JPH09306647A - Transparent surface heater, electromagnetic wave shield, and liquid crystal device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent surface heater or an electromagnetic wave shield capable of driving at low voltage, with high surface temperature distribution uniformity, high environment resistance stability durable to pollutants, and high reliabihty. SOLUTION: In a transparent surface heater 1 or an electromagnetic wave shield using a transparent conductive film 3 formed on at least one main surface of a transparent substrate 2 as a heating surface or an electric wave receiving surface and having a pair of electrodes 5 for passing electricity to the transparent conductive film 3 or earthing, the transparent conductive film 3 has a prescribed pattern, forms the heating surface or the electric wave receiving surface, and a corrosion resistant layer 8 is formed in at least the cross section and/or part or the whole of the circumferential end part of the transparent conductive film 3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display element or a transparent planar heater used for a temperature compensator of a liquid crystal display element, a freezing showcase, a refrigerating showcase, an automobile defroster, a helmet or goggles. The present invention relates to an electromagnetic shield body for a screen of a backlight, a liquid crystal display body, a CRT, a plasma display or the like. In particular, a transparent planar heater having a uniform temperature distribution on the surface and a liquid crystal display device including the transparent planar heater, a liquid crystal display device including an electromagnetic shield body and an electromagnetic wave shield body having improved light transmittance, The liquid crystal display device includes a transparent sheet heater and an electromagnetic wave shield. Further, in the liquid crystal display device, it is particularly useful as a ferroelectric liquid crystal having a chiral smectic C phase in which the temperature uniformity is important. Further, by providing a metal fitting for external connection, the stability of the transparent heater or the electromagnetic wave shield is improved. Furthermore, by providing an adhesive layer or an adhesive, the grounding to the support was facilitated.

[0002]

2. Description of the Related Art Conventionally, it has been necessary to prevent dew condensation on the glass surface forming the window of a freezing or refrigerating showcase. Therefore, a transparent conductive film is formed on the glass surface and a predetermined electric power is applied to it. It is applied to heat the window surface. Further, in recent years, the demand for liquid crystal display elements has increased, but there is a problem that the operation of the liquid crystal becomes slower when used in cold regions, and the liquid crystal display element also includes a transparent planar heater for temperature control. The need for things has increased.

A conventional liquid crystal display element used under conditions such as cold regions is, for example, Japanese Patent Laid-Open No. 58-126517.
As proposed in Japanese Patent Laid-Open Publication No. 2003-242242, there is a device in which a mesh-shaped heat generating resistor is arranged and heated. But with this method,
It is difficult to uniformly heat the entire liquid crystal element, and there is a disadvantage that the heating resistor made of an opaque metal becomes an obstacle when viewing the liquid crystal display. In addition, JP-A-3
As proposed in JP-A-172820, an ITO (indium tin oxide) film and a SnO ₂ (tin dioxide) film are used for the transparent conductive film, and the transparent conductive film is divided into a thick region and a thin region. There was a panel heater which had temperature uniformity and visibility when coexisted. However, with this method, it is difficult to control the film formation, and a low-resistance transparent conductive film is required to uniformly heat a large-screen liquid crystal, and it is difficult to form a durable low-resistance transparent conductive film. .

In Japanese Patent Application No. 5-189560, the inventors of the present invention formed a metal thin film layer having a substantially light-transmitting property on a transparent conductive film and then formed a metal electrode on the metal thin film layer by a wet process. It has been disclosed that a transparent sheet heater can be provided.

However, a typical structure of the transparent conductive film used in these transparent planar heaters is a laminated body in which a metal thin film is sandwiched by a transparent high refractive index thin film, for example, vacuum deposition, reactive deposition or sputtering. In formed by
_{O X / Ag / In O X} , SiN X / Ag / SiN X, T
A laminate having a sandwich structure such as iO ₂ / Ag / TiO ₂ has been proposed. The one using the metal thin film containing silver as the main component as the metal layer has excellent transparency in the visible light region due to the optical characteristics of silver itself,
It is also preferable in terms of conductivity, and is particularly excellent as a material in terms of excellent heat generation at low voltage.

However, in a transparent planar heater using as a heat generating layer a laminate comprising a thin film layer containing silver or copper as a main component covered with a transparent high refractive index thin film layer, the laminate has moisture, dust, and It deteriorates due to gas, acid and other pollutants, and cannot be used as a transparent heater. Usually, both surfaces of the heat generating surface are covered and protected by a substrate or a protective film layer, but since the end surface or the cross section exposed by etching is exposed to the outside air as it is, moisture, dust, gas, acid content, etc. And other contaminants cause deterioration of the characteristics of transparent conductivity and heat generation at low voltage from the end face and / or cross section, and eventually progress to the center of the laminate and to the center of the heat generation surface. Was promoted, which was a significant problem in environmental stability (see FIGS. 1 and 2). Since most of the causes of this deterioration are surface diffusion or corrosion of the metal that is a constituent component of the metal thin film layer due to environmental factors, this improvement was very important. The same thing can be said for the electromagnetic shield.

In any case, when the heater is made of the transparent conductive film as described above, there is a problem in transparency, the temperature of the heat generating surface is high in the center and low in the periphery, and the in-plane temperature is uniform. There was a problem with the conversion. In particular, in the case of a liquid crystal display, the liquid crystal is a ferroelectric liquid crystal having a chiral smectic C phase, which is a particular problem. Further, as the screen of the display body becomes larger, it has been desired to reduce the surface resistance of the conductive film and make the in-plane temperature uniform.

[0008]

The object of the present invention is that it can be driven at a low voltage, has a uniform temperature distribution on the surface, and has durability against moisture, dust, gas, acid and other pollutants. Another object of the present invention is to provide a transparent surface heater or an electromagnetic wave shield, and a liquid crystal display device including the transparent surface heater.

Further, among the liquid crystal display devices, the use of the transparent planar heater of the present invention in a liquid crystal display device using a ferroelectric liquid crystal having a chiral smectic phase or the like, which is strongly influenced by temperature distribution, is more advantageous. It is effective.

Another object of the present invention is to provide a transparent planar heater or an electromagnetic wave shield body in which a conductive surface or an electrode formed on the conductive surface is provided with a connecting electrode fitting for external connection. is there.

Another object of the present invention is to provide a transparent planar heater or an electromagnetic wave shield provided with an adhesive material or an adhesive material for attachment to another support.

[0012]

In order to solve the above-mentioned problems, the inventors of the present invention have conducted extensive studies and as a result, as a result of using a transparent conductive film provided on a transparent substrate as a heat generating surface and conducting electricity to the transparent conductive film. In a transparent planar heater provided with a pair of electrodes for having a low resistance conductive film surface having a predetermined pattern, at least part or all of the transparent conductive film cross section and / or the peripheral edge part Part or all may be treated with an anticorrosive component, an organic protective layer may be provided, or an organic protective layer may be provided on a conductive film treated with an anticorrosive component, or an organic protective layer containing an anticorrosive component may be provided. As a result, the present invention has been completed.

Further, the present invention has been completed which is a transparent planar heater or an electromagnetic wave shield body which can be easily connected to the outside by soldering, heat fusion or the like by means of the transparent planar heater or the electromagnetic wave shield body provided with a fitting for connection. did.

Further, by providing a pressure-sensitive adhesive or an adhesive on a transparent sheet heater or an electromagnetic wave shield, the present invention has been completed which is a transparent sheet heater or an electromagnetic wave shield which can be easily attached to another support.

That is, the transparent conductive film provided on at least one main surface of the transparent substrate is used as a heat generating surface or a radio wave receiving surface, and at least a pair of electrodes are provided for energizing or grounding the transparent conductive film. In the transparent sheet heater or the electromagnetic wave shield, the heating surface or the radio wave receiving surface is made of a transparent conductive film having a predetermined pattern, and a transparent protective layer is provided on the transparent conductive film, and at least the transparent conductive film. A transparent planar heater or an electromagnetic wave shield having a cross-section of the film and / or a part or all of the peripheral edge part thereof provided with a corrosion-resistant layer, or silver having a transparent conductive film covered on one or both sides with a transparent thin film, and Alternatively, it is a transparent planar heater or electromagnetic wave shield made of a metal thin film containing copper as a main component, or the transparent thin film is an oxide, a nitride, an oxynitride, or a nitride. It is a transparent planar heater or an electromagnetic wave shield that is a single layer or a multilayer of a thin film made of at least one or more kinds selected from the group consisting of hydrides and carbides, or a transparent surface provided with an external connection metal fitting on the electrode. Heater or electromagnetic shield, or
A transparent planar heater or an electromagnetic wave shield body having an adhesive layer provided on at least one main surface.

A liquid crystal device with the transparent sheet heater and / or the electromagnetic wave shield, provided with the transparent sheet heater and / or the electromagnetic wave shield, is also provided.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamides, polyethers, polysulfones, polyethersulfones ( PE
S), polycarbonate, polyarylate, polyetherimide, polyetheretherketone (PEEK),
Polyimide, aramid, polymethylmethacrylate,
Examples include polyacetate, poly-4-methylpentene-1 polyacrylonitrile-based resin, phenoxy resin, polyphenylene oxide-based resin, polystyrene, norbornene-based polymer, and homopolymer or copolymer of polyparabanic acid. Any transparent or flexible sheet or film can be used as the transparent substrate, and the present invention is not limited to these examples.

Further, in order to improve the adhesion between the transparent substrate and the transparent conductive film, an undercoat may be provided on the transparent substrate to form a transparent substrate. Here, the undercoat is a cured product of the crosslinkable resin or a cured product of the crosslinkable resin provided on the anchor agent. As the crosslinkable resin cured product, acrylic epoxy resin, acrylic silicone resin, epoxy resin, acrylic resin, phenoxyether type crosslinkable resin, melamine resin, phenol resin, urethane resin,
Alternatively, UV-curable acrylates are preferably used. As the anchor agent, water-soluble polyurethane resin, water-soluble polyamide resin, water-soluble polyester resin,
A-PET (amorphous polyethylene terephthalate), ethylene-vinyl acetate emulsion, or (meth) acrylic emulsion is preferably used. Needless to say, any material can be used as long as it improves the adhesion between the transparent substrate and the transparent conductive film. The thickness of the undercoat is usually 1 to 100 μm
And preferably 10 to 50 μm.

Further, at least one component selected from air-permeable resins such as polyacrylonitrile, polyvinyl alcohol or PVDC (polyvinylidene chloride), that is, a cellulose component, a polyamide resin component, a vinyl alcohol component, a vinylidene halide component, and an acrylonitrile component is used. A transparent substrate may be provided by providing a gas-proof resin, which is a polymer or mixture containing 60 mol% or more, with a thickness of 1 to 100 μm and imparting functions such as moisture resistance and gas barrier property. Anchor coat of polyurethane etc.
You may match and use it by 5-200 micrometers thickness.

When the product of the present invention is used between liquid crystal elements or between polarizing plates, the retardation value is 30 nm or less from the viewpoint of uniaxially stretched PET and optical isotropy (low birefringence, low retardation). A transparent substrate having a thickness of preferably 15 nm or less, more preferably 10 nm or less, and further preferably 5 nm or less is preferable. Examples of preferable film materials include PES, polyarylate, polycarbonate, norbornene-based polymer, poly-4-methylpentene-1 and the like.

The thickness of the plastic sheet or film used in the present invention is usually 5 to 1 mm, preferably 8 to 500 μm, more preferably 10 to 5.
The thickness is more preferably 200 μm and more preferably 50 to 150 μm. As a method for producing such a film, conventional methods such as an extrusion molding method, a casting method, and a rolling method can be applied.

In the present invention, as the transparent conductive film, a single layer or a laminate of a metal thin film, a semiconductor thin film, or a laminate of a metal thin film and a transparent thin film can be applied. The laminations may be each single layer or more layers.

As the semiconductor thin film, indium, tin,
Any oxide that contains zinc, antimony, or the like and exhibits conductivity may be used, but indium oxide, tin oxide, ITO (indium tin oxide), I
ZO (indium oxide / zinc oxide), ITZO (indium oxide / zinc / tin), AZO (zinc oxide / antimony), AIZO (indium oxide / zinc / antimony)
And the like. The thickness is 80 to 10,000 Å, preferably 200 to 6,000 Å.

As the metal thin film, metals such as silver, gold, copper, aluminum, nickel, chromium are used.
Gold and copper are preferable. Particularly preferably, a metal thin film made of a metal or alloy thin film of silver, copper or the like, a metal thin film of a single metal such as silver or copper or an alloy containing them, and a nitride such as silicon nitride or a metal such as indium oxide or titanium oxide. A transparent thin film such as an oxide or a metal carbide such as silicon carbide, in particular, a laminate of a transparent high refractive index thin film is used. From the viewpoint of transparency and conductivity, a laminate of a metal thin film and a transparent thin film or a laminate of metal thin films in a sandwich structure is preferable. Particularly, it is preferable that at least one layer of a transparent thin film containing at least one selected from the group of nitrides, oxides or carbides and at least one layer of a substantially transparent metal thin film are laminated. A transparent thin film having a multilayer structure or a metal thin film having a multilayer structure can also be used. A preferable example is AB, ABAB, and ABA where the metal thin film is A and the transparent thin film is B.
BAB, BA, BABA, BABABA, BAB, BA
BAB, BABABAB and the like. Other multi-layered bodies can also be used.

Here, the metal thin film of the transparent conductive film comprising a combination of the transparent thin film and the metal thin film may be a single layer or a laminate containing at least one of silver or an alloy or mixture containing silver. In the case of an alloy or mixture containing silver and / or copper, the content of silver is preferably 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight or more, and the content of copper is preferably 30%.
It is at least 50% by weight, preferably at least 50% by weight, more preferably at least 70% by weight. Of course, even if it is out of the range described here, it can be used in some cases.

As the metal contained in the silver alloy or the mixture, gold, copper, palladium,
In addition to platinum, tungsten, titanium, cobalt, chromium, nickel, tin, indium, IT (indium
Metals such as tin), silicon and zinc are preferred.

The content of the metal contained here can be used as long as it can prevent deterioration, but it is preferably 2 to 60% by weight, more preferably 5 to 50% by weight, further preferably 8% by weight. % To 30% by weight.
The thickness of each of these metal thin films is basically 1 nm to 500 n.
m, preferably 5 nm to 50 nm, and more preferably 10 nm to 30 nm.

In order to improve the adhesion of silver or a metal thin film containing silver to the transparent thin film layer, a metal thin film other than silver is laminated on at least one surface of silver or a thin film containing silver as a main component. When using a metal thin film to be used, as the metal other than silver for improving the adhesion of the metal thin film to the transparent thin film layer, nickel, chromium, titanium, gold, copper, platinum, tungsten, molybdenum, iridium, lead, A single metal selected from tin, indium, zinc, palladium, cobalt, silicon, aluminum, germanium, manganese, gallium, tantalum, vanadium, zirconium, barium, and niobium, an alloy containing one or more of these, or a mixture thereof is preferable. The thickness of the metal other than the silver is 0.
1 nm to 50 nm is desirable. Preferably 0.3 nm ~
30 nm, more preferably 0.5 nm to 10 nm, and still more preferably 0.5 nm to 5 nm.

In the present invention, the transparent thin film is preferably a high refractive index dielectric, and the high refractive index dielectric is exemplified by a nitride thin film, an oxide thin film or a carbide thin film.

In the present invention, the material forming the nitride thin film is preferably a nitride such as silicon nitride, aluminum nitride, indium nitride, gallium nitride, tin nitride, boron nitride, chromium nitride, silicon nitride carbide or silicon oxynitride. , Tin oxynitride, boron oxynitride, aluminum oxynitride,
Indium oxynitride, gallium oxynitride, chromium oxynitride, oxynitride such as silicon oxynitride carbide, or aluminum hydronitride, indium hydronitride, gallium hydronitride,
Examples thereof include hydronitrides such as silicon hydronitride, tin hydronitride, boron hydronitride, chromium hydronitride, and silicon hydronitride carbide. Usually, any of nitrides, oxynitrides, and hydrogenated nitrides can be used, but nitrides having a refractive index of 1.6 or more, further preferably 1.8 or more, and more preferably 2.0 or more. And / or a high refractive index transparent thin film made of oxynitride and / or hydrogenated nitride is preferable. The light transmittance is usually 50% or more, preferably 70% or more, more preferably 80% or more.

The components of these oxynitrides excluding the metal are mainly oxygen and nitrogen, and the ratio of the total atomic weight of contained nitrogen divided by the sum of the total atomic weight of contained nitrogen and the total atomic weight of oxygen contained. The nitrogen content is 1 atomic% or more, preferably 3 atomic% or more, more preferably 30 atomic% or more, and further preferably 50 atomic% or more. Further, the nitrogen content in the components other than the metal of these hydronitrides is 50 atomic% or more preferably 80 atomic% or more. The thickness of these nitride layers is usually 0.3 nm to 100 nm, preferably 1 nm to 100 nm, and more preferably 5 n.
m to 50 nm, more preferably 10 nm to 30 nm.

The material forming the oxide thin film in the present invention is preferably indium oxide, tin oxide, indium tin oxide (ITO), indium zinc oxide (IZ).
O), indium oxide / zinc / tin (ITZO), oxides containing indium such as indium oxide / zinc / antimony (AIZO), zinc oxide / antimony (AZO),
Examples thereof include aluminum oxide, germanium oxide, zinc oxide, zirconium oxide, titanium oxide, yttrium oxide, cerium oxide, tantalum oxide, and hafnium oxide. Usually, any oxide can be used, but a high refractive index transparent thin film made of an oxide having a refractive index of 1.6 or more, more preferably a refractive index of 1.8 or more, and more preferably a refractive index of 2.0 or more is preferable. preferable. The light transmittance is usually 5
0% or more, preferably 70% or more, more preferably 8
0% or more.

The thickness of at least one layer of these oxide thin films is usually 5 nm to 600 nm, preferably 60 nm to 10 nm.
It is 0 nm, more preferably 20 nm to 80 nm.
Further, even if each layer is formed in a mixed state containing components of each other between the layers forming the transparent conductive film or between the transparent conductive film and the transparent substrate, the function of the present invention is not impaired.

As a method for forming these metal thin film, transparent thin film and transparent conductive film on a transparent substrate, known methods such as a physical vapor deposition method as well as a spray method and a coating method can be used.
Here, the physical vapor deposition method is a method of forming a thin film of a metal or the like under reduced pressure or under vacuum, and it is a vacuum vapor deposition method, a sputtering method, an ion plating method, an ion beam assisted vapor deposition method, an ion cluster beam. Examples of the methods include a film method, a molecular beam epitaxy method (MBE), a CVD method, a MOCVD method, and a plasma CVD method. As the transparent protective layer, any layer can be used as long as it can protect the conductive surface or the electrode. Preferred transparent protective layers include, for example, a known UV curable resist ink applied and cured, an electron beam curable resist ink applied and cured, and a thermosetting resist ink applied and cured. Examples thereof include those obtained by applying and curing a UV-curable resin, those obtained by applying and curing an electron beam curing resin, those obtained by applying and curing a thermosetting resin, and thermoplastic resin layers and dry films. In addition to this, a transparent protective layer can be used as long as a transparent film having water resistance and chemical resistance can be obtained. For example, a transparent paint, a curable monomer or oligomer, a plastic film such as polyester with an adhesive ( A transparent protective layer can be formed by laminating a self-adhesive film such as an ethylene-vinyl acetate copolymer or the like coated with a pressure-sensitive adhesive). Needless to say, a mixture or a laminate of these can be used as the transparent protective layer.

Here, as the UV curable resin, alkyl acrylate, epoxy acrylate, urethane acrylate, polyester acrylate, polyfunctional acrylate, monofunctional acrylate, polyether acrylate, silicon acrylate, polybutadiene acrylate, unsaturated polyester / styrene, polyene are used. / Thiol, polystyryl acrylate, UV-curable lacquer and the like are preferably used.

Examples of electron beam curable resins include alkyl acrylate, epoxy acrylate, urethane acrylate, polyester acrylate, polyfunctional acrylate, monofunctional acrylate, polyether acrylate, silicon acrylate, polybutadiene acrylate, unsaturated polyester / styrene, polyene / Thiol, polystyryl acrylate, UV curing lacquer and the like are preferably used.

The above acrylates also include methacrylates.

As the thermosetting resin, epoxy resin, xylene resin, guanamine resin, diallyl phthalate resin, polyurethane, vinyl ester resin, unsaturated polyester resin, polyimide, melamine resin, maleic acid resin, urea resin, acrylic resin, Acrylic ester resin, phenoxy ether cross-linking resin, xylene resin,
Guanamine resin, diallyl phthalate resin, phenol resin, silicon resin, alkyd resin and the like are preferably used.

Examples of the thermoplastic resin include polyolefins such as polypropylene, polyethylene and ethylene-propylene copolymer, polyesters, polyamides, ionomers, ethylene-vinyl acetate copolymers, acrylic resins such as acrylic acid ester and methacrylic acid stellate, and polyacrylics. Vinyl acetal, phenol, modified epoxy resin, vinyl acetate resin, silicone RTV, polymer alloy type polyimide, copolymers thereof, and mixtures thereof are preferable. Needless to say, different types, for example, a mixture of thermosetting resin and UV curable resin is used as a curing resin,
For example, a mixture of UV-curable resins of alkyl acrylate and urethane acrylate can be used as the cured resin. That is, a mixture with any of these resins can be used.

Examples of the paint include fibrin derivative paints such as nitrocellulose lacquer, acrylic lacquer and acetylcellulose lacquer, alkyd resin paints, aminoalkyd resin paints, guanamine resin paints, vinyl chloride resin paints, butyral resin paints, styrene-butadiene resins. Paint, thermosetting acrylic resin paint, epoxy resin paint,
Unsaturated polyester paint, polyurethane resin paint, silicon resin paint and the like are preferably used.

The thickness of the transparent protective layer is usually 1 μm to 10 μm.
It is 0 μm, preferably 5 μm to 50 μm, and more preferably 10 μm to 30 μm. You may use these transparent protective layers as an undercoat of a transparent substrate.

A transparent plastic film with an adhesive, which is a transparent plastic film provided with an adhesive layer, may be used as the transparent protective layer. Here, as the transparent plastic film used, the material used for the transparent substrate can be used. As the adhesive, any adhesive can be used as long as it can be adhered or adhered to the transparent substrate and / or the conductive film. Here, as an example, pressure-sensitive adhesive (adhesive): Acrylic, etc. Solvent-type adhesive: Vinyl acetate resin, chloroprene rubber, nitrile rubber, cellulose, multi-liquid mixed system, etc. Emulsion type adhesive Agent: α-olefin type, cured vinyl acetate resin type, vinyl acetate resin type, vinyl acetate-acrylic type, acrylic copolymer type, vinyl / urethane type, epoxy type,
Vinylidene chloride type, vinyl chloride type, non-aqueous emulsion type, powder emulsion type, synthetic rubber latex type, etc. Chemical reaction type adhesives: cyanoacrylate type, epoxy type, polyurethane resin type, etc. Hot melt type adhesives: EVA type, polyamide type , Polyester, etc., and other adhesives using urea resin, melamine resin, phenol resin, resorcinol resin, α-olefin resin, epoxy resin, polyurethane, acrylic resin, methacrylic resin or their derivative resins or copolymers, etc. Can also be used. Further, an ultraviolet curable adhesive, an electron beam curable adhesive, a thermosetting adhesive, etc. can also be used.

In some cases, a coupling agent such as a silane coupling agent may be used in the film of the transparent substrate and / or the transparent plastic film with an adhesive to improve the adhesive strength. Examples of the silane coupling agent include vinyltrichlorosilane, vinylethoxysilane, vinyl-tris- (β-methoxyethoxy) silane, γmethacryloxypropyltrimethoxysilane, β- (3,4epoxycyclohexyl) ethyl. Trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
N-β- (aminoethyl) -γ aminopropyltrimethoxysilane, N (dimethoxymethylsilylpropyl) ethylenediamine, N- (trimethoxysilylpropyl)
-Such as ethylenediamine.

The thickness of the transparent plastic film with an adhesive used in the present invention is usually 1 μm to 2 m.
m, preferably 5 to 500 μm, more preferably 10 to 250 μm, and more preferably 50.
１５０150 μm. The thickness of the adhesive is usually 0.
It is 1 to 300 μm, preferably 1 to 100 μm, and more preferably 5 to 50 μm.

As the electrode used in the present invention, any electrode can be used as long as it has conductivity, but preferable examples of the electrode are 1) conductive resin 2)
Conductive resin and metal foil 3) Metal plating layer on conductive resin
4) Metal plating layer.

As the conductive resin, resin such as polypyrrole having conductivity, metal powder such as silver or copper such as silver paste, copper paste or silver-copper paste, or carbon such as carbon black is used. Examples thereof include a single resin or a mixture of resins and the like. As the metal foil, any metal foil can be used, but preferably, a metal foil such as a copper foil or a nickel foil is exemplified. Examples of the metal plating layer include a layer made of a metal such as nickel and copper that can be normally plated. These can be used alone or as a layer or a mixed layer to form an electrode. Needless to say, these may be used in multiple layers.

The conductive resin layer is set by an ordinary printing method or the like. When a metal foil is used, an adhesive is provided on one side of the metal foil to adhere it to the conductive resin layer, and the surface not coated with the adhesive. The formation of an electrode provided with a conductive resin is exemplified.
The metal plating layer is formed by a method selected from wet processes such as electroplating, electroless plating and direct plating.

The electrode may have any thickness as long as the transparent conductive film can pass an electric current capable of functioning as a heating surface, but it is usually 0.1 μm or more, preferably 0.5 to 100 μm, and more preferably. Is 1 to 50μ
m, more preferably 5 to 20 μm.

When the electrode includes a plated metal layer, the plated metal may reach any part of the transparent conductive film, or the components of the transparent conductive film and the plated metal may be mixed. good. That is, when the transparent conductive film is a multi-layered body, the plated metal further penetrates to reach the transparent thin film component metal oxide and / or nitride and / or carbide, and the metal layer and the transparent thin film component below the metal layer penetrate further. Some metal oxides and / or nitrides and / or carbides and even transparent substrates may be reached. Furthermore, the plating metal and the metal oxide, nitride or carbide and / or the metal component of the metal layer may be present in a state of being at least partially mixed. Further, a part or all of the transparent conductive film of the electrode installation part may be replaced with the plating metal. Any state may be provided between the electrode and the transparent conductive film as long as a current flows from the electrode to the transparent conductive film and the heating surface can generate heat.

In the case of adhering the transparent sheet heater of the present invention to a support, an adhesive layer may be provided on at least a part of the surface of a transparent substrate or a transparent protective plastic including a transparent protective plastic film. In the case of a transparent heater covered with a transparent protective plastic film, an adhesive layer may be provided on at least a part of one side. In addition, an adhesive layer may be provided on both surfaces of the transparent planar heater, and one surface may be bonded to the liquid crystal element side and the other surface may be bonded to the backlight side such as a cold cathode tube.

As the adhesive layer, the adhesive used in the transparent protective film with an adhesive, a general transparent adhesive, an adhesive, or a double-sided adhesive tape can be used. Examples of preferable adhesives include acrylic pressure-sensitive adhesives (adhesives) and cyanoacrylate-based reactive adhesives. Also, the adhesive used in the transparent protective plastic film with an adhesive layer can be used.

The adhesive can be applied to the transparent sheet heater of the present invention at the time of use and pressure-bonded to a support such as a liquid crystal display to fix it to the transparent sheet heater. When it is provided in the heater, it is desirable that the adhesive surface is laminated with a separator (release sheet) if necessary so that the adhesive surface does not adhere when the product is transported or stored. As a matter of course, when the transparent sheet heater is actually attached to the support, the separator is peeled off. As the separator, polyethylene, polypropylene film, polyester film, etc. can be used in addition to the release paper usually used. The thickness of the separator is usually 1 μm to 200 μm.
m, preferably 2 μm to 100 μm, and more preferably 5 μm to 50 μm.

When a wire or the like is attached to the connecting electrode fitting of the transparent sheet heater having the connecting electrode fitting of the present invention mounted thereto by soldering or the like, the connecting electrode fitting may be anywhere on the electrode. Needless to say, it may be installed on the adhesive layer or the separator to electrically connect with the electrode. In addition, an integrated conductor and the metal fitting can be used.

When the transparent sheet heater of the present invention is adhered to a support, an adhesive layer may be provided on at least part of the surface of a transparent substrate or a transparent protective plastic including a transparent protective plastic film. In the case of a transparent heater covered with a transparent protective plastic film, an adhesive layer may be provided on at least a part of one side. In addition, an adhesive layer may be provided on both surfaces of the transparent planar heater, and one surface may be bonded to the liquid crystal element side and the other surface may be bonded to the backlight side such as a cold cathode tube.

As the adhesive layer, the adhesive used in the transparent protective film with an adhesive, a general transparent adhesive, an adhesive, or a double-sided adhesive tape can be used. As a preferred adhesive, an acrylic pressure-sensitive adhesive,
A cyanoacrylate-based reactive adhesive can be exemplified. Further, the adhesive used in the transparent protective plastic film with an adhesive layer can also be used.

The adhesive can be applied to the transparent sheet heater of the present invention at the time of use and pressure-bonded to a support such as a liquid crystal display to fix it to the transparent sheet heater. When it is provided in the heater, it is desirable that the adhesive surface is laminated with a separator (release sheet) if necessary so that the adhesive surface does not adhere when the product is transported or stored. As the separator, polyethylene, polypropylene film, polyester film and the like can be used in addition to release paper which is usually used. The thickness of the separator is usually 1 μm to 200 μm.
m, preferably 2 μm to 100 μm, and more preferably 5 μm to 50 μm.

As the resist in the present invention, any resist that is usually used can be used, but alkali peeling type or solvent peeling type etching resist, plating resist, hole filling ink, solder resist, active resist and the like are preferable. That is, cyclized rubber, negative photoresist based on polycinnamic acid and the like, and photoresist such as phenol and cresol, positive photoresist based on novolac resin, melamine resin-based, epoxy resin-based and imide-modified photoresist Examples thereof include heat-curable solder resists such as, radical polymerization type, cationic polymerization type, UV curing type solder resists such as polyene / polythiol type, UV / heat combined type solder resists and dry film resists.

Further, a positive type X-ray resist based on a methacrylate copolymer or the like, a negative type X-ray resist based on an acrylate or the like, an X-ray resist or a methacrylate and its copolymer or the like are used as a base. An electron beam resist such as a positive type electron beam resist, a negative type electron beam resist such as a photoresist type, a silicone resin type, an epoxy polymer type, or a polycioxane type can also be used.

The anticorrosion layer of the present invention is treated with an anticorrosion agent, is made of transparent plastic, is made of a mixture of transparent protective plastic and anticorrosion agent, is laminated with transparent plastic on the anticorrosion agent-treated layer, etc. The anticorrosive agent is 1) benzotriazole, indazole, imidazole and / or its derivative 2) amino acid and / or its derivative 3) mercaptan and / or its derivative 4) an active ingredient containing at least one or more selected from copper chelate compounds or Mention may be made of mixtures thereof.

The benzotriazoles, indazoles and imidazoles used in the anticorrosion treatment of the present invention may be any as long as they have a benzotriazole nucleus, an indazole nucleus and an imidazole nucleus, respectively.
A preferred example is as follows.

One example of the preferred benzotriazoles used in the anticorrosion treatment of the present invention is 1,2,3 benzotriazole and its derivatives, which are 2-alkylated benzotriazoles such as 2-methylbenzotriazole, 2-phenylbenzotriazole and 5 , 6-methylbenzotriazole,
5 benzotriazolecarboxylic acid, halogenated benzotriazole, hydroxybenzotriazole, dodecylbenzotriazole, carboxybenzotriazole,
And esters of carboxybenzotriazole, for example, esters or soluble salts of methyl, ethyl, isopropyl, butyl, hexyl, octyl, dodecyl and the like.

Examples of preferable indazoles used in the corrosion protection treatment of the present invention include 4-chloroindazole, 4-nitroindazole, 4-chloro-5nitroindazole, 5-nitro-3methylindazole, and 4.6 dinitro-5. * 7 dimethylindazole, 5.7 dinitro-6
Methylindazole and the like.

Examples of preferable imidazoles used for the anticorrosion treatment of the present invention include 2-octylimidazole and 2-octylimidazole.
Examples include alkylimidazoles such as undecylimidazole and 2-heptandecylimidazole, imidazole, nitroimidazole, oxyimidazole, benzimidazole, N-acetylimidazole, N-benzoylimidazole and picrate.

The amino acid used in the anticorrosion treatment of the present invention includes a neutral amino acid, a basic amino acid and an acidic amino acid which can react with copper and a copper-based metal to form a complex compound.
Sulfur-containing amino acids, aromatic amino acids and heterocyclic amino acids are included. Examples of preferred amino acids include glycine, alanine, valine, leucine, disoloucine, ruisin, serine, arginine, glutamine, glutamic acid, aspartic acid, cysteine, methionine, phenylalanine, histidine, oxyproline, hydroxyprotein, etc., and their esters. Can be mentioned, and those having a particularly high hydrophilicity are desirable. Here, the alcohol component of the esters preferably has 8 or less carbon atoms, and may be a saturated or unsaturated hydrocarbon group, such as methyl, ethyl, propyl, benzyl, amyl, octyl and the like.

The mercaptans used in the anticorrosion treatment of the present invention are mercaptoacetic acid, 3-mercaptopropionic acid,
1-mercaptoundecyl acid, thiophenol, phenyldisulfide, N- (2-hydroxymethyl) mercaptoacetamide, 2,2'-dimercaptodiethyl ether, 2,2'-dimercapto-diethylthioether, 1,2- Examples thereof include ethanedithiol, 3-mercaptopropyltrimethoxysilane, glycol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), and glycol dimercaptoacetate.

The copper chelate compound used in the anticorrosion treatment of the present invention is mainly an organic copper chelate compound, and includes acetylacetone copper, trifluoroacetylacetone copper, ethylenediamine copper, trifluoroacetylacetone copper, ethylenediamine copper, phthalocyanine copper, hemocyanin, ethylenediamine. Examples include tetraacetate copper, dimethyldithiocarbamate copper, diethyldithiocarbamate copper, hydroxyquinoline copper and the like. Further, organic acid copper salts such as copper citrate, copper tartrate, copper lactate, and copper acetate can also be used equivalently.

The transparent plastic used for the anticorrosion treatment of the present invention can be made of the same material as the transparent protective layer,
UV curable type such as modified acrylate, thermosetting type such as epoxy sealant, and curable type combined with UV heating such as mixture thereof, epoxy resin, urethane resin, phenol resin, silicone resin, silicone epoxy resin,
Sealing agent made of DPA epoxy resin or the like, construction sealing agent made of polysulfide type, acrylic type, acrylic urethane type, butyl rubber type, SBR type, etc., edge coating used to prevent corrosion of the peripheral edge of the mirror, Sealing agent, or other acrylic ester resin such as polymethylmethacrylate, acrylic resin such as polyacrylonitrile or polymethacrylonitrile, polyolefin resin such as polyethylene or polypropylene, silicon resin such as polymer obtained from ethyl silicate , Polyester resin, melamine resin, fluororesin,
Organic substances such as phenolic resin can be applied.

Besides, materials used for the transparent substrate and materials used for the anticorrosion layer can be applied. Depending on the purpose, from among the above compounds, several resins or substances may be mixed,
It can be used for any purpose even if it is used by stacking.

When copper is used as the electrode material, it is particularly effective to use amino acids, benzotriazoles or amino acids in combination with benzotriazoles to prevent corrosion of the electrodes from the end faces.

The anticorrosion layer containing the anticorrosion active ingredient used in the anticorrosion treatment of the present invention is at least one or two selected from the above benzimidazoles, indazoles, imidazoles, amino acids and their esters.
Examples include a mixture of at least one kind of the above materials. In the moisture-proof treatment, one or more kinds of treatments and / or laminates selected from the above-mentioned anticorrosive active ingredient, the above-mentioned anticorrosive layer, and the anticorrosive layer containing the above anticorrosive active ingredient can be used.

A method well known in the art as a method for incorporating an anticorrosion effective component into the cross-section of a metal layer containing a first metal layer containing silver and / or copper as a main component in the laminate for the purpose of the present invention. Can be done in. That is, the anticorrosion component (benzotriazoles, indazoles, imidazoles, amino acids, mercaptans, which is dissolved in a suitable solvent or the like on the metal layer of the cross section of the transparent planar heater and / or the electrode and / or a part or all of the cross section, Copper chelate compounds), a spraying method of spraying with a spray gun, or a method of immersing the cross section in such a solvent. Alternatively, when the anticorrosion component has a sublimation property, the object of the present invention can be achieved also by subjecting the cross-section of the transparent sheet heater to a contact treatment on the compound heated to an appropriate temperature. The state of being in contact with or entering the surface or the inside of the cross section is referred to as containing, and the object of the present invention is sufficiently achieved by this. The present invention can also be achieved as a corrosion-resistant layer by coating, spraying, or immersing the organic resin component on the metal layer and / or the electrode of the cross section or a part or all of the cross section to cure or dry the solvent. Further, the anticorrosion component is mixed with the resin component, or after mixing with a solvent, the resin component is provided on the metal layer and / or the electrode of the cross section or a part or all of the cross section by the above-mentioned method, followed by heating, drying and UV irradiation. You may provide an anticorrosion layer.
Further, a polymer film or sheet provided with an adhesive layer containing one or more types of the above-mentioned anticorrosive components may be adhered to the metal layer and / or the electrode or a part or all of the cross section so that the adhesive layer contacts. The invention can be achieved. Further, at least a part or all of the cross section of the conductive film or in addition to the peripheral edge portion, the electrode, the transparent protective layer, the anticorrosion layer and / or the transparent substrate, the anticorrosion active ingredient, the anticorrosion layer,
The provision of the anticorrosion layer containing the anticorrosion effective component does not impair the function of the present invention. Needless to say, if two or more of these methods are used together and laminated, the effect is further enhanced.

The concentration of the anticorrosion component is preferably as high as possible, but is preferably 20% by weight or less based on the solid component amount of the resin capable of forming the surface protective layer.
It is particularly preferably 0% by weight or less. Further, as a solution dissolved in a solvent, an acid, an alkali or the like, the cross section or the whole can be directly subjected to anticorrosion treatment by a method such as coating, spraying or dipping as described above. In this case, any solvent, acid, or alkali may be used as long as these corrosion inhibitors can be dissolved.
As a preferred example, the solvent is methanol, toluene, methyl ethyl ketone or the like, the acid is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid or the like, and the alkali is NaOH, KOH, LiOH, Na ₂ CO ₃ , K ₂
CO ₃ , Li ₂ CO _{3 and the} like. The higher the concentration, the better, but the solution concentration is preferably 20% by weight or less, preferably 5% by weight or less, and more preferably 3% by weight or less.

When a transparent plastic layer, a resin layer, a paint or a sealant is used as the anticorrosion layer, its thickness is not particularly limited, but it is 1 μm to 1,000 μm, preferably 5 μm to 500 μm, more preferably 10 μm. ~
200 μm.

Next, an example of a method of installing the anticorrosion layer using transparent plastic will be described.

1. A transparent flat conductive sheet is prepared by removing the heat generating surface made of a conductive film having a predetermined pattern and the transparent conductive film other than the electrodes covered with the transparent protective layer provided on the transparent conductive film by etching or the like. .

1) A transparent protective plastic is provided on the entire transparent protective layer side of the raw material of the heater by printing or the like, and dried or cured. Next, the region where the transparent conductive film of the transparent substrate is removed is separated at the joint covered with transparent plastic,
At least a cross section of the transparent conductive film and / or a part or all of the peripheral edge portion is covered with a transparent plastic heater.

2) A transparent plastic is provided on the entire surface of the raw material of the heater by printing or the like, except for the area corresponding to the external electrode connection of the electrode, and dried or cured. Next, the area where the transparent conductive film of the transparent substrate is removed is cut off at the joint covered with the transparent plastic, and at least part or all of the cross section and / or the peripheral edge of the transparent conductive film is covered with the transparent plastic. Use a sheet heater.

3) A transparent plastic film is combined with the transparent conductive film side of the raw material of the heater, and thermocompression bonding is performed in the region of the transparent substrate where the transparent conductive film is removed. Next, the region of the transparent substrate where the transparent conductive film was removed was separated at the joint covered with the transparent plastic, and at least part or all of the cross section and / or the peripheral edge portion of the transparent conductive film was covered with the transparent protective plastic. Use a transparent sheet heater.

4) As a region for external electrode connection, a transparent plastic film having a hole formed in a part of a corresponding portion overlapping the electrode region is formed on the transparent conductive film side of the raw material of the heater so that the hole overlaps the electrode region. In addition, thermocompression bonding is performed in a region of the transparent substrate where the transparent conductive film is removed. Then, in the same manner as in 3), the transparent sheet heater is separated from the raw material of the heater to obtain a transparent sheet heater in which at least a part of the cross section and / or the peripheral edge portion of the transparent conductive film is covered with transparent plastic.

5) A transparent plastic film with an adhesive or a pressure-sensitive adhesive is combined with the conductive sheet side of the transparent sheet heater, and then separated from the heater sheet in the same manner as in 3) to remove at least the transparent conductive film. A transparent planar heater in which a part or all of the cross section and / or the peripheral edge portion is covered with transparent plastic is used.

6) As a region for connecting an external electrode, a transparent plastic film with an adhesive or a pressure sensitive adhesive is prepared by forming a hole in a portion of the corresponding region overlapping the electrode region so that the hole overlaps the electrode region. Align and bond with the conductive film side of the original fabric. Then, in the same manner as in 3), the transparent sheet heater is separated from the raw material of the heater to obtain a transparent sheet heater in which at least a part of the cross section and / or the peripheral edge portion of the transparent conductive film is covered with transparent plastic.

7) A connecting metal fitting is attached to a part of the electrode of the transparent sheet heater prepared in 1) to obtain a transparent sheet heater.

8) A connecting metal fitting is attached to the electrode of the transparent sheet heater prepared in 2) that is not covered with the transparent plastic to obtain a transparent sheet heater.

9) A transparent metal heater is prepared by attaching a connecting metal fitting to the electrode portion of the transparent metal heater covered with the transparent plastic film prepared in 3).

10) A transparent metal heater is prepared by attaching a connecting metal fitting to the electrode portion of the transparent metal heater prepared in 4) that is not covered with the transparent plastic film.

11) A connecting metal fitting is attached to the electrode portion covered with the adhesive or the transparent plastic film with an adhesive of the transparent sheet heater prepared in 5) to obtain a sheet heater.

12) The transparent flat heater is prepared by attaching the connecting metal fittings to the electrode portion of the transparent flat heater prepared in 6) which is not covered with the adhesive or the transparent plastic film with the adhesive.

Further, at least a transparent plastic film or a transparent plastic film with an adhesive layer may be provided on the transparent plastic.

2. A transparent protective layer placed on a transparent conductive film covers the heating surface with a transparent protective layer made of a conductive film having a predetermined pattern, and a transparent planar heater made of an electrode from the heating surface with a transparent protective layer to the electrode portion. Cut out and use as a transparent sheet heater.

1) A transparent plastic film is attached to the conductive film side of the raw material of the transparent planar heater, a transparent plastic film is also attached to the opposite surface, and thermocompression bonding is performed around the raw material of the transparent planar heater to form a transparent planar heater. The original sheet is a transparent sheet heater covered with a transparent protective plastic film.

2) As a region for connecting an external electrode, a hole is made in a part of the corresponding portion which overlaps with the electrode region, and a transparent plastic film is formed so that the hole overlaps with the electrode region. And a transparent plastic film with no holes on the opposite side, and thermocompression-bonded the surrounding area of the transparent sheet heater, and the transparent sheet heater covered with transparent plastic film. And

3) An adhesive or a transparent plastic film with a pressure-sensitive adhesive was put together with the conductive film side of the raw material of the transparent sheet heater, then the transparent plastic film was put on the opposite side, and the whole surface or the peripheral part was pressure-bonded. , Transparent sheet heater The original sheet of transparent sheet heater is covered with a transparent plastic film. Needless to say, an adhesive or a transparent plastic film with an adhesive may be used on the surface opposite to the conductive film side.

4) A transparent sheet heater is immersed in a solution containing an anticorrosive agent such as benzimidazole, washed with water, and dried to obtain a transparent sheet heater whose end faces are protected from corrosion.

5) As a region for external electrode connection, a transparent plastic film with an adhesive or a pressure-sensitive adhesive, in which a hole is made in a portion corresponding to the electrode region so that the hole overlaps the electrode region, is a transparent sheet heater. Align with the conductive film side of the original fabric, then align the transparent plastic film with no holes on the opposite side, press-bond it, transparent planar heater Transparent planar heater in which the original fabric is covered with transparent plastic film And Needless to say, an adhesive or a transparent plastic film with an adhesive may be used on the surface opposite to the conductive film side.

6) A transparent metal heater is prepared by attaching a connecting metal fitting to the electrode portion of the transparent metal heater prepared in 1) that is not covered with the transparent plastic film.

7) A transparent metal heater is prepared by attaching a connecting metal fitting to the electrode portion of the transparent metal heater prepared in 2) which is not covered with the transparent plastic film.

8) Attach a fitting for connection to the electrode portion of the transparent sheet heater prepared in 3) that is not covered with the transparent plastic film to obtain a transparent sheet heater.

9) A transparent metal heater is prepared by attaching a connecting metal fitting to the electrode portion of the transparent metal heater prepared in 4) which is not covered with the transparent plastic film.

10) A transparent metal heater is prepared by attaching a connecting metal fitting to the electrode portion of the transparent metal heater prepared in 5) which is not covered with the transparent plastic film.

3. Covered with a transparent protective layer placed on a transparent conductive film, a heating surface with a transparent protective layer made of a conductive film having a predetermined pattern and a transparent planar heater made of an electrode are connected to the head of each sheet electrode Create a transparent sheet heater with the metal fittings for. next,
The heat generating surface with transparent protective layer and the electrode part are cut out from the sheet with the metal fittings for connection to make the raw material of the transparent planar heater.

The transparent sheet heater is immersed in a solution containing an anticorrosive such as benzimidazole, washed with water and dried,
A transparent flat heater with end faces protected from corrosion. of course,
A bag-shaped transparent plastic film or a transparent protective plastic film with an adhesive can also be used. In addition, the electrode installation method used when manufacturing elements in the field of EL (electroluminescence) and electroluminescence, the thermocompression bonding method with a protective sheet or film for protecting the light emitting surface, the sealing method or the moistureproof method is also used. it can. Needless to say, any other method can be applied as long as the conductive film can be covered with a transparent plastic, a transparent plastic film or a transparent plastic film with an adhesive or a pressure-sensitive adhesive to protect the conductive film and electrodes. An example of the cross section covered by the anticorrosion layer of the transparent sheet heater is as follows: A: semiconductor thin film, metal thin film, metal thin film / transparent thin film, metal thin film / transparent thin film / metal thin film / transparent thin film, metal thin film / transparent thin film / metal Thin film / transparent thin film / metal thin film / transparent thin film, transparent thin film / metal thin film, transparent thin film / metal thin film / transparent thin film, transparent thin film / metal thin film / transparent thin film / metal thin film / transparent thin film, transparent thin film / metal thin film / transparent thin film / Metal thin film / transparent thin film / metal thin film / transparent thin film, B: A / transparent protective layer, C: transparent substrate / A, A / transparent substrate / A, D: transparent substrate / B, B / transparent substrate / B, F: A / transparent substrate / B, etc., and any other cross-sectional structure having at least a cross section of the transparent conductive film and / or a part or all of the peripheral edge portion covered with an anticorrosion protective layer may be used.

Even if the unnecessary transparent conductive film is not removed and remains, the conductive component is immobilized by acid, alkali, anticorrosive or other chemicals, and the cross section and / or the peripheral edge portion due to moisture or the like. The unnecessary transparent conductive film may remain as long as the transparent conductive film is prevented from being eroded. Here, the material of the transparent substrate or the transparent protective layer can be used as the anticorrosion layer.

Any method can be used as the pattern forming method of the conductive film as long as it can form a predetermined pattern with the conductive film. As an example, a method used for a printed circuit board or a printing method can be used. A resist having a predetermined pattern is provided on the conductive film, and the conductive film is etched with an acid such as hydrochloric acid, nitric acid, sulfuric acid or a mixed solution of these acids and an etching solution, and further, resist stripping, washing with water,
There is a method of forming a conductive film having a predetermined pattern by drying. It is also possible to form a predetermined pattern on the conductive film by a photoresist method (photoetching method) instead of the printing method, and after etching and removing the resist, form a conductive film having a predetermined pattern. As the resist used here, any resist can be used as long as it is a commonly used resist, but examples thereof include an alkali peeling type or solvent peeling type etching resist, a plating resist, a filling ink, a solder resist, an active resist and the like. .

The material used for the transparent protective layer or the anticorrosion layer may be used in place of the resist. Alternatively, a transparent resin or a monomer, an oligomer or a mixture thereof which can form the transparent resin can be used. In this case, an anticorrosion layer installation method using transparent plastic can be used.
In this case, the protective layer of the conductive film at the time of etching becomes the transparent protective film of the final heater. A resist stripping solution containing the anticorrosive agent may be used at the time of stripping the resist.

The shape of the pattern may be any as long as the heating surface is uniform, but as an example, the density of the region where the transparent conductive film does not exist or has no conductivity is the central portion of the heating surface. One example is a pan that is higher in the area and lower in the area. It is also useful to reduce the density of the conductive film region near the electrode portion to avoid excessive heating around the electrode portion. When the visibility such as the pattern shape of the transparent electrode is visible, a region where the transparent conductive film does not exist, for example, the transparent conductive line width is usually
Better visibility may be obtained by setting the thickness to 500 μm or less, preferably 200 μm or less, more preferably 100 μm or less, and further preferably 50 μm or less. In addition, regions where the transparent conductive film of various sizes does not exist may be mixed on the heating surface.

A moisture-proof and / or gas-barrier transparent film having a moisture-proof layer and / or a gas barrier layer provided on at least one side of a polymer film can be used as a transparent substrate or a transparent plastic film. Here, the moisture-proof layer and / or the gas barrier layer is one kind of thin film selected from the group consisting of oxides, nitrides, nitrided oxides, hydrogen nitrides, carbides and transparent polymers used in transparent thin films, or these. When it is a single layer or a multi-layer of a thin film containing at least two or more kinds, and when the thin films selected from these groups are provided in the multi-layer, each layer may be a mixed layer containing each.

The oxide is prepared by decomposing polysilazane or is prepared by chemical-plasma-deposition (CPD) in the presence of oxygen with a silane derivative such as tetramethyldisiloxane or hexaethyldisiloxane. A silicon oxide film is given as an example,
Needless to say, other substances and materials created by other methods can be used as long as they have similar functions. The oxide layer, the nitride layer, the oxynitride layer, the hydronitride layer, and the carbide layer each have a thickness of usually 0.3 nm to 500 nm, preferably 1 nm to 100 nm, and more preferably 5 nm. -80 nm, more preferably 5-60 nm.

Further, in order to improve the light transmittance, an inorganic compound such as MgF ₂ or SiO ₂ having a refractive index of 1.5 or less or a fluorine-containing organic compound may be provided on the transparent substrate, the transparent protective layer and / or the anticorrosion layer. It may be used as a transparent protective layer and / or an anticorrosion layer.

As a preferred example, the inorganic compound is prepared by decomposing polysilazane, or a silane derivative such as tetramethydisiloxane or hexaethyldisiloxane is used in the presence of oxygen in the chemical-plasma-deposition (CPD). An example is a silicon oxide film formed by, but it goes without saying that the same applies to the above oxides, nitrides, oxynitrides, hydronitrides, carbides and other substances, and those formed by other methods. It can be used if it has such functions.

Examples of the fluorine-containing organic compound include acrylic acid -3,3,4,4,5,5,6,6,7,7,8, which is a polymerizing monomer having a perfluoroalkyl group in its side chain.
Polymer containing acrylic acid fluorine-containing alkyl ester such as 8,9,9,10,10,10,10-heptadecafluorodecyl or methacrylic acid fluorine-containing alkyl ester, and polymer containing di (meth) acrylic acid fluorine-containing alkyl ester Is.

Here, as an example of a monomer constituting a polymer containing a fluorine-containing alkyl ester of di (meth) acrylic acid, diacrylic acid-2,2,3,3,4,4,5,5
5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl ethylene glycol, dimethacrylic acid
2,2,3,3,4,4,5,5,6,6,7,7,
General formula CH ₂ such as 8,8,9,9,9-heptadecafluorononylethylene glycol and diacrylic acid-perfluoro-9-methyloctylmethylethylene glycol
= In _{CBCOOC (A) HCH 2 OOCCB '} = represented by CH ₂ di (meth) acrylate San含fluorine alkyl ester, ultraviolet fluorinated curable liquid containing the same 50 wt% or more, electron beam, a cured film by heat or the like Can be used as a low refractive index film.

Here, B and B ′ are the same or different groups and represent a hydrogen atom or a methyl group, and A is a fluoroalkyl group having 3 or more fluorine atoms and having 2 to 12 carbon atoms or 4 fluorine atoms. 4 or more carbons with 1 or more
2 represents a fluorocycloalkyl group. The fluorine-containing curing liquid contains a polymerization initiator and, if necessary, a solvent and the like. Here, as an example of a polymerization initiator, an azo radical polymerization initiator such as azobisisobutyronitrile,
Polymerization initiators for organic peroxides such as benzoyl peroxide and photopolymerization initiators for carbonyl compounds such as acetophenone and benzophenone. 0.01 to 10 parts by weight per 100 parts by weight of the fluorine-containing curing agent coating liquid. It is preferable to add.

The solvent is 1,1,2-trichloro-1,
2,2-trifluoroethane, trifluoromethylbenzene, 1,4-bis (trifluoromethyl) benzene and the like.

The leveling and drying conditions of the coating film of the fluorine-containing curing liquid are room temperature to 200 ° C. and time is 0.1 minutes to 100.
Time is preferred. Even when the polymerization is initiated by heating, it may be selected from the above conditions. The light energy in the case of photo-curing with ultraviolet rays is not particularly limited as long as the coating film is cured, but one example is 50 μm thick and 3
It is sufficient to use 1000 nmJ with 30 nm ultraviolet light. Also, the transparent plastic containing or coated with the above-mentioned anticorrosive agent can be used.

Further, a polarizing film may be used for the transparent substrate, or a polarizing film may be attached to at least one main surface with a pressure sensitive adhesive or an adhesive to provide a planar heater or an electromagnetic wave shield that is antireflection or light adjusted. Here, the polarizing film may be any one as long as it is an ordinary polarizing film, but it is obtained by dispersing a dye in a polyester (PET) film and stretching it, or when the stretched film is dyed with dye or TAC is dyed with dye. There are things. Furthermore, by using an inorganic material or a fluorine-containing organic compound having a refractive index of 1.5 or less as an antireflection layer, it is combined with a polarizing film or an antiglare layer to reduce the influence of external light (with light control) transparent planar heater. Also, electromagnetic wave shields can be manufactured.

As the external connection fitting, eyelets, castellates, or other external connection fittings can be used. In addition, a transparent planar heater can be electrically connected to the conductive film or the electrode provided on the conductive film by pressure bonding or thermocompression bonding (thermal fusion) with the conductive film or the electrode provided on the conductive film. Connection to external electrodes etc. is facilitated via solder connection. Another example of the external connection metal fitting is a conductive metal fitting for connection in which at least two flat metal plates are bonded to each other at least at a part of one side of each metal. Good with slits.

Depending on the purpose, at least a conductive surface or a surface formed on the conductive surface and in contact with an electrode may be provided with a convex portion and / or a concave portion. The shape may be a Δ shape, an Ω shape, or any shape.

Further, the outermost layer of the metal fitting for connection having a flat surface and the metal fitting for connection provided with the projections and / or recesses is made of a corrosion-resistant metal or a low melting point metal or alloy for facilitating connection with the outside. It may be covered with etc. This metal or low melting point metal or alloy may be provided on one side or both sides or the whole of the connecting fitting.

By electrically crimping the connecting electrode fitting and the electrode, for example, the connecting electrode fitting and the electrode are brought into contact with each other to electrically connect. A connection electrode fitting provided with a low melting point metal or alloy, for example, a connection electrode fitting plated with solder on copper can be thermocompression-bonded at a lower temperature, and the solder is fused to the electrode to physically It can be electrically connected and reliability is increased.

In the present invention, the metal constituting the connection fitting is gold, copper, palladium, platinum, tungsten, nickel, tin, zinc, iridium, chromium, cobalt, manganese, cadmium, iron, silicon, indium, germanium, A single metal selected from the group consisting of molybdenum, lead, niobium, barium, gallium, and titanium, or an alloy or mixture containing at least one of these is preferable, but a metal, an alloy, or a mixture other than these is a metal having conductivity. Alternatively, it is also used as a mixture. In order to improve the adhesion of the metal to the conductive surface or the electrode, at least a metal thin film may be laminated on at least the surface of the metal in contact with the conductive surface or the electrode to form a metal fitting. When a metal thin film is laminated on one side or both sides of a metal, the same type of metal thin film may be used, or different types of metal thin films may be used. The thickness of each of the metal and the metal thin film is preferably 0.3 nm to 5 mm. Preferably 5 nm to 1 mm, more preferably 10 n
It is m to 0.5 mm.

In the present invention, the metal constituting the metal thin film is a single metal or an alloy or mixture containing at least one selected from the group consisting of copper, zinc, gold, tin, lead, silver, and solder. Although it is a layered body or a laminated body,
If the adhesion to the conductive surface or electrode is improved,
Any material can be used, but a material having a melting point of 1,100 ° C. or less is preferable from the viewpoint of connection processing.

When solder is used as the metal thin film, the thickness of the solder plating layer is usually 0.05 μm to 80 μm.
m, preferably 0.5 μm to 50 μm, more preferably 2 μm to 10 μm. In the present invention, solder refers to a low melting point metal or alloy used for joining materials. Such metals or alloys have a melting point especially lower than 723 K in absolute temperature.
Examples include simple metals or alloys of n, Sn, Pb, and Zn. A common one is Sn-Pb alloy which produces eutectic solder. In addition, Homberg alloy, Mellotte alloy, Newton metal, Dals metal, Lichtenberg alloy, Close alloy, Rose metal, Wood metal, Revouchi metal, Low melting point solder, Alkali resistant solder, Eutectic solder, JIS solder, Small thermoelectric power Examples include solder and aluminum solder. Furthermore, even alloys other than those listed as alloy names can be used as the metal thin film as long as they can be used for bonding.

The transparent sheet heater thus obtained is, for example, adhered to the polarizing plate (1) opposite to the display screen of the liquid crystal display composed of the polarizing plate (1) / liquid crystal element / polarizing plate (2). Those fixed with an agent or the like can be mentioned. Further, a liquid crystal display body composed of polarizing plate (1) / liquid crystal element / low retardation transparent planar heater / liquid crystal element / polarizing plate (2) can be mentioned. The liquid crystal display may be used in any manner as long as it can improve the switching characteristics and simplify the driving circuit, especially in a low temperature environment (see FIG. 6).

The product of the present invention is also an electromagnetic wave shield having a conductive film of a transparent conductive film provided with a metal fitting for external connection for grounding.

Further, in a transparent conductor provided with one or more electrodes, a metal for external connection may be attached to the electrodes to establish a ground to serve as an electromagnetic wave shield for LCDs, etc., or an adhesive, an adhesive or a double-sided adhesive tape. It can be used by attaching it to another support using the above. In addition to the above electromagnetic wave shield, the transparent sheet heater of the present invention may be used as an electromagnetic wave shield.

An ammeter may be provided between both electrodes of the present invention to measure a current flowing between the electrodes due to a change in a magnetic field (magnet or the like) or an electric field to be used as a magnetic field or electric field detector. If necessary, a weak current may be passed between the electrodes to increase the change in the current, thereby providing a detector.

At least one of the electrodes of the transparent sheet heater may be used as an electromagnetic wave shield for LCD (liquid crystal display) by using an electrode provided with an external connection metal fitting as a ground, or as an adhesive layer or double-sided adhesive. It may be used by attaching it to a support such as an LCD using a tape. In this case, the function can be sufficiently achieved even if only one electrode provided with the connecting electrode fitting is installed, or if the grounding electrode is provided all around the receiving radio wave surface. Further, when the anticorrosion layer made of transparent plastic is provided on the grounding electrode made of a conductive resin, it can be used as a grounding electrode if the electrode has electrical conductivity.

[0128]

The present invention will be described below in more detail with reference to examples.

<Example 1> Visible light transmittance 89%, 10
Silver (thickness 10 nm) / copper (thickness 1 nm) / silicon nitride thickness 30 nm) / indium oxide (thickness 60 n) on a 0 μm thick polyethylene terephthalate (PET) film.
Reactivity D using a metal target for the laminated film consisting of m)
It was deposited by the C magnetron sputtering method to form a transparent conductive film. The visible light transmittance of the obtained transparent conductive film was 76%, and the surface resistance was 7Ω / □.

On the obtained transparent conductive film, a region to be joined between the transparent substrate and the anticorrosion layer, a region other than the patterned conductive film on the heating surface, a heater electrode forming region and a plating electrode are removed. Then, a solvent-type UV (ultraviolet) curable transparent urethane acrylate was applied and cured to form a transparent protective layer having a predetermined pattern and a thickness of 10 μm. Next, a resist was provided in a region where the transparent substrate and the anticorrosion layer were to be joined. Then, electroplating was performed in a nickel sulfamate plating bath having a pH of 4.5 to form a nickel film having a thickness of 5 μm, which was used as an electrode. Further, after removing the resist, it is dipped in a hydrochloric acid-based etching solution so that the conductive film line width at the center is 200 μm.
While forming a conductive film having a predetermined pattern
The unnecessary conductive film was removed (see FIG. 5). The size of the electrodes was 125 mm (length) × 4 mm (width), and the distance between the electrodes was 90 mm. Further, an anticorrosion layer was formed from a transparent urethane acrylate having a thickness of 20 μm, leaving a region corresponding to the connection portion with the external electrode in the electrode.

At the junction between the transparent substrate area from which the transparent conductive film is removed and the anticorrosion layer, the connection metal fitting is placed in the area corresponding to the connection area with the external electrode on which no anticorrosion layer is provided. The electrodes were heat-sealed by welding and attached. Then, a pressure sensitive adhesive layer (adhesive layer) with a separator (release sheet) was provided on the transparent substrate side to complete a transparent sheet heater with connecting terminals.

The resistance between both electrodes of the formed transparent sheet heater was 5Ω. Peel off the separator of the transparent sheet heater to which the power supply wire is connected by soldering to the metal fittings and stick it on a glass plate. Put this transparent sheet heater together with the glass plate in a constant temperature bath at -20 ° C and leave it there. ,
When a voltage of 13 V was applied, the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C. The temperature distribution within the heating surface was ± 1 ° C, which was uniform.

Next, when immersed in 1N hydrochloric acid for 1 hour,
There was no change in the end faces. Further, a high temperature and high humidity test was performed at 65 ° C. × 95%, but after 1,000 hours, no change was observed on the end faces. After that, a heat generation test was conducted, and heat was generated without any abnormality.

Example 2 Visible Light Transmittance 89%, 10
Silver (thickness 10 nm) / copper (thickness 1 nm) / silicon nitride thickness 30 nm) / indium oxide (thickness 60 n) on a 0 μm thick polyethylene terephthalate (PET) film.
Reactivity D using a metal target for the laminated film consisting of m)
It was deposited by the C magnetron sputtering method to form a transparent conductive film. The visible light transmittance of the obtained transparent conductive film was 76%, and the surface resistance was 7Ω / □. On the obtained transparent conductive film, an alkali peeling resist was applied and cured except for the heater electrode formation region and the plating electrode to form a plating protective layer.

Next, electroplating was carried out in a nickel sulfamate plating bath having a pH of 4.5 to form a nickel film having a thickness of 9 μm, which was used as an electrode, after which the resist was removed, washed with water and dried. Next, an alkali peeling resist is applied and cured so that a conductive film having the same pattern as that of Example 1 is formed, and then immersed in a hydrochloric acid-based etching solution to form a conductive film having the same pattern as that of Example 1, and unnecessary. The conductive film was removed. Then, UV (ultraviolet) curable transparent urethane acrylate was applied and cured to form a corrosion-resistant layer having a thickness of 10 μm. The size of the electrodes was 125 mm (length) × 4 mm (width), and the distance between the electrodes was 90 mm. Further, an anticorrosion layer was formed from a transparent urethane acrylate having a thickness of 20 μm, leaving a region corresponding to the connection portion with the external electrode in the electrode.

After separating the transparent substrate region from which the transparent conductive film is removed and the anticorrosion layer, the connection metal fitting is removed in the region corresponding to the connection portion with the external electrode on which the anticorrosion layer is not provided on the electrode. The electrodes were heat-sealed by welding and attached. Then, a pressure sensitive adhesive layer (adhesive layer) with a separator (release sheet) was provided on the transparent substrate side to complete a transparent sheet heater with connecting terminals.

The resistance between both electrodes of the formed transparent sheet heater was 5Ω. Peel off the separator of the transparent sheet heater to which the power supply wire is connected by soldering to the connecting metal fitting, and stick it on a glass plate. Put this transparent sheet heater together with the glass plate in a constant temperature bath at -20 ° C and leave it there. ,
When a voltage of 13 V was applied, the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C. The temperature distribution in the heat generation surface was ± 1 ° C, which was uniform. Next, when it was immersed in 1N hydrochloric acid for 1 hour, there was no change in the end surface. Further, a high temperature and high humidity test was performed at 65 ° C. × 95%, but after 1,000 hours, no change was observed on the end faces. After that, a heat generation test was conducted, and heat was generated without any abnormality.

Example 3 Visible Light Transmittance 89%, 10
Silicon oxynitride (thickness 8 nm) / copper (thickness 1 nm) / on 0 μm thick polyether sulfone (PES) film
A laminated film of silver (thickness 10 nm) / copper (thickness 1 nm) / silicon nitride (thickness 10 nm) / indium oxide (thickness 60 nm) is deposited by a reactive RF magnetron sputtering method using a metal target, A transparent conductive film was formed. The visible light transmittance of the obtained transparent conductive film was 73%, and the surface resistance was 7Ω / □.

Using this conductive film, in the same manner as in Example 1, without the anticorrosion layer, with the transparent protective layer and the conductive film surface having a predetermined pattern, 125 mm (length) × 4 mm
A transparent planar heater having two (width) electrodes and a distance between the electrodes of 90 mm was produced (see FIG. 5).

Next, using a 4% KOH aqueous solution, a 4% benzimidazole solution was prepared and immersed at room temperature for 1 minute. Next, it was washed with water and dried to prepare a heater in which the cross section of the conductive film was subjected to anticorrosion processing. Further, a metal for external connection was heat-bonded to the electrode by resistance welding to complete a transparent planar heater with a metal for external connection. Hereinafter, the same test as that of Example 1 was performed, and the same result as that of Example 1 was obtained.

Example 4 Visible Light Transmittance 88%, 10
Indium tin oxide (ITO) was deposited on a 0 μm thick polyethylene terephthalate (PET) film by the reactive DC magnetron sputtering method using a metal target, and the visible light transmittance was 81% and the surface resistance was 31 Ω / □. A transparent conductive film was formed. Print silver paste on the obtained transparent conductive film and
Hold for 0 minutes to form an electrode. Next, solvent-type UV (ultraviolet) curing is performed except for a region to be joined with the transparent substrate and the anticorrosion layer, a region other than the patterned conductive film on the heating surface, a heater electrode forming region and a plating electrode. A type transparent urethane acrylate was applied and cured to form a transparent protective layer having a predetermined pattern and a thickness of 10 μm. Furthermore, it was immersed in a 5% hydrochloric acid aqueous solution to remove the unnecessary conductive film. Then, except for the area in the electrode where the external connection electrode is attached, UV
(UV) curable transparent urethane acrylate was applied and cured to form a corrosion-resistant layer having a thickness of 10 μm. Next, a metal for external connection was heat-welded to the electrode by resistance welding to complete a transparent planar heater with a metal film for external connection and having a conductive film surface of a predetermined pattern (see FIGS. 3 and 4).

A voltage of 18 V was applied at room temperature, and after 2 minutes, 6
The temperature rose to 0 ° C. The temperature distribution is ± 1 ° C,
It was uniform. Next, when it was immersed in 1N hydrochloric acid for 1 hour, there was no change in the end surface. After immersion, a voltage of 18 V was applied and the same test as above was performed, but it was the same as before immersion.

Example 5 A transparent conductive film having a visible light transmittance of 76% and a surface resistance of 7 Ω / □ prepared in Example 1 was used, and a silver paste was used according to the method of Example 4. An electromagnetic wave shield body illustrated in FIGS. 7 and 8 having a line spacing of 200 μm and a line width of 500 μm was produced. The visible light transmittance was 82%, and when the electric field shielding effect was measured by the advance method with the ground (ground) taken from the electrode provided around the radio wave receiving surface, the electromagnetic wave shielding force was as follows.

[0144]

[Table 1] <Comparative Example 1> Example 1 except that a predetermined pattern is not provided.
When the same transparent planar heater as in Example 1 was prepared and the same test as in Example 1 was performed, the temperature distribution was ± 4 ° C.

<Comparative Example 2> The same transparent planar heater as in Example 1 was prepared except that the anticorrosion layer was not provided, and when immersed in 1N hydrochloric acid for 1 hour in the same manner as in Example 1, whitening occurred from the end faces. It invaded and could not be used as a transparent heater. Next, a high temperature and high humidity test was performed at 65 ° C. × 95%, but after 200 hours, whitening occurred from the end face to the central part, and it could not be used as a transparent planar heater.

<Comparative Example 3> A transparent planar heater was produced in the same manner as in Example 4 except that a flat conductive film surface having a heating pattern having no predetermined pattern was used and no anticorrosion layer was provided. Then, the same test as in Example 4 was performed, and after 2 minutes, 7
The temperature increased to 5 ° C, but the temperature distribution was ± 5 ° C. After immersion in 1N hydrochloric acid for 1 hour, the conductive film was eroded and did not generate heat.

[0147]

As is apparent from the above Examples and Comparative Examples, according to the present invention, it is possible to drive not only high voltage but also low voltage, the uniformity of temperature distribution on the surface is improved, moisture, dust, gas It is a useful invention that makes it possible to manufacture a highly reliable transparent planar heater or an electromagnetic wave shield having durability against acidic components and other pollutants.

Further, it has become possible to manufacture a low-temperature driving liquid crystal display device equipped with this transparent sheet heater.

Further, in the liquid crystal display device, particularly, when the transparent planar heater of the present invention is used in a liquid crystal display device using a ferroelectric liquid crystal having a chiral smectic phase or the like, which is strongly influenced by temperature distribution, It is effective.

[Brief description of drawings]

FIG. 1 is a plan view of a conventional example.

FIG. 2 is a cross-sectional view (cross-section in XY) of a conventional example.

FIG. 3 is a plan view of the configuration of the present invention.

FIG. 4 is a sectional view of a structure showing a preferred example of the present invention (A
-B).

FIG. 5 is a plan view of a configuration showing a preferred example of the present invention.

FIG. 6 is a conceptual cross-sectional view when used in combination with the transparent sheet heater of the present invention and a liquid crystal element.

FIG. 7 is a plan view of a configuration showing a preferred example of the electromagnetic wave shield of the invention.

FIG. 8 is a sectional view of a structure showing a preferred example of the present invention (C
It is a cross section at -D).

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent planar heater 2 Transparent substrate 3 Transparent conductive film 5 Electrode 6 Connection part 7 Transparent protective layer 8 Corrosion preventive layer 9 Adhesive layer 10 External connection metal fitting 11 Liquid crystal display element 12 Liquid crystal display element screen 13 Backlight 14 Electromagnetic wave shield body 15 Grounding Electrode 51 transparent substrate 52 transparent conductive film 53 electrode 54 transparent protective layer 55 external connection electrode 56 connection part

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yuichiro Harada 2-1-1 Tango-dori, Minami-ku, Nagoya City, Aichi Prefecture Inside Mitsui Toatsu Chemicals Co., Ltd. (72) Inventor Sakai 2-1-1, Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Toshihiro Hyodo 3-5-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Akira Suzuki Minami-ku, Nagoya-shi, Aichi 2-1-1 Tango-dori, Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Akemi Nakajima 2-1-1 Tangodori, Minami-ku, Nagoya-shi, Aichi Mitsui Toatsu Chemical Co., Ltd.

Claims (11)

[Claims] 1. A transparent conductive film provided on at least one main surface of a transparent substrate is used as a heating surface or a radio wave receiving surface,
A transparent planar heater having at least a pair of electrodes for energizing or grounding the transparent conductive film, wherein the heating surface or the radio wave receiving surface is made of a transparent conductive film having a predetermined pattern. Has a transparent protective layer on top,
Furthermore, a transparent sheet heater in which a corrosion-resistant layer is provided on at least a part of the cross section of the transparent conductive film and / or the peripheral edge portion. 2. The transparent planar heater according to claim 1, wherein the transparent conductive film comprises a metal thin film containing silver and / or copper as a main component, one surface or both surfaces of which is covered with a transparent thin film. 3. The transparent thin film is an oxide, a nitride, an oxynitride,
The transparent planar heater according to claim 2, which is a single layer or a multilayer of a thin film made of at least one selected from the group consisting of hydronitrides and carbides. 4. The transparent sheet heater according to claim 1, wherein the electrode is provided with a metal fitting for external connection. 5. The transparent planar heater according to claim 1, wherein an adhesive layer is provided on at least one main surface. 6. A transparent conductive film provided on at least one main surface of a transparent substrate is used as a heat generating surface or a radio wave receiving surface,
An electromagnetic wave shield body having at least a pair of electrodes for energizing or grounding the transparent conductive film, wherein the heating surface or the receiving wave surface is made of a transparent conductive film having a predetermined pattern, and on the transparent conductive film. Has a transparent protective layer on
Furthermore, an electromagnetic wave shield body in which a corrosion-resistant layer is provided on at least a cross section of the transparent conductive film and / or a part or all of the peripheral edge portion. 7. The electromagnetic wave shield according to claim 6, wherein the transparent conductive film is a metal thin film containing silver and / or copper as a main component, one surface or both surfaces of which is covered with a transparent thin film. 8. The transparent thin film is an oxide, a nitride, an oxynitride,
The electromagnetic wave shield according to claim 7, which is a single layer or a multi-layer of a thin film made of at least one selected from the group consisting of hydrogenated nitrides and carbides. 9. The electromagnetic wave shield according to claim 6, wherein the electrode is provided with a metal fitting for external connection. 10. The electromagnetic wave shield according to claim 6, wherein an adhesive layer is provided on at least one main surface. 11. A transparent sheet heater and / or a liquid crystal device with an electromagnetic wave shield provided with the transparent sheet heater and / or the electromagnetic wave shield body according to claim 1.