JP2009071146A - Conductive layered product and protection plate for plasma display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive layered product which has high conductivity (electromagnetic wave shielding), high visible-light transmittance, and high resistance to fingerprint corrosion, and a protection plate for a plasma display with superior electromagnetic wave shielding properties, a wide transmission/reflection band and high resistance to fingerprint corrosion. <P>SOLUTION: A conductive layered product 10 is a multilayer structure having a conductive film 14 formed on a substrate 12, wherein the conductive film 14 has oxide films 201, 202, ... and metal films 301, 302, ... which are alternately disposed from the substrate 12, the number of metal films is n, and the number of oxide films is n+1 (n is an integer of at least 1). The oxide films 201 to 20n, which are the first to n-th films from the substrate 12, have zirconium oxide layers 221 to 22n. The zirconium oxide layer 22i of the oxide film 20i, which is the i-th film (i is an integer of 1 to n) from the substrate 12, is in contact with the metal film 30i which is the i-th film from the substrate 12. The metal film 30i is a film made of pure silver or a film made of a silver alloy. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a conductive laminate and a protective plate for plasma display.

  The conductive laminate having transparency is used as a transparent electrode such as a liquid crystal display element, an automobile windshield, a heat mirror (heat ray reflective glass), and an electromagnetic wave shielding window glass.

As the conductive laminate, for example, the following has been proposed.
(1) A heat ray reflective transparent body having a conductive film in which an oxide film made of titanium oxide or the like, a metal film made of noble metal such as silver, and an oxide film made of titanium oxide or the like are sequentially laminated on a transparent substrate (patent Reference 1).
(2) A conductive laminate having a total of (2n + 1) layers (n ≧ 2) of conductive films in which an oxide film made of zinc oxide and a metal film made of silver are alternately laminated on a transparent substrate (Patent Document 2) ).

  In addition, the conductive laminate is used as a filter that shields electromagnetic waves generated from a plasma display panel (hereinafter referred to as PDP). For example, on the observer side of the PDP, a conductive film in which an oxide film made of a metal oxide having a high refractive index and a metal film made of silver or a silver alloy are alternately laminated in total (2n + 1) layers on the substrate. A protective plate for plasma display in which a conductive laminate having the above is further provided on a support substrate is disposed.

As the conductive laminate, for example, the following has been proposed.
(3) A conductive laminate in which an oxide film contains indium oxide and tin oxide as main components (Patent Document 3).
(4) A conductive laminate in which an oxide film contains zinc oxide and another metal oxide such as aluminum oxide as main components (Patent Document 4).
(5) A conductive laminate in which an oxide film contains zinc oxide and titanium oxide as main components (Patent Document 5).

High visible light transmittance is required for the conductive laminates (1) to (5). Further, the plasma display protective plate is required to have a high transmittance and a low reflectance over the entire visible light region, that is, a wide transmission / reflection band. However, when the thickness of the metal film is reduced to further improve the visible light transmittance of the conductive laminate, the resistance of the metal film increases and the conductivity (electromagnetic wave shielding) of the conductive laminate decreases. There is a problem to do. In the conductive laminates (1) to (5), if the fingerprint-shaped sebum adhering to the conductive film due to contact with a human finger is left for a long time, the oxide film corrodes and the conductive film has fingerprints. There is a problem that traces are likely to remain (problem of fingerprint corrosion).
JP-A-1-188446 Japanese Patent Publication No. 8-32436 Japanese Patent Laid-Open No. 10-217380 International Publication No. 98/13850 Pamphlet JP 2006-186309 A

  The present invention has a conductive laminate excellent in conductivity (electromagnetic wave shielding property), high visible light transmittance, excellent in fingerprint corrosion resistance, and excellent electromagnetic wave shielding properties, having a wide transmission / reflection band, and fingerprint corrosion resistance. Provided is a plasma display protective plate that is excellent in performance.

  The conductive laminate of the present invention is a conductive laminate having a substrate and a conductive film formed on the substrate, and the conductive film has an oxide film and a metal film alternately from the substrate side. And a multilayer structure in which the number of metal films is n and the number of oxide films is n + 1 (where n is an integer of 1 or more), and the 1st to nth oxide films from the substrate side Has a zirconium oxide layer, and the zirconium oxide layer of the i-th oxide film from the substrate side (where i is an integer of 1 to n) is in contact with the i-th metal film from the substrate side, The metal film is a film made of pure silver or a film made of a silver alloy. That is, the zirconium oxide layers of the 1st to nth oxide films from the substrate side are in contact with the 1st to nth metal films from the substrate side, respectively.

The (n + 1) th oxide film from the substrate side may have a zirconium oxide layer.
The oxide film preferably has a high refractive index layer made of a metal oxide having a refractive index of 1.8 or more (excluding zirconium oxide).
A barrier layer is preferably provided between the i-th metal film from the substrate side and the (i + 1) th oxide film from the substrate side.

  The protective plate for plasma display of the present invention has a support base, the conductive laminate of the present invention provided on the support base, and an electrode that is in electrical contact with the conductive film of the conductive laminate. It is characterized by that.

The conductive laminate of the present invention is excellent in conductivity (electromagnetic wave shielding property), has high visible light transmittance, and is excellent in resistance to fingerprint corrosion.
The protective plate for plasma display of the present invention has excellent electromagnetic wave shielding properties, a wide transmission / reflection band, and excellent resistance to fingerprint corrosion.

<Conductive laminate>
FIG. 1 is a cross-sectional view showing an example of the conductive laminate of the present invention. The conductive laminate 10 has a base 12 and a conductive film 14.

(Substrate)
The substrate 12 is preferably a transparent substrate. The term “transparent” means that light having a wavelength in the visible light region is transmitted.
As the material of the transparent substrate, glass (including tempered glass such as air-cooled tempered glass and chemically tempered glass); polyethylene terephthalate (PET), triacetyl cellulose (TAC), polycarbonate (PC), polymethyl methacrylate (PMMA) And the like.

The thickness of the transparent substrate made of glass is preferably 0.1 to 15 mm, more preferably 1.0 to 2.3 mm, and particularly preferably 1.6 to 2 mm.
The thickness of the transparent substrate made of plastic is preferably 1 to 500 μm, more preferably 10 to 200 μm, and particularly preferably 40 to 110 μm.

(Conductive film)
The conductive film 14 has oxide films 201, 202,... And metal films 301, 302,... Alternately from the substrate 12 side, the number of metal films is n, and the number of oxide films is n + 1. (Where n is an integer greater than or equal to 1), i-th metal film 30i from the substrate 12 side (where i is an integer from 1 to n), and i + 1-th oxidation from the substrate 12 side. It is a multilayer structure having barrier layers 32i (321, 322,...) Between the physical film 20 (i + 1). In the illustrated example, n = 4.
n is preferably from 2 to 8, and more preferably from 2 to 6. If n is 2 or more, it is excellent in electroconductivity (electromagnetic wave shielding). If n is 8 or less, the increase in the internal stress of the conductive film 14 is suppressed.

(Oxide film)
An oxide film means a film made of a metal oxide.
The first to nth oxide films 201 to 20n (n = 4 in the illustrated example) from the substrate 12 side are composed of zirconium oxide layers 221 to 22n (n = 4 in the illustrated example) and high refractive index layers 241 to 24n (n = 4 in the illustrated example). In the illustrated example, n = 4), and the zirconium oxide layer 22i of the i th oxide film 20i from the substrate 12 side (where i is an integer from 1 to n) is i th from the substrate 12 side. In contact with the metal film 30i.
The (n + 1) th oxide film 20 (n + 1) (reference numeral 205 in the illustrated example) from the substrate 12 side is composed of a high refractive index layer 24 (n + 1) (reference numeral 245 in the illustrated example).

The physical film thickness of the oxide film (hereinafter simply referred to as the film thickness) is preferably 10 to 60 nm at the first and n + 1th from the substrate 12, more preferably 20 to 50 nm, and more preferably 2 to n from the substrate 12. 10-120 nm is preferable and 20-100 nm is more preferable.
The film thickness is a value obtained by converting from the sputtering time during film formation using a calibration curve prepared in advance by the following method.
Method for preparing a calibration curve: A film is formed by sputtering on a surface of a substrate on which a part of the surface is coated with oil pen ink at an arbitrary time. After film formation, the oil-based pen ink is removed from the substrate. On the surface of the substrate, the difference in height between the part where the ink of the oil-based pen is removed and the part where the film is formed is measured by a stylus type surface roughness measuring instrument. The difference in height is the film thickness at the sputtering time. Next, the film thickness is measured in the same manner as described above except that the sputtering time during film formation is changed. Repeat the same measurement three or more times as necessary. A calibration curve between the sputtering time and the film thickness is created from the values obtained by the above measurement.
The oxide films 201 to 20n may all have the same configuration and material, or may have different configurations and materials. In addition, the oxide films 201 to 20n may be the same or different from each other.

(Zirconium oxide layer)
The zirconium oxide layer means a layer mainly composed of zirconium oxide (refractive index: 2.19).
The zirconium oxide layer 22i has high flatness and improves the crystallinity of the metal film 30i formed on the surface of the zirconium oxide layer 22i. Therefore, by having the zirconium oxide layer 22i, the resistance value of the metal film 30i can be lowered even if the metal film 30i is thin. Further, the zirconium oxide layer 22i is less likely to be corroded by sebum than other metal oxides.

In the zirconium oxide layer 22i, it is considered that zirconium oxide exists as a mixture of ZrO, ZrO ₂ and ZrO ₃ . The content of zirconium atoms in the zirconium oxide layer 22i can be measured by ESCA (X-ray photoelectron spectroscopy) or Rutherford backscattering method (RBS: Rutherford Backscattering Spectroscopy).

  The content of zirconium atoms is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 99% by mass or more with respect to the total amount of metal atoms in the zirconium oxide layer 22i. If the content of zirconium atoms is 90% by mass or more, even if the metal film 30i formed on the surface of the zirconium oxide layer 22i is thin, the resistance value of the metal film 30i can be sufficiently reduced.

  The zirconium oxide layer 22i may contain other metals other than zirconium as oxides as long as the physical properties are not impaired. Examples of other metals include magnesium, calcium, scandium, titanium, vanadium, strontium, yttrium, niobium, barium, hafnium, tantalum, iron, chromium, and the like.

  The thickness of the zirconium oxide layer 22i is preferably 3 to 40 nm, more preferably 5 to 20 nm, and particularly preferably 6 to 15 nm. If the film thickness of the zirconium oxide layer 22i is within this range, the flatness of the zirconium oxide layer 22i is good, and even if the metal film 30i formed on the surface is thin, the resistance value of the metal film 30i is sufficiently high. Can be lowered.

(High refractive index layer)
The high refractive index layer 24i (where i is an integer of 1 to n + 1) is a layer made of a metal oxide (however, excluding zirconium oxide) having a refractive index of 1.8 or more. A more preferable refractive index is 1.8 to 2.5. By having the high refractive index layer 24i, the visible light reflectance of the conductive laminate 10 can be kept low. Further, if a material capable of increasing the deposition rate is selected as the material for the high refractive index layer 24i, the conductive laminate of the present invention can be manufactured with a shorter tact.
The refractive index means a refractive index at a wavelength of 550 nm.

  Examples of the metal oxide having a refractive index of 1.8 or more include niobium oxide (refractive index 2.35), titanium oxide (refractive index 2.45), tantalum oxide (refractive index 2.1 to 2.2), and oxidation. Indium, tin oxide, ITO (composite oxide of indium and tin) (refractive index 2.0), etc. are mentioned, and niobium oxide, titanium oxide, ITO are used in terms of high refractive index and high film formation speed. Niobium oxide and ITO are more preferable.

  The content of niobium atoms, titanium atoms, tantalum atoms, tin atoms or indium atoms in the high refractive index layer 24i can be measured by ESCA or Rutherford backscattering method.

The content of niobium atoms, titanium atoms, or tantalum atoms is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 99% by mass or more based on the total amount of metal atoms in the high refractive index layer 24i.
When ITO is used as the material for the high refractive index layer 24i, the total amount of indium atoms and tin atoms is preferably 90% by mass or more, more preferably 95% by mass or more, based on the total amount of metal atoms in the high refractive index layer 24i. Preferably, 99 mass% or more is especially preferable. Moreover, 33-75 mass% is preferable in the high refractive index layer 24i, and, as for content of an indium atom, 41-58 mass% is more preferable. 7-48 mass% is preferable in the high refractive index layer 24i, and, as for content of a tin atom, 23-40 mass% is more preferable.

The film thickness of the high refractive index layer 24i is preferably 3 to 60 nm, more preferably 10 to 50 nm, and particularly preferably 30 to 45 nm.
The high refractive index layer 24i may be a multilayer structure including a plurality of layers having different types of metal oxides. For example, a multilayer structure including a niobium oxide layer and a titanium oxide layer may be used.

(Metal film)
The metal film 30i is a film made of pure silver or a film made of a silver alloy.
The metal film 30i is preferably a film made of pure silver from the viewpoint of reducing the sheet resistance of the conductive laminate 10. Pure silver means that 99.9% by mass or more of silver is contained in the metal film 30i (100% by mass).
The metal film 30i is preferably a film made of a silver alloy containing one or more selected from the group consisting of gold, bismuth and palladium from the viewpoint of suppressing migration of silver and consequently improving moisture resistance. The total of gold, bismuth and palladium is preferably 1 to 25 atomic%, more preferably 3 to 15 atomic%, and particularly preferably 4 to 11 atomic% in the metal film 30i (100 atomic%).

  The total film thickness of the total film thickness of the metal films 301 to 30n is preferably 15 to 70 nm, and more preferably 20 to 60 nm, for example, when the sheet resistance target of the conductive laminate 10 is 1.5Ω / □. 30 to 50 nm is particularly preferable, and when the sheet resistance target is 0.9 Ω / □, 20 to 80 nm is preferable, 30 to 70 nm is more preferable, and 40 to 60 nm is particularly preferable. As for the film thickness of each metal film 30i, the total film thickness is appropriately distributed by the number n of metal films. As the number n of metal films increases, the film thickness of each metal film 30i decreases, and the specific resistance of each metal film 30i increases. Therefore, when the number n of metal films increases, the total film thickness tends to increase in order to reduce the resistance.

(Barrier film)
The barrier film 32i is a film that prevents oxidation of the metal film 30i when the oxide film 20 (i + 1) is formed in an oxygen atmosphere.
Examples of the barrier film 32i include a film that can be formed in the absence of oxygen. Examples thereof include a niobium oxide film, a niobium film, a zirconium film, a titanium film, a tantalum film, and an indium film.
The thickness of the barrier film 32i is preferably 0.1 to 10 nm.

(Method for forming conductive film)
Examples of the method for forming the conductive film 14 include a sputtering method, a vacuum deposition method, an ion plating method, a chemical vapor deposition method, and the like, and the sputtering method is preferable from the viewpoint of good quality and stability of characteristics.
Examples of the sputtering method include a DC sputtering method, a pulse sputtering method, and an AC sputtering method.

For example, the conductive film 14 is formed by sputtering as follows.
(I) While introducing argon gas mixed with oxygen gas, DC sputtering is performed using a metal oxide target having a refractive index of 1.8 or more, or a metal target, and a high refractive index layer 241 is formed on the surface of the substrate 12. Is deposited.
(Ii) DC sputtering is performed using a zirconium target while introducing an argon gas mixed with an oxygen gas, and a zirconium oxide layer 221 is formed on the surface of the high refractive index layer 241.
(Iii) DC sputtering is performed using a silver target or a silver alloy target while introducing argon gas or nitrogen gas, and a metal film 301 is formed on the surface of the zirconium oxide layer 221.
(Iv) While introducing argon gas, DC sputtering is performed using a target such as niobium oxide to form a barrier film 321 on the surface of the metal film 301.
The operations of (i) to (iv) are repeated n times in total, and finally a high refractive index layer 24 (n + 1) (reference numeral 245 in the illustrated example) is formed in the same manner as in (i), thereby forming a multilayer. A conductive film 14 having a structure is formed.

The gas pressure during sputtering is preferably 0.20 Pa or less.
Power density, when the oxide film is preferably 3.57W / cm ^2, when the metal film, 0.29 W / cm ² is preferred.
The metal oxide target is prepared by mixing high-purity (usually 99.9%) powders of each metal oxide and sintering by hot pressing, HIP (hot isostatic pressing), or normal pressure firing. Can be manufactured.
When the high refractive index layer 24i is formed using a metal oxide target, the composition ratio of each metal atom and oxygen atom of the high refractive index layer 24i is equal to the composition ratio of each metal atom and oxygen atom of the metal oxide target. It will be almost the same.

  Zirconium targets used for forming the zirconium oxide layer 22i include other metals such as magnesium, calcium, scandium, titanium, vanadium, strontium, yttrium, niobium, barium, hafnium, tantalum, iron, and chromium. It may be. The content of other metals is preferably as small as possible. Usually, the total content of other metals in the zirconium target is 0.1 to 5.0 atomic%. The composition ratio of each metal atom in the zirconium oxide layer 22i is substantially the same as the composition ratio of the metal atoms in the target.

The visibility transmittance of the conductive laminate 10 is preferably 60% or more, and more preferably 70% or more.
The sheet resistance of the conductive laminate 10 is preferably 0.1 to 3.5Ω / □, more preferably 0.3 to 2.5Ω / □, in order to sufficiently secure conductivity (electromagnetic wave shielding). .3-1.0Ω / □ is particularly preferable.

In the conductive laminate 10 described above, the first to nth oxide films 201 to 20n (n = 4 in the illustrated example) from the substrate 12 side are the zirconium oxide layers 221 to 22n (n in the illustrated example). = 4)), and the zirconium oxide layer 22i of the i-th oxide film 20i from the substrate 12 side (where i is an integer of 1 to n) is the i-th metal film 30i from the substrate 12 side. Since it is in contact with, it is excellent in conductivity (electromagnetic wave shielding property). That is, since the metal film 30i is formed on the surface of the zirconium oxide layer 22i having good flatness, the crystallinity of the metal film 30i is improved, and the resistance of the metal film 30i is improved even when the metal film 30i is thin. The value can be lowered.
Moreover, in the conductive laminated body 10 demonstrated above, since the film thickness of the metal film 30i can be made thin, suppressing the resistance value of the metal film 30i, visible light transmittance is high.
In the conductive laminate 10 described above, since the zirconium oxide layer 22i is not easily corroded by sebum, it is not easily corroded by adhesion of fingerprint-shaped sebum when a human finger comes into contact, that is, anti-fingerprint corrosion. Excellent in properties.

The conductive laminate of the present invention is not limited to the conductive laminate 10 shown in FIG. For example, the high refractive index layer 24i is not necessarily provided. As shown in FIG. 2, all oxide films 20i (where i is an integer of 1 to n + 1) are formed of the zirconium oxide layer 22i. It may be.
Further, the barrier layer 32i is not necessarily provided, and the barrier layer may be omitted as shown in FIGS.

  Further, the (n + 1) th oxide film 20 (n + 1) (reference numeral 205 in the illustrated example) from the substrate 12 side may have a zirconium oxide layer, may have a high refractive index layer, and may be oxidized. You may have both a zirconium layer and a high refractive index layer. The n + 1th oxide film 20 from the substrate 12 side is preferably a zirconium oxide layer 22 as the outermost layer from the viewpoint of fingerprint corrosion resistance. The n + 1-th oxide film 20 (n + 1) (reference numeral 205 in the illustrated example) from the substrate 12 side has a high refractive index layer 24 (n + 1) (made of niobium oxide) in terms of visible light reflectance and film formation speed. In the illustrated example, reference numeral 245.) is preferable.

The conductive laminate 10 may have a protective film (not shown) on the surface of the (n + 1) th oxide film 20 (n + 1) (reference numeral 205 in the illustrated example) from the base 12. The protective film protects the oxide film and the metal film from moisture, and an arbitrary resin film (moisture-proof film, scattering prevention film, anti-reflection) on the (n + 1) th oxide film 20 (n + 1) (reference numeral 205 in the illustrated example). Film, protective film for shielding near infrared rays, functional film such as near infrared ray absorbing film, etc.) for protecting an oxide film from an adhesive (particularly an alkaline adhesive).
Examples of the protective film include oxide films or nitride films of tin, indium, titanium, silicon, gallium, and the like, and a film containing indium oxide and tin oxide as main components is preferable.
2-30 nm is preferable and, as for the film thickness of the protective film 16, 3-20 nm is more preferable.

The conductive laminate of the present invention is excellent in conductivity (electromagnetic wave shielding property), has high visible light transmittance, and has a wide transmission / reflection band when laminated on a supporting substrate such as glass. Useful as an electromagnetic shielding film.
Moreover, the electroconductive laminated body of this invention can be used as transparent electrodes, such as a liquid crystal display element. The transparent electrode has good responsiveness because of low sheet resistance, and good visibility because of low reflectance.
Moreover, the electroconductive laminated body of this invention can be used as a motor vehicle windshield. The car windshield can exhibit the function of anti-fogging or melting ice by energizing the conductive film, and since it has low resistance, the voltage required for energization is low, and the reflectance is kept low, so Visibility is not impaired.
Moreover, since the electroconductive laminated body of this invention has the very high reflectance in an infrared region, it can be used as a heat mirror provided in the window etc. of a building.
In addition, since the conductive laminate of the present invention has a high electromagnetic shielding effect, the electromagnetic waves radiated from the electric / electronic device are prevented from leaking outside, and the electromagnetic waves that affect the electric / electronic device enter the room from the outside. It can be used for an electromagnetic wave shielding window glass that prevents intrusion.

<Protective plate for plasma display>
The protective plate for plasma display of the present invention (hereinafter referred to as a protective plate) is electrically connected to a supporting substrate, the conductive laminate of the present invention provided on the supporting substrate, and the conductive film of the conductive laminate. In contact with the electrode.

(First embodiment)
FIG. 5 shows the protective plate of the first embodiment. The protective plate 40 adheres to the surface of the support base 42 such that the support base 42, the colored ceramic layer 44 provided on the peripheral portion of the support base 42, and the peripheral portion of the conductive laminate 10 overlap the colored ceramic layer 44. The conductive laminate 10 bonded via the adhesive layer 46, the scattering prevention film 48 bonded via the adhesive layer 46 to the surface of the support base 42 opposite to the conductive laminate 10, and the adhesive The protective film 50 bonded to the surface of the conductive laminate 10 via the layer 46, and provided on the peripheral portions of the conductive laminate 10 and the protective film 50, and electrically connected to the conductive film 14 of the conductive laminate 10. And an electrode 52 to be used. The protection plate 40 is an example in which the conductive laminate 10 is provided on the PDP side of the support base 42.

The support base 42 is a transparent base having higher rigidity than the base 12 of the conductive laminate 10. By providing the support base 42, even when the material of the base 12 of the conductive laminate 10 is a plastic such as PET, no warp occurs due to a temperature difference between the PDP side and the observer side.
Examples of the material of the support base 42 include the same materials as those of the base 12 described above.

  The colored ceramic layer 44 is a layer for concealing the electrode 52 so as not to be directly visible from the viewer side. The colored ceramic layer 44 can be formed, for example, by printing on the support base 42 or pasting a colored tape.

The scattering prevention film 48 is a film for preventing the fragments of the supporting base 42 from scattering when the supporting base 42 is damaged. As the scattering prevention film 48, a known film can be used.
The anti-scattering film 48 may have an antireflection function. As a film having both a scattering prevention function and an antireflection function, ARCTOP (trade name) manufactured by Asahi Glass Co., Ltd. may be mentioned. ARCTOP (trade name) is an anti-reflective treatment by forming a low-refractive index anti-reflective layer made of an amorphous fluoropolymer on one side of a polyurethane-based soft resin film having self-healing properties and anti-scattering properties. Is given. Moreover, the film etc. which formed the antireflective layer of a low refractive index on the film which consists of polymers, such as PET, by the wet type or the dry type are mentioned.

The electrode 52 is provided so as to be electrically connected to the conductive film 14 so that the electromagnetic wave shielding effect by the conductive film 14 of the conductive laminate 10 is exhibited. The electrode 52 is preferably provided on the entire periphery of the conductive laminate 10 in order to ensure the electromagnetic wave shielding effect by the conductive film 14.
The material of the electrode 52 is superior in terms of electromagnetic shielding properties when the resistance is lower. The electrode 52 is formed, for example, by applying and baking a silver paste containing silver and glass frit and a copper paste containing copper and glass frit.

  The protective film 50 is a film that protects the conductive laminate 10 (conductive film 14). In the case where the conductive film 14 is protected from moisture, a moisture-proof film is provided. Examples of the moisture-proof film include plastic films such as PET and polyvinylidene chloride. Further, as the protective film 50, the above-described scattering prevention film may be used.

  Examples of the pressure-sensitive adhesive for the pressure-sensitive adhesive layer 46 include commercially available pressure-sensitive adhesives. For example, acrylic ester copolymer, polyvinyl chloride, epoxy resin, polyurethane, vinyl acetate copolymer, styrene-acrylic copolymer, polyester, polyamide, polyolefin, styrene-butadiene copolymer rubber, butyl rubber, silicone resin, etc. The pressure-sensitive adhesive is mentioned. Among these, an acrylic pressure-sensitive adhesive is particularly preferable because good moisture resistance can be obtained. The pressure-sensitive adhesive layer 46 may contain additives such as an ultraviolet absorber.

(Second Embodiment)
FIG. 6 shows a protection plate according to the second embodiment. The protective plate 60 is provided on the support base 42, the conductive laminate 10 bonded to the surface of the support base 42 via the pressure-sensitive adhesive layer 46, and the periphery of the conductive laminate 10. An electrode 52 electrically connected to the conductive film 14, an anti-scattering film 48 bonded to the surface of the conductive laminate 10 via an adhesive layer 46 so as not to overlap the electrode 52, and the conductive laminate 10 Has a colored ceramic layer 44 provided at the peripheral edge of the surface of the support substrate 42 on the opposite side. The protection plate 60 is an example in which the conductive laminate 10 is provided on the viewer side of the support base 42.
Note that in the second embodiment, the same components as those in the first embodiment are denoted by the same reference numerals as those in FIG. 5 and description thereof is omitted.

(Third embodiment)
FIG. 7 shows a protective plate according to the third embodiment. The protective plate 70 includes the support base 42, the conductive laminate 10 bonded to the surface of the support base 42 via the adhesive layer 46, and the scattering bonded to the surface of the conductive laminate 10 via the adhesive layer 46. The prevention film 48 and the colored ceramic layer 44 provided on the peripheral portion of the surface of the support base 42 opposite to the conductive laminate 10, and the peripheral portion of the conductive mesh film 54 overlap the colored ceramic layer 44. The conductive mesh film 54 bonded to the surface of the support base 42 via the adhesive layer 46, the conductive film 14 of the conductive laminate 10, and the conductive mesh layer (not shown) of the conductive mesh film 54 are electrically connected. And a conductor 56 provided on the peripheral side portion of the protective plate 70 so as to be connected to. The protection plate 70 is an example in which the conductive laminate 10 is provided on the viewer side of the support base 42 and the conductive mesh film 54 is provided on the PDP side of the support base 42.
Note that in the third embodiment, the same components as those in the first embodiment are denoted by the same reference numerals as in FIG. 5 and description thereof is omitted.

  By using the conductive mesh film 54 together with the conductive laminate 10, the surface resistance of the entire protective plate is reduced compared to a protective plate having the conductive laminate 10 and no conductive mesh film 54. The electromagnetic wave shielding effect can be further improved. Moreover, compared with the protective plate having the conductive mesh film 54 and not having the conductive laminate 10, the combined use with the conductive laminate 10 can provide the near-infrared shielding effect as well as the electromagnetic wave shielding effect. . In order to prevent malfunction of the remote control, the protective plate for plasma display is required to have a near infrared shielding ability, but the conductive mesh film 54 does not have a near infrared shielding effect and includes a near infrared absorbing dye-containing layer, etc. Need to be used together. Since the conductive laminate 10 has a near-infrared shielding effect, the near-infrared shielding effect is imparted to the conductive mesh film 54 by the combined use.

The conductive mesh film 54 is obtained by forming a conductive mesh layer made of copper on a transparent film. Usually, after manufacturing a copper foil on a transparent film, it manufactures by processing in a mesh form.
The copper foil may be either rolled copper or electrolytic copper, and a known one may be used as appropriate. The copper foil may be subjected to various surface treatments. Examples of the surface treatment include chromate treatment, roughening treatment, pickling, zinc / chromate treatment, and the like. 3-30 micrometers is preferable, as for the thickness of copper foil, 5-20 micrometers is more preferable, and 7-10 micrometers is especially preferable. By setting the thickness of the copper foil to 30 μm or less, the etching time can be shortened, and by setting the thickness to 3 μm or more, the electromagnetic wave shielding property is enhanced.

The opening ratio of the conductive mesh layer is preferably 60 to 95%, more preferably 65 to 90%, and particularly preferably 70 to 85%.
The shape of the opening of the conductive mesh layer is a regular triangle, a regular square, a regular hexagon, a circle, a rectangle, a rhombus, or the like. It is preferable that the openings have the same shape and are aligned in the plane. The size of the opening is preferably 5 to 200 μm on one side or diameter, and more preferably 10 to 150 μm. By setting one side or diameter of the opening to 200 μm or less, the electromagnetic wave shielding property is improved, and by setting it to 5 μm or more, there is little influence on the image of the PDP.
The width of the metal part other than the opening is preferably 5 to 50 μm. That is, the arrangement pitch of the openings is preferably 10 to 250 μm. By making the width of the metal part 5 μm or more, processing becomes easy, and by making the width 50 μm or less, the influence on the image of the PDP is small.

  If the sheet resistance of the conductive mesh layer is lowered more than necessary, the film becomes thick and adversely affects the optical performance and the like of the protective plate 70, such as being unable to secure a sufficient opening. On the other hand, if the sheet resistance of the conductive mesh layer is increased more than necessary, sufficient electromagnetic wave shielding properties cannot be obtained. Therefore, the sheet resistance of the conductive mesh layer is preferably 0.01 to 10Ω / □, more preferably 0.01 to 2Ω / □, and particularly preferably 0.05 to 1Ω / □.

The sheet resistance of the conductive mesh layer may be measured by a four-terminal method using an electrode that is at least five times larger than one side or diameter of the opening and an electrode interval that is five times or more than the arrangement pitch of the openings. For example, if the openings are squares with a side of 100 μm and are regularly arranged via a metal part with a width of 20 μm, electrodes having a diameter of 1 mm may be arranged at intervals of 1 mm. Alternatively, the conductive mesh film is processed into a strip shape, electrodes are provided at both ends in the longitudinal direction, the resistance value R is measured, the longitudinal length a, the lateral length b, You may ask for it.
Sheet resistance = R × b / a.

  When laminating a copper foil on a transparent film, a transparent adhesive is used. Examples of the adhesive include acrylic adhesives, epoxy adhesives, urethane adhesives, silicone adhesives, and polyester adhesives. The adhesive type is preferably a two-component type or a thermosetting type. Moreover, as an adhesive agent, what was excellent in chemical-resistance is preferable.

  As a method of processing the copper foil into a mesh shape, a photoresist method can be mentioned. In the printing method, the opening pattern is formed by screen printing. In the photoresist method, a photoresist material is formed on a copper foil by a roll coating method, a spin coating method, a full surface printing method, a transfer method, and the like, and an opening pattern is formed by exposure, development, and etching. As another method of forming the conductive mesh layer, a method of forming a pattern of openings by a printing method such as screen printing can be given.

  The conductor 56 electrically connects the conductive film 14 of the conductive laminate 10 and the conductive mesh layer of the conductive mesh film 54. Examples of the conductor 56 include a conductive tape. By electrically connecting the conductive film 14 of the conductive laminate 10 and the conductive mesh layer of the conductive mesh film 54, the overall surface resistance can be further reduced, so that the electromagnetic wave shielding effect is further improved. Can do.

  Since the protective plates 40, 60, and 70 are disposed on the front surface of the PDP, the visibility transmittance is preferably 35% or more so that the image of the PDP does not become difficult to see. Further, the visibility reflectance is preferably less than 6%, particularly preferably less than 3%. Further, the transmittance at a wavelength of 850 nm is preferably 5% or less, and particularly preferably 2% or less.

  The protective plates 40, 60, and 70 described above use the conductive laminate 10 that has excellent conductivity (electromagnetic wave shielding properties), high visible light transmittance, and excellent fingerprint corrosion resistance. Excellent shielding properties, wide transmission and reflection bands, and excellent fingerprint corrosion resistance.

Note that the protective plate of the present invention is not limited to the first to third embodiments. For example, heat bonding may be performed without providing the pressure-sensitive adhesive layer 46.
Moreover, you may provide the antireflection layer which is an antireflection film or a low refractive index thin film in the protective plate of this invention as needed.
A known film can be used as the antireflection film, and a fluororesin film is particularly preferable from the viewpoint of antireflection properties.
In the antireflection layer, the reflectance of the protective plate is lowered, and a preferable reflected color is obtained. Therefore, the wavelength at which the reflectance is lowest in the visible light region is preferably 500 to 600 nm, and is preferably 530 to 590 nm. Is particularly preferred.

  Further, the protective plate may have a near infrared shielding function. As a method for providing a near-infrared shielding function, a method using a near-infrared shielding film, a method using a near-infrared absorbing substrate, a method using a pressure-sensitive adhesive added with a near-infrared absorber during film lamination, a near-infrared ray in an antireflection film, etc. Examples thereof include a method of adding an absorbent to have a near infrared absorption function, a method of using a conductive film having a near infrared reflection function, and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
Examples 1 to 13 are reference examples, and Example 14 is an example.

(Visibility transmittance)
The luminous transmittance of the conductive laminate was measured with a transmittance meter (Model 304, manufactured by Asahi Spectroscopic Co., Ltd.).

(Sheet resistance)
The sheet resistance of the conductive laminate was measured using an eddy current resistance measuring instrument (717 Conductor, manufactured by DELCOM).

(Fingerprint corrosion resistance)
After the fingerprint was attached to the surface of the oxide film, the conductive laminate was placed in a high temperature and high humidity tank having a temperature of 40 ° C. and a relative humidity of 90% for 120 hours. The fingerprint was wiped off, and the state of the oxide film at the wiped portion was visually confirmed.

[Example 1]
A glass substrate subjected to a dry cleaning treatment was prepared.
While introducing a mixed gas of 80% by volume argon gas and 20% by volume oxygen gas, a zirconium target (zirconium 99.8% by mass, hafnium 0.01% by mass, iron and chromium 0.09% by mass) was used. DC sputtering was performed under the conditions of a pressure of 0.24 Pa and a power density of 3.57 W / cm ² to form a 40 nm thick zirconium oxide layer on the surface of the glass substrate. The content of zirconium atoms with respect to the total amount of metal atoms in the zirconium oxide layer is 98% by mass or more.

Using a silver alloy target doped with 0.5 atomic% of gold while introducing argon gas, DC sputtering was performed under the conditions of pressure 0.24 Pa and power density 0.29 W / cm ² , and the surface of the zirconium oxide layer A metal film having a thickness of 10 nm was formed on the substrate to obtain a conductive laminate. The silver content in the metal film is 99.5 atomic%, and the gold content is 0.5 atomic%.
The luminous transmittance of the conductive laminate and the sheet resistance on the surface of the metal film were measured. The results are shown in Table 1.

[Example 2]
A conductive laminate was obtained in the same manner as in Example 1 except that the argon gas in the mixed gas at the time of forming the zirconium oxide layer was changed to 60% by volume and the oxygen gas was changed to 40% by volume. The content of zirconium atoms with respect to the total amount of metal atoms in the zirconium oxide layer is 98% by mass or more. The silver content in the metal film is 99.5 atomic%, and the gold content is 0.5 atomic%.
The luminous transmittance of the conductive laminate and the sheet resistance on the surface of the metal film were measured. The results are shown in Table 1.

[Example 3]
A conductive laminate was obtained in the same manner as in Example 1 except that the argon gas in the mixed gas at the time of forming the zirconium oxide layer was changed to 20% by volume and the oxygen gas was changed to 80% by volume. The content of zirconium atoms with respect to the total amount of metal atoms in the zirconium oxide layer is 98% by mass or more. The silver content in the metal film is 99.5 atomic%, and the gold content is 0.5 atomic%.
The luminous transmittance of the conductive laminate and the sheet resistance on the surface of the metal film were measured. The results are shown in Table 1.

[Example 4]
A conductive laminate was obtained in the same manner as in Example 1 except that the mixed gas at the time of forming the zirconium oxide layer was changed to 100% by volume of oxygen gas. The content of zirconium atoms with respect to the total amount of metal atoms in the zirconium oxide layer is 98% by mass or more. The silver content in the metal film is 99.5 atomic%, and the gold content is 0.5 atomic%.
The luminous transmittance of the conductive laminate and the sheet resistance on the surface of the metal film were measured. The results are shown in Table 1.

  From the results of Examples 1 to 4, it was confirmed that the oxygen gas in the mixed gas is preferably 80% by volume.

[Example 5]
A glass substrate subjected to a dry cleaning treatment was prepared.
While introducing a mixed gas of 97% by volume argon gas and 3% by volume oxygen gas, using a niobium oxide target, DC sputtering was performed under conditions of a pressure of 0.24 Pa and a power density of 3.57 W / cm ² , A niobium oxide layer (high refractive index layer) having a thickness of 40 nm was formed on the surface of the glass substrate. The content of niobium atoms with respect to the total amount of metal atoms in the niobium oxide layer is 98% by mass or more.

Using a silver alloy target doped with 0.5 atomic% of gold while introducing argon gas, DC sputtering was performed under the conditions of pressure 0.24 Pa and power density 0.29 W / cm ² , and the surface of the niobium oxide layer A metal film having a thickness of 10 nm was formed on the substrate to obtain a conductive laminate. The silver content in the metal film is 99.5 atomic%, and the gold content is 0.5 atomic%.
The luminous transmittance of the conductive laminate and the sheet resistance on the surface of the metal film were measured. The results are shown in Table 2.

[Example 6]
A glass substrate subjected to a dry cleaning treatment was prepared.
While introducing a mixed gas of 97% by volume argon gas and 3% by volume oxygen gas, using a niobium oxide target, DC sputtering was performed under conditions of a pressure of 0.24 Pa and a power density of 3.57 W / cm ² , A 37 nm-thick niobium oxide layer (high refractive index layer) was formed on the surface of the glass substrate. The content of niobium atoms with respect to the total amount of metal atoms in the niobium oxide layer is 100% by mass.

A zirconium target (zirconium 99.8 mass%, hafnium 0.01 mass%, iron and chromium 0.09 mass%) was used while introducing a mixed gas of 20 volume% argon gas and 80 volume% oxygen gas. DC sputtering was performed under the conditions of a pressure of 0.24 Pa and a power density of 3.57 W / cm ² to form a 3 nm-thickness zirconium oxide layer on the surface of the niobium oxide layer. The content of zirconium atoms with respect to the total amount of metal atoms in the zirconium oxide layer is 98% by mass or more.

Using a silver alloy target doped with 0.5 atomic% of gold while introducing argon gas, DC sputtering was performed under the conditions of pressure 0.24 Pa and power density 0.29 W / cm ² , and the surface of the zirconium oxide layer A metal film having a thickness of 10 nm was formed on the substrate to obtain a conductive laminate. The silver content in the metal film is 99.5 atomic%, and the gold content is 0.5 atomic%.
The luminous transmittance of the conductive laminate and the sheet resistance on the surface of the metal film were measured. The results are shown in Table 2.

[Example 7]
A conductive laminate was obtained in the same manner as in Example 6 except that the thickness of the niobium oxide layer (high refractive index layer) was changed to 35 nm and the thickness of the zirconium oxide layer was changed to 5 nm. The content of niobium atoms with respect to the total amount of metal atoms in the niobium oxide layer is 100% by mass. The content of zirconium atoms with respect to the total amount of metal atoms in the zirconium oxide layer is 98% by mass or more. The silver content in the metal film is 99.5 atomic%, and the gold content is 0.5 atomic%.
The luminous transmittance of the conductive laminate and the sheet resistance on the surface of the metal film were measured. The results are shown in Table 2.

[Example 8]
A conductive laminate was obtained in the same manner as in Example 6 except that the thickness of the niobium oxide layer (high refractive index layer) was changed to 30 nm and the thickness of the zirconium oxide layer was changed to 10 nm. The content of niobium atoms with respect to the total amount of metal atoms in the niobium oxide layer is 100% by mass. The content of zirconium atoms with respect to the total amount of metal atoms in the zirconium oxide layer is 98% by mass or more. The silver content in the metal film is 99.5 atomic%, and the gold content is 0.5 atomic%.
The luminous transmittance of the conductive laminate and the sheet resistance on the surface of the metal film were measured. The results are shown in Table 2.

[Example 9]
A conductive laminate was obtained in the same manner as in Example 6 except that the thickness of the niobium oxide layer (high refractive index layer) was changed to 20 nm and the thickness of the zirconium oxide layer was changed to 20 nm. The content of niobium atoms with respect to the total amount of metal atoms in the niobium oxide layer is 100% by mass. The content of zirconium atoms with respect to the total amount of metal atoms in the zirconium oxide layer is 98% by mass or more. The silver content in the metal film is 99.5 atomic%, and the gold content is 0.5 atomic%.
The luminous transmittance of the conductive laminate and the sheet resistance on the surface of the metal film were measured. The results are shown in Table 2.

  From the results of Examples 4 to 9, it was confirmed that the thickness of the zirconium oxide layer was preferably 10 nm.

[Example 10]
A glass substrate subjected to a dry cleaning treatment was prepared.
While introducing a mixed gas of 97 volume% argon gas and 3 volume% oxygen gas, a mixture of zinc oxide and aluminum oxide (hereinafter referred to as AZO) target [zinc oxide: aluminum oxide = 97: 3 ( DC ratio sputtering was performed under the conditions of a pressure of 0.24 Pa and a power density of 3.57 W / cm ² to form an AZO layer (oxide film) having a thickness of 40 nm on the surface of the glass substrate.

While introducing argon gas, using a silver alloy target doped with 0.5 atomic% of gold, DC sputtering was performed under the conditions of a pressure of 0.24 Pa and a power density of 0.29 W / cm ² to form a surface of the AZO layer. A metal film having a thickness of 10 nm was formed to obtain a conductive laminate. The silver content in the metal film is 99.5 atomic%, and the gold content is 0.5 atomic%.
The luminous transmittance of the conductive laminate and the sheet resistance on the surface of the metal film were measured. The results are shown in Table 3.

[Example 11]
A glass substrate subjected to a dry cleaning treatment was prepared.
While introducing a mixed gas of 90% by volume of argon gas and 10% by volume of oxygen gas, a mixture of zinc oxide and titanium oxide (hereinafter referred to as SZO) target [zinc oxide: titanium oxide = 90: 10 ( DC ratio sputtering was performed under the conditions of a pressure of 0.24 Pa and a power density of 3.57 W / cm ² to form an SZO layer (oxide film) having a thickness of 40 nm on the surface of the glass substrate.

While introducing argon gas, using a silver alloy target doped with 0.5 atomic% of gold, DC sputtering was performed under the conditions of a pressure of 0.24 Pa and a power density of 0.29 W / cm ^{2 on} the surface of the SZO layer. A metal film having a thickness of 10 nm was formed to obtain a conductive laminate. The silver content in the metal film is 99.5 atomic%, and the gold content is 0.5 atomic%.
The luminous transmittance of the conductive laminate and the sheet resistance on the surface of the metal film were measured. The results are shown in Table 3.

  From the results of Examples 5, 8, 10, and 11, it was confirmed that a multilayer structure of a niobium oxide layer (high refractive index layer) and a zirconium oxide layer is preferable as the oxide film.

[Example 12]
A glass substrate subjected to a dry cleaning treatment was prepared.
A zirconium target (zirconium 99.8 mass%, hafnium 0.01 mass%, iron and chromium 0.09 mass%) was used while introducing a mixed gas of 20 volume% argon gas and 80 volume% oxygen gas. DC sputtering was performed under the conditions of a pressure of 0.33 Pa and a power density of 3.57 W / cm ² to form a 20 nm-thickness zirconium oxide layer (oxide film) on the surface of the glass substrate. The content of zirconium atoms with respect to the total amount of metal atoms in the zirconium oxide layer is 98% by mass or more.
When the fingerprint corrosion resistance was evaluated, the zirconium oxide layer was not peeled off.

[Example 13]
A glass substrate subjected to a dry cleaning treatment was prepared.
While introducing a mixed gas of 97 volume% argon gas and 3 volume% oxygen gas, using an AZO target [zinc oxide: aluminum oxide = 97: 3 (mass ratio)], pressure 0.25 Pa, power density 2 DC sputtering was performed under the condition of 147 W / cm ² to form an AZO layer (oxide film) having a thickness of 35 nm on the surface of the glass substrate.
When the fingerprint corrosion resistance was evaluated, peeling of the AZO layer was observed.

[Example 14]
A conductive laminate 10 shown in FIG. 1 was produced as follows.
A glass substrate subjected to a dry cleaning treatment was prepared.

(I) DC sputtering using a niobium oxide target while introducing a mixed gas of 90% by volume argon gas and 10% by volume oxygen gas under the conditions of pressure 0.27 Pa and power density 3.57 W / cm ^2. A high refractive index layer having a film thickness of 37 nm was formed on the surface of the glass substrate. The content of niobium atoms with respect to the total amount of metal atoms in the high refractive index layer is 100% by mass.

(Ii) While introducing a mixed gas of 20 volume% argon gas and 80 volume% oxygen gas, a zirconium target (zirconium 99.8 mass%, hafnium 0.01 mass%, iron and chromium 0.09 mass% DC sputtering was performed under the conditions of a pressure of 0.33 Pa and a power density of 3.57 W / cm ² to form a zirconium oxide layer having a thickness of 30 nm on the surface of the high refractive index layer. The content of zirconium atoms with respect to the total amount of metal atoms in the zirconium oxide layer is 98% by mass or more.

(Iii) DC sputtering was performed using a silver alloy target doped with 0.5 atomic% of gold while introducing argon gas under the conditions of pressure 0.25 Pa and power density 0.286 W / cm ² , and zirconium oxide A metal film having a thickness of 10 nm was formed on the surface of the layer. The silver content in the metal film is 99.5 atomic%, and the gold content is 0.5 atomic%.

(Iv) DC sputtering is performed using a niobium oxide target while introducing argon gas under the conditions of a pressure of 0.25 Pa and a power density of 2.14 W / cm ² , and a barrier layer having a thickness of 3 nm is formed on the surface of the metal film. A film was formed. The content of niobium atoms with respect to the total amount of metal atoms in the barrier layer is 100% by mass.

The operations (i) to (iv) were repeated three more times. However, in the operation (i), a high refractive index layer was formed on the surface of the barrier layer.
Finally, the operation (i) was performed, and a high refractive index layer having a thickness of 37 nm was formed on the surface of the fourth barrier layer from the glass substrate side to obtain a conductive laminate.

The luminous transmittance of the conductive laminate was 54%, and the sheet resistance on the surface of the conductive film of the conductive laminate was 1.6Ω / □.
Moreover, when the anti-fingerprint corrosion resistance was evaluated, no peeling of the conductive film was observed.

  The conductive laminate of the present invention has excellent conductivity (electromagnetic wave shielding), high visible light transmittance, excellent fingerprint corrosion resistance, and when laminated on a support substrate, the transmission / reflection band is wide. It is useful as a protective plate for plasma display. Moreover, the electroconductive laminated body of this invention can be used as transparent electrodes, such as a liquid crystal display element, a motor vehicle windshield glass, a heat mirror, and an electromagnetic wave shielding window glass.

It is sectional drawing which shows an example of the electroconductive laminated body of this invention. It is sectional drawing which shows the other example of the electroconductive laminated body of this invention. It is sectional drawing which shows the other example of the electroconductive laminated body of this invention. It is sectional drawing which shows the other example of the electroconductive laminated body of this invention. It is sectional drawing which shows 1st Embodiment of the protection plate for plasma displays of this invention. It is sectional drawing which shows 2nd Embodiment of the protection plate for plasma displays of this invention. It is sectional drawing which shows 3rd Embodiment of the protection plate for plasma displays of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 Conductive laminated body, 12 base | substrate, 14 electrically conductive film, 201-205 oxide film, 221-225 zirconium oxide layer, 241-245 high refractive index layer, 301-304 metal film, 40 protective plate, 42 support base | substrate, 52 Electrode, 60 protective plate, 70 protective plate

Claims (5)

A conductive laminate having a base and a conductive film formed on the base,
The conductive film has oxide films and metal films alternately from the substrate side, the number of metal films is n, and the number of oxide films is n + 1 (where n is an integer of 1 or more). A multilayer structure that is
The 1st to nth oxide films from the substrate side have a zirconium oxide layer,
The zirconium oxide layer of the i-th oxide film from the substrate side (where i is an integer from 1 to n) is in contact with the i-th metal film from the substrate side;
A conductive laminate, wherein the metal film is a film made of pure silver or a film made of a silver alloy.   The conductive laminate according to claim 1, wherein the (n + 1) th oxide film from the substrate side has a zirconium oxide layer.   The conductive laminate according to claim 1, wherein the oxide film has a high refractive index layer made of a metal oxide having a refractive index of 1.8 or more (excluding zirconium oxide).   4. The conductive laminate according to claim 1, further comprising a barrier layer between the i-th metal film from the substrate side and the i + 1-th oxide film from the substrate side. A support substrate;
The conductive laminate according to any one of claims 1 to 4, provided on the support substrate,
A protective plate for plasma display, comprising: an electrode in electrical contact with the conductive film of the conductive laminate.

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