive layer that imparts conductivity to the light transmissive conductive layer 4 together with the first oxide layer 6 and the second oxide layer 8. The metal layer 7 is also a low resistance layer that lowers the surface resistance value of the light transmissive conductive layer 4. The metal layer 7 is also preferably an infrared reflecting layer for imparting a high infrared reflectance (particularly, an average reflectance of near infrared rays).

The metal layer 7 has a film shape (including a sheet shape), and is disposed on the upper surface of the first oxide layer 6 so as to be in contact with the upper surface of the first oxide layer 6.

The metal forming the metal layer 7 is not limited as long as it has a small surface resistance. For example, Ti, Si, Nb, In, Zn, Sn, Au, Ag, Cu, Al, Co, Cr, Ni , Pb, Pd, Pt, Cu, Ge, Ru, Nd, Mg, Ca, Na, W, Zr, Ta, and Hf, or one or more of them An alloy containing these metals can be given.

The metal is preferably silver (Ag) or a silver alloy, more preferably a silver alloy. If the metal is silver or a silver alloy, the resistance value of the light-transmitting conductive layer 4 can be reduced, and in addition, the light-transmitting conductive layer 4 having a particularly high average reflectance in the near infrared region can be obtained. It can also be suitably applied to applications used outdoors or in windows.

The silver alloy contains silver as a main component and other metals as subcomponents, and specifically includes, for example, an Ag—Cu alloy, an Ag—Pd alloy, an Ag—Sn alloy, and an Ag—In alloy. , Ag-Pd-Cu alloy, Ag-Pd-Cu-Ge alloy, Ag-Cu-Au alloy, Ag-Cu-Sn alloy, Ag-Cu-In alloy, Ag-Ru-Cu alloy, Ag-Ru-Au An alloy, an Ag—Nd alloy, an Ag—Mg alloy, an Ag—Ca alloy, an Ag—Na alloy, and the like can be given. From the viewpoint of low resistance and wet heat durability, the silver alloy is preferably an Ag—Cu alloy, an Ag—Cu—In alloy, an Ag—Cu—Sn alloy, an Ag—Pd alloy, or an Ag—Pd—Cu alloy. It is done.

The silver content in the silver alloy is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, and for example, 99.9% by mass or less. The content ratio of the other metals in the silver alloy is the balance of the silver content ratio described above.

The thickness T3 of the metal layer 7 is, for example, 1 nm or more, preferably 5 nm or more, more preferably 8 nm or more, and for example, 20 nm or less, preferably 10 nm or less. By setting the thickness of the metal layer 7 in the above range, the surface resistance value and the bending resistance of the light-transmitting conductive layer 4 are good, and the visible light transmittance and infrared reflectance can be further improved. . As a result, the color uniformity, responsiveness, and heat shielding properties of the EC light control device 13 are excellent. The thickness T3 of the metal layer 7 is measured by, for example, cross-sectional observation with a transmission electron microscope (TEM).

7). Second Indium-Based Conductive Oxide Layer The second oxide layer 8 is a conductive layer that imparts conductivity to the light-transmissive conductive layer 4 together with the first oxide layer 6 and the metal layer 7. The second oxide layer 8 is also an optical adjustment layer for suppressing the visible light reflectance of the metal layer 7 and improving the visible light transmittance of the light-transmissive conductive layer 4.

The second oxide layer 8 is the uppermost layer in the light transmissive conductive layer 4 and has a film shape (including a sheet shape). The second oxide layer 8 is in contact with the entire upper surface of the metal layer 7 and the upper surface of the metal layer 7. To be arranged.

Examples of the conductive oxide that forms the second oxide layer 8 include the conductive oxides exemplified in the first oxide layer 6. Preferably, the conductive oxide whose main metal element is indium (In). Thing, More preferably, ITO is mentioned. The second oxide layer 8 is preferably an amorphous film, more preferably an amorphous ITO film.

The conductive oxide that forms the second oxide layer 8 may be the same as or different from the conductive oxide that forms the first oxide layer 6, but from the viewpoint of flex resistance, conductivity, and transparency. Preferably, the conductive oxide is the same as the first oxide layer 6.

In the second oxide layer 8, the ratio of the number of impurity metal element atoms to the number of atoms of the main metal element In (the number of impurity metal element atoms / the number of In atoms) It is equal to or greater than (number of element atoms / number of In atoms) (for example, 0.001 or more).

When the second oxide layer 8 is made of ITO, the content of tin oxide (SnO ₂ ) contained in the ITO and the atomic ratio of Sn to In are the same as those of the first oxide layer 6.

The content ratio of ITO in the second oxide layer 8 is, for example, 95% by mass or more, preferably 98% by mass or more, more preferably 99% by mass or more, and for example, 100% by mass or less.

The thickness T2 of the second oxide layer 8 is, for example, 5 nm or more, preferably 20 nm or more, more preferably 30 nm or more, and for example, 60 nm or less, preferably 50 nm or less. If the thickness T2 of the second oxide layer 8 is in the above range, the visible light transmittance of the light transmissive conductive layer 4 can be easily adjusted to a high level. The thickness T2 of the second oxide layer 8 is measured by, for example, cross-sectional observation with a transmission electron microscope (TEM).

The ratio (T2 / T1) of the thickness T2 of the second oxide layer 8 to the thickness T1 of the first oxide layer 6 is, for example, 0.5 or more, preferably 0.75 or more. 5 or less, preferably 1.25 or less.

The ratio (T2 / T3) of the thickness T2 of the second oxide layer 8 to the thickness T3 of the metal layer 7 is, for example, 2.0 or more, preferably 3.0 or more, and for example, 10 or less, Preferably, it is 8.0 or less.

8). EC Light Control Layer The EC light control layer 5 is a light control layer whose light transmittance and color are changed by a current passed through the light transmissive conductive layer 4.

The EC light control layer 5 is the uppermost layer of the EC light control member 1 and has a film shape (including a sheet shape), and the light transmissive conductive layer 4 is formed on the entire upper surface of the light transmissive conductive layer 4. It arrange | positions so that the upper surface of may be contacted.

The EC light control layer 5 includes, in order, a first electrochromic compound layer 10 (first EC layer), an electrolyte layer 11, and a second electrochromic compound layer 12 (second EC layer). That is, the EC light control layer 5 is disposed on the first EC layer 10 disposed on the light transmissive conductive layer 4, the electrolyte layer 11 disposed on the first EC layer 10, and the electrolyte layer 11. The second EC layer 12 is provided. The EC light control layer 5 preferably includes only the first EC layer 10, the electrolyte layer 11, and the second EC layer 12.

The thickness of the EC light control layer 5, that is, the total thickness of the first EC layer 10, the electrolyte layer 11, and the second EC layer 12 is, for example, 0.1 μm or more and 5000 μm or less.

9. First Electrochromic Compound Layer The first EC layer 10 is a light control layer that changes its light transmittance and color according to the current flowing through the first EC layer 10 together with the second EC layer 12 described later.

The first EC layer 10 is the lowermost layer in the EC light control layer 5 and has a film shape (including a sheet shape). The light transmissive conductive layer 4 is formed on the entire upper surface of the light transmissive conductive layer 4. It arrange | positions so that an upper surface may be contacted.

The electrochromic compound that forms the first EC layer 10 is not limited, and examples thereof include tungsten oxide (for example, WO ₃ ), molybdenum oxide, vanadium oxide, vanadium oxide, indium oxide, iridium oxide, nickel oxide, and Prussian blue. Inorganic electrochromic compounds; for example, organic electrochromic compounds such as phthalocyanine compounds, styryl compounds, viologen compounds, polypyrrole, polyaniline, polythiophene (for example, poly (ethylenedioxythiophene) -poly (styrenesulfonic acid)) Etc. Preferably, tungsten oxide and polythiophene are used.

The thickness of the first EC layer 10 is, for example, 0.01 μm or more, preferably 0.05 μm or more, and for example, 3000 μm or less, preferably 100 μm or less, more preferably 10 μm or less, still more preferably 0 .5 μm or less.

10. Electrolyte Layer The electrolyte layer 11 is a layer that efficiently conducts electricity to the electrochromic compound in the first EC layer 10 and the second EC layer 12.

The electrolyte layer 11 is arranged on the entire upper surface of the first EC layer 10 so as to be in contact with the upper surface of the first EC layer 10.

The electrolyte layer 11 may be formed from a liquid electrolyte and a sealing material that seals the liquid electrolyte, or may be formed from a solid electrolyte membrane.

The electrolyte that forms the electrolyte layer 11 is not limited. For example, LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ COO, KCl, NaClO ₃ , NaCl, NaBF ₄ , NaSCN, KBF ₄ , Mg (ClO ₄ ) ₂ , Mg (BF ₄ ) ₂ and other alkali metal salts or alkaline earth metal salts. Moreover, a quaternary ammonium salt, a quaternary phosphonium salt, etc. are mentioned.

When a liquid electrolyte is used as the electrolyte layer 11, an organic solvent is preferably used together with the electrolyte. The organic solvent is not limited as long as the electrolyte can be dissolved, carbonates such as ethylene carbonate, propylene carbonate, and methyl carbonate; for example, furans such as tetrahydrofuran; for example, γ-butyrolactone, 1,2-dimethoxyethane, 1, Examples include 3-dioxolane, 4-methyl-1,3-dioxolane, methyl formate, methyl acetate, methyl propionate, acetonitrile, propylene carbonate, N, N-dimethylformamide and the like.

The electrolyte layer 11 is preferably an electrolyte membrane containing an electrolyte, an organic solvent, and a binder resin. Such an electrolyte layer can be obtained, for example, by mixing an electrolyte solution in which an electrolyte is dissolved in an organic solvent and a binder resin, and drying.

Examples of the binder resin include acrylic resins such as polymethyl methacrylate.

The thickness of the electrolyte layer 11 is, for example, 0.01 μm or more, preferably 1 μm or more, and for example, 3000 μm or less, preferably 1000 μm or less, more preferably 100 μm or less.

11. Second Electrochromic Compound Layer The second EC layer 12 is a light control layer that changes its light transmittance and color in accordance with the current flowing through the second EC layer 12 together with the first EC layer 10.

The second EC layer 12 is the uppermost layer of the EC light control layer 5 and has a film shape (including a sheet shape) so that the entire upper surface of the electrolyte layer 11 is in contact with the upper surface of the electrolyte layer 11. Have been placed.

The electrochromic compound that forms the second EC layer 12 is not limited, and examples include the compounds exemplified in the first EC layer 10. Preferably, tungsten oxide and polythiophene are used.

The thickness of the second EC layer 12 is, for example, 0.01 μm or more, preferably 0.05 μm or more, and for example, 3000 μm or less, preferably 100 μm or less, more preferably 10 μm or less, and still more preferably 0 .5 μm or less.

12 Light-transmissive conductive film Among the members constituting the EC light control member 1, the transparent substrate 2, the protective layer 3 and the light-transmissive conductive layer 4 constitute one embodiment of the light-transmissive conductive film 9 of the present invention. .

That is, as shown in FIG. 2, the light transmissive conductive film 9 is a laminated film including a transparent substrate 2, a protective layer 3, and a light transmissive conductive layer 4 in order. That is, the light transmissive conductive film 9 includes the transparent base material 2, the protective layer 3 disposed above the transparent base material 2, and the light transmissive conductive layer 4 disposed above the protective layer 3. Preferably, the light transmissive conductive film 9 includes only the transparent substrate 2, the protective layer 3, and the light transmissive conductive layer 4.

The light transmissive conductive film 9 has a film shape (including a sheet shape) having a predetermined thickness, extends in the surface direction, and has a flat upper surface and a flat lower surface. The light transmissive conductive film 9 is a component for producing the EC light control member 1, specifically, an electrode substrate used for the EC light control member 1. The light transmissive conductive film 9 does not include a light source such as an LED or an external power supply, and is a device that can be distributed industrially and used industrially. The light transmissive conductive film 9 is a film that transmits visible light, and includes a transparent conductive film.

The light-transmitting conductive film 9 may be a heat-shrinkable light-transmitting conductive film 9 or may be a non-heated, that is, non-shrinkable light-transmitting conductive film 9. From the viewpoint of excellent bending resistance, the heat-transparent conductive film 9 is preferably heat-shrinked.

The total thickness of the light transmissive conductive film 9 is, for example, 2 μm or more, preferably 20 μm or more, and for example, 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less.

13. Next, a method for manufacturing the EC light control member 1 will be described.

To manufacture the EC light control member 1, first, the light transmissive conductive film 9 is produced, and then the EC light control layer 5 is disposed on the light transmissive conductive film 9.

The light transmissive conductive film 9 is obtained, for example, by disposing the protective layer 3 and the light transmissive conductive layer 4 on the transparent substrate 2 in the order described above.

In this method, as shown in FIG. 1, first, a transparent substrate 2 is prepared.

Next, the resin composition is disposed on the upper surface of the transparent substrate 2 by, for example, wet processing.

Specifically, first, the resin composition is applied to the upper surface of the transparent substrate 2. Thereafter, when the resin composition contains an active energy ray-curable resin, the active energy ray is irradiated.

Thereby, a film-shaped protective layer 3 is formed on the entire upper surface of the transparent substrate 2. That is, a transparent substrate with a protective layer comprising the transparent substrate 2 and the protective layer 3 is obtained.

Then, if necessary, the protective layer-equipped transparent base material is degassed.

In order to degas the transparent substrate with a protective layer, the transparent substrate with a protective layer is, for example, 1 × 10 ⁻¹ Pa or less, preferably 1 × 10 ⁻² Pa or less, and for example, 1 × 10 Leave in a vacuum atmosphere of ^-3 Pa or higher. The degassing process is performed using, for example, an exhaust device (specifically, a turbo molecular pump or the like) provided in a dry apparatus.

By this degassing treatment, a part of the water contained in the transparent substrate 2 and a part of the organic substance contained in the protective layer 3 are released to the outside.

Next, the light transmissive conductive layer 4 is disposed on the upper surface of the protective layer 3 by, for example, a dry method.

Specifically, each of the first oxide layer 6, the metal layer 7, and the second oxide layer 8 is sequentially disposed by a dry method.

Examples of the dry method include a vacuum deposition method, a sputtering method, and an ion plating method. Preferably, a sputtering method is used. Specifically, a magnetron sputtering method can be mentioned.

Examples of the gas used in the sputtering method include an inert gas such as Ar. Moreover, reactive gas, such as oxygen, can be used together as needed. When the reactive gas is used in combination, the flow rate ratio of the reactive gas is not particularly limited, and is a ratio of the reactive gas flow rate to the inert gas flow rate, for example, 0.1 / 100 or more, preferably 1/100 or more, and for example, 5/100 or less.

Specifically, in the formation of the first oxide layer 6, an inert gas and a reactive gas are preferably used in combination as the gas. In forming the metal layer 7, an inert gas is preferably used alone as the gas. In the formation of the second oxide layer 8, an inert gas and a reactive gas are preferably used in combination as the gas.

When employing the sputtering method, examples of the target material include the above-described conductive oxides or metals constituting each layer.

There is no limitation in the power supply used by sputtering method, For example, DC power supply, MF / AC power supply, and RF power supply are used individually or together, Preferably, DC power supply is mentioned.

Also preferably, when the first oxide layer 6 is formed by a sputtering method, the transparent substrate 2 (and the protective layer 3) is cooled. Specifically, the transparent substrate 2 (and the protective layer 3) is cooled by bringing the lower surface of the transparent substrate 2 into contact with a cooling device (for example, a cooling roll). Thereby, when the first oxide layer 6 is formed, water contained in the transparent substrate 2 and organic matter contained in the protective layer 3 are released by vapor deposition heat generated by sputtering, and the water is first. Excessive inclusion in the oxide layer 6 can be suppressed. The cooling temperature is, for example, −30 ° C. or more, preferably −10 ° C. or more, and for example, 60 ° C. or less, preferably 40 ° C. or less, more preferably 20 ° C. or less, and further preferably 0 ° C. Is less than.

Thereby, as shown in FIG. 2, the transparent base material 2, the protective layer 3, and the light transmissive conductive layer 4 (the 1st oxide layer 6, the metal layer 7, and the 2nd oxide layer 8) are provided in order. A light transmissive conductive film 9 is obtained.

Next, a heating step is performed as necessary. That is, the light transmissive conductive film 9 is heated. Bending resistance can be improved by heating and shrinking the light-transmitting conductive film 9.

As heating conditions, the heating temperature is, for example, 50 ° C. or higher, preferably 80 ° C. or higher, and for example, 180 ° C. or lower, preferably 140 ° C. or lower. The heating time is, for example, 1 minute or more, preferably 10 minutes or more, and for example, 120 minutes or less, preferably 60 minutes or less. By setting the heating condition within the above range, the light transmissive conductive film 9 can be easily contracted while maintaining the amorphousness of the first oxide layer 6 and the second oxide layer 8.

Heating may be performed in any of air atmosphere, inert atmosphere, and vacuum.

By this heating step, the light transmissive conductive film 9 is obtained in which the light transmissive conductive film 9 is slightly contracted in at least one direction (preferably in any one direction) of the front and rear direction and the left and right direction.

The shrinkage rate is, for example, 0.1% or more, preferably 0.2% or more, with respect to the front-rear direction length or the left-right direction length 100% of the light-transmitting conductive film 9 before shrinkage, For example, it is 1.0% or less, preferably 0.5% or less, and more preferably 0.3% or less.

Next, the EC light control layer 5 is disposed on the light transmissive conductive film 9.

A known material can be used for the EC light control layer 5.

The EC light control layer 5 is disposed on the upper surface of the light transmissive conductive film 9 so that the EC light control layer 5 and the second indium conductive oxide layer 8 are in contact with each other.

Thereby, as shown in FIG. 1, an EC light control member 1 including a transparent base material 2, a protective layer 3, a light-transmissive conductive layer 4, and an EC light control layer 5 in this order is obtained.

In addition, the above-described manufacturing method can be performed by a roll-to-roll method. Moreover, a part or all can also be implemented by a batch system.

Further, the light transmissive conductive layer 4 can be formed into a pattern shape such as a wiring pattern by etching, if necessary.

14 Action Effect According to the EC light control member 1, the light-transmitting conductive layer 4 has a low surface resistance value and excellent low resistance. Therefore, the responsiveness and energy saving of the EC light control layer 5 are excellent. Moreover, since the EC light control member 1 is excellent in bending resistance, the occurrence of cracks in the light transmissive conductive layer 4 can be suppressed even when the EC light control member 1 is bent. Therefore, it is possible to suppress a decrease in the light control function of the EC light control layer 5.

In addition, if both the first oxide layer 6 and the second oxide layer 8 are amorphous films, the bending resistance of the EC light control member 1 is further improved.

Further, according to the light transmissive conductive film 9 used for the EC light control member 1, the light transmissive conductive layer 4 has a low surface resistance value and excellent low resistance. Therefore, the responsiveness and energy saving of the EC light control layer 5 arrange | positioned on the surface of the transparent conductive film 9 can be improved. Moreover, since the light transmissive conductive film 9 is excellent in bending resistance, the occurrence of cracks in the light transmissive conductive layer 4 can be suppressed even when the light transmissive conductive film 9 is bent. Therefore, the fall of the light control function of the EC light control layer 5 arrange | positioned on the surface of the transparent conductive film 9 can be suppressed.

Further, according to the light transmissive conductive film 9, since the light transmissive conductive layer 4 including the first oxide layer 6 and the second oxide layer 8 is provided on the upper surface and the lower surface of the metal layer 7, the light transmissive conductive film 9 is provided. The layer 4 generally includes a metal layer 7 having a high visible light reflectivity (specifically, for example, a metal layer 7 having a reflectivity of 15% or more, more preferably 30% or more at a wavelength of 550 nm). Visible light transmittance can be realized. The visible light transmittance of the light transmissive conductive film 9 is, for example, 60% or more, preferably 80% or more, more preferably 85% or more, and for example, 95% or less. Thereby, it is excellent in transparency.

Further, according to the light transmissive conductive film 9, the light transmissive conductive layer 4 includes the metal layer 7 (for example, the metal layer 7 containing silver or silver alloy) having a high reflectance in the near infrared region. The average reflectance is high, and heat rays such as sunlight can be blocked efficiently. Therefore, it can be suitably applied to a light control device used in an environment where the panel temperature is likely to rise (for example, outdoors, windows, etc.).

The average reflectance in the near infrared (wavelength 800 nm or more and 1500 nm or less) of the light-transmissive conductive film 9 is, for example, 10% or more, preferably 20% or more, more preferably 40% or more, and further preferably 50% or more. For example, it is 95% or less, preferably 90% or less.

The average transmittance of the light transmissive conductive film 9 in the near infrared (wavelength 800 nm or more and 1500 nm or less) is, for example, 80% or less, preferably 60% or less, more preferably 50% or less, and still more preferably 40% or less. Also, for example, 10% or more, preferably 20% or more.

15. Electrochromic Dimming Element The electrochromic dimming element 13 (hereinafter also abbreviated as EC dimming element) has a film shape (including a sheet shape) having a predetermined thickness, and a predetermined direction (front and back) orthogonal to the thickness direction. And a flat upper surface and a flat lower surface (two main surfaces). The EC light control element 13 is a component such as a light control panel provided in the light control device, that is, it is not a light control device. That is, the EC dimming element 13 is a component for manufacturing a dimming device and the like, and does not include a light source such as an LED or an external power source, and is a device that can be distributed and used industrially.

Specifically, as shown in FIG. 3, the EC light control device 13 is a laminated film including the EC light control member 1 and an electrode substrate (upper electrode substrate) 15. That is, the EC light control element 13 includes the EC light control member 1 and the electrode substrate 15 disposed on the upper side of the EC light control member 1. Preferably, the EC light control element 13 includes only the EC light control member 1 and the electrode substrate 15. Hereinafter, each layer will be described in detail.

The electrode substrate 15 is preferably the light transmissive conductive film 9 described above, and includes the light transmissive conductive layer 4, the protective layer 3, and the transparent base material 2 in this order. The electrode substrate 15 is disposed on the upper side of the EC light control member 1. Specifically, the electrode substrate 15 is formed on the entire surface of the EC light control layer 5 (the surface opposite to the transparent base material 2 of the lower light-transmitting conductive film 9) of the EC light control layer 5. It arrange | positions so that the upper surface and the lower surface of the transparent conductive layer 4 may contact.

That is, in the EC light control element 13, the two light transmissive conductive films 9 are disposed so as to face each other so that each light transmissive conductive layer 4 is in contact with the surface (lower surface or upper surface) of the EC light control layer 5. ing.

According to the EC light control device 13, the light-transmitting conductive layer 4 has a low surface resistance value and excellent low resistance. Therefore, the responsiveness and energy saving of the EC light control layer 5 are excellent. Moreover, since the EC light control element 13 is excellent in bending resistance, the occurrence of cracks in the light transmissive conductive layer 4 can be suppressed even when the EC light control element 13 is bent. Therefore, it is possible to suppress a decrease in the light control function of the EC light control layer 5. That is, it is possible to suppress a decrease in uniformity during coloring or decoloring of the EC light control layer 5 and to suppress occurrence of color unevenness. Moreover, since the EC light control element 13 has a good near-infrared reflectance, it is also excellent in heat shielding properties.

16. Modified Example In the modified example, the same reference numerals are assigned to the same members and steps as those in the above-described embodiment, and the detailed description thereof is omitted.

In one embodiment of the EC light control member 1, as shown in FIG. 1, the protective layer 3 is interposed between the transparent substrate 2 and the first oxide layer 6. However, for example, as shown in FIG. 4, the first oxide layer 6 can be disposed directly on the upper surface of the transparent substrate 2. That is, the EC light control member 1 includes the transparent base material 2, the light transmissive conductive layer 4, and the EC light control layer 5 in this order. On the other hand, the EC light control member 1 does not include the protective layer 3.

In one embodiment of the EC light control member 1, the first oxide layer 6 is directly disposed on the upper surface of the protective layer 3 as shown in FIG. However, for example, as shown in FIG. 5, the inorganic layer 16 can be interposed between the protective layer 3 and the first oxide layer 6.

The inorganic layer 16 is an optical adjustment layer that adjusts the optical physical properties of the EC light control member 1 so as to suppress the visual recognition of the wiring pattern in the light transmissive conductive layer 4 together with the protective layer 3. The inorganic layer 16 has a film shape (including a sheet shape), and is disposed on the entire upper surface of the protective layer 3 so as to be in contact with the upper surface of the protective layer 3. The inorganic layer 16 has predetermined optical properties, and is prepared from inorganic materials such as oxides and fluorides, for example. The thickness of the inorganic layer 16 is 1 nm or more, preferably 5 nm or more, more preferably 10 nm or more, and for example, 80 nm or less, preferably 40 nm or less, more preferably 25 nm or less.

In addition, although the said modification demonstrated EC light control member 1, it is the same also about the transparent conductive film 9 and the EC light control element 13. FIG.

Further, as shown in FIG. 3, the EC light control device 13 uses the light-transmitting conductive film 9 of the present invention as the upper electrode substrate 15. For example, although not shown, the upper electrode substrate 15 is transparent. It can also be comprised from the base material 2 and a single conductive layer. Examples of the single conductive layer include an ITO film (crystalline ITO film, amorphous ITO film), an IGO film, and an IGZO film.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not limited to an Example and a comparative example at all. In addition, specific numerical values such as a blending ratio (content ratio), physical property values, and parameters used in the following description are described in the above-mentioned “Mode for Carrying Out the Invention”, and a blending ratio corresponding to them ( Substituting the upper limit value (numerical value defined as “less than” or “less than”) or the lower limit value (number defined as “greater than” or “exceeded”) such as content ratio), physical property values, parameters, etc. be able to.

[Light transmissive conductive film]
Example 1
(Preparation of film substrate and formation of protective layer)
First, a transparent substrate made of a long polyethylene terephthalate (PET) film and having a thickness of 50 μm was prepared.

Next, an ultraviolet curable resin made of an acrylic resin was applied to the upper surface of the transparent substrate, and cured by ultraviolet irradiation to form a protective layer made of a cured resin layer and having a thickness of 2 μm. Thereby, the transparent base material roll with a protective layer provided with a transparent base material and a protective layer was obtained.

(Formation of first indium-based conductive oxide layer)
Next, the transparent substrate roll with a protective layer was installed in a vacuum sputtering apparatus, and was evacuated until the atmospheric pressure when not transported was 4 × 10 ⁻³ Pa (degassing treatment). At this time, a part of the transparent substrate with a protective layer was transported without introducing the sputtering gas (Ar and O ₂ ), and it was confirmed that the atmospheric pressure increased to 2 × 10 ⁻² Pa. Thereby, it was confirmed that a sufficient amount of gas remained in the transparent substrate roll with a protective layer.

Next, while feeding the transparent base material roll with a protective layer, a first indium conductive oxide layer made of amorphous ITO and having a thickness of 40 nm was formed on the upper surface of the cured resin layer by sputtering.

Specifically, using a direct current (DC) power source under a vacuum atmosphere of Ar pressure and a pressure of 0.3 Pa into which Ar and O ₂ were introduced (flow rate ratio: Ar: O ₂ = 100: 1.4) A target made of a sintered body of tin oxide and 88% by mass of indium oxide was sputtered.

When the first indium conductive oxide layer is formed by sputtering, the lower surface of the transparent substrate roll with a protective layer (specifically, the lower surface of the transparent substrate) is brought into contact with a −5 ° C. cooling roll. Then, the transparent substrate roll with a protective layer was cooled.

(Formation of metal layer)
A metal layer made of an Ag—Cu alloy and having a thickness of 8 nm was formed on the upper surface of the first indium-based conductive oxide layer by sputtering.

Specifically, an Ag alloy (manufactured by Mitsubishi Materials, product number “No. 317”) was sputtered using a direct current (DC) power source as a power source in a vacuum atmosphere of 0.3 Pa at which Ar was introduced.

(Formation of second indium-based conductive oxide layer)
A second indium-based conductive oxide layer made of amorphous ITO and having a thickness of 38 nm was formed on the upper surface of the metal layer by sputtering.

Specifically, using a direct current (DC) power source in a vacuum atmosphere at a pressure of 0.4 Pa into which Ar and O ₂ were introduced (flow rate ratio: Ar: O ₂ = 100: 1.5), A target made of a sintered body of tin oxide and 88% by mass of indium oxide was sputtered.

As a result, a light-transmitting conductive film in which a protective layer, a first indium-based conductive oxide layer, a metal layer, and a second indium-based conductive oxide layer were sequentially formed on the transparent substrate was obtained ( (See FIG. 2).

Example 2
The light transmissive conductive film obtained in Example 1 was subjected to a heating step under the atmosphere at 140 ° C. for 30 minutes. Thereby, each direction (conveyance direction) of the light-transmitting conductive film was contracted by 0.3% to obtain the light-transmitting conductive films of the examples.

Examples 3-7
Except having changed the thickness of a metal layer or a transparent base material into the thickness of Table 1, it carried out similarly to Example 1, and obtained the translucent conductive film of each Example.

Examples 8-9
A light-transmissive conductive film of each example was obtained in the same manner as in Example 1 except that the material of the transparent substrate was changed to the material shown in Table 1 (COP: cycloolefin polymer, PC: polycarbonate resin). .

Comparative Example 1
The light transmittance of Comparative Example 1 was the same as Example 1 except that the thickness of the first indium-based conductive oxide layer was 30 nm and the metal layer and the second indium-based conductive oxide layer were not formed. A conductive film was obtained.

Comparative Example 2
The light transmittance of Comparative Example 2 was the same as Example 1 except that the thickness of the first indium-based conductive oxide layer was 100 nm and the metal layer and the second indium-based conductive oxide layer were not formed. A conductive film was obtained.

Comparative Example 3
A light-transmitting conductive film was obtained in the same manner as in Example 1 except that the thickness of the first indium-based conductive oxide layer was 25 nm and the metal layer and the second indium-based conductive oxide layer were not formed. It was. Next, a heating step was performed on the light transmissive conductive film under the atmosphere at 140 ° C. for 60 minutes. Thereby, one direction (conveying direction) of the light transmissive conductive film was contracted by 0.3%, and the light transmissive conductive film of Comparative Example 3 was obtained.

(Measurement)
(1) Thickness Sections of the protective layer, the first indium conductive oxide layer, the metal layer, and the second indium conductive oxide layer using a transmission electron microscope (manufactured by Hitachi, Ltd., HF-2000) It was measured by observation. Further, the thickness of the transparent substrate was measured using a film thickness meter (Digital Dial Gauge DG-205 manufactured by Peacock).

(2) Surface resistance value of light-transmitting conductive layer The initial surface resistance value _R0 of the light-transmitting conductive layer was measured according to the four-probe method of JIS K7194 (1994). The results are shown in Table 1.

(3) Flexural resistance test The light transmissive conductive films of each Example and each Comparative Example were cut into a width of 10 mm and a length of 150 mm, respectively. The cut light-transmitting conductive film 9 was placed on the mandrel 20 having a diameter of 5 mm so that the light-transmitting conductive layer 4 was on the outside and the transparent substrate 2 was in contact with the mandrel 20. Subsequently, both ends of the light transmissive conductive film 9 in the length direction were fastened with clips 21, and a 500 g weight 22 was attached to the center of the clip 21 (see FIG. 6). That is, the light transmissive conductive film 9 was bent by applying a load of 50 g / mm toward the width of the light transmissive conductive film 9 downward. This bent state was maintained for 10 seconds.

The surface resistance value R ₁ after bending is measured in the same manner as the above-mentioned four-probe method, and then the ratio (R ₁ / R) between the initial surface resistance value R ₀ and the surface resistance value R ₁ after bending. ₀ ) was calculated. The results are shown in Table 1.

Further, the diameter of the mandrel 20 is changed, and the light transmissive conductive film 9 is bent by the same method (see FIG. 6) as described above to obtain the diameter (limit diameter) where R ₁ / R ₀ exceeds 1.05. It was. Specifically, the diameter of the mandrel 20 was changed from a large diameter to a small diameter every 1 mm, and the diameter of the mandrel 20 immediately before R ₁ / R ₀ exceeded 1.05 was measured. The results are shown in Table 1.

(4) Visible light transmittance Using a haze meter (manufactured by Suga Test Instruments Co., Ltd., device name “HGM-2DP”), the total light transmittance of the light transmissive conductive film was measured and taken as the visible light transmittance. The results are shown in Table 1.

(5) Near-infrared average transmittance, near-infrared average reflectance Using a spectrophotometer (manufactured by Hitachi Keiki Co., Ltd., device name “U-4100”), the average transmittance of the light-transmitting conductive film at a wavelength of 800-1500 nm. The rate and average reflectance were measured. The results are shown in Table 1.

[EC light control device]
Example 1
Two light-transmitting conductive films of Example 1 were prepared and bent by a method similar to the above (see FIG. 6) using a mandrel having a diameter of 5 mm. These films were used as a lower electrode substrate and an upper electrode substrate, respectively.

EC light control layer (laminated body of first electrochromic compound layer / electrolyte layer / second electrochromic compound layer) was prepared. The EC light control layer is laminated between the lower electrode substrate and the upper electrode substrate so that each light-transmissive conductive layer is in contact with the surface (upper surface or lower surface) of the EC light control layer. A light control element was manufactured (see FIG. 3).

The EC light control layer has a first EC compound layer of a WO ₃ film having a thickness of 200 nm, and a second EC compound layer having a thickness of 60 nm of poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid). ) It was a membrane. The electrolyte layer was an electrolyte membrane (thickness 80 μm) obtained by mixing polymethyl methacrylate with an electrolyte solution obtained by dissolving LiCF ₃ SO ₃ in acetonitrile / propylene carbonate solvent and drying.

(Examples 2 to 9)
An EC light control device of each example was manufactured in the same manner as described above except that the light-transmitting conductive film of each example was used for each of the lower electrode substrate and the upper electrode substrate.

(Comparative Examples 1 to 3)
An EC light control device of each comparative example was manufactured in the same manner as described above except that the light-transmissive conductive film of each comparative example was used for each of the lower electrode substrate and the upper electrode substrate.

(1) Color uniformity test (flexibility test)
A current was passed through the EC light control elements of each Example and each Comparative Example, and changes in the color of the EC light control layer at the bent portion were confirmed.

When the EC light control layer is uniformly changed in the bent portion, it is evaluated as ◯, and when the EC light control layer is slightly uneven, it is evaluated as △, and the EC light control layer is uneven. The case was evaluated as x. The results are shown in Table 1.

(2) Responsiveness test The EC light control device of each Example and each Comparative Example was manufactured in the same manner as described above, without performing mandrel bending on the light transmissive conductive film. When current was passed through each EC light control element and the responsiveness of the EC light control layer was measured, it was confirmed that excellent response was exhibited according to the low surface resistance value of the light transmissive conductive layer. .

Specifically, the evaluation was as follows. The results are shown in Table 1.

O: The color of the EC light control element changed within 10 seconds after the voltage was applied.

Δ: The color of the EC light control element changed within 10 seconds to 1 minute after the voltage was applied.

X: The color of the EC light control element did not change even after 1 minute after the voltage was applied.

(3) Heat-shielding test EC dimming elements of Examples and Comparative Examples were produced in the same manner as described above without performing mandrel bending on the light-transmitting conductive film. The heat shielding property at the time of coloring of each EC light control element was measured. Specifically, the EC light control device during coloring was irradiated with an infrared lamp, and the heat passing through the EC light control device was subjected to sensory evaluation by hand. At that time, the case where heat was not felt was evaluated as “◯”, the case where heat was slightly felt was evaluated as “Δ”, and the case where heat was clearly felt was evaluated as “X”. The results are shown in Table 1.

Although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an example and should not be interpreted in a limited manner. Variations of the present invention that are apparent to one of ordinary skill in the art are within the scope of the following claims.

The electrochromic light control member, the light-transmissive conductive film and the electrochromic light control element of the present invention can be applied to various industrial products, and can be suitably used for light control devices such as light control panels. .

DESCRIPTION OF SYMBOLS 1 Electrochromic light control member 2 Transparent base material 4 Light transmission conductive layer 5 Electrochromic light control layer 6 1st indium type conductive oxide layer 7 Metal layer 8 2nd indium type conductive oxide layer 9 Light transmission conductive Film 13 Electrochromic light control element 15 Electrode substrate

Claims

A transparent base material, a light transmissive conductive layer, and an electrochromic light control layer are provided in this order.
The electrochromic light control member, wherein the light transmissive conductive layer includes a first indium conductive oxide layer, a metal layer, and a second indium conductive oxide layer in order.
The electrochromic light control member according to claim 1, wherein a surface resistance value of the light transmissive conductive layer is 50Ω / □ or less.
The electrochromic light-modulating member according to claim 1, wherein the light-transmitting conductive layer has an average near-infrared transmittance of 800 nm or more and 1500 nm or less of 80% or less.
The electrochromic light control member according to claim 1, wherein a near-infrared average reflectance at 800 nm to 1500 nm of the light transmissive conductive layer is 10% or more.
The light-transmitting conductive layer has a ratio (R 1 / R 0 ) between the initial surface resistance value R 0 and the surface resistance value R 1 after bending the light-transmitting conductive layer is 1.05 or less. The electrochromic light control member according to claim 1, wherein the electrochromic light control member is provided.
The electrochromic light control member according to claim 1, wherein the transparent substrate is a flexible film.
2. The electrochromic light control member according to claim 1, wherein each of the first indium conductive oxide layer and the second indium conductive oxide layer is an amorphous film.
A light transmissive conductive film for use in the electrochromic light control member according to claim 1,
A transparent base material and a light-transmitting conductive layer are provided in order,
The light transmissive conductive layer includes a first indium conductive oxide layer, a metal layer, and a second indium conductive oxide layer in order from the transparent base material. Conductive film.
The electrochromic light control member according to claim 1;
An electrochromic light control device comprising: an electrode substrate provided on a surface opposite to the electrochromic light control layer with respect to the transparent substrate.