JP2017083833A - Light-transmissive conductive film, production method thereof, lighting control film and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light-transmissive conductive film allowing quick and secure etching of a light-transmissive conductive layer, a production method thereof, a production method of a lighting control film allowing a lighting control function layer with a uniform thickness to be formed by a wet process on a surface of an inorganic layer, and a lighting control film obtained by the method.SOLUTION: A light-transmissive conductive film 1 sequentially includes a light-transmissive substrate 2, a light-transmissive conductive layer 3, and an inorganic layer 4. The thickness T4 of the inorganic layer 4 is 20 nm or less. The water contact angle θ1 of the inorganic layer 4 is 50 degrees or less after an elapse of 80 hours or more since formation of the inorganic layer 4.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a light-transmitting conductive film, a manufacturing method thereof, a light control film, and a manufacturing method thereof.

  2. Description of the Related Art Conventionally, a liquid crystal optical element is known that includes a liquid crystal resin composite in which liquid crystal is dispersed and held in a resin matrix, and two substrates that sandwich them.

  For example, a liquid crystal optical device in which at least one substrate surface in contact with a liquid crystal resin composite is covered with a thin film having substantially uniform wettability with respect to an uncured mixed liquid for forming the liquid crystal resin composite An element has been proposed (see, for example, Patent Document 1).

In the substrate of Patent Document 1, after forming ITO on a glass plate, SiO ₂ is deposited on ITO with a thickness of 60 nm to form a thin film.

  And in patent document 1, since an uncured liquid mixture shows the substantially uniform wettability on the whole substrate surface, it is hard to remain bubbles on the substrate surface.

JP-A-5-34667

However, after forming a thin film of SiO ₂ , ITO may be patterned by etching. Patent Document 1 discloses a process of forming a SiO ₂ thin film after patterning ITO, but this process cannot be substantially employed in terms of product quality and manufacturing cost. On the other hand, when a thin film having uniform wettability (for example, a SiO ₂ film having a thickness of 60 nm) is formed after ITO is formed and then ITO patterning is performed, it takes a long time for ITO patterning, or substantially There is a problem that patterning cannot be performed.

  An object of the present invention is to form a light-transmitting conductive film capable of quickly and reliably etching a light-transmitting conductive layer, a method for manufacturing the light-transmitting conductive film, and a light-controlling functional layer having a uniform thickness on the surface of the inorganic layer by a wet process. An object of the present invention is to provide a method for producing a light control film and a light control film obtained thereby.

  [1] The present invention includes a light-transmitting substrate, a light-transmitting conductive layer, and an inorganic layer in order, the inorganic layer has a thickness of 20 nm or less, and the water contact angle of the inorganic layer is 50 It is a light-transmitting conductive film characterized by being less than or equal to a degree.

  In this light transmissive conductive film, since the thickness of the inorganic layer is not more than a specific upper limit, the light transmissive conductive layer can be etched quickly and reliably together with the inorganic layer.

  In addition, since the water contact angle after the elapse of 80 hours or more after the inorganic layer is formed is not more than a specific value, a light control function layer having a uniform thickness is formed on the surface of the inorganic layer by a wet method. Can do. Therefore, the light control film excellent in reliability can be obtained.

  [2] The present invention includes the light transmissive conductive film according to the above [1], wherein the inorganic layer has a water contact angle of 50 degrees or less after elapse of 80 hours or more after the inorganic layer is formed. It is out.

  [3] In the present invention, the inorganic layer includes the light transmissive conductive film according to the above [1] or [2] made of an inorganic oxide.

  In this light-transmitting conductive film, the inorganic layer is made of an inorganic oxide, so that it is excellent in hydrophilicity.

  [4] In the present invention, the light-transmissive conductive layer includes an indium-based conductive oxide layer, and the thickness of the indium-based conductive oxide layer is 50 nm or less. The light-transmitting conductive film according to any one of the above items is included.

  In this light transmissive conductive film, since the thickness of the indium-based conductive oxide layer is not more than a specific upper limit, the light transmissive conductive layer can be etched quickly and reliably together with the inorganic layer.

  [5] The present invention includes a step (1) of preparing a light-transmitting substrate, a step (2) of forming a light-transmitting conductive layer on the surface of the light-transmitting substrate, and an inorganic layer that transmits the light. A step (3) of forming on the surface of the conductive conductive layer, and a step (4) of etching the light transmissive conductive layer after the step (3), wherein the thickness of the inorganic layer is 20 nm or less. The water contact angle of the inorganic layer after 80 hours or more after the formation of the inorganic layer is 50 degrees or less.

  According to this method, in step (3), an inorganic layer having a thickness below a specific upper limit is formed. Therefore, in step (4) after step (3), the light-transmitting conductive layer is quickly formed together with the inorganic layer. And it can etch reliably.

  In addition, since the water contact angle after the elapse of 80 hours or more after the inorganic layer is formed is not more than a specific value, a light control function layer having a uniform thickness is formed on the surface of the inorganic layer by a wet method. Can do.

  [6] In the present invention, in the step (2), the amorphous light transmissive conductive layer is formed, and after the step (3), the amorphous light transmissive conductive layer is crystallized. The method for producing a light transmissive conductive film according to the above [5], further comprising a step (5).

  According to this method, since the amorphous light transmissive conductive layer is crystallized in the step (5) after the step (3), the surface resistance of the light transmissive conductive layer can be reduced.

  [7] The present invention includes a first light transmissive conductive film, a light control functional layer, and a second light transmissive conductive film in order, and the first light transmissive conductive film and / or the first light transmissive conductive film. The light transmissive conductive film 2 is the light transmissive conductive film according to any one of the above [1] to [4], and the light control functional layer is an inorganic provided in the light transmissive conductive film. It is a light control film characterized by being in contact with the layer.

  In this light control film, since the light control function layer is contacting the inorganic layer with which a light transmissive conductive film is equipped, it can have uniform thickness. Therefore, this light control film is excellent in reliability.

  [8] The present invention includes a step (6) of manufacturing two light-transmitting conductive films and a step (7) of sandwiching a light control functional layer between the two light-transmitting conductive layers. ), At least one light transmissive conductive film is produced by the production method according to the above [5] or [6], and in the step (7), the light control function layer is formed by at least one light transmissive film. It is a manufacturing method of the light control film characterized by making it contact the inorganic layer of a conductive conductive film.

  Moreover, according to this method, in the step (6), the dimming function layer is brought into contact with the inorganic layer of at least one light-transmitting conductive film. Therefore, the dimming function having a uniform thickness in the step (7). A layer can be obtained. Therefore, this light control film is excellent in reliability.

  In the light-transmitting conductive film of the present invention, the light-transmitting conductive layer can be etched quickly and reliably together with the inorganic layer, and a light-modulating functional layer having a uniform thickness can be formed on the surface of the inorganic layer by a wet process. . Therefore, the light transmissive conductive film is excellent in reliability.

  According to the method for producing a light transmissive conductive film of the present invention, a light transmissive conductive layer can be etched quickly and reliably, and a light control function layer having a uniform thickness is formed on the surface of an inorganic layer by a wet process. Can do.

  Since the light control film of this invention is equipped with the light transmissive conductive film excellent in reliability, it is excellent in reliability.

  According to the method for producing a light control film of the present invention, in step (6), the light control function layer is brought into contact with the inorganic layer of at least one light-transmitting conductive film. The light control function layer which has can be obtained.

FIG. 1 shows a cross-sectional view of a first embodiment of a light-transmitting conductive film of the present invention. FIG. 2 shows a cross-sectional view of a light control film comprising the light transmissive conductive film shown in FIG. FIG. 3 shows a modification of the light transmissive conductive film shown in FIG. FIG. 4 shows a cross-sectional view of a second embodiment of the light transmissive conductive film of the present invention. FIG. 5 shows a cross-sectional view of a light control film comprising the light transmissive conductive film shown in FIG. FIG. 6 shows a modification of the light transmissive conductive film shown in FIG.

  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.

<First Embodiment>
1. Light-transmissive conductive film This light-transmissive conductive film 1 has a film shape (including a sheet shape) having a predetermined thickness, as shown in FIG. 1, and a predetermined direction (front-rear direction and left-right direction) orthogonal to the thickness direction. That is, in the plane direction), and has a flat upper surface and a flat lower surface (two main surfaces). The light transmissive conductive film 1 is, for example, one component such as a light control film 20 (see FIG. 2 described later), that is, not a light control device (described later). That is, the light transmissive conductive film 1 is a component for producing the light control film 20 and the like, and does not include the light control function layer 5 (refer to the phantom line in FIG. 1 and reference to the solid line in FIG. 2). It is a device that can be distributed industrially and used by industry.

  Specifically, the light transmissive conductive film 1 includes a light transmissive substrate 2, a light transmissive conductive layer 3, and an inorganic layer 4 in this order. That is, the light transmissive conductive film 1 is disposed on the light transmissive substrate 2, the light transmissive conductive layer 3 disposed on the top surface of the light transmissive substrate 2, and the top surface of the light transmissive conductive layer 3. And an inorganic layer 4. Preferably, the light transmissive conductive layer 3 and the inorganic layer 4 are in contact with each other. More preferably, the light transmissive conductive film 1 includes only the light transmissive substrate 2, the light transmissive conductive layer 3, and the inorganic layer 4. Hereinafter, each layer will be described in detail.

2. Light transmissive substrate The light transmissive substrate 2 is the lowermost layer of the light transmissive conductive film 1 and is a support material that ensures the mechanical strength of the light transmissive conductive film 1. The light transmissive substrate 2 includes a base substrate 6. The light transmissive substrate 2 further includes a functional layer 7 disposed on one main surface (upper surface) of the base substrate 6. That is, the light transmissive substrate 2 includes the base substrate 6 and the functional layer 7 in order.

2-1. Base Substrate The base substrate 6 is a layer that forms the lower surface of the light-transmitting substrate 2 and has a film shape (including a sheet shape).

  The base substrate 6 is made of an organic film, for example, an inorganic plate such as a glass plate. The base substrate 6 is preferably an organic film, more preferably a polymer film, from the viewpoint of efficiently producing the light-transmitting conductive film 1 by a continuous production method such as roll-to-roll.

  The polymer film has light transmittance. 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 light transmittance, heat resistance, mechanical properties, and the like, preferably, a polyester resin is used, and more preferably, PET is used.

  The thickness of the base substrate 6 is, for example, 2 μm or more, preferably 20 μm or more, more preferably 40 μm or more, and for example, 300 μm or less, preferably 200 μm or less.

2-2. Functional layer The functional layer 7 is a layer that is provided on one main surface (upper surface) of the base substrate 6 and imparts functionality according to the purpose. Examples of the functional layer 7 include an easy adhesion layer, an undercoat layer, and a hard coat layer. The easy adhesion layer has a function of improving adhesion with a layer (for example, the light-transmissive conductive layer 3) formed on the base substrate 6. The undercoat layer has a function of adjusting the reflectance and optical hue of the light transmissive conductive film 1. The hard coat layer enhances the scratch resistance of the light transmissive conductive film 1.

  The functional layer 7 preferably includes a resin composition, and more preferably includes only the resin composition.

  The resin composition contains, for example, a resin and particles. The resin composition preferably contains only 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.

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

  The thickness of the functional layer 7 is, for example, 0.01 μm or more, preferably 0.1 μm or more, more preferably 1 μm or more, and for example, 10 μm or less, preferably 5 μm or less.

  The thickness of the light transmissive substrate 2, that is, the total thickness of the base substrate 6 and the functional layer 7 is, for example, 5 μm or more, preferably 20 μm or more, more preferably 45 μm or more, For example, it is 300 micrometers or less, Preferably, it is 200 micrometers or less.

3. Light-transmissive conductive layer The light-transmissive conductive layer 3 is a conductive layer that can be arbitrarily patterned by etching in a later step.

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

  The light transmissive conductive layer 3 includes a first inorganic oxide layer 8, a metal layer 9, and a second inorganic oxide layer 10 in this order. That is, the light transmissive conductive layer 3 includes a first inorganic oxide layer 8 disposed on the light transmissive substrate 2, a metal layer 9 disposed on the first inorganic oxide layer 8, and a metal And a second inorganic oxide layer 10 disposed on the layer 9. The light transmissive conductive layer 3 is preferably composed of only the first inorganic oxide layer 8, the metal layer 9, and the second inorganic oxide layer 10. The first inorganic oxide layer 8 and the second inorganic oxide layer 10 are preferably amorphous.

3-1. First Inorganic Oxide Layer The first inorganic oxide layer 8 is a conductive layer that imparts conductivity to the light transmissive conductive layer 3 together with the metal layer 9 and the second inorganic oxide layer 10. Although the 1st inorganic oxide layer 8 does not need to hold | maintain electroconductivity, Preferably, it has electroconductivity. The first inorganic oxide layer 8 is also a barrier layer that prevents an active gas derived from an organic substance contained in the light transmissive substrate 2 from invading the metal layer 9. The first inorganic oxide layer 8 is the lowest layer in the light transmissive conductive layer 3 and has a film shape (including a sheet shape). It arrange | positions so that the upper surface of the base material 2 may be contacted.

  The 1st inorganic oxide layer 8 contains the inorganic oxide which can be melt | dissolved with respect to the etching liquid mentioned later as a main component.

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

  The inorganic oxide preferably includes indium oxide (including indium-based conductive oxide) from the viewpoint of reducing specific resistance and ensuring excellent light transmittance, and more preferably, indium. Tin complex oxide (ITO) is mentioned. That is, the first inorganic oxide layer 8 is preferably an indium conductive oxide layer, and more preferably an ITO layer.

Indium tin composite oxide in (ITO), the content of tin oxide and indium oxide _(In 2 _{O 3)} tin oxide to the total weight of the _{(SnO 2) (SnO 2)} (SnO 2 / (SnO 2 + In 2 O 3 ) Is, for example, 6% by mass or more, preferably 8% by mass or more, more preferably 10% by mass or more, still more preferably 12% by mass or more, and for example, 30% by mass. % Or less, preferably 20% by mass or less, more preferably 17% by mass or less, and the first inorganic oxide layer when the mass ratio of tin oxide (SnO ₂ ) is less than the lower limit described above. crystalline aging of 8 is increased, there is a possibility that it is difficult to control the etching properties. When the mass ratio of tin oxide (SnO ₂₎ exceeds the upper limit described above, the humidification reduced reliability There is a case.

  For example, the first inorganic oxide layer 8 may be crystalline or amorphous. The first inorganic oxide layer 8 is preferably amorphous from the viewpoint of easily performing patterning in a later step.

  The thickness T8 of the first 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. If the thickness T8 of the first inorganic oxide layer 8 is less than or equal to the above-described upper limit, the light transmissive conductive layer 3 can be etched quickly and reliably in the subsequent steps, and the thickness of the first inorganic oxide layer 8 If T8 is not less than the above lower limit, it can function as a barrier layer.

3-2. Metal Layer The metal layer 9 is a conductive layer that imparts conductivity to the light-transmissive conductive layer 3 together with the first inorganic oxide layer 8 and the second inorganic oxide layer 10. The metal layer 9 is also a low specific resistance layer that reduces the specific resistance of the light transmissive conductive layer 3.

  The metal layer 9 has a film shape (including a sheet shape), and is disposed on the upper surface of the first inorganic oxide layer 8 so as to be in contact with the upper surface of the first inorganic oxide layer 8.

  The metal forming the metal layer 9 is, for example, a metal having a small specific resistance and a metal that can be dissolved in the same etching solution as the etching solution for etching the first inorganic oxide layer 8. The metal is not particularly limited. 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 an alloy containing one or more metals selected from the group consisting of Hf and alloys containing two or more metals.

  As a metal, Preferably, silver (Ag) and a silver alloy are mentioned, More preferably, a silver alloy is mentioned.

  The silver alloy contains silver as a main component and other metals as subcomponents, and its composition is not limited. Examples of the composition of the silver alloy include an Ag—Pd alloy, an Ag—Pd—Cu alloy, an Ag—Pd—Cu—Ge alloy, an Ag—Cu—Au alloy, an Ag—Cu alloy, an Ag—Cu—Sn alloy, and Ag. -Ru-Cu alloy, Ag-Ru-Au alloy, Ag-Pd alloy, Ag-Nd alloy, Ag-Mg alloy, Ag-Ca alloy, Ag-Na alloy and the like. The silver alloy is preferably an Ag—Pd alloy.

  The silver content in the silver alloy (preferably, Ag—Pd alloy) is, for example, 80% by mass or more, preferably 85% by mass or more, more preferably 90% by mass or more, and further preferably 95.0% by mass. % Or more, 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. When the metal is an Ag—Pd alloy, the content ratio of Pd in the Ag—Pd alloy is specifically 0.1% by mass or more, for example, 10% by mass or less, preferably, 5 mass% or less, More preferably, it is 1.0 mass% or less.

  From the viewpoint of increasing the transmittance of the light-transmitting conductive layer 3, the thickness of the metal layer 9 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 10 nm or less.

3-3. Second Inorganic Oxide Layer The second inorganic oxide layer 10 is a conductive layer that imparts conductivity to the light transmissive conductive layer 3 together with the first inorganic oxide layer 8 and the metal layer 9. Although the 2nd inorganic oxide layer 10 does not need to hold | maintain electroconductivity, Preferably, it has electroconductivity. The second inorganic oxide layer 10 is also a barrier layer that prevents the metal layer 9 from being eroded by oxygen, water vapor, or a small amount of sulfur oxide (SO _x ) that is always present in the atmosphere. is there. The second inorganic oxide layer 10 is the uppermost layer in the light transmissive conductive layer 3 and has a film shape (including a sheet shape). The second inorganic oxide layer 10 is formed on the entire upper surface of the metal layer 9 and on the upper surface of the metal layer 9. It is arranged to come into contact.

  The second inorganic oxide layer 10 contains the inorganic oxide exemplified in the first inorganic oxide layer 8, and specifically, with respect to the same etching solution as the etching solution for etching the first inorganic oxide layer 8. It is an inorganic oxide that can be dissolved, and preferably contains indium oxide, and more preferably consists of ITO. That is, the second inorganic oxide layer 10 is preferably an indium conductive oxide layer, and more preferably an ITO layer.

Indium tin composite oxide in (ITO), the content of tin oxide and indium oxide _(In 2 _{O 3)} tin oxide to the total weight of the _{(SnO 2) (SnO 2)} (SnO 2 / (SnO 2 + In 2 O 3 ) Is, for example, 6% by mass or more, preferably 8% by mass or more, more preferably 10% by mass or more, still more preferably 12% by mass or more, and for example, 30% by mass. % Or less, preferably 20% by mass or less, more preferably 17% by mass or less The second inorganic oxide layer when the content ratio of tin oxide (SnO ₂ ) is less than the lower limit described above. crystalline aging of 10 increases, there is a possibility that it is difficult to control the etching properties. If the content of tin oxide (SnO ₂₎ exceeds the upper limit described above, to decrease the humidification reliability If there is a.

  For example, the second inorganic oxide layer 10 may be crystalline or amorphous. The second inorganic oxide layer 10 is preferably amorphous from the viewpoint of easily performing patterning in a later step.

  The first inorganic oxide layer 8 and the second inorganic oxide layer 10 are preferably the same film quality, more preferably both amorphous, from the viewpoint of obtaining a good pattern cross section during etching. is there.

  The thickness T10 of the second inorganic oxide layer 10 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.

  If the thickness T10 of the second inorganic oxide layer 10 is less than or equal to the above-described upper limit, the light transmissive conductive layer 3 can be etched quickly and reliably in the subsequent steps, and the thickness of the second inorganic oxide layer 10 is increased. If T10 is not less than the above lower limit, it can function as a barrier layer.

  Further, among the thickness T8 of the first inorganic oxide layer 8 and the thickness T10 of the second inorganic oxide layer 10, the thickness of at least one layer is, for example, 80 nm or less, preferably 50 nm or less. Preferably, both the thickness T8 of the first inorganic oxide layer 8 and the thickness T10 of the second inorganic oxide layer 10 are both 50 nm or less, for example. If the thickness T8 of the first inorganic oxide layer 8 and / or the thickness T10 of the second inorganic oxide layer 10 is equal to or less than the above-described upper limit, the light-transmissive conductive layer 3 is etched quickly and reliably in the subsequent steps. be able to.

  The thickness of the light-transmissive conductive layer 3, that is, the total thickness of the first inorganic oxide layer 8, the metal layer 9, and the second inorganic oxide layer 10 is preferably 20 nm or more, more preferably 40 nm or more. For example, it is 230 nm or less, preferably 120 nm or less, and more preferably 100 nm or less.

4). Inorganic Layer The inorganic layer 4 is the uppermost layer of the light transmissive conductive film 1 and has a film shape (including a sheet shape). The inorganic layer 4 is disposed on the entire upper surface of the second inorganic oxide layer 10 so as to be in contact with the upper surface of the second inorganic oxide layer 10.

  The inorganic layer 4 is a hydrophilic layer that imparts hydrophilicity to the upper surface (surface) of the light transmissive conductive layer 3 (specifically, the second inorganic oxide layer 10).

  Moreover, although the inorganic layer 4 is mentioned later, since it is preferably formed by a sputtering method, it is a sputtered layer.

The inorganic layer 4 is made of a hydrophilic material, for example. Although there is no limitation as a hydrophilic material, it consists of a hydrophilic material, for example. Examples of the hydrophilic material include silicon oxide, titanium oxide (specifically, TiO ₂ ), aluminum oxide (specifically, inorganic oxides such as Al ₂ O ₃ , for example, metal salts such as zeolite). The hydrophilic material is preferably an inorganic oxide, more preferably silicon oxide.

The silicon oxide is specifically represented by SiO _x , and x is, for example, 1.0 or more, preferably 1.5 or more, and, for example, 2.0 or less. Specifically, examples of silicon oxide include SiO and SiO ₂ (silica), and preferably, SiO ₂ is used.

  The thickness T4 of the inorganic layer 4 is 20 nm or less, preferably 10 nm or less, more preferably less than 10 nm, still more preferably 5.0 nm or less, particularly preferably less than 5.0 nm, and most preferably 4.5 nm or less. Furthermore, it is 3.0 nm or less, for example, 0.01 nm or more, preferably 0.1 nm or more, more preferably 0.5 nm or more, and further preferably 1.0 nm or more.

  If the thickness T4 of the inorganic layer 4 exceeds the above upper limit, the light transmissive conductive layer 3 cannot be etched quickly and reliably. Furthermore, if the thickness T4 of the inorganic layer 4 exceeds the above upper limit, the water contact angle θ0 immediately after the inorganic layer 4 is formed can be set low, but the water contact angle ratio (described later) ( (θ1 / θ0) is increased (specifically, 4.0 or more). Therefore, the water contact angle θ1 of the inorganic layer 4 after 80 hours or more after the formation of the inorganic layer 4 is increased. Therefore, the water contact angle θ1 of the inorganic layer 4 after 80 hours or more after the formation of the inorganic layer 4 may vary.

  On the other hand, if the thickness T4 of the inorganic layer 4 is equal to or greater than the above lower limit, excellent wettability can be obtained.

  The ratio of the thickness T4 of the inorganic layer 4 to the thickness T10 of the second inorganic oxide layer 10 (thickness T4 of the inorganic layer 4 / thickness T10 of the second inorganic oxide layer 10) is, for example, 0.01 or more. Preferably, it is 0.02 or more, for example, 0.50 or less, preferably 0.25 or less, more preferably 0.15 or less, and further preferably 0.10 or less.

  If the above-described thickness ratio is equal to or greater than the above lower limit, excellent wettability can be obtained.

  If the above thickness ratio exceeds the above upper limit, the light transmissive conductive layer 3 cannot be etched quickly and reliably. If the above thickness ratio exceeds the above lower limit, the water contact angle θ1 of the inorganic layer 4 after 80 hours or more after the inorganic layer 4 is formed may vary.

  The water contact angle θ1 of the inorganic layer 4 (which will be described later, the water contact angle θ1 after the elapse of 80 hours from the formation of the inorganic layer 4) is 50 degrees or less, preferably 40 degrees or less, more preferably 30 degrees or less, more preferably 20 degrees or less, particularly preferably less than 20 degrees, most preferably 10 degrees or less, and for example, 0 degrees or more, preferably 1 degree or more, more preferably, 5 degrees or more.

  The water contact angle θ1 of the inorganic layer 4 is normal temperature (specifically 20 to 40 ° C.) and normal humidity (specifically, relative humidity 30% or more and 70% or less) after the inorganic layer 4 is formed. The inorganic layer 4 left for 80 hours or more in the atmosphere is measured based on JIS R1753: 2013. A more specific method for measuring the water contact angle θ1 will be described in a later example.

  If the water contact angle θ1 after the elapse of 80 hours or more after the inorganic layer 4 is formed exceeds the upper limit described above, the light control function layer 5 (described later) having a uniform thickness is wetted with the inorganic layer 4. Can not be formed on the surface of.

5. Next, a method for producing the light transmissive conductive film 1 will be described.

  This method includes a step (1) of preparing a light-transmitting substrate 2, a step (2) of forming a light-transmitting conductive layer 3 on the surface of the light-transmitting substrate 2, and an inorganic layer 4 having a light-transmitting property. And (3) forming on the surface of the conductive layer 3. Hereinafter, each process is explained in full detail.

5-1. Process (1)
In step (1), first, a base substrate 6 is prepared.

  Next, the functional layer 7 is disposed on the upper surface of the base substrate 6. For example, the functional layer 7 is disposed by wet processing. Specifically, first, the resin composition is applied to the upper surface of the base substrate 6. Thereafter, when the resin composition contains an active energy ray-curable resin, the active energy ray is irradiated.

  Thereby, the film-shaped functional layer 7 is formed on the entire upper surface of the light-transmitting substrate 2. That is, the light transmissive substrate 2 including the base substrate 6 and the functional layer 7 is produced.

5-2. Process (2)
In the step (2), after the step (1), the light transmissive conductive layer 3 is disposed (laminated) on the upper surface of the functional layer 7 by, for example, a dry method.

  Specifically, each of the first inorganic oxide layer 8, the metal layer 9, and the second inorganic oxide layer 10 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.

  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 ratio of the flow rate of the reactive gas to the flow rate of the inert gas (reactive gas flow rate / inert gas flow rate) is, for example, 0.1 / 100 or more, preferably It is 0.5 / 100 or more, for example, 10/100 or less, preferably 5/100 or less.

  Specifically, in each formation of the first inorganic oxide layer 8 and the second inorganic oxide layer 10, an inert gas and a reactive gas are preferably used in combination as the gas.

  On the other hand, in the formation of the metal layer 9, an inert gas is preferably used alone as the gas. In forming the second inorganic oxide layer 10, an inert gas and a reactive gas are preferably used in combination as the gas.

  Preferably, the light transmissive conductive layer 3 is formed as an amorphous material. Specifically, the amorphous first inorganic oxide layer 8 and the amorphous second inorganic oxide layer 10 are formed.

  Thereby, the light transmissive conductive layer 3 in which the first inorganic oxide layer 8, the metal layer 9, and the second inorganic oxide layer 10 are formed in order is formed on the light transmissive substrate 2.

  The surface resistance of the light-transmitting conductive layer 3 (specifically, the surface resistance of the amorphous light-transmitting conductive layer 3) is, for example, 1Ω / □ or more, preferably 3Ω / □ or more, more preferably For example, it is 100Ω / □ or less, preferably 50Ω / □ or less, and more preferably 30Ω / □ or less.

5-3. Step (3)
In the step (3), after the step (2), the inorganic layer 4 is disposed (laminated) on the upper surface of the second inorganic oxide layer 10 by, for example, 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 from the viewpoint of forming the inorganic layer 4 uniformly and with the above-described thickness T4. On the other hand, if the vacuum deposition method is used, the variation in the thickness T4 of the inorganic layer 4 may increase, the wettability of the inorganic layer 4 may decrease, and the inorganic layer 4 may be separated from the light-transmitting conductive layer 3. May peel.

  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 ratio of the flow rate of the reactive gas to the flow rate of the inert gas is (reactive gas flow rate / inert gas flow rate), for example, 1/100 or more, preferably 10 / 100 or more, more preferably 20/100 or more, and for example, 90/100 or less, preferably 50/100 or less.

  The water contact angle θ0 of the inorganic layer 4 immediately after the inorganic layer 4 is formed (specifically, within 500 minutes after the inorganic layer 4 is formed) is 50 degrees or less, preferably 40 degrees or less. The angle is preferably 20 degrees or less, more preferably 10 degrees or less, and for example, 0 degrees or more, preferably 5 degrees or more, more preferably more than 6 degrees, more preferably 7 degrees or more.

  On the other hand, the water contact angle θ1 of the inorganic layer 4 after 80 hours or more after the inorganic layer 4 is formed changes with respect to the water contact angle θ0 immediately after the inorganic layer 4 is formed. Specifically, the ratio (θ1 / θ0) of the water contact angle θ0 immediately after the inorganic layer 4 is formed to the water contact angle θ1 after the elapse of 80 hours or more after the inorganic layer 4 is formed is, for example, 0 .3 or more, preferably 0.5 or more, more preferably 1.0 or more, further preferably 2.0 or more, and for example, less than 4.5, preferably 4.0 or less, more Preferably, it is 3.5 or less, more preferably 3.0 or less, and particularly preferably less than 3.0. If the above-described ratio is equal to or less than the above upper limit, it is possible to suppress variation in the water contact angle θ1 of the inorganic layer 4 after 80 hours or more after the inorganic layer 4 is formed.

  Thereby, the light transmissive conductive film 1 including the light transmissive substrate 2, the light transmissive conductive layer 3, and the inorganic layer 4 in order is obtained.

  The total thickness of the light-transmitting conductive film 1 is, for example, 2 μm or more, preferably 20 μm or more, and for example, 300 μm or less, preferably 200 μm or less, and more preferably 150 μm or less.

  The light transmissive conductive film 1 is an industrially available device.

5-4. Process (4)
The method for manufacturing the light transmissive conductive film 1 further includes a step (4) of etching the light transmissive conductive layer 3 after the step (3).

  In the step (4), the light transmissive conductive layer 3 is etched after the step (3). Specifically, the light transmissive conductive layer 3 is etched together with the inorganic layer 4, and the light transmissive conductive layer 3 and the inorganic layer 4 are patterned into a predetermined shape.

  The etching solution is not particularly limited as long as it is a solution that can dissolve the light-transmitting conductive layer 3, and examples thereof include nitric acid, phosphoric acid, acetic acid, hydrochloric acid, sulfuric acid, oxalic acid, and a mixed solution thereof.

  The etching time is, for example, 5 minutes or less, preferably 4 minutes or less, more preferably 3 minutes or less, and for example, 0.05 minutes or more, preferably 0.1 minutes or more, more preferably 0.5 minutes or longer. If etching time is below the upper limit mentioned above, the manufacturing method of the transparent conductive film 1 can be implemented by the roll to roll system with the outstanding production efficiency.

  As a result, a light transmissive conductive film 1 including the light transmissive substrate 2, the patterned light transmissive conductive layer 3, and the patterned inorganic layer 4 in order is obtained.

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

6). 2. Manufacturing method of light control film Next, the method of manufacturing the light control film 20 using the above-mentioned light-transmitting conductive film 1 is demonstrated with reference to FIG.

  In this method, as shown in FIG. 2, the step (6) of manufacturing the two light transmissive conductive films 1 and the step (7) of sandwiching the light control function layer 5 between the two light transmissive conductive films 1. With.

6-1. Step (6)
In the step (6), two light transmissive conductive films 1 described above are manufactured. In addition, the two light transmissive conductive films 1 can also be prepared by cutting one light transmissive conductive film 1.

  The two light transmissive conductive films 1 are a first light transmissive conductive film 1A and a second light transmissive conductive film 1B.

6-2. Step (7)
Step (7) is performed after step (6). In the step (7), the light control function layer 5 is formed on the upper surface (surface) of the inorganic layer 4 in the first light-transmissive conductive film 1A by, for example, wet processing.

  The dimming function layer 5 is, for example, an electrochromic layer or a liquid crystal layer, and is preferably a liquid crystal layer.

  In this step (7), for example, a solution containing a liquid crystal composition is applied to the upper surface of the inorganic layer 4 in the first light-transmissive conductive film 1A. Examples of the liquid crystal composition include known ones contained in a solution, for example, a liquid crystal dispersion resin described in JP-A-8-194209.

  Subsequently, the second light-transmissive conductive film 1B is laminated on the surface of the coating film so that the inorganic layer 4 of the second light-transmissive conductive film 1B and the surface of the coating film are in contact with each other. Thus, the coating film is sandwiched between the two light transmissive conductive films 1, that is, the first light transmissive conductive film 1A and the second light transmissive conductive film 1B.

  Thereafter, an appropriate treatment is applied to the coating film (in the case where the liquid crystal composition contains an ultraviolet curable composition, ultraviolet irradiation) to form the light control function layer 5. The light control function layer 5 is formed between the inorganic layer 4 of the first light-transmissive conductive film 1A and the inorganic layer 4 of the second light-transmissive conductive film 1B.

  Thereby, the light control film 20 provided with the 1st light transmissive conductive film 1A, the light control function layer 5, and the 2nd light transmissive conductive film 1B in order is obtained.

  The light control film 20 is provided in a light control device (not shown, for example, a light control window) including a power source (not shown), a control device (not shown), and the like. In a light control device (not shown), a voltage is applied to the light transmissive conductive layer 3 in the first light transmissive conductive film 1A and the light transmissive conductive layer 3 in the second light transmissive conductive film 1B by a power source. , Thereby generating an electric field between them.

  And the light control function layer 5 located between the 1st light transmissive conductive film 1A and the 2nd light transmissive conductive film 1B by controlling the above-mentioned electric field based on a control device, Block or transmit light.

7). Effects of First Embodiment Since the light-transmitting conductive film 1 includes the inorganic layer 4, the hydrophilic performance can be stably maintained. Therefore, the light transmissive conductive film 1 is excellent in reliability.

  And since this light-transmitting conductive film 1 has the thickness T4 of the inorganic layer 4 equal to or less than the upper limit described above, the light-transmitting conductive layer 3 can be etched together with the inorganic layer 4 quickly and reliably. Therefore, the light transmissive conductive film 1 is excellent in pattern processability.

  In addition, since the water contact angle θ1 after the elapse of 80 hours from the formation of the inorganic layer 4 of the inorganic layer 4 is equal to or less than the above upper limit, the light control function layer 5 having a uniform thickness is wetted with the inorganic layer 4. Can be formed on the surface. Therefore, the light control film 20 excellent in reliability can be obtained.

  Moreover, in this light transmissive conductive film 1, if the inorganic layer 4 is formed by sputtering, that is, if the inorganic layer 4 is a sputter layer, the inorganic layer 4 is uniform and has the thickness T4 described above. Moreover, it has excellent scratch resistance and adhesion to the light-transmitting substrate 2 (specifically, the functional layer 7).

  Moreover, in this light transmissive conductive film 1, if the inorganic layer 4 consists of an inorganic oxide, it will be especially excellent in hydrophilicity.

  Moreover, in this light transmissive conductive film 1, if at least one of the thickness T8 of the first inorganic oxide layer 8 and the thickness T10 of the second inorganic oxide layer 10 is not more than the above upper limit, The light-transmitting conductive layer 3 together with the inorganic layer 4 can be etched quickly and reliably.

  Further, according to this method, if the inorganic layer 4 having the thickness T4 equal to or less than the upper limit described above is formed in the step (3), the light transmission is performed together with the inorganic layer 4 in the step (4) after the step (3). The conductive conductive layer 3 can be etched quickly and reliably.

  In addition, since the water contact angle θ1 after the elapse of 80 hours from the formation of the inorganic layer 4 of the inorganic layer 4 is equal to or less than the above upper limit, the light control function layer 5 having a uniform thickness is wetted with the inorganic layer 4. Can be formed on the surface.

  In this light control film 20, the light control function layer 5 contacts the inorganic layer 4 provided in the first light-transmissive conductive film 1A and the inorganic layer 4 provided in the second light-transmissive conductive film 1B. Therefore, it can have a uniform thickness. And since this light control film 20 is provided with the above-mentioned light transmissive conductive film 1 excellent in reliability, it is excellent in reliability.

  Moreover, according to the manufacturing method of the light control film 20, in a process (6), the inorganic layer 4 is made into the inorganic layer 4 of the 1st light transmissive conductive film 1A, and the inorganic of the 2nd light transmissive conductive film 1B. Since it is brought into contact with the layer 4, the light control function layer 5 having a uniform thickness T5 can be obtained. Therefore, this light control film 20 is excellent in reliability.

8). Modification of First Embodiment Further, in the manufacturing method of the light control film 20 described above, the amorphous light-transmitting conductive layer 3 is formed in the step (2) according to the use and purpose of the light control film 20. In this case, the step (5) of crystallizing the amorphous light-transmitting conductive layer 3 can be provided before and after the step (4). Preferably, after the step (4), the amorphous light-transmitting conductive layer 3 is amorphous. The step (5) of crystallizing the light-transmissive conductive layer 3 is provided.

  In the step (2), an amorphous light transmissive conductive layer 3 is formed. Specifically, an amorphous first inorganic oxide layer 8 and an amorphous second inorganic oxide layer 10 are formed.

  Step (5) is preferably performed after step (4). In the step (5), the amorphous first inorganic oxide layer 8 and the second inorganic oxide layer 10 are crystallized.

  In order to crystallize the light-transmitting conductive layer 3, for example, the patterned light-transmitting conductive layer 3 is subjected to, for example, a temperature of 80 ° C. or higher and 150 ° C. or lower, for example, 30 minutes or longer in an air atmosphere , Heating (annealing) for 90 minutes or less.

  The surface resistance of the crystallized light-transmissive conductive layer 3 is, for example, 0.5Ω / □ or more, preferably 1Ω / □ or more, more preferably 5Ω / □ or more, and for example, 50Ω / □. □ or less, preferably 20 Ω / □ or less, more preferably 15 Ω / □ or less.

  Moreover, in 1st Embodiment, although the functional layer 7 was provided in the light transmissive base material 2, as shown in FIG. 3, for example, without providing the functional layer 7, only the light transmissive group is provided from the base base material 6. The material 2 can be configured. That is, as shown in FIG. 3, in this case, the light transmissive substrate 2 is not provided with the functional layer 7 and is composed only of the base substrate 6.

  The light transmissive conductive layer 3 (specifically, the first inorganic oxide layer 8) is disposed so as to be in contact with the upper surface of the base substrate 6 (light transmissive substrate 2).

  The light transmissive conductive layer 3 is disposed on the upper surface of the base substrate 6. Specifically, the first inorganic oxide layer 8 is disposed on the entire upper surface of the base substrate 6.

  Further, as shown in FIG. 2, each of the two light-transmitting conductive films 1, that is, the first light-transmitting conductive film 1 </ b> A and the second light-transmitting conductive film 1 </ b> B, each has a specific inorganic layer 4. For example, although not illustrated, specifically, the first light-transmissive conductive film 1A is provided with the inorganic layer 4 and the second light-transmissive conductive film 1B is provided with the inorganic layer 4. Alternatively, the second light-transmissive conductive film 1B can be configured.

  In this modification, although not shown, the second light transmissive conductive film 1B includes a light transmissive substrate 2 and a light transmissive conductive layer 3 in this order.

  Further, as shown in FIG. 1, in the light transmissive conductive film 1 of the first embodiment, the light transmissive conductive layer 3 includes, in order, a first inorganic oxide layer 8, a metal layer 9, and a second inorganic oxide. A physical layer 10. However, for example, although not shown, a second metal layer and a third inorganic oxide layer can be further disposed in order on the second inorganic oxide layer 10. In that case, the transparent conductive layer 3 includes the first inorganic oxide layer 8, the metal layer 9, the second inorganic oxide layer 10, the second metal layer, and the third inorganic oxide layer in order. Prepare. Furthermore, a 3rd metal layer and a 4th inorganic oxide layer can be arrange | positioned in order on a 3rd inorganic oxide layer. In that case, the transmissive conductive layer 3 includes the first inorganic oxide layer 8, the metal layer 9, the second inorganic oxide layer 10, the second metal layer, the third inorganic oxide layer, 3 metal layers and a 4th inorganic oxide layer are provided.

  In the second light transmissive conductive film 1B, the surface of the light transmissive conductive layer 3, specifically, the surface of the second inorganic oxide layer 10 is exposed. The second inorganic oxide layer 10 of the second light transmissive conductive film 1 </ b> B is in direct contact with the light control function layer 5.

  In the first embodiment, as shown in FIG. 1, the functional layer 7 is disposed on the upper surface of the base substrate 6. However, although not shown, the functional layer 7 is disposed on the upper surface of the base substrate 6. It can also be arranged on both sides of the lower surface.

  According to each modification mentioned above, there can exist an effect similar to 1st Embodiment.

Second Embodiment
In the second embodiment, the same members and steps as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof is omitted.

1. Light-transmissive conductive film The light-transmissive conductive layer 3 includes three layers of a first inorganic oxide layer 8, a metal layer 9, and a second inorganic oxide layer 10 as shown in FIG. As shown in FIG. 4, in the second embodiment, only one layer of the first inorganic oxide layer 8 is provided. As shown in FIG. 4, the light-transmissive conductive layer 3 does not include the metal layer 9, and is preferably crystalline from the viewpoint of obtaining a low specific resistance.

1-1. Light-transmissive conductive layer The light-transmissive conductive layer 3 includes only the first inorganic oxide layer 8.

  The thickness T3 of the light-transmissive conductive layer 3 is the same as the thickness T8 of the first inorganic oxide layer 8, and specifically, for example, 15 nm or more, preferably 20 nm or more, and, for example, 300 nm or less. The thickness is preferably 150 nm or less, more preferably 50 nm or less, still more preferably 40 nm or less, and particularly preferably 35 nm or less.

  If the thickness T3 of the light-transmitting conductive layer 3 is equal to or less than the above upper limit, the light-transmitting conductive layer 3 can be quickly and reliably etched together with the inorganic layer 4 in the subsequent step. If the thickness T3 of the light-transmitting conductive layer 3 is equal to or greater than the lower limit described above, it can be surely crystallized even when crystallinity is required.

  The light transmissive conductive layer 3 is preferably crystalline. The crystalline film may be clearly inferior in hydrophilicity as compared with the amorphous film, but the light-transmitting conductive film 1 of the present application has an inorganic layer 4 having excellent hydrophilicity on the light-transmitting conductive layer 3. Therefore, even if the light-transmitting conductive layer 3 is a crystalline film, it can be suitably used.

  The light transmissive conductive layer 3 may be a first inorganic oxide layer 8 made of a laminate of a plurality of inorganic oxide layers (see reference numerals 13 and 14 in FIG. 4). Preferably, the 1st inorganic oxide layer 8 consists of a laminated body of the several (for example, two) indium tin complex oxide (ITO) from which a composition differs. Specifically, the first inorganic oxide layer 8 is disposed on the upper surface of the third indium tin composite oxide layer 13 and the third indium tin composite oxide layer 13 disposed on the upper surface of the light-transmitting substrate 2. And a fourth indium tin composite oxide layer 14. Among the first inorganic oxide layers 8, in the indium tin composite oxide layer (specifically, the fourth indium tin composite oxide layer 14) disposed on the inorganic layer 4 side (facing the inorganic layer 4), The tin oxide content is not the maximum, preferably the minimum, compared to the tin oxide content in each indium tin composite oxide layer constituting the first inorganic oxide layer 8. That is, in the first inorganic oxide layer 8, preferably, the tin oxide content decreases from the lower layer to the upper layer. Specifically, when the first inorganic oxide layer 8 is composed of a laminate of the third indium tin composite oxide layer 13 and the fourth indium tin composite oxide layer 14, the fourth indium tin composite oxide. The tin oxide content of the layer 14 is smaller than the tin oxide content of the third indium tin composite oxide layer 13. More specifically, the fourth indium tin composite oxide layer 14 includes the first inorganic oxide. The physical layer 8 has the smallest tin oxide content.

  Thereby, even if the inorganic layer 4 is arrange | positioned on the transparent conductive layer 3, it can turn into a crystalline ITO film | membrane in a short time.

  The tin oxide content of the fourth indium tin composite oxide layer 14 is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, More preferably, it is 3 mass% or more, for example, 8 mass% or less, Preferably, it is 6 mass% or less, More preferably, it is 5 mass% or less.

  On the other hand, the tin oxide content of the layers other than the fourth indium tin composite oxide layer 14 (specifically, the third indium tin composite oxide layer 13) is, for example, 5% by mass or more, preferably 6 % By mass or more, more preferably 9% by mass or more, further preferably 10% by mass or more, for example, 20% by mass or less, preferably 15% by mass or less, more Preferably, it is 13 mass% or less.

1-2. Inorganic Layer The inorganic layer 4 is disposed on the upper surface of the first inorganic oxide layer 8.

2. The manufacturing method of a transparent conductive film The manufacturing method of a transparent conductive film is provided with a process (5) in addition to above-described process (1) -process (4).

2-1. Process (2)
In the step (2), the light transmissive conductive layer 3 is formed only from the amorphous first inorganic oxide layer 8.

2-2. Process (5)
Step (5) is performed after step (4).

  In step (5), the light-transmitting conductive layer 3 composed of the patterned amorphous first inorganic oxide layer 8 is crystallized.

  In order to crystallize the light-transmitting conductive layer 3, for example, the patterned light-transmitting conductive layer 3 is subjected to, for example, a temperature of 80 ° C. or higher and 150 ° C. or lower, for example, 30 minutes or longer in an air atmosphere , Heating (annealing) for 90 minutes or less.

  The surface resistance of the crystallized light transmissive conductive layer 3 is, for example, 30Ω / □ or more, preferably 60Ω / □ or more, and for example, 200Ω / □ or less, preferably 150Ω / □ or less, or more. Preferably, it is 100Ω / □ or less, more preferably 90Ω / □ or less.

3. Effects of the Second Embodiment The second embodiment can achieve the same effects as the first embodiment.

  Further, in the step (5) after the step (3), more specifically, in the step (5) after the step (4), the light transmittance made of the amorphous first inorganic oxide layer 8 is achieved. Since the conductive layer 3 is crystallized, the surface resistance of the light transmissive conductive layer 3 can be reduced.

4). Modified Example of Second Embodiment In the second embodiment, the step (5) is performed after the step (4), but after the step (3) and before the step (4), the step (5) can also be implemented.

  That is, the inorganic layer 4 is formed in the step (3), and then the light transmissive conductive layer 3 is crystallized in the step (5), and then the light transmissive conductive layer 3 is etched in the step (4). .

  In 2nd Embodiment, a process (5) can also be implemented following a process (2).

  For example, in step (2), an amorphous light-transmitting conductive layer 3 is formed, and then in step (5), the amorphous light-transmitting conductive layer 3 is crystallized, and then in step (3) The inorganic layer 4 is formed on the crystalline light-transmitting conductive layer 3.

  For example, in step (2), an amorphous light-transmitting conductive layer 3 is formed, and then in step (5), the amorphous light-transmitting conductive layer 3 is crystallized, and then in step (3) In the method, the inorganic layer 4 can be formed on the crystalline light-transmitting conductive layer 3, and the crystalline light-transmitting conductive layer 3 can be etched in the step (4).

  Although it is inferior in practicality, for example, in step (2), an amorphous light-transmitting conductive layer is formed, and then in step (5), the amorphous light-transmitting conductive layer is crystallized. Thereafter, in step (4), the crystalline light-transmitting conductive layer can be etched, and in step (3), an inorganic layer can be formed on the crystalline light-transmitting conductive layer.

  In 2nd Embodiment, although the functional layer 7 was provided in the light transmissive base material 2, for example, as shown in FIG. Can be configured. That is, as shown in FIG. 6, in this case, the light-transmitting base material 2 is not provided with the functional layer 7 and is composed of only the base base material 6.

  The light transmissive conductive layer 3 (specifically, the first inorganic oxide layer 8) is disposed so as to be in contact with the upper surface of the base substrate 6 (light transmissive substrate 2).

  Also according to these modified examples, the same effects as those of the second embodiment can be achieved.

  Moreover, the above-described first embodiment, second embodiment, and modifications thereof can be appropriately combined.

  Hereinafter, the present invention will be described in detail using examples. However, the present invention is not limited to the examples as long as the gist thereof is not exceeded, and various modifications and changes are made based on the technical idea of the present invention. Is possible.

  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 ( It may be replaced with the upper limit (numerical values defined as “less than” or “less than”) or lower limit (numerical values defined as “greater than” or “exceeded”) such as content ratio), physical property values, parameters, etc. it can.

Example 1
Step (1): Production of light-transmitting substrate A base substrate 6 made of a polyethylene terephthalate (PET) film (Mitsubishi Resin) having a thickness of 50 μm is prepared, and then the surface of the base substrate 6 (light-transmitting conductive material). An ultraviolet curable resin made of an acrylic resin was applied to the main surface on the side on which the layer 3 was formed, and cured by ultraviolet irradiation to form a hard coat layer 7 ′ having a thickness of 2 μm. Thereby, the light transmissive base material 2 provided with the base base material 6 and the hard coat layer 7 ′ in this order was produced.

Step (2): Production of Light-Transparent Conductive Layer Subsequently, the first inorganic oxide layer 8, the metal layer 9, and the second inorganic oxide layer 10 are formed on the hard coat layer 7 ′ of the light-transmissive substrate 2. A light-transmitting conductive layer 3 made of a laminated body provided in this order was formed.

The first inorganic oxide layer 8 and the second inorganic oxide layer 10 were both indium tin oxide layers made of indium tin oxide. Specifically, each of the first inorganic oxide layer 8 and the second inorganic oxide layer 10 is an ITO target (Mitsui Metals) made of a sintered body of 12% by mass of tin oxide and 88% by mass of indium oxide. 40 nm-thick indium tin formed by sputtering in a vacuum atmosphere into which a film forming gas (mixed gas composed of Ar and O ₂ (flow rate ratio Ar: O ₂ = 100: 3)) was introduced. It was a conductive oxide.

  The metal layer 9 was made of an Ag—Pd alloy. Specifically, the metal layer 9 was formed by sputtering a silver alloy target made of an alloy in which 99% by mass of Ag and 1% by mass of Pd were mixed in a vacuum atmosphere into which a film forming gas (Ar) was introduced. It was a silver alloy layer.

Step (3): Production of Inorganic Layer Next, an inorganic layer 4 having a thickness of 0.5 nm made of silicon oxide (SiO ₂ ) was formed on the second inorganic oxide layer 10 of the light-transmitting conductive layer 3. The inorganic layer 4 is made of a Si target (manufactured by Daido Steel Co., Ltd.) made of a Si plate having a purity of 99.99% or more, and made of a film forming gas (Ar and O ₂ (flow rate ratio Ar: O ₂ = 100: 41)). It was formed by sputtering in a vacuum atmosphere in which a mixed gas) was introduced.

  Thereby, the light transmissive conductive film 1 which comprises the light transmissive conductive layer 3, the inorganic layer 4, and the light control function layer 5 in order was manufactured.

Examples 2-8
As shown in Table 1, a light-transmitting conductive film 1 was manufactured in the same manner as in Example 1 except that the thickness of the inorganic layer 4 and the manufacturing method were changed.

Comparative Example 1
As shown in Table 1, a light-transmissive conductive film 1 was produced in the same manner as in Example 1 except that the inorganic layer 4 was not formed.

Example 9
In the step (2), except that the flow rate ratio of Ar and O _{2 as} the film forming gas was Ar: O ₂ = 100: 1, and the light-transmitting conductive layer 3 was produced only from the first inorganic oxide layer 8. According to Table 1, it processed like Example 1 and manufactured the transparent conductive film 1. FIG.

  The first inorganic oxide layer 8 includes a third indium tin composite oxide layer 13 having a tin oxide content of 10% by mass, and a fourth indium tin composite oxide layer 14 having a tin oxide content of 3% by mass. It formed from the laminated body of.

Example 10
In step (3), the inorganic layer 4 was treated in the same manner as in Example 1 except that the inorganic layer 4 was formed from a SiO ₂ layer having a thickness of 0.5 nm by vacuum deposition (electron beam heating method). Film 1 was produced.

Evaluation The following items were evaluated and the results are shown in Table 1.

(1) Water contact angle The water contact angle (θ0, θ1) of the inorganic layer 4 of Examples 1 to 10 is formed by forming a water droplet having a diameter of 1.5 mm on the needle tip and bringing it into contact with the surface of the inorganic layer 4. Then, a water droplet was transferred onto the inorganic layer 4, and the static contact angle between the water droplet and the inorganic layer 4 was measured with a contact angle meter (CA-X type, manufactured by Kyowa Interface Science Co., Ltd.). If the difference between the maximum angle and the minimum angle is 5.0 degrees or less when measured at 5 locations, it is determined that the measurement is accurate, and the wettability is measured using the simple average value of the water contact angle. It was judged. When the water contact angle exceeds 5.0 degrees, accurate measurement cannot be performed and partial repelling of the light control function layer 5 is assumed. Therefore, the wettability is “low” regardless of the numerical value. .

  Regarding the water contact angle θ1, the water contact angle of the inorganic layer 4 that was left for 80 hours in an atmosphere of 25 ° C. and 40% relative humidity after the inorganic layer 4 was formed was measured.

  Moreover, about the comparative example 1, since it did not have the inorganic layer 4, the water contact angle of the transparent conductive layer 3 was measured like the above.

  In addition, although the light transmissive conductive film 1 of Example 10 had a water contact angle of 50 degrees or less, the numerical value of the water contact angle varied depending on the measurement position, and it was difficult to measure the true value.

(2) Thickness The thickness of the base substrate 6 was measured using a film thickness meter (manufactured by Peacock (registered trademark), device name “Digital Dial Gauge DG-205”).

  Cross-sectional observation of the thickness of the hard coat layer 7, the first inorganic oxide layer 8, the metal layer 9, and the second inorganic oxide layer 10 using a transmission electron microscope (manufactured by Hitachi, Ltd., device name “HF-2000”) It was measured by.

  The thickness of the inorganic layer 4 was measured using a fluorescent X-ray analyzer (manufactured by Rigaku Corporation, apparatus name “ZSX Primus II”) (the thickness of the inorganic layer was determined by subtracting the SiKa intensity derived from the light-transmitting substrate). )

  In addition, in carrying out the fluorescent X-ray analysis, it prepared in advance as follows.

That is, a specimen in which a silicon oxide (SiO ₂ ) layer having a target thickness of 100 nm, 150 nm, and 200 nm is formed on a PET substrate having a thickness of 50 μm is prepared, and the intensity of SiKa (PET base) of each specimen is measured with each fluorescent X-ray analyzer. The value obtained by subtracting the SiKa intensity derived from the material) was measured, and the actual film thickness of the silicon oxide layer of each specimen was determined with a transmission electron microscope. A calibration curve was created from the SiKa strength value and the actual film thickness thus obtained, and the thickness of the inorganic layer 4 was determined from the SiKa strength.

(3) Etching time and etching properties 20 light-transmitting conductive films 1 cut into a 5 cm square size were prepared and heated to 40 ° C. (product name “Adeka Kermica SET-500” manufactured by ADEKA) ). Thereafter, one sheet was taken out every 15 seconds, washed with water and wiped (dried), and the appearance of the light-transmitting conductive film 1 was confirmed and the resistance between two terminals was measured at three arbitrary points. The resistance between the two terminals was measured with a tester, and the distance between the terminals when measuring was 1.5 cm. In the evaluation of the etching time, the residual derived from the light-transmitting conductive layer 3 or the inorganic layer 4 cannot be confirmed in the light-transmitting conductive film 1 of 5 cm square visually, and two terminals at arbitrary three points It was judged that the etching was completed when all the inter-resistances exceeded 60 MΩ.

The etching property was evaluated according to the following criteria.
A: The etching time was less than 60 seconds.
○: Etching time was 60 seconds or more and 180 seconds or less.
(Triangle | delta): Etching time exceeded 180 second and was 300 second or less.
X: Etching time exceeded 300 seconds.

(4) Surface resistance value of light-transmitting conductive layer The surface resistance value of the light-transmitting conductive layer 3 was measured using a four-terminal method according to JIS K 7194 (1994).

(5) Crystallinity The light transmissive conductive layer 3 in Example 9 was heat-treated at 140 ° C., and the crystallinity of the light transmissive conductive layer 3 was evaluated. Specifically, after immersing the light-transmitting conductive film of each example in hydrochloric acid (concentration: 5% by mass) for 15 minutes, washing and drying, and measuring the resistance between terminals between about 15 mm, The crystallization rate was evaluated according to the criteria.
A: The resistance between terminals between 15 mm was 10 kΩ or less.
X: Resistance between terminals between 15 mm exceeded 10 kΩ.

Also in Comparative Example 1, the crystallization rate was evaluated in the same manner as in Example 9.
(6) Repellency An aqueous solution in which 5 mg of sodium chloride is dissolved in 100 mL of water is applied to the light-transmitting conductive layer 3 of each Example and Comparative Example, or when there is no light-transmitting conductive layer 3, a light-transmitting group It dripped on the material 2 and visually repellency was evaluated according to the following reference | standard.
○: No repelling was observed.
Δ: Slight repellency was observed, but the aqueous solution was generally well adapted to the light-transmitting conductive layer 3 or the light-transmitting substrate 2 as a whole.
X: Repelling was observed.
(7) Peeling The inorganic layers of Examples 1 to 10 were observed and the peelability was evaluated as follows.
A: No peeled parts were found on the inorganic layer 4.
(Triangle | delta): The peeling location was scattered on the inorganic layer 4.

DESCRIPTION OF SYMBOLS 1 Light transmissive conductive film 2 Light transmissive base material 3 Light transmissive conductive layer 4 Inorganic layer 5 Light control function layer T4 Inorganic layer thickness T8 First inorganic oxide layer thickness T10 Thickness of second inorganic oxide layer

Claims (8)

A light transmissive substrate, a light transmissive conductive layer, and an inorganic layer are provided in this order.
The inorganic layer has a thickness of 20 nm or less;
A light transmissive conductive film, wherein the inorganic layer has a water contact angle of 50 degrees or less.   2. The light-transmissive conductive film according to claim 1, wherein a water contact angle of the inorganic layer after 50 hours or more has elapsed from the formation of the inorganic layer is 50 degrees or less.   The light transmissive conductive film according to claim 1, wherein the inorganic layer is made of an inorganic oxide. The light transmissive conductive layer has an indium-based conductive oxide layer,
The light-transmissive conductive film according to claim 1, wherein the indium-based conductive oxide layer has a thickness of 50 nm or less. Preparing a light transmissive substrate (1);
Forming a light transmissive conductive layer on the surface of the light transmissive substrate (2);
Forming an inorganic layer on the surface of the light-transmitting conductive layer (3);
A step (4) of etching the light-transmissive conductive layer after the step (3);
The inorganic layer has a thickness of 20 nm or less;
A method for producing a light-transmitting conductive film, wherein the inorganic layer has a water contact angle of 50 degrees or less after 80 hours or more from the formation of the inorganic layer. In the step (2), the amorphous light-transmitting conductive layer is formed,
Step (5) of crystallizing the amorphous light-transmitting conductive layer after the step (3)
The method for producing a light-transmitting conductive film according to claim 5, further comprising: A first light transmissive conductive film, a light control functional layer, and a second light transmissive conductive film in order,
The first light transmissive conductive film and / or the second light transmissive conductive film is the light transmissive conductive film according to any one of claims 1 to 4,
The said light control functional layer is contacting the inorganic layer with which the said transparent conductive film is equipped, The light control film characterized by the above-mentioned. A step (6) of producing two light-transmissive conductive films;
And a step (7) of sandwiching the light control functional layer between the two light transmissive conductive layers,
In the step (6), at least one light transmissive conductive film is produced by the production method according to claim 5 or 6,
In the step (7), the dimming functional layer is brought into contact with at least one inorganic layer of the light-transmitting conductive film.

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