JP2018041059A - Liquid-crystal light-adjusting member, translucent conductive film, and liquid-crystal light-adjusting element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid-crystal light-adjusting member having excellent near infrared reflection properties without attaching an IR reflection layer to on the surface of a transparent substrate, a translucent conductive film for use therein, and a liquid-crystal light-adjusting element having the same.SOLUTION: A liquid-crystal light-adjusting member 1 is provided with, in the following order, a transparent substrate 2, a translucent conductive layer 4, and a liquid-crystal light-adjusting layer 5, the translucent conductive layer 4 being provided with, in the following order, a first inorganic oxide layer 6, a metal layer 7, and a second inorganic oxide layer 8.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a liquid crystal light control member, a light-transmitting conductive film for use therein, and a liquid crystal light control device including the same.

  In recent years, the demand for liquid crystal light control devices represented by smart windows and the like has been increasing from the viewpoints of reduction in heating and cooling loads and design. Liquid crystal light control elements are used for various applications such as window glass, partitions, and interiors of buildings and vehicles.

  As a liquid crystal light control device, for example, a liquid crystal light control device including a base, a conductive film, and a liquid crystal-resin composite in order has been proposed (see, for example, Patent Document 1 below).

JP 2009-133922 A

  On the other hand, in the liquid crystal light control device of Patent Document 1, indium tin composite oxide (ITO) is used as the conductive film. Indium tin composite oxide (ITO) is inferior in heat shielding properties because of its low near-infrared reflection characteristics. Therefore, when the liquid crystal light control device of Patent Document 1 is used in an environment (such as outdoors) that is affected by sunlight, the liquid crystal-resin composite of the liquid crystal light control device of Patent Document 1 There is a problem of deterioration due to heat.

  In order to solve such a problem, it is also considered to attach an IR reflecting layer for blocking heat rays such as sunlight on the surface of the substrate. However, in such a case, there is a problem that the thickness of the liquid crystal light adjusting device increases corresponding to the thickness of the IR reflecting layer, and the manufacturing cost increases.

  An object of the present invention is to provide a liquid crystal light control member having excellent near-infrared reflection characteristics without attaching an IR reflection layer to the surface of a transparent substrate, a light-transmitting conductive film for use therein, and the same The object is to provide a liquid crystal light control device.

  The present invention [1] includes a transparent base material, a light transmissive conductive layer, and a liquid crystal light control layer in this order, and the light transmissive conductive layer includes a first inorganic oxide layer, a metal layer, and a second inorganic layer. The liquid crystal light control member is sequentially provided with an oxide layer.

  In this liquid crystal light control member, the light transmissive conductive layer includes a metal layer having a high reflectance in the near infrared region. Therefore, for example, the light-transmitting conductive layer has a higher near-infrared reflectance than that of only a conductive oxide, and can efficiently block heat rays such as sunlight from the liquid crystal light control layer. It can be used in environments affected by light (such as outdoors).

  Moreover, in this liquid-crystal light control member, it is excellent in a near-infrared reflective characteristic, without sticking an IR reflection layer on the surface of a transparent base material. Therefore, the thickness of the liquid crystal light control member can be reduced, and the manufacturing cost can be reduced.

  In the present invention [2], the second inorganic oxide layer includes the liquid crystal light control member according to the above [1] containing crystal grains.

  According to this liquid crystal light control member, the light transmissive conductive layer includes the second inorganic oxide layer containing crystal grains. Therefore, when the liquid crystal light control layer contains water as a solvent, the water can be prevented from passing through the second inorganic oxide layer in the thickness direction and entering the metal layer.

  The present invention [3] includes the liquid crystal light control member according to the above [1] or [2], wherein the second inorganic oxide layer is a semi-crystalline film having an amorphous part and a crystalline part. It is out.

  According to this liquid crystal light control member, the second inorganic oxide layer is a semi-crystalline film having an amorphous part and a crystalline part. Therefore, the wet heat durability is further improved.

  The present invention [4] is a light transmissive conductive film for use in the liquid crystal light control member according to any one of the above [1] to [3], comprising a transparent substrate and a light transmissive conductive layer. The light-transmitting conductive layer includes a light-transmitting conductive film including a first inorganic oxide layer, a metal layer, and a second inorganic oxide layer in order.

  In this light transmissive conductive film, the light transmissive conductive layer includes a metal layer having a high reflectance in the near infrared region. Therefore, when a light-transmitting conductive film is used for the above-mentioned liquid crystal light control member, the light-transmitting conductive layer has, for example, an average near-infrared reflectance as compared with a case where the light-transmitting conductive layer is made of only a conductive oxide. High, can efficiently block heat rays such as sunlight from the liquid crystal light control layer, and can be used in environments that are affected by sunlight (such as outdoors).

  In addition, this light-transmitting conductive film is excellent in near-infrared reflection characteristics without attaching an IR reflection layer to the surface of the transparent substrate. Therefore, the thickness of the light transmissive conductive film can be reduced, and the manufacturing cost can be reduced.

  This invention [5] is provided in the surface on the opposite side of the said liquid-crystal light control layer with respect to the liquid-crystal light control member as described in any one of said [1]-[3], and the said transparent base material. The liquid crystal light control element provided with an electrode substrate is included.

  This liquid crystal light control device includes the liquid crystal light control member described above. Therefore, the liquid crystal light control device can efficiently block heat rays such as sunlight from the liquid crystal light control layer, and can be used in an environment affected by sunlight (such as outdoors).

  Moreover, this liquid crystal light control element is equipped with the above-mentioned liquid crystal light control member. Therefore, the thickness of the liquid crystal light control device can be reduced, and the manufacturing cost can be reduced.

  According to the liquid crystal light control member of the present invention, the light-transmitting conductive film used for the same, and the liquid crystal light control device including the same, it is possible to perform the operation without attaching an IR reflection layer to the surface of the transparent substrate. Excellent infrared reflection characteristics. Therefore, the thickness of the liquid crystal light control member can be reduced, and the manufacturing cost can be reduced.

FIG. 1 shows a cross-sectional view of an embodiment of the liquid crystal light control member of the present invention. 2A and B show a partially enlarged view of the light-transmitting conductive film shown in FIG. 1, FIG. 2A shows a schematic view when the second inorganic oxide layer is a completely crystalline film, and FIG. The schematic diagram in case the 2nd inorganic oxide layer is a semi-crystalline film | membrane is shown. FIG. 3 shows a cross-sectional view of one embodiment of the light-transmitting conductive film of the present invention constituting the liquid crystal light control member shown in FIG. FIG. 4 shows a cross-sectional view of an embodiment of the liquid crystal light control device of the present invention including the liquid crystal light control member shown in FIG. FIG. 5 is a modification of the liquid crystal light control member, and shows a cross-sectional view of the liquid crystal light control member in which the first inorganic oxide layer is directly disposed on the upper surface of the transparent substrate. FIG. 6 is a modification of the liquid crystal light control member, and shows a cross-sectional view of the liquid crystal light control member in which the inorganic layer is interposed between the protective layer and the first inorganic oxide layer.

  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 is the left-right direction (width direction, second direction orthogonal to the first direction), the left side of the paper is the left side (second direction one side), and the right side of the paper is the right side (second 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. Liquid crystal light control member The liquid crystal light control member has a film shape (including a sheet shape) having a predetermined thickness, and extends in a predetermined direction (front and rear direction and left and right direction, that is, a surface direction) orthogonal to the thickness direction, and is flat. It has an upper surface and a flat lower surface (two main surfaces). A liquid crystal light control member is one component, such as a light control panel with which a light control apparatus is equipped, that is, it is not a light control apparatus. That is, the liquid crystal light control member is a component for producing a light control 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 used industrially and distributed alone.

  Specifically, as shown in FIG. 1, the liquid crystal light control member 1 includes a transparent base material 2, a protective layer 3, a light-transmissive conductive layer 4, and a liquid crystal light control layer 5 in order in the thickness direction. Is a laminated film. That is, the liquid crystal 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 a liquid crystal light control layer 5 disposed on the upper side of the conductive layer 4. Preferably, the liquid crystal light control member 1 includes only the transparent base material 2, the protective layer 3, the light transmissive conductive layer 4, and the liquid crystal 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 liquid crystal light control member 1, is the lowermost layer of the liquid crystal light control member 1, and is a support material that ensures the mechanical strength of the liquid crystal light control member 1. . The transparent substrate 2 supports the light transmissive conductive layer 4 and the liquid crystal 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, And olefin resins such as polyethylene, polypropylene, and cycloolefin polymers such as polycarbonate resin, polyether sulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, cellulose resin, polystyrene resin, norbornene resin, and the like. These polymer films can be used alone or in combination of two or more. From the viewpoints of transparency, flexibility, heat resistance, mechanical properties, and the like, preferably, olefin resins and polyester resins are used, and more preferably, cycloolefin polymers and PET are used.

  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.

  The transparent substrate 2 preferably contains a small amount of water from the viewpoint of maintaining the amorphous nature of the first inorganic oxide layer 6. That is, in the transparent substrate 2, the polymer film preferably contains water.

3. Protective layer The protective layer 3 is a part of the electrode substrate of the liquid crystal light control member 1, and makes it difficult to cause scratches on the upper surfaces of the light-transmissive conductive layer 4 and the liquid crystal 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 liquid crystal 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.

  A resin composition contains resin, particle | grains, etc., for example. 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, 0.01 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 liquid crystal light control member 1 and is used to apply an electric field from an external power source (not shown) to the liquid crystal light control layer 5. It is a conductive layer. 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 transmissive conductive layer 4 includes a first inorganic oxide layer 6, a metal layer 7, and a second inorganic oxide layer 8 in order from the transparent substrate 2 side in the thickness direction. That is, the light transmissive conductive layer 4 includes the first inorganic oxide layer 6 disposed on the protective layer 3, the metal layer 7 disposed on the first inorganic oxide layer 6, and the metal layer 7. And a second inorganic oxide layer 8 disposed thereon. The light transmissive conductive layer 4 is preferably composed of only the first inorganic oxide layer 6, the metal layer 7, and the second inorganic oxide layer 8.

  The surface resistance value of the light-transmitting conductive layer 4 is, for example, 40Ω / □ or less, preferably 30Ω / □ or less, more preferably 20Ω / □ or less, and further preferably 15Ω / □ or less. 1Ω / □ or more, preferably 1Ω / □ or more, more preferably 5Ω / □ or more.

  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-transmissive conductive layer 4 is, for example, 2.5 × 10 ⁻⁴ Ω · cm or less, preferably 2.0 × 10 ⁻⁴ Ω · cm or less, and 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 includes the thickness of the light transmissive conductive layer 4 (total thickness of the first inorganic oxide layer, the metal layer 7 and the second inorganic oxide layer 8) and the light transmissive conductive layer 4. It is calculated using the surface resistance value.

  Further, the average reflectance of the near-infrared ray (wavelength 850 to 2500 nm) of the light-transmitting conductive layer 4 is, for example, 10% or more, preferably 20% or more, more preferably 50% or more. 95% or less, preferably 90% or less.

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

5. First Inorganic Oxide Layer In the first inorganic oxide layer 6, hydrogen derived from water contained in the transparent substrate 2 and carbon derived from organic substances contained in the protective layer 3 enter the metal layer 7. This is a barrier layer that prevents this. Further, the first inorganic oxide layer 6, together with the second inorganic oxide layer 8 described later, suppresses the visible light reflectance of the metal layer 7 and improves the visible light transmittance of the light-transmissive conductive layer 4. It is also an optical adjustment layer. The first inorganic oxide layer 6 is preferably a conductive layer that imparts conductivity to the light-transmissive conductive layer 4 together with the metal layer 7 described later, and more preferably a transparent conductive layer.

  The first inorganic 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 inorganic oxide layer 6 is formed on the entire upper surface of the protective layer 3 and on the upper surface of the protective layer 3. It is arranged to come into contact.

  Examples of the inorganic oxide forming the first inorganic oxide layer 6 include In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, W, Fe, Examples thereof include metal oxides formed from at least one metal selected from the group consisting of Pb, Ni, Nb, and Cr. If necessary, the metal oxide can be further doped with a metal atom shown in the above group.

  The inorganic oxide preferably includes an oxide containing indium oxide (indium oxide-containing oxide) from the viewpoint of reducing the surface resistance value and securing excellent transparency. The indium oxide-containing oxide may contain only indium (In) as a metal element, or may contain a (semi) metal element other than indium (In). In the indium oxide-containing oxide, the main metal element is preferably indium (In). The indium oxide-containing oxide whose main metal element is indium has an excellent barrier function and can easily suppress corrosion of the metal layer 7 due to the influence of water or the like.

  The indium oxide-containing oxide can further improve conductivity, transparency, and durability by containing one or more (semi) metal elements as impurity elements. In the first inorganic oxide layer 6, the content atomic ratio of the impurity metal element to the number of atoms of the main metal element In (the number of impurities metal atoms / the number of In atoms) is, for example, less than 0.50, Preferably, it is 0.40 or less, more preferably 0.30 or less, and further preferably 0.20 or less. For example, 0.01 or more, preferably 0.05 or more, more preferably 0. 10 or more. Thereby, the inorganic oxide layer excellent in transparency and wet heat durability is obtained.

  Specific examples of the indium oxide-containing oxide include, for example, indium zinc composite oxide (IZO), indium gallium composite oxide (IGO), indium gallium zinc composite oxide (IGZO), and indium tin composite oxide (ITO). More preferably, indium tin composite oxide (ITO) is used. “ITO” in this specification may be a complex oxide containing at least indium (In) and tin (Sn), and may contain additional components other than these. As an additional component, metal elements other than In and Sn are mentioned, for example, For example, the metal element shown by the said group, and these combination are mentioned. The content of the additional component is not particularly limited, but is, for example, 5% by weight or less.

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 ).

  The atomic number ratio Sn / In of Sn to In contained in ITO is, for example, 0.004 or more, preferably 0.02 or more, more preferably 0.03 or more, and further preferably 0.04 or more. Particularly preferably, it is 0.05 or more, and for example, 0.4 or less, preferably 0.3 or less, more preferably 0.2 or less, and still more preferably 0.10 or less. The atomic ratio of Sn to In can be determined by X-ray photoelectron spectroscopy (ESCA: Electron Spectroscopy for Chemical Analysis). By setting the atomic ratio of In and Sn within the above range, it is easy to obtain a film quality excellent in environmental reliability.

  The first inorganic oxide layer 6 preferably does not contain crystal grains. That is, the first inorganic oxide layer 6 is preferably amorphous. Thereby, the wettability of the surface of the 1st inorganic oxide layer 6 can be improved, and the metal layer 7 mentioned later can be more reliably formed into a thin and uniform film on the upper surface of the 1st inorganic oxide layer 6. Therefore, the film quality of the light transmissive conductive layer 4 can be improved, and the wet heat durability can be improved.

  In the present invention, “does not contain crystal grains” means that the first inorganic oxide layer 6 is observed in a plane direction (left-right direction) perpendicular to the thickness direction when observed using a cross-sectional TEM image at 200,000 times magnification. Or, in the range of 500 nm, the crystal grains are not observed.

  The content ratio of the inorganic oxide in the first inorganic 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. It is.

  The thickness T1 of the first inorganic oxide layer 6 is, for example, 5 nm or more, preferably 20 nm or more, more preferably 30 nm or more, and for example, 100 nm or less, preferably 60 nm or less, more preferably 50 nm. It is as follows. When the thickness T1 of the first inorganic oxide layer 6 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 T1 of the first inorganic oxide layer 6 is measured by, for example, 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 inorganic oxide layer 6 and the second inorganic oxide layer 8. The metal layer 7 is also a low resistance layer that reduces the surface resistance value of the light transmissive conductive layer 4. The metal layer 7 is also an IR reflecting layer for imparting a high IR reflectance (near-infrared average reflectance).

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

  The metal forming the metal layer 7 is not limited as long as it has a low surface resistance. For example, Ti, Si, Nb, In, Zn, Sn, Au, Ag, Cu, Al, Co, Cr, Ni, It consists of one metal selected from the group consisting of Pb, Pd, Pt, Cu, Ge, Ru, Nd, Mg, Ca, Na, W, Zr, Ta, and Hf, or two or more thereof Examples include alloys containing metals.

  As a metal, Preferably, silver (Ag) and a silver alloy are mentioned, More preferably, a silver alloy is mentioned. 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 transmittance has a particularly high average reflectance in the near-infrared region (wavelength 850 to 2500 nm). The conductive layer 4 is obtained and can be suitably applied to a liquid crystal light control device used outdoors.

  The silver alloy contains silver as a main component and other metals as subcomponents. The metal element of the accessory component is not limited. Examples of the silver alloy include an Ag—Cu alloy, an Ag—Pd alloy, an Ag—Pd—Cu alloy, an Ag—Pd—Cu—Ge alloy, an Ag—Cu—Au alloy, an Ag—Cu—In alloy, and an Ag—Cu. -Sn alloy, Ag-Ru-Cu alloy, Ag-Ru-Au alloy, Ag-Nd alloy, Ag-Mg alloy, Ag-Ca alloy, Ag-Na alloy, Ag-Ni alloy, Ag-Ti alloy, Ag- In alloys, Ag-Sn alloys, and the like can be given. From the viewpoint of 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.

  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.

  From the viewpoint of increasing the transmittance of the light-transmissive conductive layer 4, the thickness T3 of the metal layer 7 is, for example, 1 nm or more, preferably 5 nm or more, and, for example, 30 nm or less, preferably 20 nm or less, more preferably Is 10 nm or less. The thickness T3 of the metal layer 7 is measured by, for example, cross-sectional observation with a transmission electron microscope (TEM).

7). Second Inorganic Oxide Layer The second inorganic oxide layer 8 is a barrier layer that prevents water (described later) contained in the liquid crystal light control layer 5 from entering the metal layer 7. It is a barrier layer that suppresses discoloration of the metal layer 7 over time. The second inorganic 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 inorganic oxide layer 8 is preferably a conductive layer that imparts conductivity to the light-transmissive conductive layer 4 together with the metal layer 7, and more preferably a transparent conductive layer.

  The second inorganic 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 inorganic oxide layer 8 is formed on the entire upper surface of the metal layer 7 and on the upper surface of the metal layer 7. It is arranged to come into contact.

  Examples of the inorganic oxide forming the second inorganic oxide layer 8 include the inorganic oxides exemplified in the first inorganic oxide layer 6, preferably containing indium oxide, and more preferably containing indium oxide. More preferably, an oxide containing indium oxide whose main metal element is indium (In) is mentioned, and ITO is more preferred.

  The inorganic oxide that forms the second inorganic oxide layer 8 may be the same as or different from the inorganic oxide that forms the first inorganic oxide layer 6, but preferably from the viewpoint of etching property and wet heat durability. The first inorganic oxide layer 6 is the same inorganic oxide.

  When the second inorganic oxide layer 8 is made of an indium oxide-containing oxide, the ratio of the number of contained impurity metal elements to the number of atoms of the main metal element In in the second inorganic oxide layer 8 (the number of atoms of the impurity metal element) / The number of atoms of In) is equal to or greater than (for example, 0.001 or more) of “number of atoms of impurity metal element / number of atoms of In” in the first inorganic oxide layer 6.

When the second inorganic 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 inorganic oxide layer 6.

When both the first inorganic oxide layer 6 and the second inorganic oxide layer 8 are made of ITO, the content of tin oxide (SnO ₂ ) contained in the second inorganic oxide layer 8 is preferably The content is equal to or higher than the content of tin oxide (SnO ₂ ) contained in one inorganic oxide layer 6 (for example, 0.1 mass% or more). Specifically, the content of tin oxide contained in the second inorganic oxide layer 8 content (SnO ₂₎ of the _{(S 2),} tin oxide contained in the first inorganic oxide layer 6 (SnO ₂₎ the amount ratio _{(S 1) (S 2 /} S 1) , for example, 1.0 or more, or preferably 1.2 or more, and is, for example, 3.0 or less, preferably 2.5 or less is there.

By adjusting the content of tin oxide (SnO ₂ ) contained in ITO within the above range, the crystallinity of the ITO film can be adjusted. In particular, by increasing the content of tin oxide in the ITO film, complete crystallization of the ITO film due to heating is suppressed, and a semi-crystalline film can be easily obtained.

The Sn atomic ratio Sn / In with respect to In contained in the second inorganic oxide layer 8 is preferably equal to or equal to the Sn atomic ratio with respect to In contained in the first inorganic oxide layer 6. This is the above (specifically, 0.001 or more). By setting the content of tin oxide (SnO ₂ ) in the second inorganic oxide layer 8 or the atomic ratio of Sn to In to be equal to or higher than those of the first inorganic oxide layer 6, 2 The degree of crystallinity of the inorganic oxide layer 8 can be increased.

  The content ratio of the inorganic oxide in the second inorganic 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. It is.

  The second inorganic oxide layer 8 contains crystal grains 10 (see FIG. 2A or FIG. 2B). As a result, since the crystal grains 10 have a stable film structure and are difficult to transmit water, water (described later) contained in the liquid crystal light control layer 5 as a solvent passes through the second inorganic oxide layer 8. Intrusion into the metal layer 7 can be suppressed. Therefore, the moisture resistance durability of the light transmissive conductive layer 4 can be improved.

  Specifically, the second inorganic oxide layer 8 is a crystalline film. As the crystalline film, for example, as shown in FIG. 2A, in a side sectional view (particularly, a sectional TEM image), it may be a completely crystalline film containing crystal grains 10 continuously in the entire plane direction, Further, as shown in FIG. 2B, it may be a semi-crystalline film containing an amorphous portion 11 (a portion not crystallized) and a crystalline portion 12 (that is, a portion made of crystal grains 10). From the viewpoint that the second crystal grains 10b described later can be contained and the wet heat durability is further improved, a semi-crystalline film is preferable.

  In the present invention, “having crystal grains” means that the second inorganic oxide layer 8 is at least one or more in the range of 500 nm in the plane direction when observed using a cross-sectional TEM image at 200,000 times. It has the crystal grain 10 of. In the above range, the number of crystal grains 10 is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 50 or less, more preferably 40 or less, still more preferably. Has 30 or less crystal grains 10.

  Further, when the upper surface of the second inorganic oxide layer 8 is observed by a planar TEM image at a magnification of 100,000, the area ratio occupied by the crystal grains 10 is, for example, 5% or more, preferably 10% or more. More preferably, it is 20% or more, for example, 100% or less, preferably 90% or less, more preferably 80% or less, further preferably 70% or less, particularly preferably 60% or less. is there.

  In addition, when calculating the area ratio which a crystal grain occupies with a plane TEM image, the cross-sectional TEM image of the 1st inorganic oxide layer 6 is confirmed on the above-mentioned conditions, and a crystal grain exists in the 1st inorganic oxide layer 6 After confirming that it does not, a planar TEM image will be observed. It may be difficult to determine which of the first inorganic oxide layer 6 and the second inorganic oxide layer 8 is a crystal grain by using only a planar TEM image. Therefore, in this invention, after confirming that a crystal grain does not exist in the 1st inorganic oxide layer 6 by a cross-sectional TEM image, the crystal grain 10 of the 2nd inorganic oxide layer 8 is observed by observing a plane TEM image. Judge that it is observable.

  The size of the crystal grains 10 included in the second inorganic oxide layer 8 is, for example, 3 nm or more, preferably 5 nm or more, more preferably 10 nm or more, for example, 200 nm or less, preferably 100 nm or less, more Preferably, it is 80 nm or less, More preferably, it is 50 nm or less. Within the observation area of the second inorganic oxide layer 8, crystal grains other than the above range may be included, but the area ratio is preferably 30% or less, more preferably 20% or less. More preferably, all the crystal grains 10 included in the second inorganic oxide layer 8 are made of crystal grains having a size in the above range. The size of the crystal grain 10 is the maximum value of the length that each crystal grain 10 can take when the second inorganic oxide layer 8 is observed using a cross-sectional TEM image at 200,000 times.

  The size of the largest crystal grain 10 (maximum crystal grain) among the crystal grains 10 included in the second inorganic oxide layer 8 is, for example, 10 nm or more, preferably 20 nm or more, and, for example, 200 nm or less. The thickness is preferably 100 nm or less.

  The shape of the crystal grains is not limited, and examples thereof include a substantially triangular shape in cross section and a substantially rectangular shape in cross section.

  Examples of the crystal grain 10 include a first crystal grain 10a that penetrates the second inorganic oxide layer 8 in the thickness direction and a second crystal grain 10b that does not penetrate the second inorganic oxide layer 8 in the thickness direction.

  The first crystal grain 10 a is a crystal grain grown so that its upper end is exposed from the upper surface of the second inorganic oxide layer 8 and its lower end is exposed from the lower surface of the second inorganic oxide layer 8. The length in the thickness direction of the first crystal grain 10 a is the same as the thickness of the second inorganic oxide layer 8.

  The second crystal grain 10 b is a crystal grain grown so that at least one end of the upper end and the lower end thereof is not exposed from the surface (upper surface or lower surface) of the second inorganic oxide layer 8. The second crystal grain 10b is preferably formed such that its upper end is exposed from the upper surface of the second inorganic oxide layer 8 and its lower end is not exposed from the lower surface of the second inorganic oxide layer 8. .

  The average length of the second crystal grains 10b in the thickness direction is shorter than the thickness (T2) of the second inorganic oxide layer 8, and is, for example, 98% with respect to 100% of the thickness of the second inorganic oxide layer 8. % Or less, preferably 90% or less, more preferably 80% or less, and for example, 5% or more, preferably 10% or more, more preferably 20% or more.

  The second inorganic oxide layer 8 preferably has second crystal grains 10b. Thereby, since the grain boundary of the crystal grain 10 does not penetrate in the thickness direction, it is possible to suppress water from passing through the second inorganic oxide layer 8 in the thickness direction along the grain boundary.

  The number of first crystal grains 10a is, for example, 0 or more, preferably 1 or more, and is, for example, 30 or less, preferably 10 or less.

  The number of the second crystal grains 10b is preferably larger than the number of the first crystal grains 10a, specifically, preferably 1 or more, more preferably 2 or more, and further preferably 3 or more, Moreover, Preferably it is 50 or less, More preferably, it is 40 or less, More preferably, it is 30 or less.

  The thickness T2 of the second inorganic oxide layer 8 is, for example, 5 nm or more, preferably 20 nm or more, more preferably 30 nm or more, and, for example, 100 nm or less, preferably 60 nm or less, more preferably 50 nm. It is as follows. When the thickness T2 of the second inorganic 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 inorganic 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 inorganic oxide layer 8 to the thickness T1 of the first inorganic oxide layer 6 is, for example, 0.5 or more, preferably 0.75 or more, 1.5 or less, preferably 1.25 or less. When the ratio (T2 / T1) is not less than the above lower limit and not more than the above upper limit, the deterioration of the metal layer 7 can be further suppressed even in a humid heat environment.

  The ratio (T2 / T3) of the thickness T2 of the second inorganic 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). Liquid Crystal Light Control Layer The liquid crystal light control layer 5 is a light control layer that changes light transmittance and color by applying an electric field to the light transmissive conductive layer 4.

  The liquid crystal light control layer 5 is the uppermost layer of the liquid crystal 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 liquid crystal light control layer 5 includes a liquid crystal material, and preferably includes a liquid crystal capsule.

  Examples of the liquid crystal material include known materials, such as nematic liquid crystal molecules, smectic liquid crystal molecules, and cholesteric liquid crystal molecules.

  These liquid crystal materials can be used alone or in combination of two or more.

  The liquid crystal capsule is a fine particle and includes the above-described liquid crystal material.

  Further, such a liquid crystal material and a liquid crystal capsule are dispersed by a transparent resin and / or a dispersion medium. That is, the liquid crystal material and the liquid crystal capsule are preferably dispersed by the polymer emulsion.

  The transparent resin is a matrix resin in which a liquid crystal material and a liquid crystal capsule are dispersed, and examples thereof include known resin materials, and examples thereof include, but are not limited to, acrylic resins, epoxy resins, and urethane resins. These transparent resins can be used alone or in combination of two or more.

  Examples of the solvent include water, for example, aromatic hydrocarbon compounds such as benzene, toluene, xylene, methoxybenzene, and 1,2-dimethoxybenzene, such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, and trichloroethylene. Halogenated hydrocarbon compounds such as tetrachloroethylene, chlorobenzene and orthodichlorobenzene, for example, phenol compounds such as phenol and parachlorophenol, ether compounds such as diethyl ether, dibutyl ether, tetrahydrofuran, anisole, dioxane and tetrahydrofuran, Acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-pentanone, 3-pentanone, 2-hexa Ketone compounds such as n-butanol, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 2-pyrrolidone, N-methyl-2-pyrrolidone And 2-butanol, cyclohexanol, isopropyl alcohol, t-butyl alcohol, glycerin, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol And alcohol-based compounds such as Among these, from the viewpoint of emulsion formation, preferably, an alcohol compound, water, and more preferably water. These solvents can be used alone or in combination of two or more.

  Such transparent resins and solvents can be used alone or in combination of two or more. Preferably, water is used as the solvent.

  Moreover, in such a liquid crystal light control layer 5, it is preferable to adjust so that the refractive index of transparent resin and / or a solvent may become the same as the refractive index of the major axis direction in a liquid crystal molecule.

  When no electric field is applied, the liquid crystal molecules encapsulated in the liquid crystal capsule are aligned along the inner wall of the liquid crystal capsule. Therefore, the alignment direction of the liquid crystal molecules becomes non-uniform, the refractive index mismatch occurs at the interface between the liquid crystal capsule and the transparent resin and / or solvent, and light is scattered. Thereby, the liquid crystal light control layer 5 becomes opaque.

  When an electric field is applied, the liquid crystal molecules included in the liquid crystal capsule are aligned in parallel with the direction of the electric field. Since the refractive index of the transparent resin and / or solvent is adjusted so as to be the same as the refractive index in the major axis direction of the liquid crystal molecules, there is no refractive index mismatch at the interface between the liquid crystal capsule and the transparent resin. . Thereby, the liquid crystal light control layer 5 becomes transparent.

  The thickness of the liquid crystal light control layer 5 is, for example, 0.1 μm or more and 5000 μm or less.

9. Light-transmissive conductive film Among the members constituting the liquid crystal 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. 3, the light transmissive conductive film 9 is a laminated film including the transparent substrate 2, the protective layer 3, and the light transmissive conductive layer 4 in order in the thickness direction. 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 liquid crystal light control member 1, and specifically, is an electrode substrate used for the liquid crystal light control member 1. The light-transmitting conductive film 9 is a device that does not include the liquid crystal light control layer 5 and is distributed alone as a component and can be 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.

10. Next, a method for manufacturing the liquid crystal light control member 1 will be described.

  In order to manufacture the liquid crystal light control member 1, first, the light transmissive conductive film 9 is prepared, and then the liquid crystal light control layer 5 is disposed on the light transmissive conductive film 9.

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

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

The amount of water in the transparent substrate 2 (polymer film) is not limited, but is, for example, 10 μg / cm ² or more, preferably 15 μg / cm ² or more, for example, 200 μg / cm ² or less, preferably 170 μg / cm ² or less. If the amount of water is equal to or more than the lower limit described above, a hydrogen atom or the like is imparted to the first inorganic oxide layer 6 to suppress the first inorganic oxide layer 6 from being crystallized by heating, which will be described later. It is easy to maintain the amorphous nature of the inorganic oxide layer 6. Moreover, if the amount of moisture is not more than the above upper limit, the second inorganic oxide layer 8 containing the crystal grains 10 can be reliably obtained by a heating step or the like. The water content in the transparent substrate 2 is measured according to JIS K 7251 (2002) Method B-water vaporization method.

  The content of water contained in the transparent substrate 2 (polymer film) with respect to the transparent substrate 2 is, for example, 0.05% by mass or more, preferably 0.1% by mass or more. For example, it is 1.5% by mass or less, preferably 1.0% by mass or less, and more preferably 0.5% by mass or less.

  Note that part or all of the water described above is released to the outside in a degassing process described later.

  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, the 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.

  Thereafter, the transparent substrate with a protective layer is degassed as necessary.

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, or, for example, 1 × 10 Leave in a reduced pressure atmosphere of ^-6 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 inorganic oxide layer 6, the metal layer 7, and the second inorganic 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 inorganic 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 inorganic oxide layer 8, an inert gas and a reactive gas are preferably used in combination as the gas.

  When the first inorganic oxide layer 6 and the second inorganic oxide layer 8 contain indium oxide, the resistance behavior of each layer varies depending on the amount of reactive gas introduced, and the amount of reactive gas introduced (x In the graph of (axis) -surface resistance value (y-axis), a parabola convex downward is drawn. At this time, the amount of reactive gas contained in the first inorganic oxide layer 6 and the second inorganic oxide layer 8 is an introduction amount in which the resistance value is near the minimum value (that is, the inflection point of the parabola). Specifically, it is preferable that the introduction amount is ± 20% so that the resistance value becomes the minimum value.

  When employing the sputtering method, examples of the target material include the above-described inorganic oxides or metals that constitute 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.

  In addition, preferably, when the first inorganic 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 inorganic oxide layer 6 is formed, a large amount of water contained in the transparent base material 2 and organic substances contained in the protective layer 3 are released by the heat of vapor deposition generated by sputtering, and the like. It can suppress that water is contained excessively in the first inorganic oxide layer 6. 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 30 ° C. or less, and further preferably 20 ° C. Hereinafter, it is particularly preferably less than 0 ° C. Preferably, the first inorganic oxide layer 6, the metal layer 7, and the second inorganic oxide layer 8 are all formed by sputtering while cooling in the above temperature range. Thereby, aggregation of the metal layer 7 and excessive oxidation of the second inorganic oxide layer 8 can be suppressed.

  Thereby, the light-transmitting conductive layer 4 in which the first inorganic oxide layer 6, the metal layer 7, and the second inorganic oxide layer 8 are sequentially formed in the thickness direction is formed on the protective layer 3, A light-transmitting conductive layer laminate is obtained. At this time, both the first inorganic oxide layer 6 and the second inorganic oxide layer 8 immediately after film formation (for example, within 24 hours after the formation of the light-transmitting conductive layer laminate) contain crystal grains 10. Absent.

  Next, when the second inorganic oxide layer 8 contains the crystal grains 10, a crystallization step for generating the crystal grains 10 in the second inorganic oxide layer 8 is performed. The crystallization step is not limited as long as the crystal grains 10 can be formed, but for example, a heating step can be mentioned. That is, the light transmissive conductive layer laminate is heated.

  The heating process is not only performed for the purpose of generating the crystal grains 10 but also accompanying the curl removal of the light transmissive conductive layer laminate and the dry formation of the silver paste wiring. Heating may be used.

  The heating temperature can be appropriately set, and is, for example, 30 ° C. or higher, preferably 40 ° C. or higher, more preferably 80 ° C. or higher, and for example, 180 ° C. or lower, preferably 150 ° C. or lower.

  The heating time is not limited and is set according to the heating temperature. For example, it is 1 minute or more, preferably 10 minutes or more, more preferably 30 minutes or more, and for example, 4000 hours or less, preferably Is less than 100 hours.

  Heating may be performed in any of an air atmosphere, an inert atmosphere, and a vacuum, but from the viewpoint of facilitating crystallization, it is preferably performed in an air atmosphere.

  By this heating step, the second inorganic oxide layer 8 is crystallized, and crystal grains 10 exist in the second inorganic oxide layer 8. In particular, when the second inorganic oxide layer 8 contains crystal grains 10, the second inorganic oxide layer 8 is a metal layer interposed between the transparent substrate 2 and the second inorganic oxide layer 8. 7 is a barrier for water from the transparent base material 2 that inhibits crystallization and an organic substance from the protective layer 3, and because it is exposed during the heating step, it is easy to take in oxygen necessary for crystallization. The inorganic oxide layer 8 can be easily crystallized. Note that the first inorganic oxide layer 6 is greatly influenced by water and organic substances and is difficult to take up oxygen, so that the growth of the crystal grains 10 is hindered and maintains amorphousness.

  Thereby, as shown in FIG. 1, in the thickness direction, the transparent base material 2, the protective layer 3, and the light-transmitting conductive layer 4 (the first inorganic oxide layer 6, the metal layer 7, and the second inorganic oxide layer). 8) and a light-transmissive conductive film 9 in which only the second inorganic oxide layer 8 contains crystal grains 10 is obtained.

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

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

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

  Thereby, as shown in FIG. 1, the liquid crystal light control member 1 provided with the transparent base material 2, the protective layer 3, the light transmissive conductive layer 4, and the liquid crystal light control layer 5 in order in the thickness direction is obtained. It is done.

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

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

11. Action Effect According to the liquid crystal light control member 1, the light-transmissive conductive layer 4 includes the metal layer 7 having a high reflectance in the near infrared region. For this reason, the light-transmissive conductive layer 4 has a higher near-infrared reflectance than, for example, a conductive oxide alone, and can efficiently block heat rays such as sunlight from the liquid crystal light control layer 5. Can be used in an environment affected by sunlight (such as outdoors).

  Moreover, according to the liquid-crystal light control member 1, since the transparent conductive layer 4 has electroconductivity, it can be used as an electrode. Furthermore, the liquid crystal light control member 1 is excellent in near-infrared reflection characteristics without attaching an IR reflection layer to the surface of the transparent substrate 2. Therefore, the thickness of the liquid crystal light control member can be reduced, and the manufacturing cost can be reduced.

  Moreover, according to the liquid-crystal light control member 1, even if it does not affix an IR reflection layer on the surface of the transparent base material 2, it is excellent in a near-infrared reflective characteristic. Therefore, the thickness of the liquid crystal light adjusting member 1 can be reduced, and the manufacturing cost can be reduced.

  According to the liquid crystal light adjusting member 1, the light transmissive conductive layer 4 includes the second inorganic oxide layer 8 containing the crystal grains 10. Therefore, when the liquid crystal light control layer 5 contains water as a solvent, the water can be prevented from passing through the second inorganic oxide layer 8 in the thickness direction and entering the metal layer 7. .

  According to the liquid crystal light control member 1, the second inorganic oxide layer is a semicrystalline film having 7, an amorphous portion 11, and a crystalline portion 12. Therefore, the wet heat durability is further improved.

  According to the light transmissive conductive film 9, the light transmissive conductive layer 4 includes the metal layer 7 having a high reflectance in the near infrared region. Therefore, when the light-transmitting conductive film 9 is used for the liquid crystal light adjusting member 1 described above, the light-transmitting conductive layer 4 is, for example, an average of near infrared rays compared to the case where the light-transmitting conductive layer 4 is made of only a conductive oxide. It has high reflectivity, can efficiently block heat rays such as sunlight from the liquid crystal light control layer 5, and can be used in an environment affected by sunlight (such as outdoors).

  Moreover, in the light transmissive conductive film 9, since the light transmissive conductive layer 4 has conductivity, it can be used as an electrode. Furthermore, even if an IR reflection layer is not attached to the surface of the transparent substrate 2, the near-infrared reflection characteristics are excellent. Therefore, the thickness of the light transmissive conductive film 9 can be reduced, and the manufacturing cost can be reduced.

12 Liquid crystal light control device The liquid crystal light control device 13 has a film shape (including a sheet shape) having a predetermined thickness, and extends in a predetermined direction (front and rear direction and left and right direction, that is, a surface direction) perpendicular to the thickness direction. A flat upper surface and a flat lower surface (two main surfaces). The liquid crystal light adjusting element 13 is one component such as a light adjusting panel provided in the light adjusting device, that is, it is not a light adjusting device. That is, the liquid crystal dimming element 13 is a component for producing a dimming device or the like, and 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.

  Specifically, as shown in FIG. 4, the liquid crystal light control element 13 is a laminated film including the liquid crystal light control member 1 and an electrode substrate (upper electrode substrate) 14. That is, the liquid crystal light control element 13 includes the liquid crystal light control member 1 and the electrode substrate 14 disposed on the upper side of the liquid crystal light control member 1. Preferably, the liquid crystal light adjusting element 13 includes only the liquid crystal light adjusting member 1 and the electrode substrate 14. Hereinafter, each layer will be described in detail.

  The electrode substrate 14 is the light-transmitting conductive film 9 described above, and includes the light-transmitting conductive layer 4, the protective layer 3, and the transparent base material 2 in order in the thickness direction. The electrode substrate 14 is disposed on the upper side of the liquid crystal light adjusting member 1. Specifically, the electrode substrate 14 is formed on the entire surface of the upper surface of the liquid crystal light control layer 5 (the surface opposite to the transparent base material 2 of the lower light-transmitting conductive film 9). It arrange | positions so that the upper surface and the lower surface of the transparent conductive layer 4 may contact.

  That is, in the liquid crystal light control device 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 liquid crystal light control layer 5. ing.

  The liquid crystal light adjusting element 13 includes the liquid crystal light adjusting member 1 described above. Therefore, the liquid crystal light control device 13 can efficiently block heat rays such as sunlight from the liquid crystal light control layer 5 and can be used in an environment (such as outdoors) that is affected by sunlight.

  The liquid crystal light adjusting element 13 includes the liquid crystal light adjusting member 1 described above. Therefore, the thickness of the liquid crystal light adjusting device 13 can be reduced, and the manufacturing cost can be reduced.

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

  In one embodiment of the liquid crystal light control member 1, the first inorganic oxide layer 6 is directly disposed on the upper surface of the protective layer 3 as shown in FIG. 1. However, for example, as shown in FIG. 6, the inorganic layer 15 can be interposed between the protective layer 3 and the first inorganic oxide layer 6.

  The inorganic material layer 15 is an optical adjustment layer that adjusts the optical physical properties of the liquid crystal 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 15 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 15 has predetermined optical properties, and is prepared from inorganic materials such as oxides and fluorides, for example. The thickness of the inorganic layer 15 is 1 nm or more, preferably 5 nm or more, more preferably 10 nm or more, and for example, 200 nm or less, preferably 80 nm or less, more preferably 40 nm or less, still more preferably 25 nm. It is as follows.

  In one embodiment of the liquid crystal light control member 1, as shown in FIG. 1, the light transmissive conductive layer 4 includes only the first inorganic oxide layer 6, the metal layer 7, and the second inorganic oxide layer 8. I have. However, for example, although not shown, a second metal layer and a third inorganic oxide layer can be disposed in order on the upper surface of the second inorganic oxide layer 8, and further, the third inorganic oxide A third metal layer and a fourth inorganic oxide layer can also be disposed on the upper surface of the layer.

  Moreover, although not shown in figure, functional layers, such as an antifouling layer, adhesion | attachment, a water repellent layer, an antireflection layer, an oligomer prevention layer, can also be arrange | positioned on the upper surface and / or lower surface of the transparent base material 2, for example.

  The functional layer preferably includes the above-described resin composition, and more preferably includes the resin composition.

  Further, an insulating layer (not shown) (preferably having a thickness of 50 nm or less) may be disposed between the light-transmissive conductive layer 4 and the liquid crystal light control layer 5 in whole or in part. The insulating layer is made of, for example, a resin composition or an inorganic oxide.

  In one embodiment of the liquid crystal light control member 1, as shown in FIG. 1, the liquid crystal light control member 1 includes a transparent base material 2, but the transparent base material 2 is not a colored base material (not shown). ). For example, a polarizer or a polarizing film may be arranged on the opposite side of the transparent base material 2 from the light-transmissive conductive layer 4. A polarizer and a polarizing film can be bonded to the transparent substrate 2 via, for example, an adhesive layer or an adhesive layer.

  Such a functional layer is appropriately selected according to a required function.

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

  In the liquid crystal light adjusting device 13, as shown in FIG. 3, the light transmissive conductive film 9 of the present invention is used as the upper electrode substrate 14. For example, although not shown, the upper electrode substrate 14 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 inorganic oxide layer)
Subsequently, the transparent base material roll with a protective layer was installed in a vacuum sputtering apparatus, and was evacuated until the atmospheric pressure when not transported was 2 × 10 ⁻³ Pa (degassing treatment). At this time, a part of the transparent substrate with a protective layer was conveyed without introducing the sputtering gas (Ar and O ₂ ), and it was confirmed that the atmospheric pressure increased to 1 × 10 ⁻² Pa. Thereby, it was confirmed that a sufficient amount of gas remained in the transparent substrate roll with a protective layer.

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

Specifically, under a vacuum atmosphere of atmospheric pressure 0.2 Pa into which Ar and O ₂ were introduced (flow rate ratio: Ar: O ₂ = 100: 3.8), using a direct current (DC) power source, A target made of a sintered body of tin oxide and 88% by mass of indium oxide was sputtered.

  In addition, when forming a 1st inorganic oxide layer by sputtering, the lower surface (specifically, the lower surface of a transparent base material) of a transparent base material roll with a protective layer is made to contact a -5 degreeC cooling roll, and is protected. The layered transparent substrate roll was cooled.

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

  Specifically, an Ag alloy (manufactured by Mitsubishi Materials Corporation, product number “No. 317”) was sputtered using a direct current (DC) power source as a power source in a vacuum atmosphere at a pressure of 0.4 Pa into which Ar was introduced.

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

Specifically, under a vacuum atmosphere of atmospheric pressure 0.2 Pa into which Ar and O ₂ were introduced (flow rate ratio: Ar: O ₂ = 100: 4.0), using a direct current (DC) power source, An ITO target made of a sintered body of tin oxide and 88% by mass of indium oxide was sputtered.

  Then, the heating process was implemented on condition of 80 degreeC and 12 hours in air | atmosphere. Thereby, the second inorganic oxide layer was crystallized.

  Thereby, the transparent conductive film in which the protective layer, the first inorganic oxide layer, the metal layer, and the second inorganic oxide layer were formed in this order on the transparent substrate in the thickness direction was obtained.

Example 2
The flow ratio of Ar and O ₂ was Ar: O ₂ = 100: 3.1, and the sputtering was performed by sputtering an ITO target composed of a sintered body of 12% by mass of tin oxide and 88% by mass of indium oxide. A light-transmitting conductive film of Example 2 was obtained in the same manner as Example 1 except that 2 inorganic oxide layers were formed.

Example 3
A light-transmitting conductive film of Example 3 was obtained in the same manner as in Example 1 except that the heating step in the second inorganic oxide layer was not performed.

Comparative Example 1
The flow ratio of Ar and O ₂ during sputtering was Ar: O ₂ = 100: 1.0, the thickness of the second inorganic oxide layer was changed to the thickness described in Table 1, and the first inorganic oxide layer Comparative Example 1 was performed in the same manner as in Example 1 except that a light-transmitting conductive layer was formed without forming a metal layer, and then a heating step was performed at 140 ° C. for 1 hour in an air atmosphere. A light-transmitting conductive film was obtained.

[Liquid crystal light control device]
(Production Example 1)
The light transmissive conductive film of Example 1 and the light transmissive conductive film of Comparative Example 1 were prepared. Next, a coating liquid in which a nematic liquid crystal and a resin were mixed was prepared. Subsequently, the coating liquid was apply | coated to the upper surface of the light transmissive conductive film of Example 1, and the liquid-crystal light control layer was formed. Thereafter, the light transmissive conductive film of Comparative Example 1 was laminated on the upper surface of the liquid crystal light control layer, and the liquid crystal light control device of Production Example 1 was produced.

  After removing the liquid crystal light control layer at the end of the obtained liquid crystal light control element, a conductive copper foil adhesive tape (trade name No. 8323 manufactured by Teraoka Seisakusho Co., Ltd.) was applied to the portion where the liquid crystal light control layer was removed, and a voltage was applied. However, it was confirmed that a change in permeability was visually recognized depending on the presence or absence of an electric field and functioned as a light control element.

(Production Example 2)
A liquid crystal light control device of Production Example 2 was produced in the same manner as Production Example 1, except that the light transmissive conductive film of Example 1 was changed to the light transmissive conductive film of Example 2.

(Production Example 3)
A liquid crystal light control device of Production Example 3 was produced in the same manner as Production Example 1, except that the light transmissive conductive film of Example 1 was changed to the light transmissive conductive film of Example 3.

(Production Comparative Example 1)
Except that two light transmissive conductive films of Comparative Example 1 were prepared and laminated so that each light transmissive conductive layer was in contact with the surface (upper surface or lower surface) of the liquid crystal light control layer, the same as in Production Example 1. Thus, a liquid crystal light control device of Production Comparative Example 1 was produced.

(Measurement)
(1) Thickness The thicknesses of the protective layer, the first inorganic oxide layer, the metal layer, and the second inorganic oxide layer were measured by cross-sectional observation using a transmission electron microscope (manufactured by Hitachi, Ltd., HF-2000). The thickness of the transparent substrate was measured using a film thickness meter (Digital Dial Gauge DG-205 manufactured by Peacock).

(2) Observation of crystal grains by cross-sectional TEM Cross sections of the first inorganic oxide layer and the second inorganic oxide layer using a transmission electron microscope (manufactured by Hitachi, “HF-2000”, magnification 200,000 times) Was observed. The number of crystal grains per plane direction distance of 500 nm in the cross-sectional view at that time was counted. Moreover, the length of the largest crystal grain of the crystal grain produced in the inorganic oxide layer was measured. The results are shown in Table 1.

(3) Observation of crystal grains by planar TEM In the light transmissive conductive films of Examples and Comparative Examples in which crystal grains were confirmed by cross-sectional TEM, a transmission electron microscope (manufactured by Hitachi, "H-7650") was used. The top surface of the second inorganic oxide layer was observed to obtain a planar image with a magnification of 100,000. Next, the ratio of the area of the crystal grains (the crystallized portion) to the area of the entire second inorganic oxide layer was measured. The results are shown in Table 1. In Example 1, the number of second crystal grains was larger than the number of first crystal grains.

(4) Wet heat durability The light transmissive conductive film of each Example and each Comparative Example was cut into a size of 10 cm × 10 cm, and an adhesive layer (“CS9904U” manufactured by Nitto Denko Corporation) was formed on the light transmissive conductive layer. After being bonded to the glass substrate, it was allowed to stand for 240 hours at 60 ° C. and 95% RH. Thereafter, the upper surface of the light transmissive conductive layer at the center 8 cm × 8 cm portion was visually observed.

At this time, the appearance was evaluated based on the following criteria.
A: White point defects (aggregation, corrosion sites) are not observed (0).
◯: White point defects are more than 0 and 5 or less.
X: There are more than 5 white point defects.

  The results are shown in Table 1.

(5) Near-infrared reflective property About the light-transmitting conductive film of each Example and each comparative example, the average reflectance of near-infrared (wavelength 850-2500 nm) was measured.

At this time, the average reflectance was evaluated based on the following criteria.
○: The average reflectance is 30% or more.
Δ: The average reflectance is 15% or more and less than 30%.
X: Average reflectance is less than 15%.

  The results are shown in Table 1.

DESCRIPTION OF SYMBOLS 1 Liquid crystal light control member 2 Transparent base material 4 Light transmission conductive layer 5 Liquid crystal light control layer 6 1st inorganic oxide layer 7 Metal layer 8 2nd inorganic oxide layer 9 Light transmission conductive film 13 Liquid crystal light control element

Claims (5)

A transparent base material, a light transmissive conductive layer, and a liquid crystal light control layer are provided in this order.
The light-transmitting conductive layer comprises a first inorganic oxide layer, a metal layer, and a second inorganic oxide layer in this order.   The liquid crystal light control member according to claim 1, wherein the second inorganic oxide layer contains crystal grains.   The liquid crystal light control member according to claim 1, wherein the second inorganic oxide layer is a semi-crystalline film having an amorphous part and a crystalline part. A light transmissive conductive film for use in the liquid crystal 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 film includes a first inorganic oxide layer, a metal layer, and a second inorganic oxide layer in order. Liquid crystal light control member according to any one of claims 1 to 3,
An electrode substrate provided on a surface opposite to the liquid crystal light control layer with respect to the transparent base material. A liquid crystal light control element, comprising:

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