JPH06338381A - Transparent sheet-like heater and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide a transparent sheet-like heater simplifying the manufacturing process and having high reliability. CONSTITUTION:An electrode backing layer 4 is provided on a transparent conducting film 3 laminated with at least one layer of a transparent thin film and a metal layer made of a nitride and/or a carbide is provided on at least one face of a transparent substrate 2, and a metal layer is provided on the metal backing layer 4 to form a transparent planar heater 1. A protective film 6 is formed on the metal backing layer 4 except for the region where the metal electrode 5 is to be formed, and the metal electrode 5 is formed by electric plating.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent sheet heater used for windows, and more particularly, a transparent sheet heater used for liquid crystal display devices, refrigerated showcases, frozen showcases, defrosters for automobiles and the like. And a transparent laminate used therefor.

[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. Conventionally,
As a liquid crystal display element used under conditions such as a cold region, there has been one in which a mesh-shaped heating resistor is arranged and heated, as proposed in, for example, JP-A-58-126517. However, with this method, it is difficult to uniformly heat the entire liquid crystal element, and the heating resistor made of an opaque metal becomes an obstacle when viewing the liquid crystal display.

As a transparent heating element having a transparent conductive film formed on a transparent substrate, for example, US Pat. No. 4,952,783 has been proposed. An example of the configuration of such a heating element is shown in FIG.
Is shown in. That is, the transparent conductive film 52 is formed on the entire surface of the transparent substrate 51, and the pair of electrodes 53 for supplying power to the transparent conductive film 52 are provided at both ends of the transparent conductive film 52. Further, a transparent protective layer 54 for protecting the transparent conductive film 52 and the electrodes 53 is provided on the entire surface of the heating element. Here, the electrode 53 is formed on the transparent conductive film 52 by
It is formed by applying a conductive paint such as a silver paste by a screen printing method or the like and further heat-treating it.
In order to further improve the reliability of the electrode, Japanese Patent Application Laid-Open No. 4-28
Japanese Patent No. 9685 discloses an electrode having a configuration in which a metal foil is sandwiched between conductive paints.

However, in the case of the transparent planar heater of this type, when the electrodes are made of a conductive paint such as silver paste, the resistance of the conductive paint itself is larger than that of the transparent conductive film, and the electrodes and the transparent material are transparent. The contact resistance with the conductive film tends to increase. When the contact resistance becomes large, the energization state in the transparent conductive film becomes non-uniform due to the increase in size of the transparent planar heater, resulting in non-uniform heat generation, and the entire transparent planar heater does not heat up uniformly. This causes problems such as a problem that current concentration occurs in the vicinity of the electrode contacts and abnormal heat is generated in the vicinity of the electrodes of the transparent sheet heater, resulting in disconnection.

In the case of using the electrode as disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 4-289685, although the non-uniformity of the energized state is improved, the adhesion between the transparent conductive film and the electrode is insufficient and it is used. There are problems such that both are easily peeled off, and the manufacturing process for forming the electrodes is complicated and the workability is poor, leading to an increase in the cost of the product.

The inventors of the present invention, in Japanese Patent Application No. 5-189560, form a substantially transparent electrode underlayer on a transparent conductive film and then form a metal electrode on the electrode underlayer by a wet process. It has been disclosed that a transparent sheet heater can be provided. The present invention is an effective invention for providing a transparent sheet heater, but requires skill in the process of forming the metal electrode of the transparent sheet heater by a wet process.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to have an electrode that does not use a conductive paint, improve the method for forming an electrode on a transparent conductive film, and make it transparent even in a wet process for forming a metal electrode. It is an object of the present invention to provide a transparent sheet heater which can be manufactured with high productivity without damaging a conductive film and a transparent laminate used for the heater. Another object of the present invention is to provide a method for manufacturing a transparent sheet heater in which an electrode is formed without using a conductive paint and the productivity is improved.

[0008]

In order to solve the above problems, the inventors of the present invention have made 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 performing, a substantially transparent electrode underlying layer made of metal provided on the transparent conductive film is provided, and the transparent conductive film has a nitride and / or Or a method in which at least one transparent thin film layer made of carbide and at least one substantially transparent metal layer are laminated, and the electrode is made of metal and is selected from a dry process. The present invention has been completed by combining it with a method selected from wet processes.

Thus, an electrode having good adhesion can be provided on the transparent conductive film, and the first transparent protective layer can be used to provide the effect of determining the position of the electrode and also serving as the protective layer of the transparent conductive film. In addition, the present invention provides a transparent sheet heater and a method for manufacturing the same, in which work efficiency and reliability are significantly improved. That is, the present invention provides a transparent planar heater that uses a transparent conductive film provided on a transparent substrate as a heating surface and includes a pair of metal electrodes for energizing the transparent conductive film. A transparent thin film layer made of a metal and a substantially transparent electrode underlayer, wherein the transparent conductive film is made of a nitride and / or a carbide, and at least a substantially transparent metal layer. A transparent planar heater in which the metal electrode is formed on the electrode underlayer, and the metal electrode is formed on the electrode underlayer; and a portion where the metal electrode is not formed is covered with the electrode underlayer. And a transparent thin film layer having a transparent resin protective layer of aluminum nitride, indium nitride, gallium nitride, silicon nitride, tin nitride, boron nitride, chromium nitride, silicon carbide, and amorph. Scan carbon,
A transparent planar heater, which is a high-refractive-index transparent thin film made of at least one of diamond-like carbon, and a transparent planar heater in which a material forming the transparent thin film layer is partially oxidized. The material forming the transparent thin film layer is a transparent planar heater in which a part thereof is hydrogenated, and the electrode underlayer is made of at least one of copper, nickel, chromium, palladium, lead, platinum, gold and silver. A transparent planar heater made of a metal or an alloy containing, wherein the metal electrode is copper, nickel, chromium, gold, tin,
A transparent planar heater which is a single layer or a laminated body made of a metal or alloy containing at least one of lead, silver and solder, and the electrode underlayer has a thickness of 0.5 nm to 20.
A transparent planar heater in which a thin metal film having a thickness of nm is provided on the transparent conductive film by a dry process,
Further, the metal layer is a transparent planar heater which is a thin film layer containing silver or silver as a main component, and the metal layer contains a metal other than silver on at least one surface of the thin film layer containing silver or silver as a main component. A transparent sheet heater which is a laminate of a thin film layer as a main component, and a transparent sheet heater in which a transparent intermediate layer is provided between the transparent thin film layer and the electrode underlayer. The transparent planar heater according to claim 1, wherein a transparent intermediate layer is provided between the transparent substrate and the transparent thin film layer, and the metal electrode and the first transparent resin are protected. A transparent sheet heater having a second transparent resin protective layer covering the layer, and a part of the first transparent resin protective layer and / or the electrode, or
A transparent sheet heater having an adhesive layer on the entire surface, a transparent sheet heater having an adhesive layer on the second transparent resin protective layer, and an adhesive layer on the transparent substrate. It is a transparent sheet heater provided, and is also a transparent sheet heater in which a metal for external connection is provided on the metal electrode.

The present invention also provides a method for manufacturing a transparent sheet heater, which uses a transparent conductive film provided on a transparent substrate as a heat generating surface and is provided with a pair of metal electrodes for energizing the transparent conductive film. At least one of a transparent thin film layer made of a nitride, a nitride and / or a carbide and a substantially transparent metal layer.
A first step of forming a layer-by-layer transparent conductive film on the transparent substrate by a dry process; and a step of forming a metal or alloy on the transparent conductive film by a dry process to form a substantially transparent electrode bottom. A second step of forming an underlayer, a third step of providing a first transparent resin protective layer in a place other than a site where the metal electrode is formed, and a step of forming the metal electrode on the electrode underlayer by a wet plating method. Fourth to form
A method of manufacturing a transparent planar heater having the steps of
Further, it is a method for producing a transparent sheet heater in which the metal thin film layer has a thickness of 0.5 nm to 20 nm, and a method for producing a transparent sheet heater in which the wet plating method is an electroplating method, A method of manufacturing a transparent planar heater, wherein the wet plating method is an electroless plating method, and the metal electrode is formed by combining an electroless plating method and an electroplating method in the fourth step. It is a manufacturing method of a transparent sheet heater, and the third transparent resin protective layer forming step is an ultraviolet curable resist ink, an electron beam curable resist ink, a thermosetting resist ink, an ultraviolet curable resin, an electron beam. A method for producing a transparent sheet heater, which is performed by applying and curing any one of a curable resin and a thermosetting resin, or a combination or mixture thereof. Further, the third transparent resin protective layer forming step is a method for manufacturing a transparent planar heater, which is performed by laminating a transparent film having an adhesive layer, and the third transparent resin protective layer forming step is And a method for manufacturing a transparent planar heater, which is carried out by laminating and curing a dry film, and the third transparent resin protective layer forming step is a process for manufacturing a transparent planar heater, which is carried out by coating and laminating a coating material. Is the way.

Further, the present invention provides a transparent planar heater comprising a transparent conductive film provided on a transparent substrate as a heat generating surface and comprising a pair of metal electrodes for energizing the transparent conductive film. A metal layer having a transparent intermediate layer on at least one surface of the film, wherein the metal layer as an element of the transparent conductive film is made of silver or a metal other than silver on at least one surface of the metal layer containing silver as a main component. A transparent planar heater in which the metal electrode is formed on the transparent conductive film including the transparent intermediate layer.

A preferred embodiment of the present invention will be described below with reference to the drawings.

First, referring to the attached drawings, FIG.
Is a cross-sectional view of a structure showing a comparative example, FIG. 2 is a plan view of the structure of the present invention, and FIGS. 3a, 3b and 3c are cross-sectional views of the structure showing an example of a preferred embodiment of the present invention. Figure 4
FIG. 5 is a perspective view of a configuration of the present invention, and FIG. 5 is a sectional view of a configuration showing a preferred example of another transparent conductive film of the present invention.
6a, 6b, 6c and 7 are cross-sectional views of a structure showing another preferable example. The transparent planar heater 1 shown in FIGS. 2, 3a, 3b, 3c, 4, 6a, 6b, 6c, 7, 8 and 9 has a substantially rectangular planar shape. And a transparent substrate 2 made of plastic or the like,
A transparent conductive film 3 and an electrode underlayer 4 which are sequentially stacked on the main surface of the transparent substrate 2, and a pair provided on both ends of the heater 1 on the electrode underlayer 4 for energizing the transparent conductive film 3. Electrode 5, a first transparent resin protective layer 6 that covers the surface of the electrode underlayer 4 where the electrode 5 is not formed, and a second transparent resin that covers the metal electrode 5 and the first transparent resin protective layer 6. And the protective layer 7.

The transparent conductive film 3 has a structure in which at least one transparent metal layer and at least one transparent thin film layer made of nitride and / or carbide are laminated. In the example shown in FIG. 5, the transparent conductive film 3 is a transparent thin film layer 3a / metal layer 3b.
The transparent thin film layer 3a has a three-layer structure. Further, the thickness of the metal underlayer 4 is determined so that it is substantially translucent. The metal electrode 5 has an elongated shape, and one end thereof serves as the connecting portion 5a. The connection portion 5a is a portion to which an electric wire or the like for applying a voltage to the metal electrode 5 is connected, and the second transparent resin protective layer 7 is provided on the connection portion 5a.
Is not provided. As shown in FIGS. 2 and 4, the connecting portion 5a projects in the in-plane direction from the main body portion of the heater 1. Note that FIG. 7 shows a cross-sectional view of a configuration showing an example having the intermediate layer 13.

The electrode underlayer 4 is formed on the transparent conductive film 3 by a method selected from dry processes in which the energy of vapor-deposited particles is a specific value or more, preferably 1 eV or more. The thickness of the electrode base layer 4 is, for example, 0.5 nm to
It is 20 nm. After forming the first transparent resin protective layer 6 on the surface of the electrode underlayer 4 other than the region where the electrode 5 is formed, the electrode 5 is formed on the surface of the electrode underlayer 4 by electroless plating or electroplating. It is formed by a method selected from wet processes such as plating.

The second transparent resin protective layer 7 is provided for mechanical and chemical protection of the electrode 5 and the transparent conductive film 3, and has a visible light transmittance of, for example, 70 made of resin or film. % Or more.

By configuring the transparent sheet heater as described above, an electrode made of metal can be formed substantially directly on the transparent conductive film without damaging the transparent conductive film. The electrical connection with the transparent conductive film becomes good, the contact resistance between the two becomes small, the performance as a transparent sheet heater is improved, and the reliability is significantly improved. The first transparent resin protective layer not only determines the position where the electrode should be formed in the subsequent metal electrode forming step, but also protects the transparent conductive film, which significantly improves the work efficiency during the production of the transparent planar heater. To be

Further, it is possible to provide an adhesive layer for attaching the transparent sheet heater to another support. 6a, 6b, 6c, and 7 show a configuration having an adhesive layer 8. 6a, 6b and 7 show that the adhesive layer 8 is provided on the transparent substrate 2 or the second transparent resin protective layer 7 to prevent the adhesive layer 8 from adhering to other members before use. In order to protect the adhesive layer 8, a separator (release paper) is provided on the surface of the adhesive layer 8.
9 is provided.

In FIG. 6c, a first transparent resin protective layer 6 and an adhesive layer 8 are provided on a part of the electrode 5, and a separator is laminated thereon. As a matter of course, when the transparent sheet heater is actually attached to the support, the separator (release paper) 9 is peeled off. 8 and 9 are eyelets of a metal fitting 11 for attaching an electric wire for applying a voltage to the metal electrode 5 by soldering or the like, and a connecting portion 5 of the metal electrode 5
The structure provided in a is shown. In the transparent planar heater of the present invention, the electrode underlayer and the transparent thin film layer are generally formed by a dry process, and the metal electrode is generally formed by a wet process.

In the present invention, the dry process means a method for forming a film in a non-solution, and includes a vacuum vapor deposition method, an ion plating method, a sputtering method,
Physical vapor deposition such as molecular beam epitaxy (MBE) and CV
Chemical deposition methods such as D method, MOCVD method and plasma CVD method can be mentioned. Further, the wet process means forming a film in a solution, and in particular, wet plating such as electroplating and electroless plating (chemical plating).
Is meant.

In the present invention, the transparent substrate is a substrate having a light transmittance of 70% or more, more preferably 80% or more in a visible light region having a wavelength of 400 nm to 800 nm, and a transparent plastic film other than glass is used. Can be used. From the viewpoint of thinness, flexibility, impact resistance, continuous productivity, etc., a plastic film is particularly preferably used as the transparent substrate.

As examples of preferable plastics as the material of the film constituting the transparent substrate, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamides, polyethers, polysulfones, and polyethersulfones (PE) are used.
S), polycarbonate, polyarylate, polyetherimide, polyetheretherketone (PEEK),
Examples thereof include those composed of homopolymers or copolymers of polyimide, aramid, polyparabanic acid and the like. Furthermore, 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 refers to a cured crosslinkable resin layer or an anchoring agent on which a cured crosslinkable resin layer is provided. As the crosslinkable resin cured product, acrylic epoxy resin, acrylic silicone resin, epoxy resin,
Acrylic resins, phenoxy ether type cross-linking resins, melamine resins, phenol resins, urethane resins, and UV-curable acrylates are preferably used. As the anchor agent, a water-soluble polyurethane resin, a water-soluble polyamide resin, a water-soluble polyester resin, A-PET (amorphous polyethylene terephthalate), an ethylene-vinyl acetate emulsion, a (meth) acrylic emulsion or the like 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, preferably 10 to 50 μm.

The thickness of the plastic film used in the present invention is usually 5 to 500 μm, preferably 1
0 to 200 μm, more preferably 50 to 150
μm.

In the present invention, the transparent conductive film is a laminate of at least one transparent thin film layer made of nitride and / or carbide and at least one substantially transparent metal layer. Preferably, the transparent conductive film has a three-layer structure including a transparent thin film layer made of nitride and / or carbide, a substantially transparent metal layer, and a transparent conductive film made of a transparent thin film layer made of nitride and / or carbide. Furthermore, it is also possible to alternately laminate a plurality of transparent thin film layers and a plurality of metal layers.

In the present invention, as the metal layer, gold, silver, copper,
Although any thin film of a simple substance or an alloy of a conductive metal such as palladium can be used, a thin film containing silver as a main component is preferable from the viewpoint of conductivity. In the case of a thin film containing silver as a main component, the silver content is desirably 30% by weight or more, preferably 40% by weight or more, more preferably 50% by weight or more.
It is more than weight%. Of course, it is effective to use silver itself as a thin film containing silver as a main component, and even if it is out of the range described here, it can be used in some cases. In addition,
From the viewpoint of preventing deterioration of the transparent conductive film due to energization and improving the adhesion between the metal layer and the transparent thin film layer, gold, copper, palladium and platinum are contained in the thin film containing silver as a main component, as long as conductivity and transparency are not impaired. , Tungsten, titanium, cobalt, chromium,
A metal such as nickel, tin, indium, ITO (indium tin oxide), or zinc may be included. Needless to say, other metals can be used as long as they are preferable from the viewpoint of preventing deterioration of the transparent conductive film and improving the adhesion between the metal layer and the transparent thin film layer. The thickness of the metal layer is 1n
m to 100 nm is desirable. Preferably 5 nm to 50 n
m is more preferably 10 nm to 30 nm.

In order to improve the adhesion of the metal layer to the transparent thin film layer, at least one thin film layer made of other metal is laminated on the thin film layer containing silver as a main component and used here. It may be a metal layer. When a thin film layer made of a metal other than silver is laminated on silver or a thin film layer containing silver as a main component, preferred metals for the thin film layer made of a metal other than silver include gold, copper, palladium, platinum, tungsten, titanium, and nickel. , Tin, zinc, iridium, chromium, cobalt, manganese, cadmium, iron, aluminum, silicon, indium, zirconium, germanium, molybdenum, lead, vanadium, niobium, tantalum, barium,
A metal such as gallium or an alloy containing at least one of them is used, and any other metal or alloy may be used as long as it is a preferable metal or alloy from the viewpoint of improving the adhesion of the metal layer to the transparent thin film layer. The alloy mentioned here is not limited to this.

Generally, the thickness of the thin film layer made of a metal other than silver is preferably 0.1 nm to 60 nm. Preferably 0.
3 m to 50 nm, more preferably 0.5 nm to 30 nm
Is. Needless to say, it can be used in some cases even outside the range described here. The thin film layer made of a metal other than silver is preferably formed as a uniform continuous layer on the transparent thin film layer or the thin film layer containing silver or silver as a main component. It may be formed in an island shape on the thin film, or may be formed locally.

In the present invention, the material constituting the transparent thin film layer is a nitride and / or a carbide. Preferred nitrides and / or carbides are aluminum nitride, indium nitride, gallium nitride, silicon nitride, tin nitride, boron nitride, Examples thereof include chromium nitride, silicon nitride carbide, silicon carbide, amorphous carbon and diamond-like carbon. Usually, the refractive index is 1.6 or more, preferably the refractive index is 1.
A high refractive index transparent thin film made of a nitride and / or a carbide having a refractive index of 8 or more, and more preferably 2.0 or more is preferable.
Also, in order to have sufficient durability against the plating solution,
Any material that is unnecessary or does not dissolve in an acidic solution having a pH of 5 or less, preferably pH 3 or less, and more preferably pH 1 or less, and has an optical band gap of preferably 3 eV or more, and is composed of a nitride, a carbide, or a mixture thereof. But it's okay. The light transmittance is usually 60%
Or more, preferably 70% or more, more preferably 80%
That is all.

In this case, a part may be oxidized or hydrogenated. Examples of the transparent thin film partially oxidized include oxynitrides such as aluminum oxynitride, indium oxynitride, gallium oxynitride, silicon oxynitride, tin oxynitride, boron oxynitride, chromium oxynitride, and silicon oxynitride carbide. Things can be mentioned. The nitrogen content in the components of these oxynitrides excluding the metal and / or carbon is 30 atomic% or more, and more preferably 50 atomic% or more. Examples of the transparent thin film partially hydrogenated include aluminum hydronitride, indium hydronitride, gallium hydronitride, silicon hydronitride, tin hydronitride, boron hydronitride,
Examples thereof include hydronitrides such as chromium hydronitride and silicon hydrocarbide. The nitrogen content in the components other than the metal and / or carbon of these hydronitrides is 50 atomic% or more, and more preferably 80 atomic% or more.

As described above, the transparent thin film layer is formed of these nitrides, carbides, oxynitrides, oxynitride carbides, hydronitrides,
The transparent thin film is composed of a single layer or a laminated body of a transparent thin film made of at least one of hydrogenated and nitrided carbides. The thickness of such a transparent thin film layer is usually 0.3 nm to 100 nm, preferably 1 nm to 100 nm, more preferably 5 nm to 50 nm, and further preferably 10 nm to 30 nm.
Is.

As the method for forming the metal layer, the transparent thin film layer and the transparent conductive film of the present invention on the transparent substrate, known methods such as a spray method and a coating method as well as a physical vapor deposition 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 includes a vacuum vapor deposition method, a sputtering method, an ion plating method, an ion beam assisted vapor deposition method, an ion cluster-bi-layer method. -Mum method etc. are illustrated.

In the present invention, the electrode underlayer is copper,
Nickel, palladium, chromium, gold, silver, lead, platinum, etc.
The metal used as a normal electrode material is used,
Any metal or alloy can be used as long as it functions as a plating nucleus during the wet process. The electrode underlayer is formed on the transparent conductive film by a method selected from dry processes in which vapor deposition particles directly or indirectly obtain energy from an electromagnetic field. Obtaining energy directly means obtaining energy by being accelerated by the force that an ion receives in an electromagnetic field. Obtaining energy indirectly means obtaining energy through a collision process from particles that have obtained energy directly. The energy obtained by the vapor deposition particles in the above process is preferably 0.5 eV or more and 100 eV or less, and more preferably 1 eV or more and 50 eV or less. If the energy is too small, for example, less than 0.5 eV, the adhesion of the electrode underlayer is often insufficient, and if it is too large, for example, more than 100 eV, the process in which the thin film is sputtered by vapor deposition particles becomes remarkable. Particles having no energy in the above range may be mixed in the vapor deposition particles for forming the electrode underlayer by several% to several tens%.

To exemplify a specific method of forming the electrode underlayer, a vacuum deposition method, an ion plating method, a sputtering method, a molecular beam epitaxy method (MBE), a CVD method.
Method, MOCVD method, plasma CVD method and the like, and can be appropriately selected according to the heat resistant temperature of the transparent substrate. As a more preferable method for forming the electrode underlayer, a sputtering method, an ion plating method, or the like, in which the energy of the vapor deposition particles has a specific value, for example, 1 eV or more,
Examples include ion beam assisted vapor deposition method, ion cluster beam method, ion vapor deposition thin film forming method, and the like. Further, when the nitride is provided by the reactive physical vapor deposition method, any gas may be used as long as it contains nitrogen components such as nitrogen and ammonia as a nitrogen component donating. Further, in the case of oxynitride and hydronitride, in addition to these nitrogen-donating components, oxygen, hydrogen, water, and those capable of donating these oxygen components and hydrogen components may be mixed and supplied, or they may be supplied separately. You may supply in. Needless to say, even in the case of a non-reactive system, the above component donor may be introduced into the system to replenish the components of the thin film.

The electrode underlayer is preferably formed as a uniform continuous layer on the transparent conductive film, but may be formed in an island shape on the transparent conductive film depending on the thickness to be formed. It may be locally formed on the conductive film. The thickness of the electrode underlayer is preferably 0.5 nm to 20 nm. This value itself is not particularly critical, but when the film thickness is usually less than 0.5 nm and is too thin, the thickness of the electrode formed by the plating process tends to be uneven. Also,
When the thickness exceeds 20 nm and is too thick, the visible light transmittance is remarkably lowered, and the light transmittance of the transparent planar heater is impaired, which is not suitable for the purpose of the present invention.

In the transparent sheet heater according to the present invention, when a laminate having at least one transparent thin film layer made of nitride and / or carbide and one metal layer is used as a transparent conductive film, the transparent conductive film and the wet process are used. An intermediate layer can be provided between the transparent conductive film and the electrode underlayer for the purpose of further improving the adhesiveness to the metal electrode or the smoothness of the plated film. The interlayer film of the present invention is not particularly limited as long as it has a light transmittance of usually 60% or more, preferably 70% or more, more preferably 80% or more,
Preferred examples include metal oxides such as indium oxide, tin oxide, indium tin oxide, zinc oxide, and silicon oxide.

Further, in order to prevent deterioration of floating of the conductive film due to floating of a low molecular weight compound or the like from the transparent substrate,
This intermediate film may be provided between the transparent substrate and the transparent thin film layer. The thickness of the intermediate film is usually 1 nm to 150 nm, preferably 5 nm to 50 nm, and more preferably 10 n.
m to -20 nm. It should be noted that the present invention is not limited to these, as long as it is preferable from the viewpoint of improving the adhesiveness between the transparent conductive film and the metal electrode by the wet process or the smoothness of the plating film and preventing the low molecular weight compound from rising from the transparent substrate. Can be used.

When an intermediate layer is provided on at least one side of the transparent conductive film for the purpose of further improving the adhesion between the transparent conductive film and the metal electrode by the wet process or the smoothness of the plated film, it is an element of the transparent conductive film. When a certain metal layer is a metal layer containing silver or a metal containing silver as a main component and a metal layer containing a metal other than silver as a main component is laminated on at least one surface of the metal layer, a metal other than silver may be added to the transparent conductive film in some cases. Since it contains a metal layer containing as a main component, it is not always necessary to provide an electrode underlayer on the transparent conductive film.

As the first transparent resin protective layer used in the present invention, the light transmittance at a wavelength of 550 nm is usually 70%.
As described above, any protective layer may be used as long as it is 80% or more, and can withstand the plating treatment. Examples of such a first transparent resin protective layer include a known UV curable resist ink applied and cured, an electron beam curable resist ink applied and cured, and a thermosetting resist ink. That is applied and cured, or that is applied and cured with a UV curable resin,
Examples include those obtained by applying and curing an electron beam-curable resin, those obtained by applying and curing a thermosetting resin, and dry films. In addition to this, a transparent transparent film having water resistance and chemical resistance can be used as the first transparent resin protective layer. For example, a transparent paint, a curable monomer or oligomer, a plastic film such as polyester film. The first transparent resin protective layer can be formed by laminating a film having an adhesive applied thereto or a film having self-adhesiveness such as ethylene-vinyl acetate copolymer. Needless to say, a mixture of these or a laminate thereof can be used as the transparent resin protective layer. Here, as the UV curable resin, epoxy acrylate, urethane acrylate, polyester acrylate, polyfunctional acrylate, polyether acrylate, silicon acrylate, polybutadiene acrylate, unsaturated polyester / styrene, polyene / thiol, polystyryl methacrylate, UV curable lacquer, etc. Is preferably used.

As the electron beam curable resin, epoxy acrylate, urethane acrylate, popolyester acrylate, polyfunctional acrylate, polyether acrylate, silicon acrylate, polybutadiene acrylate, unsaturated polyester / styrene, polyene / thiol, polystyryl methacrylate, UV. A hardened lacquer or the like is preferably used.

As the thermosetting resin, epoxy resin, xylene resin, guanamine resin, diallyl phthalate resin, polyurethane, vinyl ester resin, unsaturated polyester, polyimide, melamine resin, maleic acid resin,
A urea resin and an acrylic resin are preferably 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 first transparent resin protective layer is usually 1
μm to 100 μm, preferably 5 μm to 50 μm
And more preferably 10 μm to 30 μm.

In the present invention, any metal can be used as the metal electrode as long as it can be deposited by plating, but from the viewpoint of electrical characteristics and durability,
A single layer or a laminate of a metal containing at least one of copper, silver, gold, nickel, chromium, tin, lead and solder, or an alloy of these metals is preferable. The thickness of the metal electrode may be 0.5 μm as long as the transparent conductive film has a thickness sufficient to allow a current to flow therethrough as a heat generating surface.
It is preferable to have the above. As described above, this electrode is generally formed by electroplating or electroless plating. You may use electroplating and electroless plating together.

Further, in order to mechanically protect the metal electrode and the first transparent resin protective layer, and to chemically protect the metal layer from corrosion such as moisture, it is necessary to cover the electrode and the first transparent resin protective layer. It is preferable to provide the second transparent resin protective layer. For the second transparent resin protective layer, one having a light transmittance at a wavelength of 550 nm of usually 60% or more, preferably 70%, more preferably 80% or more is used. The second transparent resin protective layer can be formed by laminating the same kind of plastic film used as the transparent substrate with an adhesive, and the same kind as that used as the first transparent resin protective layer. May be used, or organic materials such as polyester, polyolefin, acrylic resin,
It can be formed by applying a silicone-based hard coating agent or the like. A silica sol agent having the same function may be used as the second transparent resin protective layer.

When a plastic film is used as the second transparent resin protective layer, a general transparent pressure-sensitive adhesive or adhesive can be used. As a preferable adhesive, an acrylic pressure-sensitive adhesive or a cyanoacrylate-based reactive adhesive is preferable. The thickness of the second transparent resin protective layer is usually 1 μm to 200 μm, preferably 2 μm to 100 μm, and more preferably 5 μm to 50 μm.

When the transparent planar heater of the present invention is adhered to a support, an adhesive layer may be provided on the surface of the transparent substrate, the first transparent resin protective layer or the second transparent resin protective layer. When the second transparent resin protective layer is not provided, an adhesive layer may be provided on the surface of part or all of the electrodes in addition to the first transparent resin protective layer.

As this adhesive layer, a general transparent pressure-sensitive adhesive or adhesive can be used. Examples of preferred adhesives include acrylic pressure-sensitive adhesives and cyanoacrylate-based reactive adhesives. A separator may be laminated on the adhesive surface as necessary, and it is desirable that the adhesive surface does not adhere when the product is transported or stored. As the separator, polypropylene film, polyester film or the like can be used in addition to release paper that is usually used. The thickness of the separator is usually 1 μm to 200 μm, preferably 2 μm to 100 μm, and more preferably 5 μm to 50 μm.

When metal fittings of the transparent sheet heater of the present invention are attached with metal fittings such as eyelets, and electric wires or the like are attached by soldering or the like to use, the metal fittings may be anywhere on the metal electrodes, but preferably. It is provided at the connection portion 5a of the metal electrode. Further, the metal fitting is not only provided on the metal electrode of the transparent planar heater of the present invention, but also provided on the transparent substrate opposite to the metal electrode, and physically fixed to the transparent planar heater of the present invention by eyelets or the like. In addition, it may be electrically connected to the metal electrode. Also, provided on both sides of the transparent flat heater on the metal electrode and on the opposite transparent substrate,
The metal fitting may be electrically connected and the metal fitting may be stabilized. Further, the metal fitting may or may not have a hole. Needless to say, it may be installed on the adhesive layer or the separator and electrically connected to the metal electrode. Hereinafter, an example of an embodiment of the present invention will be described with reference to examples.

[0049]

【Example】

Example 1 Silicon nitride (thickness: 30 nm) / silver (thickness: 12 nm) / silicon nitride (thickness: 3) on a polyethylene terephthalate (PET) film having a visible light transmittance of 89% and a thickness of 100 μm.
A laminated film of 0 nm) was deposited by a DC magnetron sputtering method to form a transparent conductive film. The visible light transmittance of the obtained transparent conductive film is 8
The surface resistance was 1% and the surface resistance was 7Ω / □. An electrode underlayer made of copper was deposited to a thickness of 2 nm on this conductive film by a DC magnetron sputtering method to form a laminate. A (UV) UV-curable transparent polyol acrylate was applied and cured on the metal underlayer on the obtained laminate except for the electrode formation region to form a first transparent resin protective layer having a thickness of 10 μm. Then, after being immersed in an acid aqueous solution having a pH of 2, electroplating was further performed in a nickel sulfamate plating bath having a pH of 4.5 to form a nickel film having a thickness of 20 μm, which was used as a metal electrode. The size of the metal electrode is 1
It was 25 mm (length) × 4 mm (width), and the distance between the electrodes was 90 mm. Furthermore, leaving the electrode connection part 20
A 25 μm-thick PET film with a pressure-sensitive adhesive having a μm-thickness was laminated to form a second transparent resin protective layer. Through the above steps, the transparent sheet heater having the structure shown in FIGS. 2 to 5 was completed.

The resistance between both electrodes of the formed transparent planar heater was 5Ω. -20 ℃ this transparent sheet heater
Then, the surface temperature was raised to + 2 ° C in 1 minute when a voltage of 13 V was applied. That is, the temperature rise was 22 ° C.

Example 2 Polyethylene terephthalate having a visible light transmittance of 89% and a thickness of 100 μm (silicon nitride (thickness 3
0 nm) / silver (thickness 10 nm) / copper (thickness 5 nm) /
A layered film made of silicon nitride (thickness 10 nm) is deposited by the DC magnetron sputtering method, and in the same method, an intermediate layer made of indium oxide (thickness 20 nm) is formed for the purpose of improving the wettability during plating. Layers were provided. Then, a metal underlayer made of palladium was deposited to a thickness of 2 nm by a DC magnetron sputtering method to form a laminated body. On the electrode underlayer of the obtained laminate, (UV) UV-curable transparent urethane acrylate was applied and cured except for the electrode formation region to form a first transparent resin protective layer. Then, this laminate was immersed in an acid aqueous solution having a pH of 1 and further electroplated in an alkanol sulfonic acid bath to form a solder layer made of a tin-lead alloy having a thickness of about 10 μm to form a metal electrode. The size of the metal electrode is 125 mm (length) x 4 mm (width),
The distance between the electrodes was 90 mm. Further, with the metal electrode connection part left, 50 μm with a 20 μm thick adhesive
A thick PET film was laminated to form a second transparent protective layer. Through the above steps, the transparent sheet heater having the structure shown in FIGS. 2 to 5 was completed. The resistance between both electrodes of the formed transparent planar heater was 6Ω. This transparent sheet heater
When placed in a constant temperature bath of 20 ° C. and left to stand and then a voltage of 13 V was applied, the surface temperature rose to + 1 ° C. in 1 minute. That is, the temperature rise was 21 ° C.

Example 3 Indium oxynitride (30%) was formed on a polyethylene terephthalate (PET) film having a visible light transmittance of 89% and a thickness of 100 μm by a high frequency (rf) magnetron sputtering method.
nm) / silver (13 nm) / silicon oxynitride (30 nm) was deposited to obtain a transparent conductive film. Furthermore,
Thickness 2 made of copper by DC magnetron sputtering
An electrode underlayer having a thickness of nm was formed. A (UV) ultraviolet-curable epoxy acrylate was applied and cured on the electrode underlayer of the obtained laminate except the electrode formation region to form a first transparent protective layer. Then, after soaking in an acid aqueous solution of pH 1,
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 20 μm, which was used as a metal electrode. The size of the metal electrode is 125 mm
(Length) x 4 mm (width), distance between electrodes is 90 m
It was m. Further, a 25 μm-thick PET film with a 20 μm-thick adhesive was laminated to leave a connection portion of the electrode, and a second transparent protective layer was obtained. Then, a pressure-sensitive adhesive layer with a separator (release sheet) is provided on the transparent substrate side, as shown in FIG.
The transparent sheet heater having the structure shown in FIG. The resistance between both electrodes of the formed transparent planar heater was 5Ω.
This transparent sheet heater was attached to a glass plate, and this transparent sheet heater was put together with the glass sheet in a constant temperature bath at −20 ° C. and allowed to stand, and then a voltage of 13 V was applied.
The surface temperature rose to + 2 ° C in minutes. That is, the temperature rise was 22 ° C.

Example 4 Polyethersulfone (PES) having a visible light transmittance of 88% and a thickness of 100 μm was coated on one side with a high-frequency ion plating method to obtain silicon nitride (40 nm) / silver + 3% by weight.
Gold metal layer (11 nm) / Silicon carbonitride (30 n
The laminated film of m) was deposited to obtain a transparent conductive film.
Further, a 2 nm-thick electrode underlayer made of palladium was formed by the same method. A (UV) ultraviolet curable resist ink was applied and cured on the metal underlayer of the obtained laminate except for the electrode formation region to form a first transparent protective layer. Then, the laminate is dipped in an acid aqueous solution having a pH of 1 and electroplated in a nickel sulfamate plating bath having a pH of 3.5 to form a nickel film having a thickness of 20 μm.
A metal electrode was used. The size of the metal electrodes was 125 mm (length) × 4 mm (width), and the distance between the electrodes was 90 mm. Further, the metal electrode and the first
A second transparent resin protective layer was formed by coating and curing an acrylic urethane UV curable resin on the transparent resin protective layer of (1) to complete the transparent planar heater. The resistance between both electrodes of the formed transparent planar heater was 5Ω. This transparent sheet heater was attached to a glass plate, and this transparent sheet heater was put together with the glass sheet in a constant temperature bath at -20 ° C and allowed to stand, and then 12 V of electric power was turned on. The temperature has risen. That is, the temperature rise was 21 ° C.

Example 5 On a PET film having a visible light transmittance of 89% and a thickness of 100 μm, silicon nitride (thickness: 12 nm) / copper (thickness: 5 n)
m) / silver (thickness 12 nm) / indium nitride (thickness 30)
(nm) laminated film was deposited by a DC magnetron sputtering method to obtain a transparent conductive film. Then D
A metal underlayer made of copper was deposited to a thickness of 2 nm on this transparent conductive film by the C magnetron sputtering method to obtain a laminate. A (UV) UV-curable acrylic resin resist ink was applied and cured on the metal underlayer of the obtained laminate except for the electrode formation region to form a first transparent protective layer. Then, this laminate was immersed in an acid aqueous solution of pH 2 and electroplated in a nickel sulfamate plating bath of pH 3.5 to form a nickel film having a thickness of 20 μm, which was used as a metal electrode. The size of the metal electrode is 125
mm (length) x 4 mm (width), the distance between the electrodes is 9
It was 0 mm. Acrylic urethane type UV is further applied on the metal electrode and the first transparent resin protective layer, leaving the electrode connecting portion.
A curable resin was applied and cured to form a second transparent resin protective layer, and the transparent planar heater was completed. The resistance between both electrodes of the formed transparent planar heater was 5Ω. When this transparent sheet heater was put in a constant temperature bath at -20 ° C and left to stand, and then an electric power of 13V was turned on, it was + 2 ° C in 1 minute.
Up to the surface temperature. That is, the temperature rise is 22 ° C
Met.

Example 6 On a polyethylene terephthalate (PET) film having a visible light transmittance of 89% and a thickness of 100 μm, silicon carbide + silicon nitride (thickness 30 nm) / silver (thickness 12 nm) / silicon carbide + silicon nitride (thickness). A 30 nm thick laminated film was deposited by a high frequency (rf) magnetron sputtering method to form a transparent conductive film. Then, by the same method, a metal base layer made of copper is formed on the transparent conductive film by 2n.
It was deposited in a thickness of m to obtain a laminated body. A (UV) UV-curable transparent resist ink was applied and cured on the electrode underlayer of the obtained laminate except the electrode formation region to form a first transparent protective layer. Then, this laminate was immersed in an acid aqueous solution of pH 2 and electroplated in a nickel sulfamate plating bath of pH 3.5 to form a nickel film having a thickness of 20 μm, which was used as a metal electrode. The size of the metal electrode is 1
It was 25 mm (length) × 4 mm (width), and the distance between the electrodes was 90 mm. Furthermore, leaving the electrode connection part 20
A 50 μm-thick PET film with a pressure-sensitive adhesive having a μm-thickness was laminated to form a second transparent resin protective layer, and a transparent surface shape and a heater were completed. The resistance between both electrodes of the formed transparent planar heater was 6Ω. This transparent sheet heater
When placed in a constant temperature bath of 20 ° C. and left to stand and then a voltage of 13 V was applied, the surface temperature rose to + 1 ° C. in 1 minute. That is, the temperature rise was 21 ° C.

Example 7 A laminated film made of silver (thickness 12 nm) / silicon nitride (thickness 30 nm) was deposited on a polycarbonate (PC) film having a visible light transmittance of 90% and a thickness of 100 μm by a DC magnetron sputtering method. To form a transparent conductive film. Then, by DC magnetron sputtering, 2 n of an electrode underlayer made of copper was formed on this transparent conductive film.
It was deposited in a thickness of m to obtain a laminated body. A (UV) UV-curable acrylic resin resist ink is applied and cured on the electrode underlayer of the obtained laminate except the electrode formation region,
To form a transparent protective layer. Then, this laminate was immersed in an acid aqueous solution having a pH of 1 and further electroplated in a nickel sulfamate plating bath having a pH of 3.5 to form a nickel film having a thickness of 20 μm, which was used as a metal electrode. The size of the metal electrodes was 125 mm (length) × 4 mm (width), and the distance between the electrodes was 90 mm. Further, an acrylic urethane resin was laminated while leaving the electrode connecting portion to form a second transparent resin protective layer, and the transparent planar heater was completed. The resistance between both electrodes of the formed transparent planar heater was 5Ω.
When this transparent planar heater was placed in a constant temperature bath at -20 ° C and left to stand, and then a voltage of 12V was applied, the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C.

Example 8 Indium oxynitride (thickness 30 nm) / silver + 10 on a PET film having a visible light transmittance of 89% and a thickness of 125 μm.
A laminated film composed of a metal layer (thickness 12 nm) / silicon oxynitride (thickness 30 nm) made of copper by weight% was deposited by a DC magnetron sputtering method to obtain a transparent conductive film. Then, a metal underlayer made of copper was deposited to a thickness of 2 nm on this transparent conductive film by a DC magnetron sputtering method to obtain a laminated body. On the metal underlayer of the obtained laminate, except for the electrode formation region (UV)
UV-curable polyester acrylate is applied and cured,
A first transparent protective layer was formed. Then, this laminate was immersed in an acid aqueous solution having a pH of 1 and further electroplated in a nickel sulfamate plating bath having a pH of 3.5 to form a nickel film having a thickness of 20 μm, which was used as a metal electrode. The size of the metal electrodes was 125 mm (length) × 4 mm (width), and the distance between the electrodes was 90 mm. Furthermore, leaving a connection part of the electrode, PE of 25 μm thickness with 20 μm of adhesive
A T-film was laminated to form a second transparent resin protective layer, and the transparent planar heater was completed. The resistance between both electrodes of the formed transparent planar heater was 5Ω. This transparent sheet heater was placed in a constant temperature bath at -20 ° C and left to stand, and then 1
When a voltage of 3 V was applied, the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C.

Example 9 On a PET film having a visible light transmittance of 89% and a thickness of 100 μm, silicon nitride (thickness: 30 nm) / silver (thickness: 12 n)
m) / silicon nitride (thickness 30 nm) / indium oxide (thickness 20 nm) was deposited by a DC magnetron sputtering method to form a transparent conductive film. Next, an electrode underlayer made of copper was deposited to a thickness of 2 nm on this transparent conductive film by a DC magnetron sputtering method to obtain a laminated body. On the electrode base layer of the obtained laminate, except for the electrode formation region (U
V) An ultraviolet curable transparent polyol acrylate was applied and cured to form a first transparent resin protective layer. Then the pH
Immerse this laminate in the acid aqueous solution of 2 and further add pH 4.5.
The nickel sulfamate plating bath was used for electroplating to form a nickel film having a thickness of 20 μm, which was used as a metal electrode.
The size of the metal electrode is 125 mm (length) x 4 mm (width)
And the distance between the electrodes was 90 mm. 25 μm with 20 μm thick adhesive, leaving the electrode connection part
A PET film having a thickness was laminated to form a second transparent resin protective layer, and the transparent planar heater was completed. The resistance between both electrodes of the formed transparent planar heater was 5Ω. This transparent sheet heater is placed in a constant temperature bath at -20 ° C and left to stand,
After that, when a voltage of 13 V was applied, +2 in 1 minute
The surface temperature rose to ℃. That is, the temperature rise is 2
It was 2 ° C.

Example 10 On a PET film having a visible light transmittance of 88% and a thickness of 100 μm, silicon oxynitride (thickness 40 nm) / titanium (thickness 1 nm) / silver + 9 wt% platinum (thickness 12 nm) / oxynitridation A laminated film made of silicon (thickness 30 nm) was deposited by a high frequency ion pooling method to obtain a transparent conductive film. Then, a metal underlayer made of palladium with a thickness of 2 nm was deposited on the transparent conductive film by a high frequency ion pooling method to obtain a laminated body. On the metal underlayer of the obtained laminate, a thermosetting polyester was applied and cured except for the electrode formation region to form a first transparent protective layer. Then, the laminate is dipped in an acid aqueous solution having a pH of 1 and electroplated in a nickel sulfamate plating bath having a pH of 3.5 to form a nickel film having a thickness of 20 μm.
A metal electrode was used. The size of the metal electrodes was 125 mm (length) × 4 mm (width), and the distance between the electrodes was 90 mm. Further, a 25 μm-thick PET film with a 20 μm-thick adhesive was laminated to leave a connection portion of the electrode as a second transparent resin protective layer to complete a transparent planar heater. The resistance between both electrodes of the formed transparent flat heater is 5
It was Ω. When this transparent planar heater was placed in a constant temperature bath at -20 ° C and allowed to stand, and then a voltage of 13V was applied, the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C.

Example 11 On a PET film having a visible light transmittance of 88% and a thickness of 100 μm, aluminum oxynitride (thickness 40 nm) / titanium (thickness 1 nm) / silver + 3% by weight gold (thickness 10 nm) / oxynitridation A laminated film made of silicon (thickness: 30 nm) was deposited by a high frequency ion pooling method to form a transparent conductive film. The transparent transparent conductive film thus obtained had a visible light transmittance of 80%, a surface resistance of 8 Ω / □ and an infrared reflectance of 92%. Then, a metal underlayer made of palladium with a thickness of 2 nm was deposited on the transparent conductive film by a high frequency ion pooling method to obtain a laminated body.
On the electrode underlayer of the obtained laminate, a thermosetting polyester was applied and cured except for the electrode formation region to form a first transparent protective layer. Then, this laminate was immersed in an acid aqueous solution having a pH of 1 and further electroplated in a nickel sulfamate plating bath having a pH of 3.5 to form a nickel film having a thickness of 20 μm, which was used as a metal electrode. The size of the metal electrode is 12
It was 5 mm (length) × 4 mm (width), and the distance between the electrodes was 90 mm. 20μ, leaving the electrode connection
A 25 μm-thick PET film with an m-thick adhesive was laminated to form a second transparent resin protective layer, and the transparent planar heater was completed. The resistance between both electrodes of the formed transparent planar heater was 5Ω. This transparent sheet heater is -20
When it was placed in a constant temperature bath at ℃ and left to stand and then a voltage of 12 V was applied, the surface temperature rose to +1 ℃ in 1 minute. That is, the temperature rise was 21 ° C.

Example 12 Silicon nitride (thickness: 30 nm) / titanium (thickness: 0.5 nm) / silver (thickness: 12) was applied on a polyethylene terephthalate (PET) film having a visible light transmittance of 89% and a thickness of 100 μm.
nm) / titanium (thickness 0.5 nm) / silicon nitride (thickness 30 nm) was deposited by the DC magnetattering method to form a transparent conductive film. Furthermore, a metal underlayer made of copper was deposited to a thickness of 2 nm by a DC magnetron sputtering method to form a laminated body. (UV) UV-curable transparent acrylic resin (polyol acrylate (12 parts), acrylate (14 parts) and urethane acrylate (8 parts) on the metal underlayer on the obtained laminate except for the electrode formation region. Was mixed and cured to form a first transparent protective layer. Then p
After soaking in H1 acid aqueous solution, electroplating is further performed in a nickel sulfamate plating bath having a pH of 3.5,
A nickel film having a thickness of μm was formed and used as a metal electrode. The size of the electrode is 125 mm (length) x 4 mm (width),
The distance between the electrodes was 90 mm. Furthermore, leaving the electrode connection part, the P of 25 μm thickness with the adhesive of 20 μm
The ET films were laminated to form a second transparent resin protective layer. Next, an adhesive layer made of an acrylic pressure-sensitive adhesive (adhesive) having a thickness of 25 μm is provided on the transparent substrate, and further,
A separator made of a polyester film having a thickness of 50 μm was laminated thereon. Through the above steps, the transparent sheet heater having the structure shown in FIGS. 2 to 5 was completed. The resistance between both electrodes of the formed transparent planar heater was 5Ω. The separator of the transparent sheet heater was peeled off and attached to glass via an adhesive layer made of an acrylic pressure-sensitive adhesive (adhesive). Next, this transparent flat heater was put together with glass in a constant temperature bath at -20 ° C and left to stand, and then 13
When a voltage of V was applied, the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C.

Example 13 Indium oxide (thickness: 30 nm) / silver (thickness: 1) on a PET film having a visible light transmittance of 89% and a thickness of 125 μm.
A laminated film of (2 nm) / silicon nitride (thickness: 30 nm) was deposited by the DC magnetron sputtering method to form a transparent conductive film. The transparent transparent conductive film thus obtained had a visible light transmittance of 80% and a surface resistance of 7
It was Ω / □. Then, a metal underlayer made of copper was deposited to a thickness of 2 nm on this transparent conductive film by a DC magnetron sputtering method to obtain a laminated body. A (UV) UV-curable acrylic resin (mixture of polyol acrylate (3 parts) and polyurethane acrylate (1 part)) was applied and cured on the metal base layer of the obtained laminate except the electrode formation region, and The transparent protective layer of No. 1 was formed.
Then, this laminate was immersed in an acid aqueous solution having a pH of 1 and further electroplated in a nickel sulfamate plating bath having a pH of 3.5 to form a nickel film having a thickness of 20 μm, which was used as a metal electrode. The size of the metal electrode is 125 mm (length)
× 4 mm (width) and the distance between the electrodes was 90 mm. Further, a 25 μm-thick PET film with a 20 μm-thick adhesive was laminated to leave a connection portion of the electrode as a second transparent resin protective layer to complete a transparent planar heater.
The resistance between both electrodes of the formed transparent planar heater was 5Ω. When this transparent planar heater was placed in a constant temperature bath at -20 ° C and left to stand, and then a voltage of 12V was applied, the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C.

Example 14 On one surface of a polyether sulfone (PES) film having a visible light transmittance of 88% and a thickness of 100 μm, indium oxide (thickness: 40 n) was formed by a high frequency (rf) magnetron sputtering method.
m) / silver + 3 wt% gold (thickness 12 nm) / silicon carbonitride (thickness 30 nm) was deposited, and a 2 nm-thick metal underlayer made of palladium was formed by the same method. A UV-curable resin resist ink was applied and cured on the electrode underlayer of the obtained laminate except for the electrode formation region to form a first transparent protective layer. Then, the laminate is dipped in an acid aqueous solution having a pH of 1 and further electroplated in a nickel sulfamate plating bath having a pH of 20.
A nickel film having a thickness of μm was formed and used as a metal electrode. The size of the metal electrodes was 125 mm (length) × 4 mm (width), and the distance between the electrodes was 90 mm. Further, an acrylic urethane type UV curable resin was applied and cured on the metal electrode and the first transparent resin protective layer leaving the electrode connection portion to form a second transparent resin protective layer, thus completing the transparent planar heater. . The resistance between both electrodes of the formed transparent flat heater is 5
It was Ω. Stick this transparent heater on a glass plate,
This transparent surface was put together with the glass plate in a constant temperature bath at -20 ° C and allowed to stand. Then, when a voltage of 12V was applied, the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C.

Example 15 A layer made of indium oxide (thickness 40 nm) / silver + 3% by weight gold (thickness 12 nm) / silicon nitride (thickness 30 nm) on a PET film having a visible light transmittance of 88% and a thickness of 100 μm. The film was deposited by radio frequency (rf) magnetron sputtering to form a transparent transparent conductive film. The visible light transmittance of the obtained transparent transparent conductive film was 80%, and the surface resistance was 7Ω / □. Then, a metal underlayer made of palladium was deposited to a thickness of 2 nm on the transparent conductive film by a high frequency magnetron sputtering method to obtain a laminated body. On the electrode underlayer of the obtained laminate, a thermosetting polyester was applied and cured except for the electrode formation region to form a first transparent protective layer. Then the pH
Immerse this laminate in the acid aqueous solution of 1 and further add pH 3.5.
The nickel sulfamate plating bath was used for electroplating to form a nickel film having a thickness of 20 μm, which was used as a metal electrode.
The size of the metal electrode is 125 mm (length) x 4 mm (width)
And the distance between the electrodes was 90 mm. 25 μm with 20 μm thick adhesive, leaving the electrode connection part
A PET film having a thickness was laminated to form a second transparent resin protective layer, and the transparent planar heater was completed. The resistance between both electrodes of the formed transparent planar heater was 5Ω. This transparent sheet heater is placed in a constant temperature bath at -20 ° C and left to stand,
After that, when a voltage of 12V was applied, +2 in 1 minute
The surface temperature rose to ℃. That is, the temperature rise is 2
It was 2 ° C.

Example 16 Silicon nitride (thickness 30 nm) / silver (thickness 12 nm) / silicon nitride (thickness 3) on a polyethylene terephthalate (PET) film having a visible light transmittance of 89% and a thickness of 100 μm.
A laminated film of 0 nm) was deposited by a DC magnetron sputtering method to form a transparent conductive film. The visible light transmittance of the obtained transparent conductive film is 8
The surface resistance was 1% and the surface resistance was 7Ω / □. An electrode underlayer made of copper was deposited to a thickness of 2 nm on this conductive film by a DC magnetron sputtering method to form a laminate. A (UV) UV-curable transparent polyester acrylate was applied and cured on the metal base layer on the obtained laminated body except for the electrode formation region to form a first transparent resin protective layer having a thickness of 10 μm. Then, it was dipped in an acid aqueous solution having a pH of 1 and further electroplated in a nickel sulfamate plating bath having a pH of 3.5 to form a nickel film having a thickness of 5 μm, which was used as a metal electrode. The size of the metal electrode is 125
mm (length x 4 mm (width), the distance between the electrodes is 90
It was mm. Further, a 25 μm-thick PET film with a 20 μm-thick adhesive was laminated by leaving the electrode connection part to form a second transparent resin protective layer. By the above,
The transparent planar heater having the structure shown in FIGS. 2 to 5 was completed. The resistance between both electrodes of the formed transparent flat heater is 5
It was Ω. When this transparent planar heater was placed in a constant temperature bath at -20 ° C and left to stand, and then a voltage of 12V was applied, the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C.

Example 17 Silicon nitride (thickness: 30 nm) / titanium (thickness: 1 nm) / silver (thickness: 12 n) was applied on a polyethylene terephthalate (PET) film having a visible light transmittance of 89% and a thickness of 100 μm.
m) / silicon nitride (thickness 20 nm) / indium oxide (thickness 30 nm) was deposited by the DC magnetron sputtering method to form a transparent conductive film. Furthermore, a metal underlayer made of copper was deposited to a thickness of 2 nm by a DC magnetron sputtering method to form a laminated body. A UV-curable transparent acrylic resin (mixture of polyol acrylate (3 parts) and polyurethane acrylate (1 part)) is applied and cured on the metal underlayer on the obtained laminate except the electrode formation region. Then, the first transparent protective layer was formed. Then, after being immersed in an acid aqueous solution having a pH of 1, electroplating was further performed in a nickel sulfamate plating bath having a pH of 3.5 to form a nickel film having a thickness of 5 μm, which was used as a metal electrode. The size of the electrodes was 125 mm (length) × 4 mm (width), and the distance between the electrodes was 90 mm. Further, a 25 μm-thick PET film with a 20 μm-thick adhesive was laminated by leaving the electrode connection part to form a second transparent resin protective layer. Next, an adhesive layer made of an acrylic pressure-sensitive adhesive (adhesive) having a thickness of 25 μm was provided on the transparent substrate, and a separator made of a polyester film having a thickness of 50 μm was further laminated thereon. Through the above steps, the transparent sheet heater having the structure shown in FIGS. 2 to 5 was completed. The resistance between both electrodes of the formed transparent planar heater was 5Ω. The separator of the transparent sheet heater was peeled off and attached to glass via an adhesive layer made of an acrylic pressure-sensitive adhesive (adhesive). Next, this transparent sheet heater together with glass-
When placed in a constant temperature bath of 20 ° C. and left to stand and then 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.

Example 18 Polyethylene terephthalate having a visible light transmittance of 89% and a thickness of 100 μm (silicon nitride (thickness 3
0 nm) / titanium (thickness 1 nm) / silver (thickness 2 nm) /
A laminated film made of silicon nitride (thickness: 30 nm) was deposited by the DC magnetattering method to form a transparent conductive film. Furthermore, a metal underlayer made of copper was deposited to a thickness of 2 nm by a DC magnetron sputtering method to form a laminated body. A (UV) UV-curable transparent acrylic resin (polyol acrylate (mixture of 3 parts acrylate (8 parts)) was applied and cured on the metal base layer on the obtained laminate except for the electrode formation region, A first transparent protective layer was formed, and after that, it was immersed in an acid aqueous solution having a pH of 1 and then electroplated in a nickel sulfamate plating bath having a pH of 3.5 to form a nickel film having a thickness of 5 μm. The size of the electrodes was 125 mm (length) × 4 mm (width), the distance between the electrodes was 90 mm, and the 25 μm-thick PET film with a 20 μm-thick adhesive was left, leaving the electrode connection part. Then, a second transparent resin protective layer was formed on the transparent substrate, and an adhesive layer made of an acrylic pressure-sensitive adhesive (adhesive) having a thickness of 25 μm was provided on the transparent substrate, and further 50 μm thereon. By laminating a separator consisting of Mino polyester film.
Through the above steps, the transparent sheet heater having the structure shown in FIGS. 2 to 5 was completed. The resistance between both electrodes of the formed transparent planar heater was 5Ω. Peel off the separator of this transparent sheet heater and use acrylic pressure sensitive adhesive (adhesive)
It was stuck to glass through an adhesive layer consisting of. Next, this transparent flat heater was put together with glass in a constant temperature bath at -20 ° C and allowed to stand. Then, when a voltage of 13V was applied, the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C.

Example 19 A laminated film made of aluminum nitride (thickness 30 nm) / silver (thickness 12 nm) / aluminum nitride (thickness 30 nm) on a polyethylene terephthalate (PET) film having a visible light transmittance of 89% and a thickness of 100 μm. Was deposited by a DC magnetron sputtering method to form a transparent conductive film. The transparent conductive film obtained had a visible light transmittance of 81% and a surface resistance of 7Ω / □. DC
An electrode underlayer made of copper was deposited to a thickness of 2 nm on this conductive film by a magnetron sputtering method to form a laminate. A (UV) UV-curable transparent polyol acrylate was applied and cured on the metal underlayer on the obtained laminate except for the electrode formation region to give a thickness of 10 μm.
m first transparent resin protective layer was formed. After that, pH 1
Was dipped in the acid aqueous solution and further electroplated in a nickel sulfamate plating bath having a pH of 3.5 to form a nickel film having a thickness of 20 μm, which was used as a metal electrode. The size of the metal electrodes was 35 mm (length) × 4 mm (width), and the distance between the electrodes was 90 mm. Further, a 25 μm-thick PET film with a 20 μm-thick adhesive was laminated by leaving the electrode connection part to form a second transparent resin protective layer. Through the above steps, the transparent sheet heater having the structure shown in FIGS. 2 to 5 was completed. The resistance between both electrodes of the formed transparent planar heater was 14Ω. 2 this transparent sheet heater
When placed in a constant temperature bath of 5 ° C. and left to stand and then a voltage of 13 V was applied, the surface temperature rose to 65 ° C. in 1 minute. That is, the temperature rise was 40 ° C.

Example 20 Silicon nitride (thickness 30 nm) / silver (thickness 12 nm) / silicon nitride (thickness 3) on a polyethylene terephthalate (PET) film having a visible light transmittance of 89% and a thickness of 100 μm.
A laminated film of 0 nm) was deposited by a DC magnetron sputtering method to form a transparent conductive film. Furthermore, a metal underlayer made of copper was deposited to a thickness of 2 nm by a DC magnetron sputtering method to form a laminated body. A (UV) UV-curable transparent acrylic resin was applied and cured on the metal underlayer on the obtained laminated body except for the electrode formation region to form a first transparent resin protective layer having a thickness of 10 μm. After that, it is dipped in an acid aqueous solution of pH 1 and washed with water, and then a 2 μm copper film is formed in an electroless plating bath of pH 12, and then electroplating of pH 4 is performed to obtain 15 μm.
m copper film was formed and used as a metal electrode. The size of the electrode is 1
It was 25 mm (length) × 4 mm (width), and the distance between the electrodes was 90 mm. Furthermore, leaving the electrode connection part 20
A 25 μm-thick PET film with a pressure-sensitive adhesive having a μm-thickness was laminated to form a second transparent resin protective layer. Through the above steps, the transparent sheet heater having the structure shown in FIGS. 2 to 5 was completed. The resistance between both electrodes of the formed transparent planar heater was 5Ω. When this transparent planar heater was placed in a constant temperature bath at -20 ° C and allowed to stand, and then a voltage of 13V was applied, the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C.

Example 21 Silicon nitride (thickness 30 nm) / silver (thickness 12 nm) / silicon nitride (thickness 3) on a polyethylene terephthalate (PET) film having a visible light transmittance of 89% and a thickness of 100 μm.
A laminated film of 0 nm) was deposited by a DC magnetron sputtering method to form a transparent conductive film. Furthermore, a metal underlayer made of copper was deposited to a thickness of 2 nm by a DC magnetron sputtering method to form a laminated body. A UV-curable transparent acrylic resin (mixture of polyol acrylate (3 parts) and polyurethane acrylate (1 part)) is applied and cured on the metal underlayer on the obtained laminate except the electrode formation region. Then, the first transparent protective layer was formed. Then, after being immersed in an acid aqueous solution having a pH of 1, electroplating was further performed in a nickel sulfamate plating bath having a pH of 3.5 to form a nickel film having a thickness of 20 μm, which was used as a metal electrode. The size of the electrodes was 125 mm (length) × 4 mm (width), and the distance between the electrodes was 90 mm. Further, a 25 μm-thick PET film with a 20 μm-thick adhesive was laminated by leaving the electrode connection part to form a second transparent resin protective layer. Next, an adhesive layer made of an acrylic pressure-sensitive adhesive (adhesive) having a thickness of 25 μm was provided on the transparent substrate, and a separator made of a polyester film having a thickness of 50 μm was further laminated thereon. Through the above steps, the transparent sheet heater having the structure shown in FIGS. 2 to 5 was completed. The resistance between both electrodes of the formed transparent planar heater was 5Ω. The separator of the transparent sheet heater was peeled off and attached to glass via an adhesive layer made of an acrylic pressure-sensitive adhesive (adhesive). Next, this transparent sheet heater together with glass-
When placed in a constant temperature bath of 20 ° C. and left to stand and then 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.

Example 22 On a polyethylene terephthalate (PET) film having a visible light transmittance of 89% and a thickness of 100 μm, silicon oxynitride / indium oxynitride [silicon: indium = 1: 1 (thickness 3
0 nm)] / silver (thickness 12 nm) / silicon nitride (thickness 3
0 nm) / indium oxide (thickness 40 nm) was deposited by a reactive DC magnetron sputtering method to form a transparent conductive film. Furthermore, a metal underlayer made of copper was deposited to a thickness of 2 nm by a DC magnetron sputtering method to form a laminated body. Example 21 except that the UV-curable transparent acrylic resin was changed to [Cellulose resin and vegetable oil-modified alkyd resin (1: 1)] and dried after coating (80 ° C. × 5 minutes).
The obtained laminate was treated in the same manner as in 1. to produce a transparent heater having a resistance of 5Ω between both electrodes provided with a nickel metal electrode. Similarly, a temperature rise test was performed, and the surface temperature rose to + 2 ° C. in 1 minute at a voltage of 13V. That is, the temperature rise was 22 ° C. Example 23 Indium oxide (thickness 40 nm) / silicon nitride (thickness 8 nm) / silver (thickness 12 nm) / silicon nitride (thickness 10 nm) on a polyethylene terephthalate (PET) film having a visible light transmittance of 89% and a thickness of 100 μm. ) / Indium oxide (thickness 40 nm) was deposited by a reactive DC magnetron sputtering method to form a transparent conductive film. Furthermore, a metal underlayer made of copper is formed to a thickness of 2 nm by DC magnetron sputtering.
To form a laminated body. The obtained laminated body was treated in the same manner as in Example 21 to prepare a transparent heater having a resistance of 5Ω between both electrodes provided with nickel metal electrodes. Similarly, a temperature rise test is performed, and at a voltage of 13 V, +2 is obtained for 1 minute.
The surface temperature rose to ℃. That is, the temperature rise is 2
It was 2 ° C.

Example 24 A 100 μm thick polyethylene terephthalate (PET) film having a visible light transmittance of 89% was coated with a thermosetting acrylic silicone in a thickness of 10 μm and cured to obtain a transparent substrate film. On this transparent substrate film, silicon hydronitride (thickness 30 nm) / silver (thickness 12 nm) / silicon hydronitride (thickness 10 nm) / indium oxide (thickness 40 n)
The laminated film of m) was deposited by a reactive DC magnetron sputtering method to form a transparent conductive film. Furthermore, a metal underlayer made of copper was deposited to a thickness of 2 nm by a DC magnetron sputtering method to form a laminated body. The laminated body thus obtained was treated in the same manner as in Example 21, and the resistance between both electrodes provided with nickel metal electrodes was 5Ω.
A transparent heater was prepared. Similarly, a temperature rise test was performed, and the surface temperature rose to + 2 ° C. in 1 minute at a voltage of 13V. That is, the temperature rise was 22 ° C.

Example 25 Indium oxide (thickness 60 nm) / silicon nitride / indium nitride [silicon: indium = 1: 1 (thickness 10 nm) on a polyethylene terephthalate (PET) film having a visible light transmittance of 89% and a thickness of 100 μm. ] / Silver (thickness 12 nm) / silicon nitride / indium nitride [silicon: indium = 1: 1 (thickness 10 nm)] / acid / indium oxide (thickness 60 nm) by a reactive DC magnetron sputtering method , And a transparent conductive film was formed. Furthermore, a metal underlayer made of copper was deposited to a thickness of 2 nm by a DC magnetron sputtering method to form a laminated body. The obtained laminated body was treated in the same manner as in Example 21 to prepare a transparent heater having a resistance of 5Ω between both electrodes provided with nickel metal electrodes. Similarly, a temperature rise test is performed, and at a voltage of 13V, + 2 ° C for 1 minute
Up to the surface temperature. That is, the temperature rise is 22
It was ℃.

Example 26 Indium oxide (thickness 70 nm) / silicon nitride (thickness 10 nm) / indium (thickness 0.5 nm) / silver on a polyethylene terephthalate (PET) film having a visible light transmittance of 89% and a thickness of 100 μm. (Thickness 12 nm) / silicon nitride (thickness 50 nm) / indium nitride (thickness 5 n)
The laminated film of m) was deposited by a reactive DC magnetron sputtering method to form a transparent conductive film. Furthermore, a metal underlayer made of copper was deposited to a thickness of 2 nm by a DC magnetron sputtering method to form a laminated body. The laminated body thus obtained was treated in the same manner as in Example 21, and the resistance between both electrodes provided with nickel metal electrodes was 5Ω.
A transparent heater was prepared. Similarly, a temperature rise test was performed, and the surface temperature rose to + 2 ° C. in 1 minute at a voltage of 13V. That is, the temperature rise was 22 ° C.

Comparative Example 1 A transparent conductive film having the same size and structure as in Example 1 was used as a transparent heater substrate, and a conductive coating material (silver paste) was applied to both ends of the transparent heater film so as to have a width of 4 mm. It was used as the electrode of the heater. When a voltage of 13 V was applied to this and a temperature rise test was performed, abnormal heat was generated between the transparent conductive film of the transparent sheet heater and the electrode portion (conductive paint), causing burns,
The transparent conductive film was broken.

Comparative Example 2 Indium oxide (3) was formed on one surface of the same PET as in Example 1 by the high frequency ion plating apparatus used in Example 2.
0 nm) / silver (10 nm) / indium oxide (30 n
m) was formed. Further, a metal underlayer made of copper was formed to a thickness of 2 nm by the same method. PH this
When the laminate was soaked in the acid aqueous solution of No. 2, pretreated, washed with water and dried, the surface resistance of the laminate was as high as 500 Ω / □, and electroplating could not be performed.

Comparative Example 3 A nickel film was formed in the same manner as in Example 1 using a transparent conductive film having the same size and structure as in Example 1 as a transparent planar heater substrate without forming a metal underlayer. The inter-electrode resistance of the formed panel heater was 10Ω. The nickel film formed by electrolytic plating had uneven plating and had many pinholes, and was easily peeled off from the transparent conductive film.

[0078]

As is clear from the above examples and comparative examples, the present invention makes it possible to improve the manufacturing process and manufacture a highly reliable transparent flat heater.

[Brief description of drawings]

FIG. 1 is a sectional view of a structure showing a comparative example 1.

FIG. 2 is a plan view of the configuration of the present invention.

FIG. 3 is a sectional view of a structure showing a preferred example of the present invention.

FIG. 4 is a perspective view of a plan view of the configuration of the present invention.

FIG. 5 is a sectional view of a structure showing an example of a transparent conductive film of the present invention.

FIG. 6 is a sectional view of a structure showing a preferred example of the present invention.

FIG. 7 is a sectional view of a structure showing a preferred example of the present invention.

FIG. 8 is a plan view of a configuration showing a preferred example of the present invention.

FIG. 9 is a perspective view of a configuration showing a preferred example of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent planar heater 2 Transparent substrate 3 Transparent conductive film 3a Transparent thin film 3b Metal layer 4 Electrode base layer 5 Metal electrode 5a Connection part 6 1st transparent protective layer 7 2nd transparent protective layer 7a Adhesive layer 7b Transparent plastic film 8 Adhesive layer 9 Separator 11 Metal fitting 12 Eyelet 13 Intermediate layer 51 Transparent substrate 52 Transparent conductive film 53 Conductive paint 54 Transparent protective layer

Claims (27)

[Claims] 1. A transparent planar heater comprising a pair of metal electrodes for energizing the transparent conductive film, wherein the transparent conductive film provided on the transparent substrate is used as a heat generating surface. At least each of the transparent thin film layer having a substantially transparent electrode underlayer made of a provided metal, the transparent conductive film being made of a nitride and / or a carbide, and the substantially transparent metal layer. A transparent planar heater in which the metal electrodes are laminated one by one, and the metal electrodes are formed on the electrode underlayer. 2. The transparent planar heater according to claim 1, further comprising a first transparent resin protective layer that covers the electrode underlayer on a portion where the metal electrode is not formed. 3. The transparent thin film layer is aluminum nitride,
The transparent planar heater according to claim 1, which is a high refractive index transparent thin film made of at least one of indium nitride, gallium nitride, silicon nitride, tin nitride, boron nitride, chromium nitride, silicon carbide, amorphous carbon, and diamond-like carbon. . 4. The transparent sheet heater according to claim 1, wherein the material forming the transparent thin film layer is partially oxidized. 5. The transparent planar heater according to claim 1, wherein the material forming the transparent thin film layer is partially hydrogenated. 6. The electrode underlayer is at least one of copper, nickel, chromium, palladium, lead, platinum, gold and silver.
The transparent planar heater according to claim 1, which is made of a metal or alloy containing a seed. 7. The metal electrode is copper, nickel, chromium,
The transparent planar heater according to claim 1, wherein the transparent planar heater is a single layer body or a laminated body made of a metal or an alloy containing at least one of gold, tin, lead, silver and solder. 8. The electrode underlayer has a thickness of 0.5 nm to 20 n.
The transparent planar heater according to claim 1, wherein a metal thin film having a thickness of m is provided on the transparent conductive film by a dry process. 9. The transparent planar heater according to claim 1, wherein the metal layer is silver or a thin film layer containing silver as a main component. 10. The transparent surface according to claim 1, wherein the metal layer is a thin film layer containing silver or a silver-based main component and a thin film layer containing a metal other than silver as a main component is laminated on at least one surface of the metal layer. heater. 11. The transparent planar heater according to claim 1, wherein a transparent intermediate layer is provided between the transparent thin film layer and the electrode underlayer. 12. The transparent planar heater according to claim 1, wherein a transparent intermediate layer is provided between the transparent substrate and the transparent thin film layer. 13. The transparent sheet heater according to claim 2, further comprising a second transparent resin protective layer that covers the metal electrode and the first transparent resin protective layer. 14. The transparent sheet heater according to claim 1, wherein an adhesive layer is provided on a part or all of the first transparent resin protective layer and / or the electrode. 15. The transparent sheet heater according to claim 13, wherein an adhesive layer is provided on the second transparent resin protective layer. 16. The transparent sheet heater according to claim 1, wherein the transparent substrate is provided with an adhesive layer. 17. The transparent planar heater according to claim 1, wherein the metal electrode is provided with a metal fitting for external connection. 18. A method for producing a transparent planar heater, comprising a pair of metal electrodes for energizing the transparent conductive film, wherein a transparent conductive film provided on a transparent substrate is used as a heat generating surface, wherein a nitride and Alternatively, a first step of forming a transparent conductive film in which at least one transparent thin film layer made of a carbide and at least one substantially transparent metal layer are laminated on the transparent substrate by dry process, A second step of depositing a metal or an alloy on the film by a dry process to form a substantially translucent electrode underlayer, and a first transparent resin protection at a place other than the site where the metal electrode is formed. A method of manufacturing a transparent planar heater, comprising a third step of providing a layer and a fourth step of forming the metal electrode on the electrode underlayer by a wet plating method. 19. The metal thin film layer has a thickness of 0.5 nm to
The method for producing a transparent planar heater according to claim 18, which has a thickness of 20 nm. 20. The method for producing a transparent planar heater according to claim 18, wherein the wet plating method is an electroplating method. 21. The method for producing a transparent planar heater according to claim 18, wherein the wet plating method is an electroless plating method. 22. The method for manufacturing a transparent planar heater according to claim 18, wherein the metal electrode is formed by combining an electroless plating method and an electroplating method in the fourth step. 23. The step of forming the third transparent resin protective layer comprises ultraviolet curable resist ink, electron beam curable resist ink, thermosetting resist ink, ultraviolet curable resin, electron beam curable resin, thermosetting resin. The method for producing a transparent planar heater according to claim 18, which is carried out by applying and curing any one of the resins, or a combination or mixture thereof. 24. The method for producing a transparent planar heater according to claim 18, wherein the third transparent resin protective layer forming step is performed by laminating a transparent film having an adhesive layer. 25. The method for producing a transparent planar heater according to claim 18, wherein the third transparent resin protective layer forming step is performed by laminating and curing a dry film. 26. The method for producing a transparent planar heater according to claim 18, wherein the third transparent resin protective layer forming step is performed by coating and laminating a coating material. 27. A transparent planar heater using a transparent conductive film provided on a transparent substrate as a heat generating surface and comprising a pair of metal electrodes for energizing the transparent conductive film, wherein at least the transparent conductive film is provided. Having a transparent intermediate layer on one side,
The metal layer, which is an element of the transparent conductive film, is formed by laminating a metal layer composed of a metal other than silver on at least one surface of the silver or a metal layer containing silver as a main component, and the metal electrode is the transparent electrode. Transparent sheet heater formed on the transparent conductive film including a transparent intermediate layer.