JP2006120916A - Transparent conductive laminate, and filter for display using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent conductive laminate wherein low surface resistivity and a good reflective characteristic are made compatible with each other. <P>SOLUTION: The transparent conductive laminate is such a laminate that, on the principal surface of a transparent substrate (A), there is formed a transparent conductive layer wherein a high-refractive-index transparent thin-film layer (B) and a metal thin-film layer (C) containing at least silver are laminated repeatedly four to seven times while using (B)/(C) as a repeated unit, and thereon, a transparent conductive layer having the laminated high-refractive-index transparent thin-film layers (B) is so formed as to form further at least a transparent-material layer on the transparent conductive layer. When projecting on the laminate a standard light source (C) with at an incident angle of 60° from the side of the transparent-material layer, an L*a*b* colorimetric system C* value measured from the transparent-material layer is made not larger than 20. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a transparent conductive laminate and its use. More specifically, the present invention relates to a transparent conductive laminate capable of efficiently reducing electromagnetic waves generated from a display device such as a plasma display (PDP), a cathode ray tube (CRT), a liquid crystal display device (LCD), and a display filter using the same. .

  With the advancement of information technology in recent social situations, the importance of display devices that play the role of man-machine interface is increasing. Among them, large-screen display devices used for televisions, personal computers, guidance displays such as stations and airports, and other various information provisions are required to have high image quality, high efficiency, and thinning.

  Currently, plasma display panels (hereinafter referred to as PDPs) are attracting attention as next-generation large-screen flat panel displays, and are already commercially available. However, the PDP has a problem that a strong leakage electromagnetic field is generated due to a problem in principle. Leaked electromagnetic fields cause malfunctions of other electrical and electronic devices and communication failures, and recently there are concerns about the effects on the human body. In particular, the PDP device has a problem that near infrared light generated from excited atoms in the plasma acts on electronic devices such as cordless phones and remote controllers.

  For this reason, a filter (hereinafter referred to as an electromagnetic wave filter) for shielding a leakage electromagnetic field and near-infrared light is generally used for a display device, particularly a PDP. The structure of a general electromagnetic wave filter includes an electromagnetic wave shielding layer formed on one side of a support plate, and an antireflection layer formed on the other side of the support plate and the film surface on which the electromagnetic wave shielding layer is formed. These members are used in combination as a PDP optical filter by bonding and coating.

  Near-infrared and electromagnetic shielding materials for electromagnetic filters are broadly classified as follows: 1) A combination of a grounded metal mesh or synthetic resin or metal fiber mesh coated with metal and a dye that absorbs near-infrared rays 2) A combination of a transparent conductive thin film typified by grounded indium oxide-tin (ITO) and (in some cases) a dye that absorbs near infrared rays.

  As an example of 1), JP-A-9-330667 (Patent Document 1) discloses an electromagnetic wave shielding plate prepared by applying and drying a conductive paste in a mesh shape on a transparent resin plate. As an example in which the transparent conductive thin film of 2) is formed on a substrate, a high refractive index transparent film is formed on one main surface of a transparent polymer film described in JP-A-10-73719 (Patent Document 2). The thin film layer (B) and the metal thin film layer (C) are sequentially laminated four or more times with (B) / (C) as a repeating unit, and a high refractive index transparent thin film layer (B) and a transparent resin layer thereon. An optical filter for a display in which a light control film formed with is bonded. When these electromagnetic wave filters are used, it is possible to efficiently shield electromagnetic waves generated from the PDP (housing) and near infrared rays. In particular, the filter using the transparent conductive thin film as the electromagnetic wave shielding layer in the example of 2) has an excellent feature that there is no generation of a light-shielding part or moire due to the mesh compared to the example of 1). Yes.

  Among these, a laminate of a high refractive index thin film layer formed of a metal oxide such as ITO and a metal thin film layer mainly composed of silver has high transparency, low surface resistivity, and good Since it has an electromagnetic wave shielding function, it can be preferably used.

When the above transparent conductive film is applied to a display device such as a plasma display (PDP), a cathode ray tube (CRT), a liquid crystal display (LCD), etc., in order to improve the color reproducibility of the display device, an antireflection film, a selective absorption The optical characteristics of the filter can be controlled by combining a light control film containing a pigment or the like, an adhesive material, or the like. However, since the reflection characteristics of the filter are determined by the laminated film thickness structure of each high refractive index thin film layer and metal thin film layer of the conductive film, it is necessary to optimize in advance. In general, the conventional filter is designed to have a preferable reflection characteristic of external light incident from the front, particularly a preferable reflection color, but the reflection characteristic of external light incident from an oblique direction, particularly the reflection color, has not been considered. In addition, when the reflected color of external light incident from an oblique direction is set to the most preferred achromatic color, the surface resistivity is increased, and a satisfactory electromagnetic shielding ability cannot be ensured.
JP-A-9-330667 JP-A-10-73719

Accordingly, the object of the present invention is to provide an electromagnetic wave shielding filter having a low surface resistivity, which is difficult to solve by the prior art, and a reflection characteristic of external light incident from an oblique direction, particularly an achromatic reflection color. It is providing the transparent conductive film obtained.

In order to solve the above problems, the present inventors have conducted intensive studies, and as a result, a transparent conductive laminate in which a high refractive index transparent thin film layer and a metal thin film layer containing at least silver as a main component are laminated in a specific configuration is obtained. The inventors have found that both low surface resistivity and good reflection characteristics can be achieved, thereby completing the present invention.
That is, the present invention provides (1) a high refractive index transparent thin film layer (B) and a metal thin film layer (C) containing at least silver on one main surface of the transparent substrate (A), and (B) / (C) as repeating units. 4 to 7 times, and a high refractive index transparent thin film layer (B) is laminated thereon to form a transparent conductive laminate, and at least one transparent material layer is further laminated on the transparent conductive layer. When the standard light source C is incident at an incident angle of 60 ° from the transparent material layer side, the L * a * b * color system C * value measured from the transparent material layer side is 20 It is a transparent electroconductive laminated body characterized by the following, It is a preferable aspect that the cap layer is formed in the single side | surface or both surfaces of the said metal thin film layer (C).
(2) Preferably, when the standard light source C is incident from the transparent material layer side at an incident angle of 2 °, the chromaticity coordinates a * and b * values measured from the transparent material layer side are −15 ≦ a * ≦ 15, respectively. And −40 ≦ b * ≦ 0,
(3) Preferably, the surface resistance value R of the transparent conductive layer is 0.1Ω / □ ≦ R ≦ 2.5Ω / □, and the visible region transmittance Tvis is 40% ≦ Tvis ≦ 80%, preferably Where d _DE / d _M is 7.0 or more when the total thickness of the high refractive index transparent conductive layer is d _DE and the total thickness of the metal thin film layer is d _M , and (B) / (C) Where n is the number of repeated layers, the thickness of the first and nth metal thin film layers (C) from the transparent substrate (A) side is 60 to 80% of the average thickness of the other metal thin film layers. Preferably, the 2 ° reflectance at a wavelength of 700 nm measured from the transparent material layer side is 10% or less, and the above transparent conductive laminate or the above transparent conductive laminate and dye are used. A combined display filter or a plasma display using the filter.

  When the transparent conductive laminate of the present invention is used, the same surface resistivity as that of the conventional transparent conductive film can be maintained and the reflection characteristics against obliquely incident light can be achieved. Therefore, plasma display (PDP), cathode ray tube (CRT), liquid crystal When applied to a display device such as a display device (LCD), it is possible to realize a filter that is excellent in color rendering, design, and electromagnetic shielding of the display device.

  The transparent conductive laminate of the present invention and the display filter using the same have not only good reflection characteristics with respect to oblique incident light, but also have the same transmittance and electromagnetic wave shielding ability as those of conventional transparent conductive films. is doing. Therefore, it can be suitably used as an electromagnetic wave shielding filter for displays such as a plasma display (PDP), a cathode ray tube (CRT), and a liquid crystal display (LCD).

  The transparent conductive laminate of the present invention comprises a transparent substrate (A), a high refractive index transparent thin film layer (B), a metal thin film layer (C) containing at least silver, and a transparent material layer, and these layers have a specific configuration. It is characterized by having.

  As the transparent substrate (A) used in the present invention, a glass plate, a transparent plastic plate, a transparent plastic film or the like is used. A transparent plastic film capable of continuously forming the transparent conductive layer by roll-to-roll is most preferably used. Moreover, when a transparent conductive layer is formed on a transparent plastic film, it can be bonded to a glass plate, a transparent plastic plate, and further directly to a PDP module.

  The total light transmittance of the transparent substrate (A) is not particularly limited, but is preferably 70% or more, more preferably 75% or more, and particularly preferably 80% or more. The upper limit of the total light transmittance is naturally 100%. However, in general, the light transmittance often decreases due to reflection on the surface of the substrate, and therefore, even if the total light transmittance is 92% or less, it has substantially sufficient transparency.

    The transparent substrate (A) of the present invention does not need to be colorless. For example, depending on the type of the high refractive index transparent thin film layer (B) and metal thin film layer (C) described later, when the transparent color of the transparent conductive film becomes an unfavorable color, it is colored for the purpose of correcting the color. It is also possible to use a transparent plastic film.

  As a coloring method, when forming the plastic film, a method of forming a film after mixing with a pigment in advance, a method of dispersing a pigment in a binder resin to make an ink, and applying and drying this, a colored plastic film Examples include a method of bonding.

      In the transparent substrate (A) of the present invention, for the purpose of improving the adhesion to the transparent conductive layer, a base layer such as an aqueous polyurethane-based or silicon-based coating agent is formed on the surface on which the transparent conductive layer is formed. Or corona treatment or the like.

    The transparent plastic film used in the present invention is not particularly limited as long as it is transparent. For example, polyethylene terephthalate, polyethersulfone, polyarylate, polyacrylate, polycarbonate, polyetheretherketone, polyethylene, polyester, polypropylene, polyamide, polyimide A plastic film made of a resin such as Of course, the resin may be a copolymer using another comonomer as long as it is transparent.

  As a method for molding the transparent plastic film used as the transparent substrate (A), a known plastic film production method such as various die-extrusion methods such as a T-die molding method and an inflation molding method, a casting method, and a calendar method may be used. Is possible. The thickness of the transparent plastic film is not particularly specified, but is preferably 25 to 250 μm and more preferably 30 to 200 μm from the viewpoint of handling properties.

  In the transparent conductive laminate of the present invention, a so-called transparent conductive layer comprising at least a high refractive index transparent thin film layer (B) and a metal layer (C) is formed on a transparent substrate (A), and a transparent material layer is formed thereon. At least one layer is laminated. In the case of a transparent plastic film, the transparent conductive layer is preferably formed on one side. When it is formed on both sides, it may be difficult to form a film by heat shrinking the transparent plastic film when laminated, or it may be difficult to ground both sides of the transparent conductive layer.

  The high refractive index transparent thin film layer (B) used in the present invention is preferably a metal oxide and / or a metal sulfide. A material having a refractive index of 1.8 or more is preferable. Specific materials that can form such a high refractive index transparent thin film layer (B) include indium, titanium, zirconium, bismuth, tin, zinc, antimony, tantalum, cerium, neodymium, lanthanum, thorium, magnesium, and gallium. And oxides such as tungsten, mixtures of these oxides, composite oxides and zinc sulfide. Among these materials, indium oxide, indium oxide-tin (ITO), and tin oxide have high transparency and a high refractive index. In addition, the film forming speed is high, and the metal thin film layer (C) described later is used. It can be preferably used because of its good adhesion.

  The thickness of the high refractive index transparent thin film layer (B) is not particularly limited because it varies depending on the required optical properties, but is preferably 2 to 600 nm, and more preferably 20 to 200 nm. As a method for forming the high refractive index transparent thin film layer (B), a known method such as sputtering, ion plating, ion beam assist, vacuum deposition, or wet coating can be used. Of these, the sputtering method is most preferable.

  The material of the metal thin film layer (C) of the present invention is a metal containing at least silver, and is particularly preferably a silver metal simple substance or a silver alloy. A well-known thing can be used as a silver alloy. Examples of the metal other than silver include known gold, palladium, copper and the like, and the content thereof is preferably 20% by mass or less, more preferably 10% by mass or less in the alloy. Silver is preferably used because of its low surface resistivity, good infrared reflection characteristics, and excellent visible light transmission characteristics when laminated with a high refractive index transparent thin film layer (B).

  The thickness of the metal thin film layer (C) varies depending on the required optical properties and surface resistivity and cannot be defined unconditionally. However, 4 nm or more is preferable for forming a continuous layer, and 30 nm or less is preferable from the viewpoint of transparency. If the thickness is less than 4 nm, the metal may have an island structure and conductivity may be reduced. On the other hand, if the thickness exceeds 30 nm, the total light transmittance may be insufficient. As a method for forming the metal thin film layer, a known method such as a sputtering method, an ion plating method, an ion beam assist method, a vacuum deposition method, or a wet coating method can be used. Of these, the sputtering method is most preferable.

A cap layer may be provided for the purpose of protecting the alteration and physical damage immediately after the formation of the metal thin film layer (C). The cap layer may be formed only on the upper part or the lower part of the metal thin film layer (C), or on both sides. When the cap layer is provided, the cap layer and the metal thin film layer can be collectively regarded as the metal thin film layer (C), which is one of the preferred embodiments of the present invention. However, when calculating the total thickness d _M of the metal thin film layer does not include the thickness of the cap layer. The material of the cap layer is a metal and / or metal oxide, and is different from the high refractive index transparent thin film layer (B). Metals and / or metal oxides that are excellent in gas barrier properties when formed into a thin film are preferable. In particular, those having a refractive index close to that of the high refractive index transparent thin film layer (B) are preferred. Specific examples of such metals and metal oxides include aluminum, silicon, titanium, nickel, copper, zinc, gallium, zirconium, niobium, tantalum and oxides thereof. Particularly preferred are titanium and titanium oxide.

    Since a cap layer consists of a metal and / or a metal oxide, it is excellent in adhesiveness with a high refractive index transparent thin film layer (B) and a metal thin film layer (C).

  The thickness of the cap layer is not particularly limited because it varies depending on the required optical properties, but the preferred lower limit is 2 nm, more preferably 3 nm, and the preferred upper limit is 20 nm, more preferably 10 nm. When the thickness is less than 2 nm, deterioration immediately after the formation of the metal thin film layer (C) and the protection of physical damage may be reduced, and when it exceeds 20 nm, transparency may be insufficient. When the cap layer is formed of metal, the cap layer may be observed as a metal oxide after forming the transparent conductive layer. This is one of the preferred forms because of the antioxidation effect of the cap layer. As a method for forming the cap layer, a known method such as a sputtering method, an ion plating method, an ion beam assist method, a vacuum deposition method, or a wet coating method can be used. Of these, the sputtering method is most preferable.

  The transparent conductive layer of the transparent conductive film of the present invention comprises at least a high refractive index transparent conductive layer (B) and a metal thin film layer (C), and is formed on at least one main surface of the transparent substrate (A). Furthermore, the high refractive index transparent thin film layer (B) and the metal thin film layer (C) have a structure in which 4 to 7 units are laminated with the (B) / (C) laminated structure as a unit. Of the high refractive index transparent thin film layer (B) and the metal thin film layer (C), the outermost layer opposite to the transparent substrate (A) is the high refractive index transparent thin film layer (B). When the said outermost layer is a metal thin film layer (C), a metal layer (C) is easy to be oxidized and light transmittance may fall significantly. Also, the surface reflectance may become too high. The outermost layer is particularly preferably a high refractive index transparent thin film layer (B).

As a specific example of the transparent conductive layer cross-sectional configuration of the present invention,
(A) / [(B) / (C) /] ₄ (B),
(A) / [(B) / (C) /] ₅ (B),
(A) / [(B) / (C) /] ₆ (B),
(A) / [(B) / (C) /] ₇ (B),

Is mentioned. The number of stacked units (B) / (C) is preferably 4 units to 7 units, more preferably 5 units to 6 units. If the number of stacked units exceeds 6 units, the error of the film thickness of each layer has a great influence on the accuracy of the overall optical characteristics, and it may be difficult to control the product quality, resulting in an increase in cost due to a decrease in productivity. Sometimes.

  The transparent material layer laminated on the transparent conductive layer is preferably a material having a refractive index in the visible range of 1.4 to 1.7. Specifically, an adhesive (adhesive) for bonding a functional film. ) Layer, functional transparent layer, hard coat layer, functional film and the like. One or more of these layers or films may be laminated.

  The optical characteristics, particularly the reflection characteristics, of the transparent conductive laminate of the present invention are mainly determined by the film thickness configuration of the transparent conductive layer. In other words, in order to obtain desired reflection characteristics, the optical constants of the transparent substrate (A), high refractive index thin film layer (B), metal thin film layer (C), and transparent material layer are used, and the vector method and the admittance diagram are Conducting optical design according to the method used, etc., and taking into account the conductivity to ensure the desired electromagnetic shielding ability, that is, the material of the metal thin film layer (C) and the total thickness, the thin film material of each layer, the number of layers, the film It is necessary to determine the thickness.

As a result of repeated studies by performing optical design as described above, as a specific example of the film thickness configuration that realizes the present invention, the total thickness of the high refractive index transparent conductive layer (B) is d _DE , a metal thin film layer ( When the total thickness of the C) to _{d M d} DE / _{d M} is 7.0 or more, more preferably, it has been found that it is preferable to set 7.5 or more. Further, assuming that (B) / (C) is a repeating unit and the number of repeated stacks is n, each of the first and nth metal thin film layers (C) from the transparent substrate (A) side has other metal thin film layers ( It has been found that the thickness is preferably 60 to 80%, more preferably 65 to 75% with respect to the average thickness of C).

When the standard light source C is incident at 60 ° from the transparent material layer side, the L * a * b * color system C * value measured from the transparent material layer side is 20 or less. More preferably, it is 15 or less. This indicates that the reflection color viewed obliquely from the transparent material layer side is an achromatic color, which is a preferable characteristic as a reflection characteristic for obliquely incident light. Further, in the transparent conductive laminate of the present invention, when the standard light source C is incident at 2 ° from the transparent material layer side, the chromaticity coordinates a * and b * values measured from the transparent material layer side are respectively −15 ≦ a * ≦ 15 and −40 ≦ b * ≦ 0 are preferable, and more preferably, 0 ≦ a * ≦ 15 and −15 ≦ b * ≦ −35. This indicates that the reflected color viewed from the transparent material layer side is a light blue color, which is a preferable characteristic as a reflection characteristic for normal incident light.
In this invention, a transparent material layer means the layer comprised with the material which permeate | transmits a light ray, and the below-mentioned functional transparent layer, a transparent adhesive layer, an adhesive bond layer, etc. are mentioned.

  The surface resistivity of the transparent conductive layer according to the present invention is preferably 0.1Ω / □ to 2.5Ω / □, and more preferably 0.7Ω / □ to 1.5Ω / □. When the surface resistivity is within the above range, it is possible to achieve both good shielding characteristics and optical characteristics, which is preferable. When the surface resistivity is lower than the above range, the light transmittance may be excessively lowered or good reflection characteristics may not be obtained. Further, when the surface resistivity is higher than the above range, the electromagnetic wave shielding characteristics may be deteriorated excessively. The visible light transmittance (Tvis) of the transparent conductive laminate is preferably 40% or more, more preferably 50% or more, and most preferably 55% or more. When an electromagnetic wave filter using a transparent conductive film having a visible light transmittance lower than the above value is assembled to a display, the brightness of the screen may be insufficient.

  The ideal visible light transmittance is ideally 100%, but is generally 80% or less because of the light absorption / reflection of each layer described above.

  In the transparent conductive laminate, when a standard light source is incident at 2 ° from the transparent material layer side, the 2 ° reflectance at a wavelength of 700 nm is preferably 10% or less, and more preferably 5% or less. When the 2 ° reflectance is higher than the above value, the reflected color viewed from an oblique direction becomes red, and good reflection characteristics may not be obtained.

  In the present invention, a film coater used for forming each thin film layer is preferably a generally called roll coater. A roll coater may have two or more film forming chambers, each of which includes a target, resources such as a film forming gas, film forming conditions, substrate transfer, vacuum pump control, and a partition for atmosphere separation. It is preferable to have 5 or more.

  Unlike the case of the mesh film, the transparent conductive layer of the present invention covers the entire electromagnetic shielding surface and does not degrade the display resolution of the display. It also has near-infrared reflectivity, can be produced with a more productive roll-to-roll process, and can be rolled to sheet when applied to various applications. It has many excellent features and meets the objectives of the present invention.

  When the transparent conductive laminate of the present invention is used as a display filter, a functional transparent layer is laminated on the transparent conductive layer. The functional transparent layer may indicate a functional film itself directly formed on the transparent conductive layer or a film provided with a functional film. When the functional transparent layer is a film, it may be bonded to the transparent conductive laminate via a transparent pressure-sensitive adhesive or adhesive. Examples of the function of the functional transparent layer include an antireflection function, an antiglare function, a toning function, an adhesive function, an antifouling function, an antistatic function, an infrared cut function, and an ultraviolet cut function. Specifically, a functional transparent layer described in Japanese Patent Application No. 9-132343 can be used as a preferred example.

  The display filter of the present invention preferably has a neutral gray or neutral blue transmission color, and may use a combination of toning by optical design of the transparent conductive film and toning by using a dye having absorption in the visible region. . Toning as used herein refers to improving the color purity of the display or improving the contrast. In that case, since it varies depending on the required performance of the display, it is not particularly limited, but the visible light transmittance (Tvis) after toning is preferably 30% or more and 70% or less.

    The dye used for toning may be a general dye or pigment having a desired absorption wavelength in the visible range, and the type is not particularly limited, but it depends on the characteristics of the display itself and the purpose and environment of the display. It is important to use a pigment having heat resistance, moisture resistance, light resistance and the like. As a method of containing a pigment, it is contained in the transparent substrate (A), contained in the functional transparent layer (F) forming material, or contained in a transparent adhesive used for bonding.

Hereinafter, the present invention will be described by way of examples.
The evaluation items and evaluation methods were performed as follows.
(1) Visible light transmittance (%) Using a spectrophotometer [manufactured by Hitachi, Ltd., product name: U-3500 type], calculation was performed according to JIS R 3106 from the obtained spectral characteristics. The evaluation sample was processed into the same structure as the electromagnetic wave filter actually applied to the display device. The structure was glass / transparent adhesive / transparent conductive laminate / transparent adhesive / non-reflective film. A transparent adhesive having a refractive index of 1.5 was used.
(2) Surface resistivity (Ω / □)
Arbitrary 13 points of each sample obtained by using a 4-probe type surface resistivity measuring device [product name: Loresta SP, manufactured by Mitsubishi Chemical Corporation] were measured, and the average value was used.
(3) 2 ° reflection chromaticity, 60 ° reflection chromaticity Using a spectrophotometer [manufactured by PerkinElmer, product name: Lambda900], the sample structure of (1) is 2 ° reflection by total reflection measurement, 60 ° reflection is L * a * b * values were calculated according to JIS Z 8729 from the spectral characteristics obtained from the fixed angle absolute reflectance measurement by the VN method. A C light source was used for the calculation.

Example 1
An indium oxide thin film / silver thin film / titanium thin film / indium oxide thin film / silver thin film / titanium thin film from the PET film side on one main surface of a polyethylene terephthalate (PET) film (product name: OX manufactured by Teijin Limited) having a thickness of 50 μm / Indium oxide thin film / silver thin film / titanium thin film / indium oxide thin film / silver thin film / titanium thin film / indium oxide thin film / silver thin film / titanium thin film / indium oxide thin film, each having a thickness of 35/8/3 / A transparent conductive film having a thickness of 80/11/3/80/11/3/80/11/3/80/8/3/35 nm was obtained. d _DE / d _M is about 7.9, and the thicknesses of the first and fifth silver thin film layers from the transparent substrate side are about 73% with respect to the average value of the other silver thin film layer thicknesses.
The indium oxide thin film is formed by using indium as a target and exhausting the pressure so that the pressure becomes 0.01 Pa. Then, the sputtering gas flow rate ratio is set to argon gas: oxygen gas = 1: 1, and the total pressure is 0.5 Pa. Introduced until. In this state, a film was formed by magnetron DC sputtering.
In forming the silver thin film, silver was used as a target, and after evacuating the pressure to 0.01 Pa, argon gas was introduced until the total pressure reached 0.5 Pa. In this state, a film was formed by magnetron DC sputtering.
The titanium thin film was formed by using titanium as a target, evacuating the pressure to 0.01 Pa, and then introducing argon gas until the total pressure reached 0.5 Pa. In this state, a film was formed by magnetron DC sputtering.
In order to make it into a form that is actually applied to a display, it is processed into a structure of glass / transparent adhesive material / transparent conductive film / transparent adhesive material / non-reflective film, total light transmittance, surface resistivity, 2 ° reflection chromaticity, 60 The reflection chromaticity was measured by the above method, and the results are summarized in Table 1. The 2 ° reflectance at a wavelength of 700 nm was 3%.

(Comparative Example 1)
A 75 μm thick polyethylene terephthalate (PET) film (manufactured by Teijin Limited, product name: OGX) on one main surface, from the PET film side, indium oxide thin film / silver thin film / indium oxide thin film / silver thin film / indium oxide thin film / silver A transparent conductive film having a laminated structure of a thin film / indium oxide thin film / silver thin film / indium oxide thin film having a thickness of 40/10/75/13/75/13/75/13/40 nm was obtained. d _DE / d _M is 6.2, and the thickness of the first silver thin film layer from the transparent substrate side is about 77% with respect to the average thickness of the other silver thin film layers, and the thickness of the fourth silver layer is Was 100% of the average value of the other silver thin film layer thicknesses.

The indium oxide-tin thin film was formed by using indium-tin oxide as a target, exhausting the pressure to 0.01 Pa, setting the sputtering gas flow ratio to argon gas: oxygen gas = 100: 7, It was introduced until the pressure reached 0.5 Pa. In this state, a film was formed by magnetron DC sputtering.
The silver thin film is formed by using silver as a target and exhausting the pressure so that the pressure becomes 0.01 Pa. Argon gas was introduced until the pressure reached 5 Pa. In this state, a film was formed by magnetron DC sputtering.

In order to make it into a form that is actually applied to a display, it is processed into a structure of glass / transparent adhesive material / transparent conductive film / transparent adhesive material / non-reflective film, total light transmittance, surface resistivity, 2 ° reflection chromaticity, 60 The reflection chromaticity was measured in the same manner as in Example 1. The results are shown in Table 1.
The 2 ° reflectance at a wavelength of 700 nm was 40%.

Claims (9)

A high refractive index transparent thin film layer (B) and a metal thin film layer (C) containing at least silver on one main surface of the transparent substrate (A) are repeated 4 to 7 times with (B) / (C) as a repeating unit. A transparent conductive laminate in which a high refractive index transparent thin film layer (B) is laminated thereon to form a transparent conductive layer, and at least one transparent material layer is further formed on the transparent conductive layer. When the standard light source C is incident from the transparent material layer side at an incident angle of 60 °, the L * a * b * color system C * value measured from the transparent material layer side is 20 or less. Conductive laminate. The transparent conductive laminate according to claim 1, wherein a cap layer is formed on one side or both sides of the metal thin film layer (C). When the standard light source C is incident from the transparent material layer side at an incident angle of 2 °, the chromaticity coordinates a * and b * values measured from the transparent material layer side are −15 ≦ a * ≦ 15 and −40 ≦ b *, respectively. The transparent conductive laminate according to claim 1, wherein ≦ 0. 2. The surface resistance value R of the transparent conductive layer is 0.1Ω / □ ≦ R ≦ 2.5Ω / □, and the visible region transmittance Tvis is 40% ≦ Tvis ≦ 80%. Or the transparent conductive laminated body of 2. When the total thickness of the high refractive index transparent thin film layer (B) is d _DE and the total thickness of the metal thin film layer (C) is d _M , d _DE / d _M is 7.0 or more, and (B) When the number of repeated layers of / (C) is n, the thickness of the first and nth metal thin film layers (C) from the transparent substrate side is 60 to 80 with respect to the average value of the thicknesses of the other metal thin film layers (C). The transparent conductive laminate according to claim 1, wherein the transparent conductive laminate is formed with a thickness of about 1%. The transparent conductive laminate according to claim 1, wherein the 2 ° reflectance at a wavelength of 700 nm measured from the transparent material layer side is 10% or less. A display filter comprising the transparent conductive laminate according to claim 1. The display filter according to claim 7, further comprising a dye. A plasma display using the filter according to claim 7 or 8.