WO2017170673A1

WO2017170673A1 - Transparent electroconductive laminate

Info

Publication number: WO2017170673A1
Application number: PCT/JP2017/012869
Authority: WO
Inventors: 健古田; 涼介塩野
Original assignee: 北川工業株式会社
Priority date: 2016-03-29
Filing date: 2017-03-29
Publication date: 2017-10-05

Abstract

A transparent electroconductive laminate 1 according to the present invention is provided with: a substrate layer 2 comprising a resin film and having a ten-point average surface roughness on at least one side of not more than 50 nm; a plurality of metal oxide layers 3, 3, each comprising at least one metal oxide selected from the group consisting of aluminum-doped zinc oxide, titanium-doped zinc oxide, zinc-doped indium oxide, and niobium oxide, and disposed on the one side with a distance therebetween; and a silver-based thin film layer 4 comprising a thin film of silver or a silver alloy and interposed between the metal oxide layers 3, 3 that are adjacent to each other. The thickness of a surface-side metal oxide layer 30 disposed at the position farthest from the substrate layer, among the metal oxide layers 3, is at least 20 nm.

Description

Transparent conductive laminate

The present invention relates to a transparent conductive laminate.

A laminate having excellent transparency and conductivity is known. This type of laminate (hereinafter referred to as a transparent conductive laminate) mainly comprises a base material made of transparent plastic and the like, and a transparent conductive layer formed on the base material, and transparency is required. (See, for example, Patent Documents 1 to 3).

The transparent conductive laminate of Patent Document 1 includes a transparent conductive film made of ITO (Indium Tin Oxide) as a conductive layer. Moreover, the transparent conductive laminated body of patent document 2 is equipped with the mesh-shaped metal film as a conductive layer. Moreover, the transparent conductive laminated body of patent document 3 is equipped with the layer which consists of metal nanowire as a conductive layer.

By the way, some of the transparent conductive laminates are further provided with a function of reflecting heat rays (infrared rays), and such laminates are attached to, for example, windows of buildings and automobiles, It is used to suppress the rise of the temperature in the building by reflecting solar radiation (infrared rays) (see, for example, Patent Document 4). As shown in Patent Document 4, this type of transparent conductive laminate has a base material, a metal film as a heat ray reflective layer that is a conductive layer and reflects heat rays, and sandwiches the metal film. And a metal oxide layer for increasing visible light transmittance. As the metal film, a silver-based thin film is used for reasons such as excellent heat ray reflection efficiency.

JP 2004-152727 A JP 2004-221564 A JP 2011-258578 A JP 2014-8861 A

(Problems to be solved by the invention)
When the conductive layer of the transparent conductive laminate is made of an ITO transparent conductive film, it is difficult to reduce the resistance value. Moreover, in the structure provided with the ITO transparent conductive film, a sufficient heat ray reflection effect cannot be obtained.

When the conductive layer is made of a mesh-like metal film, the mesh-like metal film is conspicuous in appearance, which is a problem. Although it may be possible to make the mesh of the metal film very fine to make it inconspicuous, such processing is technically impossible to realize.

When the conductive layer is made of a metal nanowire layer, it is possible to reduce the resistance value and ensure high transparency. However, the metal nanowire layer has a problem of poor durability.

When the conductive layer is made of a silver-based thin film, the resistance value can be lowered and high transparency can be secured, and the appearance is also good. However, the transparent conductive laminate having a conductive layer made of a silver-based thin film has a problem of low durability.

For example, when this type of transparent conductive laminate is used in a high-temperature and high-humidity environment, a fine spot-pattern-like defect may occur in the transparent conductive laminate. Such a defective portion is presumed to be caused by aggregation of silver components contained in the silver-based thin film (conductive layer), a migration phenomenon, or the like. Aggregation and migration of silver components are caused by contact with moisture such as water vapor or corrosive gas (for example, gas containing sulfur).

Such a defective part not only causes the appearance of the transparent conductive laminate to be damaged, but also can cause a decrease in strength such as inducing peeling of the laminate constituting the transparent conductive laminate. Was a problem.

An object of the present invention is to improve durability in a transparent conductive laminate including a silver-based thin film layer.

(Means for solving the problem)
As a result of intensive studies to achieve the above object, the present inventors have found that a base material layer including a resin film and having a 10-point average surface roughness of at least one surface side of 50 nm or less, and an aluminum-added zinc oxide A plurality of metal layers each including at least one metal oxide selected from the group consisting of titanium-added zinc oxide, zinc-added indium oxide and niobium oxide, and arranged on the one surface side so as to be spaced apart from each other An oxide layer and a silver-based thin film layer made of a thin film of silver or a silver alloy and interposed between the adjacent metal oxide layers, and the most of the metal oxide layers from the base material layer The transparent conductive laminate in which the thickness of the surface-side metal oxide layer disposed at a distant position is 20 nm or more was found to be excellent in durability, and the present invention was completed.

In the transparent conductive laminate, the base layer is preferably composed of a laminate of the resin film and a planarizing layer laminated on one or both sides of the resin film.

In the transparent conductive laminate, the resin film of the base material layer is preferably made of a polyester film.

In the transparent conductive laminate, the thickness of the silver thin film layer is preferably 6 nm to 30 nm.

It is preferable that the transparent conductive laminate includes a protective layer laminated on the outer side of the surface-side metal oxide layer.

In the transparent conductive laminate, the protective layer preferably has a thickness of 1 μm to 3 μm.

In the transparent conductive laminate, the metal oxide layer is preferably made of zinc-added indium oxide or aluminum-added zinc oxide.

(The invention's effect)
ADVANTAGE OF THE INVENTION According to this invention, durability can be improved in the transparent conductive laminated body containing a silver-type thin film layer.

Sectional drawing which represented typically the structure of the transparent conductive laminated body which concerns on one Embodiment. Sectional drawing which represented typically the structure of the base material layer in which the planarization layer is formed in both surfaces of the core material which consists of a resin film Sectional drawing which represented typically the structure of the transparent conductive laminated body (with a protective layer) which concerns on other embodiment. Sectional drawing which represented typically the structure of the transparent conductive laminated body which concerns on other embodiment. Sectional drawing which represented typically the composition of the light control film which applied a transparent conductive layered product Graph showing the relationship between the thickness of the protective layer and the surface resistivity in the transparent conductive laminate

A transparent conductive laminate according to an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view schematically showing the configuration of a transparent conductive laminate 1 according to an embodiment. As shown in FIG. 1, the transparent conductive laminate 1 includes a base layer 2, two metal oxide layers (optical adjustment layers) 3, 3, and a silver-based thin film layer interposed between the metal oxide layers. (Heat ray reflective layer) 4 is provided. In the present specification, the base material layer 2 side of the transparent conductive laminate may be referred to as “back side” and the opposite side may be referred to as “front side”.

(Base material layer)
The base material layer 2 is made of a resin film, and is used for the purpose of ensuring the strength of the transparent conductive laminate 1 and supporting the metal oxide layer 3 and the like. The resin material constituting the resin film is not particularly limited as long as the object of the present invention is not impaired, and examples thereof include polyester resins. As the polyester resin, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, or the like can be used. In addition, film materials other than polyester resin may be used as long as transparency is ensured. For example, polyolefin resin such as polyethylene and polypropylene, polyamide resin such as nylon 6 and nylon 12, polyvinyl alcohol and ethylene-vinyl alcohol copolymer. A film made of a synthetic resin such as polystyrene, triacetyl cellulose, acrylic, polyvinyl chloride, polycarbonate, polyimide, polyethersulfone, cyclic polyolefin, or the like can be used.

The base material layer 2 has a configuration composed only of a resin film, as shown in FIG. In the case of the present invention, as in the base material layer 2A shown in FIG. 2, planarization layers (hard coat layers) 22 and 23 are respectively formed on both surfaces of the core material 21 made of a resin film. Alternatively, it may be a base material layer having a configuration in which a flattening layer (hard coat layer) is formed only on one surface (any one surface) of the core material 21.

The thickness of the planarizing layer is not particularly limited, but is preferably 1 μm to 10 μm, for example. When the thickness of the flattening layer is less than 1 μm, it is difficult to sufficiently perform the flattening as expected. On the other hand, if the thickness of the flattening layer exceeds 10 μm, it is difficult to expect further flattening, so that it tends to be wasteful in terms of resources and economy.

Examples of the material constituting the planarizing layer include an energy ray curable acrylic resin composition. In addition, examples of the energy rays here include ultraviolet rays and electron beams. As the energy ray curable acrylic resin composition, a composition containing an acrylic monomer or oligomer as a main component and a photopolymerization initiator added thereto can be used.

Examples of the monomer include me, til (meth) acrylate, lauryl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. , Monofunctional acrylates such as isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy (meth) acrylate, and neopentyl glycol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Ritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tri (meth) acrylate Polyfunctional acrylate such as tripentaerythritol hexa (meth) triacrylate, trimethylolpropane (meth) acrylic acid benzoate, trimethylolpropane benzoate, glycerin di (meth) acrylate hexamethylene diisocyanate, pentaerythritol tri (meth) ) Urethane acrylates such as acrylate hexamethylene diisocyanate.

Examples of the oligomer include polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, alkit (meth) acrylate, melamine (meth) acrylate, and silicone (meth). An acrylate etc. can be mentioned.

The content of the polymerizable compound in the energy beam curable composition is preferably in the range of 5 to 50% by mass, preferably in the range of 10 to 40% by mass with respect to 100% by mass of the total solid content of the energy beam curable composition. More preferably, the range of 15 to 35% by mass is particularly preferable.

When ultraviolet rays are used as energy rays, the energy ray curable composition preferably contains a photopolymerization initiator. Specific examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoylformate, p-isopropyl-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2, Carbonyl compounds such as 2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, teto Sulfur compounds such as lamethylthiuram disulfide, thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone can be used. These photopolymerization initiators may be used alone or in combination of two or more.

A laminate such as a metal oxide layer 3 is formed on one surface of the base material layer 2. In the case of the present invention, the surface roughness Rz (ten-point average surface roughness) of the surface of the base material layer on the side where the laminate such as the metal oxide layer is formed is 50 nm or less.

In addition, when a base material layer consists only of a resin film (for example, base material layer 2), the surface roughness of the resin film becomes the surface roughness of a base material layer. On the other hand, when the base material layer is provided with a planarization layer, the surface of the planarization layer (for example, the planarization layer 22) on the side where a laminate such as a metal oxide layer is formed has a surface of at least 50 nm or less. The surface roughness Rz (ten-point average surface roughness) is provided.

Further, when a planarization layer is formed only on one side of the base material layer (core material), a laminate such as a metal oxide layer may be formed on any side.

The thickness of the base material layer is not particularly limited, but for example, preferably 1 μm to 200 μm, and more preferably 5 μm to 150 μm. When the thickness of the base material layer is in such a range, the surface roughness (ten-point surface roughness) of the base material layer can be easily controlled to 50 nm or less.

As long as the object of the present invention is not impaired, the surface of the base material layer may be subjected to surface treatment such as plasma treatment, corona discharge treatment, flame treatment or the like, if necessary. In addition, when these surface treatments are performed on the surface of the base material layer (the surface on which the laminate is formed), the surface roughness after surface treatment (10-point average surface roughness) is 50 nm or less. There must be.

(Silver-based thin film layer)
The silver-based thin film layer (heat ray reflective layer) 4 is made of a silver or silver alloy thin film, and has a function of reflecting heat rays (infrared rays) together with conductivity. Examples of silver or a silver alloy constituting the silver-based thin film layer 4 include silver (Ag), a silver palladium alloy (AgPd), a silver palladium copper alloy (AgPdCu), and a silver copper alloy (AgCu). The silver or silver alloy used for the silver-based thin film layer 4 is preferably a silver palladium alloy.

The thickness of the silver-based thin film layer 4 is not particularly limited, but is preferably 6 nm to 30 nm, for example, and more preferably 10 nm to 20 nm.

The silver-based thin film layer 4 is interposed between adjacent

metal oxide layers

3 and 3 as shown in FIG.

(Metal oxide layer)
The metal oxide layer (optical adjustment layer) 3 includes a layer including a specific metal oxide layer described later, suppresses reflection of visible light in the silver-based thin film layer (heat ray reflective layer) 4 and transmits visible light. It is formed for the purpose of improving. The transparent conductive laminate 1 shown in FIG. 1 includes two

metal oxide layers

3 and 3. One metal oxide layer 3 is laminated on the front side of the base material layer 2, and the other metal oxide layer 3 is laminated on the front side of the metal oxide layer 4. These

metal oxide layers

3 and 3 are formed so as to sandwich the silver-based thin film layer 4.

Note that, among the plurality of metal oxide layers, the one arranged on the most front side (that is, the one arranged most distant from the base material layer) is particularly referred to as a “surface-side metal oxide layer”. For example, in FIG. 1, the metal oxide layer 3 arranged on the most front side becomes the surface-side photometal oxide layer 30.

Further, the metal oxide layer 3 disposed at the position closest to the base material layer 2 is directly formed on the base material layer 2.

As the material (metal oxide) constituting the metal oxide layer 3, at least one metal oxide selected from the group consisting of aluminum-added zinc oxide, titanium-added zinc oxide, zinc-added indium oxide and niobium oxide is used. The When the metal oxide layer 3 is formed from such a metal oxide, even if the transparent conductive laminate is used in a high-temperature and high-humidity environment, aggregation and migration phenomenon of the silver component contained in the silver-based thin film layer 4 Etc. can be suppressed. In addition, unless the objective of this invention is impaired, the metal oxide layer 3 may contain substances other than the metal oxide mentioned above.

When the metal oxide is made of aluminum-added zinc oxide, the aluminum element content in the zinc oxide is preferably 0.1 to 20 atomic%.

Further, when the metal oxide is composed of titanium-added zinc oxide, the content of titanium element in the zinc oxide is preferably 0.1 to 20 atomic%.

When the metal oxide is made of zinc-added indium oxide, the content of zinc element in indium oxide is preferably 0.1 to 20 atomic%.

Further, the metal oxide layer 3 is preferably set to have a higher refractive index of visible light than the silver-based thin film layer 4. The refractive index (wavelength: 589.3 nm) of the metal oxide layer 3 is preferably set to, for example, 1.9 or more.

The thickness of the metal oxide layer 3 (single layer thickness) is set to 20 nm to 70 nm, for example. In addition, the thickness of the surface side metal oxide layer is set to at least 20 nm or more. When the thickness of the surface-side metal oxide layer is in such a range, even if the transparent conductive laminate is used in a high-temperature and high-humidity environment, the aggregation of silver components contained in the silver-based thin film layer, migration phenomenon, etc. Occurrence can be suppressed.

In the case of this embodiment, the plurality of metal oxide layers are made of the same material. In addition, as long as the objective of this invention is not impaired, metal oxide layers may be comprised from a mutually different material.

(Film formation method)
There is no restriction | limiting in particular as a method of forming into a film the silver-type thin film layer 4 and the

metal oxide layers

3 and 3 on the base material layer 2, According to the objective, it selects suitably. Examples of film formation methods include physical vapor deposition such as vacuum deposition (electron beam deposition, resistance heating deposition), sputtering, ion plating, ion beam, ion assist, and laser ablation. Examples thereof include a chemical vapor deposition (CVD) method such as a (PVD) method, a thermal CVD method, a photo CVD method, and a plasma CVD method. Among these, the physical vapor deposition (PVD) method is preferable, and the sputtering method is particularly preferable because the metal oxide layer 3 and the like can be reliably laminated on the base material layer 2.

Further, as the sputtering method, a DC sputtering method having a high film formation rate is preferable. Note that when a multilayer film is formed by a sputtering method, a one-chamber method in which films are alternately or sequentially formed from a plurality of targets in one chamber may be used, or a multi-chamber method in which films are continuously formed in a plurality of chambers. However, the multi-chamber method is preferable from the viewpoint of preventing productivity and material contamination.

(Other layers)
The transparent conductive laminate may include other layers in addition to the base material layer 2, the metal oxide layer 3, and the silver-based thin film layer 4 described above as long as the object of the present invention is not impaired. For example, an adhesive layer may be formed on the back surface side of the base material layer 2. Such an adhesive layer is utilized when a transparent conductive laminated body is affixed with respect to a to-be-adhered body (for example, window glass).

There is no restriction | limiting in particular as an adhesive utilized for the said adhesive layer, For example, an acrylic adhesive, a rubber adhesive, a vinyl alkyl ether adhesive, a silicone adhesive, a polyester adhesive, a polyamide adhesive And known pressure-sensitive adhesives such as an adhesive, a urethane-based pressure-sensitive adhesive, a fluorine-based pressure-sensitive adhesive, and an epoxy-based pressure-sensitive adhesive. The thickness of the pressure-sensitive adhesive layer is not particularly limited, and is appropriately set depending on the purpose.

The surface (adhesive surface) of the pressure-sensitive adhesive layer may be protected by a release liner until it is used (that is, before being attached to the adherend). The release liner is not particularly limited, and examples thereof include a polyester film such as polyethylene terephthalate and a paper surface coated with a silicone release treatment agent.

In the transparent conductive laminate, a protective layer made of a hard coat layer or the like may be formed on the surface-side metal oxide layer.

Further, the transparent conductive laminate may be provided with a barrier layer or the like as long as the object of the present invention is not impaired.

(Transparent conductive laminate including protective layer)
FIG. 3 is a cross-sectional view schematically showing the configuration of a transparent conductive laminate (with a protective layer) 1X according to another embodiment. This transparent conductive laminate 1X is obtained by forming a protective layer 11 outside the metal oxide layer 3 (surface-side photometal oxide layer 30) on the front side of the transparent conductive laminate 1 shown in FIG. Consists of.

The protective layer is used for the purpose of improving the durability (strength, wet heat durability, scratch resistance, etc.) of the transparent conductive laminate.

If the protective layer 11 is provided like the transparent conductive laminate 1X shown in FIG. 3, the wear resistance, strength, wet heat durability and the like are improved. As a material constituting the protective layer, for example, the same kind of material as that constituting the planarization layer described above (for example, an ultraviolet curable hard coat layer) is used.

The protective layer is made of, for example, a cured composition obtained by mixing an acrylic monomer, a polymerization initiator, an organic solvent, and the like. As the acrylic monomer, for example, monofunctional acrylate, bifunctional acrylate, trifunctional or higher acrylate, and the like are used. As the polymerization initiator, a photopolymerization initiator that generates light by receiving light such as ultraviolet rays, a thermal polymerization initiator that generates heat by receiving heat, and the like are used. As the organic solvent, for example, methyl isobutyl ketone (MIBK), ethyl acetate, toluene or the like is used. In addition, a leveling agent, an adhesive agent (phosphate ester compound), an acrylic oligomer, or the like may be further added to the composition for forming the protective layer. As the acrylic oligomer, copolymer acrylate, epoxy acrylate, polyester acrylate, polyurethane acrylate, or the like may be used.

The thickness of the protective layer is preferably set to 1 μm or more and 3 μm or less. When the thickness of the protective layer is in such a range, for example, long-term reliability (evaluation 7 described later: wet heat durability 2) required for in-vehicle use or the like is ensured. Moreover, when the thickness of the protective layer is in such a range, the surface resistivity of the transparent conductive laminate can be reduced to 10 ⁹ Ω / □ or less, and as a result, adhesion of dust and the like is prevented by the electrostatic diffusion function. can do. In addition, when the thickness of a protective layer will be less than 1 micrometer, the wet heat durability of a transparent conductive laminated body will be impaired. Moreover, when the thickness of a protective layer exceeds 3 micrometers, the surface resistivity of a transparent conductive laminated body will become large, and static electricity diffusivity will not be ensured.

In the material constituting the protective layer, various additives such as a leveling agent may be added as long as the object of the present invention is not impaired.

If a protective layer is provided on the transparent conductive laminate, light interference fringes may appear in the transparent conductive laminate due to the influence of the refractive index of various materials constituting the transparent conductive laminate. Depending on the use of the transparent conductive laminate, there is no problem even if such interference fringes appear, but it is preferable that no interference fringes occur.

When the transparent conductive laminate is provided with a protective layer, the metal oxide layer is preferably zinc-added indium oxide or aluminum-added zinc oxide, and particularly preferably zinc-added indium oxide.

(Transparent conductive laminate including multiple silver-based thin film layers)
FIG. 4 is a cross-sectional view schematically showing the configuration of a transparent conductive laminate 1B according to another embodiment having a plurality of silver-based thin film layers 4 and 4. As shown in FIG. This transparent conductive laminate 1B includes two silver-based thin film layers (heat ray reflective layers) 4 and 4, and the first silver-based thin film layer 4 close to the base material layer 2 is a base material layer. 2 between the first metal oxide layer 3 close to 2 and the second metal oxide layer 3. The second silver-based thin film layer 4 disposed on the front side is between the second metal oxide layer 3 and the third metal oxide layer 3 disposed on the front side. It is sandwiched. In this case, the third metal oxide layer is a surface-side metal oxide layer.

Thus, the transparent conductive laminate of the present invention may have a structure including a plurality of (two or more) silver-based thin film layers.

(Visible light transmittance)
Although the visible light transmittance of the transparent conductive laminate is not particularly limited, for example, 50% or more is preferable, and 60% or more is more preferable. The visible light transmittance can be measured according to JIS A5759.

(Effect / Use etc.)
The transparent conductive laminate of the present invention is excellent in durability. Therefore, even when used under high-temperature and high-humidity conditions (for example, a temperature of 85 ° C. and a humidity of 85% RH), the occurrence of spot-like defects derived from the silver component contained in the silver-based thin film layer is suppressed.

The transparent conductive laminate of the present invention is used for, for example, an electromagnetic wave sealing member, an electrode member, and the like. Further, since the transparent conductive laminate has flexibility, it can be attached to not only a planar adherend but also a curved adherend.

Here, a specific application example of the transparent conductive laminate will be described with reference to FIG. FIG. 5 is a cross-sectional view schematically showing the configuration of the light control film 10 to which the transparent conductive laminates 1C and 1C are applied. The light control film 10 is a film that changes the light transmittance according to the presence or absence of voltage application, and is used in a form of being attached to a window glass of a building or a vehicle.

The light control film 10 is dispersed in the pair of transparent conductive laminates 1C and 1C, the transparent matrix polymer layer 6 interposed between the pair of transparent conductive laminates 1C and 1C, and the matrix polymer layer 6. And a plurality of liquid crystal capsules 7. The liquid crystal capsule 7 is one in which liquid crystal molecules are enclosed in a microcapsule.

The transparent conductive laminate 1 </ b> C includes a base material layer 2 including a resin film and the like, and an electrode layer 5 laminated on the base material layer 2. The electrode layer 5 is composed of a laminate of a silver-based thin film layer and a metal oxide layer. The pair of transparent conductive laminates 1C and 1C sandwich the matrix polymer layer 6 with the electrode layers 5 and 5 facing each other. The pair of

electrode layers

5 and 5 are connected to each other via the battery 8 and the switch 9.

When the switch 9 of the light control film 10 is in an open state (OFF state), no potential difference is generated between the pair of

electrode layers

5 and 5, so that the liquid crystal molecules in the microcapsule are arranged in a random manner. Therefore, in the light control film 10 with the switch 9 open, the liquid crystal capsule 7 functions to prevent light transmission.

On the other hand, when the switch of the light control film 10 is in the closed state (ON state), a potential difference is generated between the pair of electrode layers 5.5, and the liquid crystal molecules in the microcapsule are aligned in the direction in which the pair of

electrodes

5 and 5 are aligned. It is oriented in a form along (the thickness direction of the light control film 10). Therefore, in the light control film 10 in which the switch 9 is closed, the liquid crystal capsule 7 functions so as to transmit light.

Thus, the transparent conductive laminate of the present invention can be used as a member constituting a light control film. Further, such a member can also be used as a screen (so-called active screen) having flexibility (by controlling the transmittance so that a projected image can be displayed when the transmittance is low). is there.

The transparent conductive laminate is used, for example, as a heat ray reflecting member by being attached to a window glass of a building from the indoor side. In that case, a transparent conductive laminated body is affixed in the form in which the base material layer side faces a window glass.

The transparent conductive laminate of the present invention may be affixed not only to the indoor side of the window glass of the building but also to the outside of the window glass as necessary. In addition, the transparent conductive laminate is attached not only to the window glass of buildings but also to various window glasses and transparent members such as vehicles (for example, automobiles, trains), and window vehicles of ships, etc. It can be used for heat insulation.

Hereinafter, the present invention will be described in more detail based on examples. In addition, this invention is not limited at all by these Examples.

In Examples and Comparative Examples shown below, each layer was formed on a base material layer using a roll-to-roll-type magnetron sputtering apparatus. In addition, the flow rate of gas (for example, argon gas and oxygen gas) supplied into each chamber of the sputtering apparatus was appropriately adjusted using a predetermined mass flow controller. The amount of oxygen contained in the metal oxide layer was adjusted by the amount of oxygen gas introduced during sputtering.

[Example 1]
As a base material layer, a PET film with a flattening layer having a thickness of 50 μm and a 10-point average surface roughness (Rz) of 13 nm, on which a flattening layer made of an acrylic resin was formed on both surfaces, was prepared. A first metal oxide layer made of an aluminum-added zinc oxide film was formed on one surface of the flattened PET film by sputtering. Next, a silver-based thin film layer made of a silver-palladium alloy film is formed on the first metal oxide layer by sputtering, and further, an aluminum-added zinc oxide film is formed on the silver-based thin film layer. A second metal oxide layer (surface-side metal oxide layer) was formed. In this way, the transparent conductive laminate of Example 1 was produced. The thickness of each layer constituting this transparent conductive laminate is as shown in Table 1. The thickness of each layer of the transparent conductive laminate was measured by fluorescent X-ray analysis (manufactured by Rigaku Corporation, ZSX-100e). Further, the surface roughness Rz of the base material layer was measured using a scanning probe microscope (product name “SPM9600”, manufactured by Shimadzu Corporation). The following examples and comparative examples were similarly measured for the surface roughness Rz of the base material layer, the thickness of each layer of the transparent conductive laminate, and the like. The film formation conditions for sputtering in Example 1 are as follows.

<Film formation conditions: each metal oxide layer>
Target: AZO target (manufactured by AGC Ceramics), film forming pressure: 0.4 Pa, DC power: 2.5 W / cm ²
<Film formation conditions: Silver-based thin film layer>
Target: Silver containing 1 atomic% of palladium, film forming pressure: 0.4 Pa, DC power: 0.6 W / cm ²

[Example 2]
As a base material layer, a PET film with a flattening layer having a thickness of 125 μm and a ten-point average surface roughness (Rz) of 13 nm in which a flattening layer made of an acrylic resin was formed on both surfaces was prepared. A first metal oxide layer made of a titanium-added zinc oxide film was formed on one surface of the planarized PET film with sputtering. Next, a silver-based thin film layer made of a silver-palladium alloy film is formed on the first metal oxide layer by sputtering, and further, a titanium-added zinc oxide film is formed on the silver-based thin film layer. A second metal oxide layer (surface side metal oxide layer) was formed to produce a transparent conductive laminate. The film formation conditions for sputtering are as follows.

<Film formation conditions: each metal oxide layer>
Target: SZO target (ZnO containing 5 atomic% of Ti, manufactured by AGC Ceramics), film forming pressure: 0.4 Pa, DC power: 2.5 W / cm ²
<Film formation conditions: Silver-based thin film layer>
Target: Silver containing 1 atomic% of palladium, film forming pressure: 0.4 Pa, DC power: 0.6 W / cm ²

Example 3
As the base material layer, the same PET film with a flattening layer as in Example 2 (thickness: 125 μm, Rz: 13 nm) was prepared. A first metal oxide layer made of a zinc-added indium oxide film was formed on one surface of the planarized PET film by sputtering. Next, a metal oxide layer made of a silver-palladium alloy film is formed on the first metal oxide layer by sputtering, and further made of a zinc-added indium oxide film on the silver-based thin film layer. A second metal oxide layer (surface side metal oxide layer) was formed to produce a transparent conductive laminate. The film formation conditions for sputtering are as follows.

<Film formation conditions: each metal oxide layer>
Target: IZO target (manufactured by Idemitsu Kosan Co., Ltd.), film forming pressure: 0.4 Pa, DC power: 2.5 W / cm ²
<Film formation conditions: Silver-based thin film layer>
Target: Silver containing 1 atomic% of palladium, film forming pressure: 0.4 Pa, DC power: 0.6 W / cm ²

Example 4
As the base material layer, the same PET film with a flattening layer as in Example 2 (thickness: 125 μm, Rz: 13 nm) was prepared. A first metal oxide layer made of a niobium oxide film was formed on one surface of the flattened PET film by sputtering. Next, a silver-based thin film layer made of a silver-palladium alloy film is formed on the first metal oxide layer by sputtering, and a second niobium oxide film made of niobium oxide is formed on the silver-based thin film layer. A transparent metal laminate was produced by forming a metal oxide layer (surface-side metal oxide layer) as the first layer. The film formation conditions for sputtering are as follows.

<Film formation conditions: each metal oxide layer>
Target: NBO target (manufactured by AGC Ceramics), film forming pressure: 0.4 Pa, DC power: 2.5 W / cm ²
<Film formation conditions: Silver-based thin film layer>
Target: Silver containing 1 atomic% of palladium, film forming pressure: 0.4 Pa, DC power: 0.6 W / cm ²

Example 5
As a base material layer, a PET film (thickness: 50 μm, Rz: 50 nm) having no hard coat layer formed on both sides was prepared. A first metal oxide layer made of an aluminum-added zinc oxide film was formed on one surface of the flattened PET film by sputtering. Next, a silver-based thin film layer made of a silver-palladium alloy film is formed on the first metal oxide layer by sputtering, and further, an aluminum-added zinc oxide film is formed on the silver-based thin film layer. A second metal oxide layer (surface-side metal oxide layer) was formed. In this way, the transparent conductive laminate of Example 1 was produced. The thickness of each layer constituting this transparent conductive laminate is as shown in Table 1. The film formation conditions for sputtering are as follows.

[Comparative Example 1]
As the base material layer, the same PET film with a flattening layer as in Example 2 (thickness: 125 μm, Rz: 13 nm) was prepared. A first metal oxide layer made of a tin-added indium oxide film was formed on one surface of the flattened PET film by sputtering. Next, a silver-based thin film layer made of a silver-palladium alloy film is formed on the first metal oxide layer by sputtering, and a second tin-added indium oxide film is formed on the silver-based thin film layer. A metal oxide layer as a first layer was formed to produce a transparent conductive laminate. The film formation conditions for sputtering are as follows.

<Film formation conditions: each metal oxide layer>
Target: ITO target (manufactured by Mitsui Mining & Smelting Co., Ltd.), film forming pressure: 0.4 Pa, DC power: 2.5 W / cm ²
<Film formation conditions: Silver-based thin film layer>
Target: Silver containing 1 atomic% of palladium, film forming pressure: 0.4 Pa, DC power: 0.6 W / cm ²

[Comparative Example 2]
As a base material layer, a PET film (thickness: 100 μm, Rz: 127 nm) having no hard coat layer formed on both surfaces was prepared.
A first metal oxide layer made of a niobium oxide film was formed on one surface of the PET film by sputtering. Next, a silver-based thin film layer made of a silver-palladium alloy film is formed on the first metal oxide layer by sputtering, and a second niobium oxide film made of niobium oxide is formed on the silver-based thin film layer. A metal oxide layer as a first layer was formed to produce a transparent conductive laminate. The film formation conditions for sputtering are as follows.

[Comparative Example 3]
As the base material layer, the same PET film with a flattening layer as in Example 2 (thickness: 125 μm, Rz: 13 nm) was prepared. A first metal oxide layer made of a zinc-added indium oxide film was formed on one surface of the planarized PET film by sputtering. Next, a first silver-based thin film layer made of a silver-palladium alloy film is formed on the first metal oxide layer by sputtering, and zinc-added oxidation is further formed on the silver-based thin film layer. A second metal oxide layer made of an indium film was formed. Then, a second silver-based thin film layer is formed on the second metal oxide layer, and a third-layer metal made of a zinc-added indium oxide film is further formed on the silver-based thin film layer. An oxide layer was formed to produce a transparent conductive laminate. The film formation conditions for sputtering are as follows.

[Evaluation 1: Visible light transmittance]
The visible light transmittance (wavelength range: 380 nm to 780 nm) of each transparent conductive laminate in Examples 1 to 5 and Comparative Examples 1 to 3 was measured in accordance with JIS A5759. The apparatus used for the measurement was UV-3010 manufactured by JASCO Corporation. The results of visible light transmittance are shown in Table 1.

[Evaluation 2: Wet heat durability 1]
Test samples (5 cm long and 5 cm wide squares) were prepared from the transparent conductive laminates in Examples 1 to 5 and Comparative Examples 1 to 3, respectively. Each test sample was laminated on a slide glass using a transparent optical adhesive film in a form in which the film formation side was bonded, and placed in a humidity environment of a temperature of 85 ° C. and a humidity of 85% RH. It was visually confirmed whether or not a defect having a diameter of 0.5 mm or more was formed on the test sample, and the wet heat durability of each test sample was evaluated. The evaluation criteria are as follows. The evaluation results are shown in Table 1.

<Evaluation criteria>
“◎”: When no defect occurs even when the elapsed time exceeds 500 hours (particularly when having excellent wet heat durability)
“◯”: When the elapsed time exceeds 250 hours and a defect occurs within 500 hours (with excellent wet heat durability)
“×”: When a defect occurs within 250 hours (when there is no wet heat durability)

As shown in Table 1, each of the transparent conductive laminates of Examples 1 to 5 was excellent in wet heat durability. In particular, each of the transparent conductive laminates of Examples 1 to 4 was inhibited from generating defects even after 500 hours or more in the wet heat durability test.

On the other hand, in the transparent conductive laminates of Comparative Examples 1 to 3, defects occurred in spots in 250 hours. The transparent conductive laminate of Comparative Example 1 uses tin-added indium oxide (ITO) as the metal oxide layer. It has been confirmed that a metal oxide layer made of such a material cannot suppress defects derived from the silver component contained in the silver-based thin film layer.

Further, in the transparent conductive laminate of Comparative Example 2, the surface roughness (Rz) of the base material layer is 127 nm, and the surface of the base material layer is rough. Since the thickness of the metal oxide layer or silver-based thin film layer is very small compared to the base material layer, if the surface of the base material layer is rough, the metal oxide layer or silver-based thin film formed on the surface of the base material layer It is presumed that there are locations where pinholes are generated in the layer or where the laminated structure is not formed and the silver component is exposed. And it is estimated that the defect originating in the silver component generate | occur | produced from such a location.

Further, in the transparent conductive laminate of Comparative Example 3, the thickness of the third metal oxide layer (surface side metal oxide layer) arranged on the most front side among the three metal oxide layers is 19 nm. Yes. As described above, it is confirmed that when the thickness of the metal oxide layer (surface side metal oxide layer) arranged on the most front side is thin, defects derived from the silver component contained in the silver-based thin film layer cannot be suppressed. It was.

Example 6
As a base material layer, the same PET film with a flattening layer as in Example 3 was prepared. On one surface of the PET film with a planarizing layer, from the first metal oxide layer made of a zinc-added indium oxide film and a silver palladium alloy film by sputtering under the same conditions as in Example 3. A metal oxide layer and a second metal oxide layer (surface-side metal oxide layer) made of a zinc-added indium oxide film were formed in this order. Further, a protective layer (thickness: 1 μm) made of an ultraviolet curable acrylic resin was formed on the second metal oxide layer to obtain a transparent conductive laminate. The thickness of each layer constituting this transparent conductive laminate is as shown in Table 2. Table 2 also shows the thickness of each layer constituting the transparent conductive laminates of the following examples and comparative examples.

The protective layer is composed of 100 parts by weight of dipentaerythritol hexaacrylate (trade name “A-DPH”, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a tri- or higher functional acrylic monomer, and a phosphate ester as an adhesive with an oxide film. 3 parts by weight of a compound (trade name “PM-21”, manufactured by Nippon Kayaku Co., Ltd.), 5 weights of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name “Irgacure 184”, manufactured by BASF) as a photopolymerization initiator And a composition comprising 160 parts by weight of ethyl acetate as a diluent is coated on the second metal oxide layer with a bar coater, and ultraviolet rays are applied to the coating film on the metal oxide layer. It was formed by irradiation.

Example 7
A transparent conductive laminate was produced in the same manner as in Example 6 except that the thickness of the protective layer was changed to 3 μm.

Example 8
As a base material layer, the same PET film with a flattening layer as in Example 1 was prepared. On one surface of the PET film with the planarizing layer, from the first metal oxide layer made of an aluminum-added zinc oxide film and a silver palladium alloy film by sputtering under the same conditions as in Example 1. A silver-based thin film layer and a second metal oxide layer (surface-side metal oxide layer) made of an aluminum-added zinc oxide film were formed in this order. Further, a protective layer (thickness: 1 μm) made of an ultraviolet curable acrylic resin was formed on the second metal oxide layer to obtain a transparent conductive laminate.

[Comparative Example 4]
A transparent conductive laminate was produced in the same manner as in Example 6 except that the thickness of the protective layer was changed to 0.6 μm.

[Comparative Example 5]
A transparent conductive laminate was produced in the same manner as in Example 6 except that the thickness of the protective layer was changed to 5 μm.

[Comparative Example 6]
As a base material layer, the same PET film with a flattening layer as in Example 2 was prepared. On one surface of the PET film with the flattening layer, by sputtering under the same conditions as in Example 2,
First metal oxide layer made of titanium-added zinc oxide film, silver-based thin film layer made of silver-palladium alloy film, and second metal oxide layer made of titanium-added zinc oxide film (surface Side metal oxide layer) was formed in this order. Further, as in Example 6, a protective layer (thickness: 1 μm) made of an ultraviolet curable acrylic resin was formed on the second metal oxide layer to obtain a transparent conductive laminate. .

[Comparative Example 7]
As a base material layer, the same PET film with a flattening layer as in Example 4 (Example 2) (thickness: 125 μm, Rz: 13 nm) was prepared. On one surface of the PET film with the flattening layer, the first metal oxide layer made of a niobium oxide film and the silver made of a silver-palladium alloy film are formed by sputtering under the same conditions as in Example 4. A second metal oxide layer (surface-side metal oxide layer) made of a system thin film layer and a niobium oxide film was formed in this order. Further, as in Example 6, a protective layer (thickness: 1 μm) made of an ultraviolet curable acrylic resin was formed on the second metal oxide layer to obtain a transparent conductive laminate. .

[Comparative Example 8]
As a base material layer, the same PET film with a flattening layer (thickness: 125 μm, Rz: 13 nm) as in Comparative Example 1 (Example 2) was prepared. From one surface of the PET film with a planarizing layer, from the first metal oxide layer made of a tin-added indium oxide film and a silver palladium alloy film by sputtering under the same conditions as in Comparative Example 1. A silver-based thin film layer and a second metal oxide layer made of tin-added indium oxide were formed in this order. Further, as in Example 6, a protective layer (thickness: 1 μm) made of an ultraviolet curable acrylic resin was formed on the second metal oxide layer to obtain a transparent conductive laminate. .

[Comparative Example 9]
As the base material layer, the same PET film with a flattening layer as in Example 2 (thickness: 125 μm, Rz: 13 nm) was prepared. A metal layer made of a copper film was formed on one surface of the planarized PET film with sputtering by sputtering. Further, a protective layer (thickness: 1 μm) made of an ultraviolet curable acrylic resin was formed on the metal layer in the same manner as in Example 6 to obtain a transparent conductive laminate. The film formation conditions for sputtering are as follows.

<Deposition conditions: metal layer>
Target: Cu target (manufactured by Toyo Success Co., Ltd.), film forming pressure: 0.4 Pa, DC power: 2.5 W / cm ²

[Evaluation 3: Visible light transmittance]
The visible light transmittance (wavelength range: 380 nm to 780 nm) of each transparent conductive laminate in Examples 6 to 8 and Comparative Examples 4 to 9 was measured in accordance with JIS A5759 as in Example 1 and the like. The results of visible light transmittance are shown in Table 3. In addition, in the case of the transparent conductive laminated body provided with the protective layer, it can be said that it is excellent in visible light transmittance | permeability that visible light transmittance is 50% or more.

[Evaluation 4: Appearance]
The transparent conductive laminates in Examples 6 to 8 and Comparative Examples 4 to 9 were visually checked for the presence of interference fringes. The results are shown in Table 3. In Table 3, a case where there is no interference fringe is indicated by “◯”, and a case where there is an interference fringe is indicated by “x”.

[Evaluation 5: Shield characteristics]
Test samples (12 cm long and 12 cm wide squares) were prepared from the transparent conductive laminates of Examples 6 to 8 and Comparative Examples 4 to 9, respectively. Each test sample was placed between a transmission jig and a reception jig, and the shielding effect (dB) in the UHF band having a frequency of 300 MHz to 1000 MHz was continuously measured according to the KEC method. In addition, as a comparison target of each test sample, a sample (comparative test sample) excluding the protective layer of each test sample is prepared, and the shield effect (dB) is continuously applied to the comparative test sample according to the KEC method. It was measured.

When the reduction rate of the shield effect (signal attenuation on the receiving side) by providing the protective layer is within minus 10% in all the UHF bands (range of 300 MHz to 1000 MHz), the shield effect is excellent (Table 3). If the rate of decrease in the shielding effect falls below minus 10% at any frequency in the UHF band (300 MHz to 1000 MHz), It was determined that there was a problem with the shielding effect (indicated as “x” in Table 3). The results are shown in Table 3. In Table 3, as a reference, the rate of decrease (%) when the frequency is 300 MHz is shown. The calculation formula of the decrease rate at each frequency is as follows.
Decrease rate (%) = {(with protective layer (dB)) − (without protective layer (dB))} / (without protective layer (dB)) × 100

[Evaluation 6: Static electricity diffusibility]
The surface resistivity of each of the transparent conductive laminates in Examples 6 to 8 and Comparative Examples 4 to 9 was measured according to a constant voltage application / leakage current measurement method. The results are shown in Table 3. In addition, when the surface resistivity is less than 10 ⁹ Ω / □, it is judged that the electrostatic diffusibility is excellent (indicated as “◯” in Table 3), and when the surface resistivity is 10 ⁹ Ω / □ or more, It was judged that there was a problem with electrostatic diffusibility (indicated as “x” in Table 2).

[Evaluation 7: Wet heat durability 2]
Test samples (5 cm long and 5 cm wide squares) were prepared from the transparent conductive laminates in Examples 6 to 8 and Comparative Examples 4 to 9, respectively. Each test sample was left for 1000 hours in a humid environment at a temperature of 85 ° C. and a humidity of 85% RH with the film formation surface exposed. Thereafter, the appearance of each test sample was visually observed, and the wet heat durability of each test sample was evaluated by confirming the presence or absence of defect formation (aggregation by migration) of 0.5 mm or more. The evaluation criteria are as follows. The evaluation results are shown in Table 3.

<Evaluation criteria>
“◯”: When there is no defect (aggregation due to migration) after 1000 hours (with excellent wet heat durability)
“×”: When a defect (aggregation due to migration) occurs after 1000 hours (when there is no wet heat durability)

As shown in Table 3, each of the transparent conductive laminates of Examples 6 and 7 in which the metal oxide layer is made of zinc-added indium oxide and includes a protective layer has wet heat durability (evaluation 7: wet heat durability). The result was excellent in property 2). The wet heat durability 2 test performed in the evaluation 7 is a severer condition than the wet heat durability 1 performed in the evaluation 2. In addition, Examples 6 and 7 resulted in excellent visible light transmittance, appearance, shielding characteristics, and electrostatic diffusibility.

In the case of Example 8, interference fringes appeared in the transparent conductive laminate due to the provision of the protective layer, but the other evaluations were the same as in Examples 6 and 7. It was.

Moreover, in the case of the comparative example 4, since the thickness of the protective layer was thin, there was a problem in wet heat durability. Moreover, in the case of the comparative example 5, since the thickness of the protective layer was too thick, a problem arose in electrostatic diffusibility.

Further, in the case of Comparative Example 6 in which the metal oxide layer was made of titanium-added zinc oxide, there was a problem in wet heat durability. Moreover, in the case of the comparative example 6, the interference fringe was also formed by providing the protective layer.

Moreover, in the case of the comparative example 7 whose metal oxide layer consists of niobium oxide, a problem arose in wet heat durability. Moreover, in the case of the comparative example 7, the interference fringe was also formed by providing the protective layer. In the case of Comparative Example 7, the surface resistivity was 10 ⁹ Ω / □ or more, which resulted in a problem with electrostatic diffusibility.

Further, in the case of Comparative Example 8 in which the metal oxide layer was made of tin-added indium oxide, there was a problem in wet heat durability. Moreover, in the case of the comparative example 8, the interference fringe was also formed by providing the protective layer.

Comparative Example 9 is a case of a transparent conductive laminate in which a metal layer (copper) and a protective layer are formed in this order on a PET film with a planarizing layer. In the case of Comparative Example 9, the visible light transmittance was less than 50%, and the shield characteristics were problematic.

Here we will refer to the shielding characteristics. It is known that the shielding effect by the KEC method is remarkably lowered in the ordinary general conductive film for shielding due to the influence of the insulating protective film. On the other hand, in the case of the transparent conductive laminates of Examples 6 to 8, it is possible to suppress the reduction of the shielding effect in the frequency band of the UHF band of 300 MHz to 1000 MHz.

As the material for the metal oxide layer, as shown in Examples 6 and 7, zinc-added indium oxide is most preferable. When zinc-doped indium oxide is used as the metal oxide layer, the reduction in visible light transmittance due to the formation of the protective layer (hard coat layer) is suppressed, and the occurrence of interference fringes is also prevented.

[Evaluation 8: Relationship between protective layer thickness and surface resistivity]
The relationship between the thickness (μm) of the protective layer in the transparent conductive laminate and the surface resistivity (Ω / □) is shown in FIG. The horizontal axis in FIG. 6 represents the thickness (μm) of the protective layer, and the vertical axis represents the surface resistivity (Ω / □). The surface resistivity is measured according to a constant voltage application / leakage current measurement method, as in the evaluation of electrostatic diffusibility.

When the protective layer is not provided (Example 3, protective layer thickness: 0 μm), the surface resistivity is 4.98Ω / □, and the protective layer thickness is 0.6 μm (Example 4). The surface resistivity is 1.15 × 10 ⁶ Ω / □, and when the thickness of the protective layer is 1 μm (Example 6), the surface resistivity is 3.32 × 10 ⁷ Ω / □. When the layer thickness is 3 μm (Example 7), the surface resistivity is 9.70 × 10 ⁸ Ω / □, and when the protective layer thickness is 5 μm (Comparative Example 5), the surface resistivity is 7 .60 × 10 ⁹ Ω / □ and is the surface resistivity in the case the thickness of the protective layer of 7μm is, 4.13 × 10 ⁹ Ω / □ and is the surface resistivity in the case the thickness of the protective layer of 14μm is 7.64 × 10 ¹¹ Ω / □.

As shown in FIG. 6, it was confirmed that the surface resistivity of the transparent conductive laminate can be controlled to be less than 1.0 × 10 ⁹ Ω / □ when the thickness of the protective layer is 3 μm or less.

DESCRIPTION OF

SYMBOLS

1,1B, 1C, 1X ... Transparent conductive laminated body, 2, 2A ... Base material layer, 3 ... Metal oxide layer (optical adjustment layer), 30 ... Surface side metal oxide layer, 4 ... Silver-type thin film layer ( Heat ray reflective layer), 11 ... protective layer

Claims

A base material layer including a resin film and having a 10-point average surface roughness of at least one surface side of 50 nm or less;
Each includes at least one metal oxide selected from the group consisting of aluminum-added zinc oxide, titanium-added zinc oxide, zinc-added indium oxide, and niobium oxide, and is arranged in such a manner as to be spaced from each other on the one surface side. A plurality of metal oxide layers;
Comprising a silver or silver alloy thin film, comprising a silver-based thin film layer interposed between the adjacent metal oxide layers,
The transparent conductive laminated body whose thickness of the surface side metal oxide layer distribute | arranged to the position most distant from the said base material layer among the said metal oxide layers is 20 nm or more.
The transparent conductive laminate according to claim 1, wherein the base material layer is composed of a laminate of the resin film and a planarization layer laminated on one side or both sides of the resin film.
The transparent conductive laminate according to claim 1 or 2, wherein the resin film of the base material layer is a polyester film.
The transparent conductive laminate according to any one of claims 1 to 3, wherein the silver-based thin film layer has a thickness of 6 nm to 30 nm.
The transparent conductive laminate according to any one of claims 1 to 4, further comprising a protective layer laminated outside the surface-side metal oxide layer.
The transparent conductive laminate according to claim 5, wherein the protective layer has a thickness of 1 μm to 3 μm.
The transparent conductive laminate according to claim 5 or 6, wherein the metal oxide layer is made of zinc-added indium oxide or aluminum-added zinc oxide.