JPH07335379A - Transparent surface heater and its manufacture - Google Patents

Abstract

PURPOSE:To improve light transmittance, and realize low cost and high productivity when the oxide of a metal compatible with a plating metal is laminated on the transparent conductive film of a heating surface having a nitride laminated on a metal layer, and an electrode is formed by electroplating. CONSTITUTION:A metal nitride layer 3a is laminated on one surface or both surfaces of a light permeable metal layer 3b, and a metal oxide layer 3c is further laminated on the outside of the nitride layer 3a to form a transparent conductive film 3 on a transparent base 2. When a pair of metal electrodes 5 are formed on both ends of the film 3 by electroplating, since the oxide layer 3c is dissolved in the plating solution, and the metal compatible with the plating metal is contained, the plating metal is closely adhered to the film 3. An electrode base layer as plating solution is dispensed with, and beam transmittance is enhanced. The electrode 5 is formed after a first transparent resin protecting layer 6 is formed in the part having no electrode 5 formed on the film 3, whereby the position of the electrode 5 is determined at plating, the film 3 is protected, and the working efficiency is also enhanced.

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 a window portion, and more particularly to 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 conductive film are The contact resistance between them tends to be high.

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 sheet heater, resulting in non-uniform heat generation, and the entire transparent sheet heater rises uniformly. There are problems such as not heating, and current concentration in the vicinity of the electrode contacts, resulting in abnormal heat generation in the vicinity of the electrodes of the transparent sheet heater, leading to disconnection.

In the case of using the electrode as disclosed in the above-mentioned Japanese Patent 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. It was found that there are problems such as easy peeling of both, and that the manufacturing process for forming the electrode 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. And proposed that a transparent sheet heater can be provided. The present invention is an effective invention for providing a transparent sheet heater, but generally, it requires skill in the process of forming the metal electrode of the transparent sheet heater by a wet process. Also, Japanese Patent Application No. 6-300630
In the above, after forming a substantially transparent electrode underlayer on the transparent conductive film in which a nitride is laminated on the metal layer, a metal electrode is formed on the electrode underlayer by a wet process to form a transparent planar heater. I suggested that I could provide it. The invention is also an effective invention to provide a transparent sheet heater,
In both cases, the plating nucleus electrode underlayer and the conductive layer had metal layers, and there was room for improvement in terms of light transmittance and cost.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to have an electrode that does not use a conductive paint, to improve the method for forming an electrode on a transparent conductive film, and to make it transparent even in electroplating when forming a metal electrode. It is an object of the present invention to provide a transparent planar heater that can be manufactured with low cost and high productivity by eliminating damage to the conductive film, reducing the number of layers on the heat generating surface, and a transparent laminate used for the same. Another object of the present invention is to provide a method for manufacturing a transparent planar heater in which an electrode is formed without using a conductive paint, the light transmittance is high, the cost is low and the productivity is improved.

[0008]

In order to solve the above-mentioned problems, the inventors of the present invention have conducted extensive studies and as a result, as a result of using a transparent conductive film provided on a transparent substrate as a heat generating surface and conducting electricity to the transparent conductive film. In a transparent planar heater provided with a pair of electrodes for performing, a transparent conductive film in which a nitride is laminated on the metal layer has at least some solubility in a plating solution and at least some compatibility with a plating metal. A stack of metal oxides containing metals, which has at least some solubility in commonly used acidic plating solutions and is a metal oxide containing metals that are compatible with the plating metal, such as indium oxide, tin oxide, and oxide. There is a monolayer or laminate containing at least one of indium tin (ITO), aluminum oxide, germanium oxide, zinc oxide, or zirconium oxide. Is obtained by laminating seen above, the electrode is composed of metal, and by combining the method and electroplating method selected from among dry process, such problems found that can be achieved, thereby completing the present invention.

That is, in a transparent planar heater using a transparent conductive film provided on a transparent substrate as a heat generating surface and provided with a pair of electrodes for energizing the transparent conductive film,
From the transparent substrate side, the transparent conductive film is a metal layer / nitride layer / oxide layer, oxide layer / nitride layer / metal layer / nitride layer, nitride layer / metal layer / nitride layer / oxide layer, Alternatively, a transparent planar heater comprising any one of laminated bodies in which oxide layer / nitride layer / metal layer / nitride layer / oxide layer are laminated in this order, and a metal electrode is formed on the transparent conductive film. Or a transparent planar heater having a first transparent resin protective layer that covers the transparent conductive film in a portion where the metal electrode is not formed, and the nitride layer is silicon nitride or aluminum nitride. , Indium nitride, gallium nitride, silicon nitride, tin nitride, boron nitride, chromium nitride, silicon nitride carbide, silicon oxynitride, tin oxynitride, boron oxynitride, aluminum oxynitride, indium oxynitride, gallium oxynitride,
Chromium oxynitride, silicon oxynitride carbide, aluminum hydronitride, indium hydronitride, gallium hydronitride, silicon hydronitride, tin hydronitride, boron hydronitride,
A transparent planar heater which is a monolayer or a laminated body containing at least one of chromium hydronitride and silicon hydronitride, wherein the oxide layer is indium oxide, tin oxide, or indium tin oxide. (I.
T. O. ), Aluminum oxide, germanium oxide, zinc oxide, or zirconium oxide at least 1
It is a single layer body or a layered body containing a seed, and is a transparent planar heater in which the thickness of at least one layer of the oxide layer is 50 nm to 600 nm, and the metal layer is silver, or 50% by weight of silver. A transparent planar heater which is a monolayer or a laminate containing at least one of the alloys or mixtures containing the above, and the metal electrode is made of copper, nickel, chromium, gold, tin, lead, silver, or solder. It is a transparent planar heater which is a single layer or a laminated body made of a metal or an alloy containing at least one of the above, and the transparent conductive film provided on the transparent substrate is used as a heat generating surface. A method of manufacturing a transparent planar heater comprising a pair of metal electrodes for energizing a film, wherein the transparent conductive film is a metal layer / nitride layer / oxide layer, an oxide layer / nitride from a transparent substrate side. Layer / Gold Layer / nitride layer, a nitride layer / metal layer / nitride layer / oxide layer or an oxide layer / nitride layer /
A first step of forming the transparent conductive film on the transparent substrate by dry process, which comprises any one of laminated bodies in which a metal layer / nitride layer / oxide layer is laminated in this order; A transparent planar heater having a second step of providing the first transparent resin protective layer in a place other than the portion to be formed and a third step of forming the metal electrode on the transparent conductive film by an electroplating method. Is a manufacturing method.

In the present invention, in particular, when the metal electrode is formed by the electroplating method, if the transparent conductive film is treated with an acidic solution and then electroplated, the metal electrode as the plated film and the transparent conductive film are brought into close contact with each other. It was found to improve. The pH of the acidic solution is usually 5 or less, preferably 3 or less, more preferably 1 or less. In some cases, when forming the metal electrode by the electroplating method, it is not necessary to perform the acidic solution treatment before the plating. Further, when a metal electrode is formed by electroplating, by providing a metal oxide containing a metal that is slightly soluble in the plating solution and is slightly compatible with the plating metal in the conductive film, the plating metal becomes a conductive film. It has been found that it is possible to install a metal electrode that adheres well.

Even if the metal oxide is soluble in the plating solution, the metal electrode can be similarly set by increasing the thickness of the film. It is also effective to shorten the plating time. This eliminates the need for an electrode underlayer consisting of a metal film, which was necessary as a nucleus for plating,
A conductive film having a high light transmittance can be used for the heating surface.

In this way, the metal electrode which is bonded to the transparent conductive film with good adhesion is provided, and at the same time, the first transparent protective layer is used to provide the effect of determining the position of the electrode and also serving as the protective layer of the transparent conductive film. The present invention provides a method for manufacturing a transparent sheet heater, which is significantly improved in work efficiency and reliability.

A preferred embodiment of the present invention will be described below with reference to the drawings. First, referring to the attached drawings, FIG. 1 is a sectional view of a configuration showing a comparative example,
2 is a plan view of the structure of the present invention, FIGS. 3 and 4 are sectional views of the structure showing a preferred example of the present invention, FIG. 5 is a perspective view of the structure of the present invention, and FIGS. FIG. 7 is a sectional view of a structure showing a preferred example of another transparent conductive film of the present invention. FIG. 8, FIG. 9, FIG. 10 and FIG. 11 are cross-sectional views of a structure showing another preferable example. The transparent planar heater 1 shown in FIG. 2, FIG. 3, FIG. 4, FIG. 5, FIG. 8, FIG. 9, FIG. And a transparent substrate 2 made of plastic, etc.
The transparent conductive film 3 sequentially stacked on the main surface of the heater 1 and the heater 1 on the transparent conductive film 4 for energizing the transparent conductive film 3.
A pair of electrodes 5 provided on both ends of the electrode, a first transparent resin protective layer 6 covering a portion of the surface of the electrode underlayer 4 where the electrode 5 is not formed, a metal electrode 5 and a first transparent resin protective layer. 6 and a second transparent resin protective layer 7 that covers the surface 6.

The transparent conductive film 3 has a structure in which at least one each of a substantially transparent metal layer and a transparent thin film layer made of nitride and / or carbide is laminated. In the example shown in FIG. 6, the transparent conductive film 3 includes the oxide layer 3c / nitride layer 3a /
It has a four-layer structure of metal layer 3b / nitride layer 3a, and in the example shown in FIG. 7, the transparent conductive film 3 has four layers of nitride layer 3a / metal layer 3b / nitride layer 3a / oxide layer 3c. It is composed. Further, the metal electrode 5 has an elongated shape, and one end thereof serves as the connecting portion 5a. The connecting 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 not provided on the connecting portion 5a. As shown in FIGS. 2 and 5, the connecting portion 5 a projects in the in-plane direction from the main body portion of the heater 1. The electrode 5 is formed on the surface of the transparent conductive film 3 by an electroplating method after forming the first transparent resin protective layer 6 on the surface other than the region where the electrode 5 is formed. It

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, 60 made of resin or film. % Or more. By configuring the transparent planar heater in this way, the electrode made of metal can be formed substantially directly on the transparent conductive film without damaging the transparent conductive film. The electrical connection between the two is improved, the contact resistance between the two is reduced, the performance as a transparent planar heater is improved, and the reliability is also significantly improved. The first transparent resin protective layer determines the position where the electrode is to be formed and also protects the transparent conductive film, so that the work efficiency at the time of manufacturing the transparent planar heater is significantly improved.

Further, it is possible to provide an adhesive layer for attaching the transparent sheet heater to another support. FIG. 8, FIG. 9, FIG. 10 and FIG. 11 show the structure having the adhesive layer 8. The adhesive layer 8 is the transparent substrate 2 in FIGS.
A separator (release paper) 9 is provided on the surface of the adhesive layer 8 in order to prevent the adhesive layer 8 from adhering to other members before use or on the second transparent resin protective layer 7. It is provided.

In FIG. 10, 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. 12 and 13 show a configuration in which a metal fitting 11 for attaching an electric wire for applying a voltage to the metal electrode 5 by soldering or the like is provided at the connection portion 5a of the metal electrode 5 with an eyelet.

In the transparent planar heater of the present invention, the transparent thin film layer is generally formed by a dry process, and the metal electrode is generally formed by electroplating. In the present invention, the dry process is a method of forming a film in a non-solution, which includes a vacuum deposition method, an ion plating method,
Physical vapor deposition methods such as sputtering method and molecular beam epitaxy method (MBE), CVD method, MOCVD method, plasma CV
A chemical deposition method such as the D method may be used. For the electroplating, a known method which has been conventionally used can be used.

In the present invention, the transparent substrate is a substrate having a light transmittance of 60% or more, preferably 70% or more, more preferably 80% or more in the visible light region having a wavelength of 400 nm to 800 nm. , A transparent plastic film can be used. From the viewpoints of thinness, flexibility, impact resistance, continuous productivity, etc., a plastic film is preferably used as the transparent substrate. To exemplify a preferable plastic as a material of a film constituting a transparent substrate, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamide, polyether, polysulfone, polyether sulfone (PES), polycarbonate, Examples thereof include those composed of homopolymers or copolymers of polyarylate, polyetherimide, polyetheretherketone (PEEK), 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 is a cured product of the crosslinkable resin or a cured product of the crosslinkable resin provided on the anchor agent. As the crosslinkable resin cured product, acrylic epoxy resin, acrylic silicone resin, epoxy resin, acrylic resin, phenoxyether type crosslinkable resin, melamine resin, phenol resin, urethane resin, or UV curable acrylates are preferably used. Further, 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, or a (meth) acrylic emulsion is preferably used. Needless to say, any material can be used as long as it improves the adhesion between the transparent substrate and the transparent conductive film. The thickness of the undercoat is usually 1 to 100 μm, 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 a nitride or oxide and at least one substantially transparent metal layer. Therefore, preferably, the transparent conductive film is a metal layer / nitride layer / oxide layer, an oxide layer / nitride layer / metal layer / nitride layer, or a nitride layer / metal layer / nitride from the transparent substrate side. It is any laminated body laminated | stacked in order of a layer / oxide layer. Further, it is also possible to alternately laminate a plurality of layers of a nitride layer and / or an oxide layer and / or a metal layer.

In the present invention, the metal layer is made of silver or silver.
At least one of alloys or mixtures containing more than wt%
It is a monolayer or a laminate containing the seed. Further, as an alloy of silver or a metal contained in the mixture, gold, copper, palladium, platinum, tungsten, titanium, cobalt, chromium,
Metals such as nickel, tin, indium, IT (indium tin) and zinc are preferable. 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 preferably 1 nm to 100 nm. It is preferably 5 nm to 50 nm, more preferably 10 nm to 30 nm.

In the present invention, the material forming the nitride layer is preferably a nitride such as silicon nitride, aluminum nitride, indium nitride, gallium nitride, tin nitride, boron nitride, chromium nitride, silicon nitride carbide or silicon oxynitride. ,
Oxynitrides such as tin oxynitride, boron oxynitride, aluminum oxynitride, indium oxynitride, gallium oxynitride, chromium oxynitride, silicon oxynitride carbide, etc., or aluminum hydronitride, indium hydronitride, gallium hydrogennitride, hydrogen Examples thereof include hydronitrides such as silicon nitride, tin hydronitride, boron hydronitride, chromium hydronitride, and silicon nitride carbonitride. Usually, a high refractive index transparent thin film made of a nitride and / or an oxynitride and / or a hydrogenated nitride having a refractive index of 1.6 or more, preferably a refractive index of 1.8 or more, more preferably 2.0 or more is preferable. Further, in order to have durability against a plating solution, pH is 5 or less, preferably p
H3 or less, more preferably, it is unnecessary or does not significantly dissolve even in an acidic solution having a pH of 1 or less, and preferably comprises a nitride and / or an oxynitride and / or a hydrogenitride and / or a mixture thereof having an optical band gap of 3 eV or more. Anything is acceptable as long as it is. The light transmittance is usually 60% or more, preferably 70% or more, more preferably 80% or more.

The nitrogen content in the components of these oxynitrides excluding the metal is 30 atom% or more, and more preferably 50 atom% or more.

The nitrogen content in the components other than the metal of these hydronitrides is 50 atomic%, more preferably 80 atomic%.
That is all. The thickness of these nitride layers is typically 0.3 nm
Is 100 nm, preferably 1 nm to 100 nm, more preferably 5 nm to 50 nm, and still more preferably 10 nm to 30 nm.

In the present invention, the material forming the oxide layer is preferably indium oxide, tin oxide, or indium tin oxide (ITO), aluminum oxide, germanium oxide, zinc oxide, or zirconium oxide. Etc. are illustrated. Here, the metal oxide is not limited to the above oxides as long as it is a metal oxide containing a metal that is more or less soluble in the plating solution and is more or less compatible with the plating metal. Since an acidic solution is usually used as the plating solution, any metal oxide other than the above oxides may be used as long as it is a metal oxide that dissolves to some extent at pH 5 or less, preferably pH 4 or less, and which dissolves metal ions. The thickness of at least one of these oxide layers is usually 50 nm to 600 nm, preferably 60 nm to 10 nm.
It is 0 nm. If the thickness is less than 50 nm, the entire oxide layer is dissolved or becomes too thin during plating, and the adhesion of the metal electrode to the conductive film is weakened. If it exceeds 600 nm, the transparency becomes poor.

As a method of forming the metal layer, the nitride layer and the oxide layer of the present invention on the transparent substrate, a known method such as a physical vapor deposition method as well as a spray method and a coating method can be used. Here, the physical vapor deposition method is a method of forming a thin film of a metal or the like under reduced pressure or under vacuum, and 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. Examples of the method include a vacuum method, a molecular beam epitaxy method (MBE), a CVD method, a MOCVD method, and a plasma CVD method.

As the first transparent resin protective layer used in the present invention, the light transmittance at a wavelength of 550 nm is usually 60%.
Or more, preferably 70% or more, more preferably 80%
Any protective layer may be used as long as it is the above and can withstand the plating process. Such a first
As the transparent resin protective layer of, for example, a known UV curable resist ink was applied and cured, an electron beam curable resist ink was applied and cured, and a thermosetting resist ink was applied and cured. Examples thereof include those obtained by applying and curing a UV-curable resin, those obtained by applying and curing an electron beam curing resin, those obtained by applying and curing a thermosetting resin, and 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.

Examples of the UV curable resin include epoxy acrylate, urethane acrylate, polyester 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. Examples of electron beam curable resins include epoxy acrylate, urethane acrylate, popolyester acrylate, polyfunctional acrylate, polyether acrylate, silicon acrylate, polybutadiene acrylate, unsaturated polyester / styrene,
Polyene / thiol, polystyryl methacrylate, U
V-curing 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. As the paint, nitrocellulose lacquer, acrylic lacquer, acetylcellulose lacquer and other fibrin derivative paints, alkyd resin paints, aminoalkyd resin paints,
Guanamine resin paints, vinyl chloride resin paints, butyral resin paints, styrene-butadiene resin paints, thermosetting acrylic resin paints, epoxy resin paints, unsaturated polyester paints, polyurethane resin paints, silicon resin paints 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.
As the metal electrode in the present invention, any metal can be used as long as it can be deposited by plating, but from the viewpoint of electrical characteristics and durability, copper, silver, gold,
It is preferably composed of a metal containing at least one of nickel, chromium, tin, lead and solder, or a single layer or a laminate of an alloy or mixture of these metals. 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. This electrode is generally formed by electroplating, as described above.

Further, for mechanical protection of the metal electrode and the first transparent resin protective layer, and chemical protection such as prevention of corrosion due to moisture, etc., the first electrode and the first transparent resin protective layer are covered so as to cover the electrodes 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 adhesive or adhesive can be used. As a preferable adhesive, an acrylic pressure sensitive adhesive or a cyanoacrylate 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 sheet 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 a 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 then electric wires or the like are soldered or the like to be used, the metal fittings may be anywhere on the metal electrode, but preferably. It is provided in 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 with eyelets or the like. In addition, it may be electrically connected to the metal electrode. Further, it may be provided on both sides of the transparent flat heater on the metal electrode and on the opposite transparent substrate, to electrically connect with the metal electrode and to stabilize the metal fitting. 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.

[0035]

【Example】

Example 1 Indium oxide (thickness 80 nm) / silicon nitride (thickness 30 nm) / silver (thickness 12 nm) / silicon nitride (thickness) on a polyethylene terephthalate (PET) film having a visible light transmittance of 89% and a thickness of 100 μm. 30 nm) by a DC magnetron sputtering method
Deposited to form a transparent conductive film. The visible light transmittance of the obtained transparent conductive film was 80%, and the surface resistance was 7Ω / □. A (UV) UV-curable transparent polyol acrylate was applied and cured on the laminated film except 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 1, electroplating was further performed in a nickel sulfamate plating bath having a pH of 4 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 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 7 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 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 2 Polyethylene terephthalate having a visible light transmittance of 89% and a thickness of 100 μm (on a PET film, silicon nitride (thickness 30 nm) / silver (thickness 10 nm) / silicon nitride (thickness 3
A laminated film of 0 nm) / indium oxide (thickness: 100 nm) was deposited by a DC magnetron sputtering method to form a transparent conductive film. A (UV) ultraviolet-curable transparent urethane acrylate was applied and cured on the obtained laminated film except for the electrode formation region to form a first transparent resin protective layer. Then, the laminate was immersed in an acid aqueous solution of pH 2 and further electroplated in an alkanol sulfonic acid bath of pH 3.5 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), and the distance between the electrodes was 90 mm. Further, a PET film having a thickness of 50 μm and a pressure-sensitive adhesive having a thickness of 20 μm was laminated, leaving a connection portion of the metal electrode, to obtain a second transparent protective layer. Through the above steps, the transparent sheet heater having the structure shown in FIGS. 2 to 7 was completed. The resistance between both electrodes of the formed transparent planar heater was 7Ω. 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 + 1 ° C in 1 minute. That is, the temperature rise is 21 ° C
Met.

Example 3 Indium oxide (thickness: 8%) 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.
0 nm) / indium oxynitride (30 nm) / silver (13 n
m) / silicon oxynitride (30 nm) laminated film was deposited to obtain a transparent conductive film. On the obtained laminated film, a (UV) ultraviolet-curable epoxy acrylate was applied and cured except for the electrode formation region to form a first transparent protective layer. Then, after soaking in an acid aqueous solution of pH 1, then p
Electroplating was performed in a nickel sulfamate plating bath of H4.5 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 m
m (width) and the distance between the electrodes was 90 mm. Further, a 50 μm-thick PET film with a pressure-sensitive adhesive having a thickness of 20 μm was laminated to leave a connection portion of the electrode as a second transparent protective layer. Then, an adhesive layer with a separator (release sheet) was provided on the transparent substrate side to complete the transparent sheet heater having the configuration 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 left to stand.
When a voltage of 13 V was applied, the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C.

Example 4 Indium oxide (thickness 100 nm) / silicon nitride (40 nm) / silver + 8% by weight on one side of 100 μm thick polyethersulfone (PES) with visible light transmittance of 88% by high frequency ion plating method. A laminated film of a metal layer (11 nm) made of gold / silicon carbonitride (30 nm) was deposited to obtain a transparent conductive film. A (UV) ultraviolet curable resist ink was applied and cured on the obtained laminated film 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 left to stand. Then, when a power of 12V was applied, the surface was raised to + 1 ° C in 1 minute. The temperature has risen. That is, the temperature rise was 21 ° C.

Example 5 Zinc oxide (thickness 90 nm) / silicon nitride (thickness 12 nm) / silver + 10% by weight platinum (thickness 12 nm) / silicon nitride on a PET film having a visible light transmittance of 89% and a thickness of 100 μm. A (20 nm thick) laminated film was deposited by a DC magnetron sputtering method to obtain a transparent conductive film. A UV-curable acrylic resin (mixture of polyol acrylate (12 parts), acrylate (14 parts) and urethane acrylate (8 parts)) is applied and cured on the obtained laminated film except for the electrode formation region. Then, the first transparent protective layer was formed. Then, this laminate was immersed in an acid aqueous solution having a pH of 2, 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 UV-curable resin is applied and cured on the metal electrode and the first transparent resin protective layer, leaving the electrode connecting portion, to form a second transparent resin protective layer, and the transparent planar heater is completed. It was 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 a power of 13V was applied, and the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C.

Example 6 Silver (thickness 12 nm) / silicon nitride (thickness 30 nm) on a PET film having a visible light transmittance of 90% and a thickness of 100 μm.
/ A layered film of indium oxide (thickness 90 nm)
A transparent conductive film was formed by depositing by the C magnetron sputtering method. On the obtained laminated film, (UV) UV-curable polyester acrylate 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, 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. This transparent sheet heater was placed in a constant temperature bath at -20 ° C and left to stand, and then 12
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 7 Indium oxide (thickness: 60 nm) on a polycarbonate film (PC) having a visible light transmittance of 90% and a thickness of 100 μm.
/ Silicon Nitride (thickness 30 nm) / Silver (thickness 12 nm) /
A laminated film made of silicon nitride (thickness 30 nm) was deposited by a DC magnetron sputtering method to obtain a transparent conductive film. On the obtained laminated film, (UV) UV-curable polyester acrylate 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 then p
Electroplating was performed in a H3.5 nickel sulfamate plating bath 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 m
m (width) and the distance between the electrodes was 90 mm. Further, a 25 μm-thick PET film with a pressure-sensitive adhesive having a thickness of 20 μm was laminated to leave a connection portion of the electrode as a second transparent resin protective layer, and a 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 a voltage of 13V was applied to it.
The surface temperature rose to + 2 ° C in minutes. That is, the temperature rise was 22 ° C.

Example 8 Indium oxide (thickness 80 nm) / silicon nitride (thickness 30 nm) / silver (thickness 12 nm) / silicon nitride (thickness 30 nm) was formed on a PET film having a visible light transmittance of 89% and a thickness of 100 μm. Was laminated by a high frequency ion pooling method to form a transparent conductive film. On the obtained laminated film, (UV) UV-curable transparent polyol acrylate was applied and cured except for the electrode formation region to form a first transparent resin protective layer. afterwards,
The laminate was dipped in an acid aqueous solution having a pH of 2, and further, copper electroplating was performed in a copper sulfate plating bath to form a copper 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. 20 μm, leaving the electrode connection
A 25 μm-thick PET film with an adhesive having a thickness was laminated to form a second transparent resin protective layer, and a transparent planar heater 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 9 Indium nitride (thickness: 30 nm) / silver (thickness: 1) was applied on a PET film having a visible light transmittance of 88% and a thickness of 100 μm.
A laminated film composed of 2 nm) / silicon nitride (thickness 30 nm) / indium oxide (thickness 90 nm) was deposited by a high frequency (rf) magnetron sputtering method to form a transparent transparent conductive film. The visible light transmittance of the obtained transparent transparent conductive film was 78%, and the surface resistance was 7Ω / □. After the mixture of the cellulosic resin and the vegetable oil-modified alkyd resin (1: 1) was applied on the obtained laminated film except the electrode formation region, the mixture was kept at 80 ° C. for 10 minutes,
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 2V was applied, the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C.

Example 10 Indium oxide (thickness 20 nm) / silicon nitride (thickness 20 nm) / silver (thickness 12 nm) / silicon nitride (on a 100 μm thick polyethylene terephthalate (PET) film with a visible light transmittance of 89%. A laminated film composed of (thickness 30 nm) / indium oxide (thickness 80 nm) was deposited by a DC magnetron sputtering method to form a transparent conductive film. On the obtained laminated film, a (UV) UV-curable transparent polyol acrylate was applied and cured 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 1, electroplating was further performed in a nickel sulfamate plating bath having a pH of 4 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 125m
m (length) x 4 mm (width), the distance between the electrodes is 90
It was mm. The resistance between both electrodes of the formed transparent planar heater was 5Ω. This transparent sheet heater is -20
When 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 +2 ℃ in 1 minute. That is, the temperature rise was 22 ° C.

Comparative Example 1 A transparent conductive film having the same size and the same 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 to form a transparent sheet. 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 and closed.

Comparative Example 2 On one side of PET similar to that used in Example 1, silicon nitride (thickness 3 was obtained by the high frequency ion plating apparatus used in Example 2).
0 nm) / silver (10 nm) / silicon nitride (thickness 30 n
m) was formed. After the first transparent resin protective layer was formed in the same manner as in Example 1, a nickel metal electrode was provided by electroplating, but the nickel metal electrode was easily peeled off.

[0047]

As is apparent from the above Examples and Comparative Examples, according to the present invention, it is possible to manufacture a transparent sheet heater having an improved manufacturing process, high reliability, and high light transmittance.

[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 showing an example of a preferable configuration of the present invention.

FIG. 4 is a sectional view showing an example of a preferable configuration of the present invention.

FIG. 5 is a perspective view of the configuration of the present invention.

FIG. 6 is a sectional view showing an example of the configuration of a transparent conductive film of the present invention.

FIG. 7 is a sectional view showing an example of the configuration of a transparent conductive film of the present invention.

FIG. 8 is a sectional view showing an example of a preferable configuration of the present invention.

FIG. 9 is a sectional view showing an example of a preferable configuration of the present invention.

FIG. 10 is a sectional view showing an example of a preferable configuration of the present invention.

FIG. 11 is a sectional view showing an example of a preferable configuration of the present invention.

FIG. 12 is a plan view showing an example of a preferable configuration of the present invention.

FIG. 13 is a perspective view showing an example of a preferable configuration of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent planar heater 2 Transparent substrate 3 Transparent conductive film 3a Nitride layer 3b Metal layer 3c Oxide layer 5 Metal electrode 5a Connection portion 6 First transparent protective layer 7 Second transparent protective layer 7a Adhesive layer 7b Transparent plastic film 8 Adhesive Layer 9 Separator 10 Intermediate Layer 11 Metal Fitting 12 Eyelet 51 Transparent Substrate 52 Transparent Conductive Film 53 Conductive Paint 54 Transparent Protective Layer

Claims (8)

[Claims] 1. A transparent planar heater using a transparent conductive film provided on a transparent substrate as a heat generating surface and comprising a pair of electrodes for energizing the transparent conductive film, wherein the transparent conductive film is a transparent substrate. From the side, metal layer / nitride layer / oxide layer,
Oxide layer / nitride layer / metal layer / nitride layer, nitride layer / metal layer / nitride layer / oxide layer, or oxide layer / nitride layer / metal layer / nitride layer / oxide layer A transparent sheet heater, which is formed by stacking any of the above layers and has a metal electrode formed on the transparent conductive film. 2. The transparent planar heater according to claim 1, further comprising a first transparent resin protective layer that covers the transparent conductive film in a portion where the metal electrode is not formed. 3. The nitride layer comprises silicon nitride, aluminum nitride, indium nitride, gallium nitride, silicon nitride,
Tin nitride, boron nitride, chromium nitride, silicon carbide nitride,
Silicon oxynitride, tin oxynitride, boron oxynitride, aluminum oxynitride, indium oxynitride, gallium oxynitride, chromium oxynitride, silicon oxynitride carbide, aluminum hydronitride,
A single layer or a laminate containing at least one of indium hydronitride, gallium hydrogennitride, silicon hydronitride, tin hydronitride, boron hydronitride, chromium hydronitride, or silicon hydronitride carbide. The transparent sheet heater according to claim 1. 4. A single layer in which the oxide layer contains at least one of indium oxide, tin oxide, or indium tin oxide (ITO), aluminum oxide, germanium oxide, zinc oxide, or zirconium oxide. The transparent planar heater according to claim 1, which is a body or a laminate. 5. The transparent sheet heater according to claim 4, wherein at least one layer of the oxide layer has a thickness of 50 nm to 600 nm. 6. The transparent planar heater according to claim 1, wherein the metal layer is a single layer body or a laminated body containing at least one kind of silver or an alloy or mixture containing 50% by weight or more of silver. 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, an alloy, or a mixture containing at least one of gold, tin, lead, silver, and solder. 8. A method for manufacturing a transparent sheet heater, comprising a pair of metal electrodes for energizing the transparent conductive film, wherein the transparent conductive film provided on a transparent substrate is used as a heat generating surface. From the transparent substrate side, the transparent conductive film is a metal layer / nitride layer / oxide layer, oxide layer / nitride layer / metal layer / nitride layer,
The transparent conductive film is made of any one of a laminated body of nitride layer / metal layer / nitride layer / oxide layer or oxide layer / nitride layer / metal layer / nitride layer / oxide layer. A first step of forming a film on the transparent substrate by dry probe, a second step of providing a first transparent resin protective layer at a place other than a site where the metal electrode is formed, and an electroplating method. And a third step of forming the metal electrode on the transparent conductive film.