JPH0963754A - Durable transparent plate heater and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide transparent plane heater having enhanced durability to contaminants, excellent environmental stability, high reliability and high beam permeability, and provide its manufacture. SOLUTION: A transparent and plane heater comprises a transparent substrate, a transparent conductive film laminated thereon, electrodes (5, 5') and a transparent protective layer laminated in an area where the electrodes are not formed. The cross section of the transparent conductive film is covered with transparent protective plastic material (7) or anticorrosive angent for anticorrosive treatment.

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 and a method for manufacturing the same. More specifically, a transparent sheet heater used for windows and the like, especially a liquid crystal display element,
The present invention relates to a transparent flat heater used for a refrigerating showcase, a freezing showcase, an automobile defroster, and the like, and a manufacturing method thereof.

[0002]

2. Description of the Related Art Conventionally, in freezing and refrigerating showcases, it is necessary to prevent dew condensation on the glass surface which constitutes the window thereof. 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 slow when used in cold regions, and the liquid crystal display element also has a transparent surface shape for temperature control. The need to have heaters has increased. 2. Description of the Related Art Conventionally, as a liquid crystal display element used under conditions such as a cold region, there is one in which a mesh-shaped heating resistor is arranged for heating, as disclosed in JP-A-58-126517. It was However, with this method, it is difficult to uniformly heat the entire liquid crystal element, and the heating resistor is made of an opaque metal, which is an obstacle to viewing the liquid crystal display.

A transparent heating element having a transparent conductive film formed on a transparent substrate is disclosed in, for example, US Pat. No. 4,952,783. FIG. 31 shows an example of the structure of such a heating element (transparent sheet heater). That is, the transparent conductive film 52 is formed on the entire surface of the transparent substrate 51, and the pair of electrodes 53 and 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, 53 'is provided on the entire surface. This electrode 53, 5
3'is formed by applying a conductive paint such as a silver paste on the transparent conductive film 52 by a screen printing method or the like and heat-treating it. To further improve the reliability of the electrode,
Japanese Patent Laid-Open No. 4-289685 discloses an electrode having a structure in which a metal foil is sandwiched between conductive paints.

The inventors of the present invention, as described in JP-A-6-283260, form a metal thin film layer having a substantially light-transmitting property on a transparent conductive film and then perform a wet process on the metal thin film layer. It has been found that a transparent planar heater can be provided by forming a metal electrode on. A typical structure of the transparent conductive film used for these transparent planar heaters is a laminate in which a metal thin film is sandwiched by a transparent high refractive index thin film. For example,
Vacuum deposition, an In O formed by reactive evaporation or sputtering _{X / Ag / In O X,} SiN X / Ag / Si
A laminate having a sandwich structure of N _x , TiO ₂ / Ag / TiO _2, etc. has been proposed. The one using a metal thin film containing silver as a main component as the metal layer is particularly excellent in transparency in the visible light region due to the optical characteristics of silver itself, and also preferable in conductivity, and particularly in heat generation at low voltage. Excel.

[0006]

A transparent sheet heater, which is covered with a transparent high-refractive-index thin film layer and uses as a heating layer a laminate comprising a thin film layer containing silver or copper as a main component, is a liquid crystal for automobiles. Strict environmental resistance is required when used for temperature compensation of display devices. In particular, moist heat resistance, heat resistance, cold resistance, etc. are required. At that time, particularly when the moist heat resistance is evaluated, the silver thin film layer is deteriorated due to the generation and aggregation of silver fine particles. When this deterioration occurs, there are problems such as agglomerated portions of silver fine particles scattered in white spots, resulting in poor appearance and uneven heat generation. For this reason, in a transparent sheet heater, a base material or a protective resin is usually used to protect the silver thin film layer from deterioration. However, when the environment resistance test of the transparent planar heater having such a protection measure was conducted, the silver thin film layer was deteriorated, and it could not be said that it has sufficient environment resistance. Further, in a transparent planar heater using a semiconductor thin film such as indium oxide as a heat generating layer, deterioration may be promoted by the presence of an acid component and the like even when protective measures are taken on both sides thereof. It could not be said to have durability.

As described above, it has been a very important problem to find out the cause of deterioration of the transparent sheet heater having protective measures on both sides and to solve it.

The object of the present invention is to investigate the cause of the above-mentioned deterioration, solve the problem, improve the durability against moisture, dust, gas, acid and other pollutants, and improve the environmental stability. An object of the present invention is to provide a transparent planar heater having excellent and high reliability, high light transmittance, excellent heat generation characteristics, and uniform heat generation characteristics, and a method for manufacturing the same.

[0009]

The inventors of the present invention have investigated the cause of deterioration in order to achieve the above-mentioned object. As a result, the deterioration occurs from a cut surface for which no protective measure is taken and spreads over the entire surface. I found out to go. Therefore, as a countermeasure, in a transparent planar heater including a transparent conductive thin film laminated on a transparent substrate and a pair of electrodes for energizing the transparent conductive film, a transparent conductive plastic member or an anticorrosive agent is used to form a transparent conductive film. It has been found that the above-mentioned deterioration does not occur when the anticorrosion treatment is carried out by means such as covering the cut surface of the film, and the present invention has been completed.

That is, according to the present invention, a transparent substrate, a transparent conductive film laminated on the transparent substrate, a first electrode extending on a first end portion of the transparent conductive film, and the first end portion. In a transparent planar heater comprising a second electrode extending away from the second end and facing each other, and a transparent protective layer laminated on a portion of the transparent conductive film where no electrode is formed. The transparent planar heater is characterized in that the cross section of the transparent conductive film is subjected to anticorrosion treatment (by means such as covering the cross section of the transparent conductive film with a transparent protective plastic member or a corrosion inhibitor).

The present invention further provides a transparent substrate, a transparent conductive film laminated on the transparent substrate, a first electrode extending on a first end portion of the transparent conductive film, and the first end portion. Of a transparent planar heater comprising: a second electrode extending away from the second end and facing each other, and a transparent protective layer laminated on a portion of the transparent conductive film where no electrode is formed. In the manufacturing method, a step of performing anticorrosion treatment on the cross section of the transparent conductive film (by means such as covering the cross section of the transparent conductive film with a transparent protective plastic member or an anticorrosive agent) is provided. It is a manufacturing method.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described below.

First, the structure of the transparent sheet heater of the present invention when the anticorrosion treatment is performed using the transparent protective plastic member will be described. FIG. 1 is a schematic plan view of a preferred example of the present invention, FIG. 2 is a schematic cross-sectional view taken along the line AA ′ of FIG. 1, and FIGS. BB '
FIG. 4 is a schematic cross-sectional view of the line, and FIG. 4 is a schematic perspective view thereof.

The transparent sheet heater 1 shown in FIGS.
It is composed of a substantially quadrangular body portion and projecting portions for electrical connection that project on the extension lines of the electrodes at both ends of the body portion. Then, the transparent sheet heater 1 includes a transparent substrate 2
And a transparent conductive film 3 constituting a heat generating surface laminated on one main surface of the transparent substrate 2 (a surface other than the end portion around which the transparent protective plastic member 7 is to be formed), and the transparent conductive film 3 A pair of electrodes 5 and 5'provided on both ends of the transparent conductive film 3 for supplying electricity to the transparent conductive film 3, and a transparent protection film covering the upper surface of the transparent conductive film 3 where the electrodes 5 and 5'are not formed. The layer 6 covers the upper surface of the transparent protective layer 6 and the upper surfaces of the electrodes 5 and 5 ′, and the cross section of the transparent conductive film 3 and the electrodes 5 and 5 ′.
The transparent protective plastic member 7 covers the cross section of the transparent substrate 2 and is joined to the upper surface around the edge of the transparent substrate 2. The transparent protective plastic member 7 is a transparent conductive film 3
The cross section of the electrode and the cross section of the electrodes 5 and 5 ',
It protects from acidic components and other contaminants and has a corrosion-proof function, which improves the environmental stability of the transparent heater 1.

In the transparent planar heater 1 shown in FIGS. 1 to 4, the electrodes 5 and 5'are elongated and one end thereof is a connecting portion 5a or 5a '. Connection parts 5a, 5
a'is a portion provided for connecting an electric wire or the like for applying a voltage to the electrodes 5, 5 '. This connecting portion 5a,
In 5a ', external connection fittings 13 and 13' are attached by eyelets 14 and 14 '.
The connecting portions 5a and 5a ', including 13', are configured to project in the in-plane direction from the main body portion of the transparent sheet heater 1. However, the present invention is not limited to this, and the connecting portions 5a, 5
The protruding direction of a'can be selected in any direction,
It does not need to project.

FIG. 5 is a schematic sectional view taken along the line AA 'in FIG. 1 to show another preferred example of the present invention. FIG.
In the example shown in, the transparent protective plastic film 9
Is bonded to the upper surface of the transparent protective plastic member 7 via an adhesive layer (not shown).

FIG. 6 is a schematic cross-sectional view taken along the line AA 'in FIG. 1 to show another preferred example of the present invention. Figure 6
In the example shown in FIG. 5, the electrodes 5 and 5 ′ are the conductive resin layer 5
b, 5b 'and plated metal layers 5c, 5c', and an adhesive layer 10 is provided on the surface (lower surface) of the transparent substrate 2 on which the transparent conductive film 3 is not provided, and a separator is further provided thereon. A (release sheet) 11 is provided. In this example, when the transparent sheet heater 1 is attached to the external support, the separator (release sheet) 11 is peeled off, and the adhesive layer 10 side is pressed to the external support for use.

FIG. 7 is a schematic plan view of another preferred example of the present invention, and FIG. 8 is a schematic sectional view taken along the line CC ′ of FIG. 7. In the example shown in FIGS. 7 and 8, the protruding portion for electrical connection protruding on the extension line of the electrode is the electrode (C
u etc. metal foil) 5 only. Further, in the main body portion of this example, the transparent substrate 2 and the transparent conductive film 3 constituting the heat generating surface are laminated on the entire surface of the transparent substrate 2, and a conductive resin layer (conductive film) is formed on the transparent conductive film 3. Paste) 5b,
The adhesive layer 8, the electrodes 5, 5 ', and the conductive resin layer (conductive paste) 5b are sequentially laminated, and the upper and lower conductive resin layers 5b are formed.
Are conducting at the ends. Further, the entire upper and lower sides and the side surface of the main body portion are covered with a transparent protective plastic member 7 to protect them from contaminants and prevent corrosion and the like.

FIG. 9 is a schematic sectional view taken along the line AA 'in FIG. 1 to show another preferred example of the present invention. In this example, the transparent protective plastic member 7 covers the upper surface of the transparent protective layer 6 and the upper surfaces of the electrodes 5 and 5 ′ via the adhesive layer 8, and the cross section of the electrodes 5 and 5 ′ and the transparent conductive film 3. It covers the cross section and protects it from contaminants. Further, the lower surface and the side surface of the transparent substrate 2 are also covered with another transparent protective plastic member 7 to prevent corrosion and the like. Further, the upper and lower transparent protective plastic members 7 are joined together with an adhesive layer 8 around the heater end portion.

FIG. 10 is a schematic sectional view taken along the line DD 'of FIG. 1 to show a preferred example of the present invention. In this example, the transparent protective plastic member 7 covers the electrode 5, the transparent conductive film 3, and the transparent substrate 2 except for the electrode attachment planned portion.

Further, FIG. 11 is a schematic cross-sectional view of another example of the DD ′ line in FIG. 1, similar to FIG. In this example, the transparent protective plastic member 7 covers the electrode 5, the transparent conductive film 3, and the transparent substrate 2 as a whole. in this case,
When attaching the electrode, the transparent protective plastic member 7 on the electrode attachment planned portion is removed using an appropriate means such as heat treatment, and then the electrode is attached.

FIG. 12 shows the transparent sheet heater of the present invention,
FIG. 4 is a schematic cross-sectional view showing a preferable example particularly when attached to a support. In this example, a transparent planar heater as shown in FIG. 5 and a liquid crystal element are combined. That is, in this example, on the transparent protective plastic film 9, a polarizing plate (P) 1 of a liquid crystal display composed of a polarizing plate (P) 15 / a liquid crystal display element 17 / a polarizing plate (Q) 16.
The fifth side is provided by pressure bonding via the adhesive layer 10, and is configured to be used by irradiating the light of the backlight 18 from the transparent substrate 2 side.

Next, the structure of the transparent planar heater of the present invention in the case of performing anticorrosion treatment using an anticorrosion agent will be described. 13 is a schematic plan view of a preferred example of the present invention, FIG. 14 is a schematic cross-sectional view taken along the line AA ′ of FIG. 13, and FIG. 15 is a schematic perspective view thereof. 13 to 1
The transparent planar heater 1 shown in FIG. 5 is composed of a substantially quadrangular main body portion and projecting portions for electrical connection that project on extension lines of the electrodes at both ends of the main body portion. The transparent planar heater 1 includes a transparent substrate 2, a transparent conductive film 3 that constitutes a heat generating surface laminated on one main surface of the transparent substrate 2, and a transparent conductive film for energizing the transparent conductive film 3. A pair of electrodes 5 and 5'provided at both ends of the electrode 3 and the electrodes 5 and 5 '
The transparent protective layer 6 that covers the upper surface of the transparent conductive film 3 in which the transparent conductive film 3 is not formed, and the transparent protective plastic film 9 that covers the upper surface of the transparent protective layer 6 and the upper surfaces of the electrodes 5 and 5 '.
(In this example, the layers are laminated without using an adhesive layer). Furthermore, the cross section of the transparent conductive film 3 is subjected to anticorrosion treatment (that is, covered with the anticorrosion component layer 31). In addition, in this example, the electrodes 5 and 5'have an elongated shape, and one end thereof serves as the connection portions 5a and 5a '. Further, eyelets 12 and 12 'for eyelets are also provided in the connection portions 5a and 5a', so that a desired external connection fitting can be attached.

FIG. 16 is a schematic sectional view taken along the line AA 'in FIG. 13 to show another preferred example of the present invention.
In this example, the transparent protective plastic film 9
Are laminated with the adhesive layer 8 interposed therebetween, and the entire end surface of the heater is covered with a resin layer (organic matter protective layer) 32 containing a corrosion inhibitor. The resin layer 32 containing the anticorrosive agent
Can be replaced with the transparent protective plastic member 7 containing no anticorrosive as described above with reference to FIGS. 1 to 11, and the same good anticorrosion effect can be obtained.

FIG. 17 is a schematic sectional view taken along the line AA 'in FIG. 13 to show another preferred example of the present invention.
In this example, the electrodes 5, 5 ′ are the conductive resin layer 5
b, 5b 'and the plated metal layers 5c, 5c', and the transparent protective plastic film 9 also on the surface (lower surface) of the transparent substrate 2 on which the transparent conductive film 3 is not provided, with the adhesive layer 8 interposed therebetween. Is provided. In this example as well, the resin layer 32 containing the anticorrosion agent may be replaced with the transparent protective plastic member 7 containing no anticorrosion agent.

FIG. 18 is a schematic sectional view taken along the line AA 'in FIG. 13 to show another preferred example of the present invention.
In this example, the cross sections of the electrodes 5 and 5'are subjected to anticorrosion treatment (that is, covered with the anticorrosion component layer 31), and further, the entire end surface of the heater is covered with a resin layer 32 containing an anticorrosion agent. There is. In this example as well, the resin layer 32 containing the anticorrosion agent may be replaced with the transparent protective plastic member 7 containing no anticorrosion agent.

In the preferred transparent sheet heater of the present invention having the constitution as illustrated in FIGS. 1 to 18, the environment resistance is improved and the performance as a transparent sheet heater is improved. Reliability is also greatly improved.

Next, preferable examples of materials and the like for each part constituting the transparent sheet heater of the present invention will be described.

The transparent substrate 2 has a wavelength of 400 nm to
In the visible light region of 800 nm, a substrate having a light transmittance of preferably 60% or more, preferably 70% or more, more preferably 80% or more, and a glass plate or a transparent plastic film can be used. Usually, the light transmittance of these plastic films does not exceed 95% unless an antireflection treatment such as an antireflection coating is performed. A plastic film or sheet is preferably used in terms of thinness, flexibility, impact resistance, continuous productivity, and the like. Preferred plastic films or sheets include, for example, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides,
Examples of the plastic film or sheet include homopolymers or copolymers such as polyether, polysulfone, polyethersulfone, polycarbonate, polyarylate, polyetherimide, polyetheretherketone, polyimide, aramid, polyparabanic acid, norbornene-based polymer. Further, a plastic film or sheet provided with a moisture-proof layer or a gas barrier layer on one side or both sides can also be used as the transparent substrate 2. As the moisture-proof layer and the gas barrier layer, the same layers as those described below for the transparent protective plastic member 7 can be preferably used.

Further, an undercoat may be provided on the surface of the transparent substrate 2 in order to improve the adhesion between the transparent substrate 2 and the transparent conductive film 3. The undercoat is preferably a crosslinkable resin or an anchoring agent on which a crosslinkable resin is provided. As the crosslinkable resin, 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. As the anchor agent, a water-soluble polyurethane resin, a water-soluble polyamide resin, a hydrophilic polyester resin, A-PET (amorphous polyethylene terephthalate), an ethylene-vinyl acetate emulsion, or a (meth) acrylic emulsion is preferably used. Any material can be used as long as it improves the adhesion between the transparent substrate 2 and the transparent conductive film 3. The thickness of the undercoat is usually 1 to 100 μm, preferably 10 to 50 μm. In addition, a substance having a refractive index of less than 1.6, which is made of an inorganic substance such as silicon oxide or magnesium fluoride, or an organic substance such as a fluorine-containing resin or an acrylic resin, is used as an antireflection film with a thickness of 0.1 nm.
It may be provided on the transparent substrate 2 with a thickness of up to 200 μm.

As the transparent conductive film 3, for example, a semiconductor thin film, a metal thin film, a laminate of a metal thin film and a transparent thin film, or the like can be applied. The lamination may be multi-layer. In particular, a laminated body composed of a transparent thin film and a metal thin film whose main component is at least one selected from the group consisting of silver and copper is desirable.

Examples of the semiconductor thin film forming the transparent conductive film 3 include thin films of indium oxide, tin oxide, ITO (indium oxide / tin), IZO (indium oxide / zinc), and the like. The thickness is usually 10 to 1,000 nm
And preferably 20 to 600 nm.

The transparent thin film forming the transparent conductive film 3 is a single layer of a material selected from the group consisting of metal oxides, metal nitrides, metal oxynitrides, metal hydrides and metal carbides, or two or more layers. A laminate of layers is preferred.

The metal thin film forming the transparent conductive film 3 is composed of a first metal thin film (A) and a second metal thin film (B), and is like AB, BAB, or BA from the transparent substrate side. The first metal thin film (A) has a laminated structure.
(i) a single layer or laminate of at least one metal selected from the group (a1) consisting of silver and copper, (ii) at least one metal selected from the group (a1), and palladium, platinum and gold A single layer or a laminate of an alloy thin film with at least one metal selected from the group (a2), or (ii
i) A single layer or a laminate of a mixture thin film composed of at least one metal selected from the group (a1) and at least one metal selected from the group (a2),
The second metal thin film (B) is (iv) a group consisting of copper, nickel, tin, indium, titanium, palladium, aluminum, chromium, silicon, tungsten, vanadium, zinc, tantalum, gold, platinum, and cobalt ( a single layer or laminate of at least one metal selected from b1), (v)
A single layer or a laminate of alloy thin films of at least one metal selected from the group (b1), or (vi) the group (b)
It is desirable that it is a single layer or a laminated body of a mixture thin film composed of at least one metal selected from 1).

However, the transparent conductive film 3 is not limited to the above examples. For example, as the metal thin film forming the transparent conductive film 3, metals such as silver, gold, copper, aluminum, nickel and chromium are used, and silver, gold and copper are preferable. The transparent conductive film 3 is, in particular, (1) a metal thin film made of a thin film of a metal or alloy such as silver or copper, (2) a metal thin film of a single metal such as silver or copper or an alloy containing them, and nitriding such as silicon nitride. It is preferable to use a transparent thin film made of a material, a metal oxide such as indium oxide or titanium oxide, or a metal carbide such as silicon carbide, in particular, a laminate of a transparent high refractive index thin film in a sandwich structure. From the viewpoint of transparency and conductivity, a laminate of a metal thin film and a transparent thin film or a laminate of metal thin films in a sandwich structure is preferable. In particular, it is preferable that one layer of each of a transparent thin film containing at least one selected from the group of nitrides, oxides or carbides and a substantially transparent metal thin film be laminated. A transparent thin film having a multi-layer structure and a metal thin film having a multi-layer structure are also useful.

The metal thin film of the transparent conductive film 3 comprising a combination of a transparent thin film and a metal thin film may be a single layer or a laminate containing at least one of silver or an alloy or mixture containing silver. In the case of an alloy or mixture containing silver, the content of silver is usually 5% by weight or more, preferably 30% by weight or more, more preferably 50% by weight or more, further preferably 70% by weight or more. In the case of an alloy or mixture containing copper, the content of copper is usually 5% by weight or more, preferably 30% by weight or more, more preferably 50% by weight or more, further preferably 70% by weight or more. Usually this value does not exceed 99.9%. The content of silver and copper in the case of copper or an alloy or mixture containing copper is usually 5% by weight, preferably 30% by weight or more, more preferably 50% by weight or more, further preferably 70% by weight or more. Normally this value does not exceed 99.9%.

From the viewpoint of preventing deterioration, the metals contained in the silver alloy or mixture include gold, copper, palladium, platinum, tungsten, titanium, cobalt, chromium, and
Metals such as nickel, tin, indium, IT (indium tin), silicon and zinc are preferable. The content of the metal contained here can be used as long as it can prevent deterioration, but it is usually 2% by weight to 60% by weight, preferably 5% by weight to
It is 50% by weight, more preferably 8% by weight to 30% by weight.

The thickness of each of these metal thin films is basically 1
nm to 500 nm is desirable, preferably 5 nm to 50 nm, more preferably 10 nm to 30 n.
m.

Further, in order to improve the adhesion of the silver or the metal thin film containing silver to the transparent thin film, the metal thin film other than silver contains silver or silver as a main component (when 5% by weight or more of silver is contained). When the metal thin film used here is laminated on at least one surface of the thin film, the metal other than silver may be nickel, chromium, titanium, gold, or copper to improve the adhesion of the metal thin film to the transparent thin film layer. , Platinum, tungsten, molybdenum, iridium, lead, tin, indium, zinc, palladium, cobalt, silicon, aluminum, germanium,
A metal containing one or more of manganese, gallium, tantalum, vanadium, zirconium, barium, and niobium, an alloy thereof, or a mixture thereof is preferable. The thickness of the metal thin film other than silver is usually 0.1 nm to 50 nm, preferably 0.3 nm to 30 nm, more preferably 0.5 n.
m to 10 nm, most preferably 0.5 to 5 nm.

The transparent thin film forming the transparent conductive film 3 is preferably a high-refractive index dielectric, and examples of this high-refractive index dielectric include a nitride thin film, an oxide thin film, and a carbide thin film. The material constituting the nitride thin film is preferably silicon nitride, aluminum nitride, indium nitride, gallium nitride, tin nitride, boron nitride, chromium nitride, nitrides such as silicon nitride carbide, silicon oxynitride, tin oxynitride, oxide. Boron nitride, aluminum oxynitride, indium oxynitride, gallium oxynitride, chromium oxynitride, oxynitride such as silicon oxynitride carbide, aluminum hydronitride, indium hydronitride, gallium hydronitride, silicon hydronitride, hydrogen Examples thereof include hydronitrides such as tin hydronitride, boron hydronitride, chromium hydronitride, and hydrogenated silicon carbide. Generally, any of nitrides, oxynitrides, and hydrogenated nitrides can be used, but a refractive index of 1.6 is preferable.
As described above, a high-refractive-index transparent thin film having a refractive index of 1.8 or more, and most preferably a refractive index of 2.0 or more and made of a nitride, an oxynitride, or a hydronitride is preferable. Usually, their refractive index does not exceed 3.0. The light transmittance is usually 50% or more, preferably 70% or more, more preferably 80% or more. Usually, these light transmittances do not exceed 98%.

The components of these oxynitrides excluding the metal are oxygen and nitrogen as the main components, and it is generally sufficient that nitrogen is present, but the ratio of nitrogen to the ratio of oxygen and nitrogen is usually 0.1.
Atomic% or more, preferably 30 atomic% or more, more preferably 50 atomic% or more, and 99.9 atomic% or less. The nitrogen content in the components other than the metal of these hydronitrides is usually 50 atom%, more preferably 80 atom%.
That is all. The thickness of these nitride layers is typically 0.3 nm
˜100 nm, preferably 1 nm to 100 nm, more preferably 5 nm to 50 nm, and most preferably 10 nm to 30 nm.

The oxide thin film forming the transparent conductive film 3 is preferably indium oxide, tin oxide, indium tin oxide (ITO), indium zinc oxide (IZ).
O), aluminum oxide, germanium oxide, silicon oxide, zinc oxide, zirconium oxide, titanium oxide, yttrium oxide, erbium oxide, cerium oxide, tantalum oxide, or hafnium oxide. Normal,
Any oxide can be used, but a high refractive index transparent thin film made of an oxide having a refractive index of 1.6 or more, more preferably 1.8 or more, and further preferably 2.0 or more is preferable. It usually does not exceed 3.0. The light transmittance is usually 50% or more, preferably 70% or more, more preferably 80% or more. Usually, the light transmittance does not exceed 98%. The thickness of at least one layer of these oxide thin films is usually 5 nm to 60.
It is 0 nm, preferably 60 nm to 100 nm, and more preferably 20 nm to 80 nm.

Further, the respective layers forming these transparent conductive films or between the transparent conductive film and the transparent substrate may be formed in a mixed state in which the respective layers contain components of each other.

Further, when the transparent conductive films are formed by being continuously laminated, for example, the nitride layer may be changed to an oxide layer, and the oxide layer may be changed to a nitride layer in part or in large part.

As a method of forming the metal thin film or the transparent thin film forming the transparent conductive film 3 on the transparent substrate 2, known methods such as a physical vapor deposition method as well as a spray method and a coating method can be used. Here, the physical vapor deposition method is a method of forming a thin film of a metal or the like under reduced pressure or under vacuum, and includes a vacuum vapor deposition method, a sputtering method, an ion plating method, an ion beam assisted vapor deposition method, an ion cluster beam method,
Molecular beam epitaxy (MBE), CVD method, MOCV
D method, plasma CVD method, etc. are illustrated.

Since the temperature dependence of the operation of a normal liquid crystal is relatively small, the operation is uniform if the in-plane temperature distribution of the transparent heater is ± 2 ° C., for example. In the case of a ferroelectric liquid crystal, the temperature dependence of its operation is large, so that temperature uniformity of about ± 1 ° C. is required. In this case, when incorporated in a liquid crystal display device, there is a problem in that the temperature of the peripheral end portion of the transparent sheet heater decreases due to the heat released from the peripheral end portion. In order to solve such a problem, it is also possible to perform patterning in the transparent planar heater, remove the heat generating layer, form a portion that does not generate heat, and make the temperature distribution in the transparent planar heater uniform. A usual etching technique can be used as a method of removing the transparent conductive layer in the heat generation unnecessary portion.

As the transparent protective layer 6, a protective layer having a light transmittance of 550 nm at a rate of usually 50% or more, preferably 70% or more, more preferably 80% or more, and capable of withstanding during plating treatment. It can be anything. As such a transparent protective layer 6, for example, a known UV curable resist ink, electron beam curable resist ink, heat curable resist ink, UV curable resin, electron beam curable resin, or heat curable is used. Examples thereof include those obtained by coating and curing a mold resin, and dry films. Other materials than the above can be used as the transparent protective layer 6 as long as a transparent film having water resistance and chemical resistance can be obtained. For example, a transparent protective layer 6 is prepared by laminating a transparent paint, a curable monomer or oligomer, a plastic film made of polyester or the like with an adhesive, or a film having self-adhesiveness such as ethylene-vinyl acetate copolymer. Can be formed. Further, a mixture or a mixture of these may be used.

UV-curable resins used for the transparent protective layer 6 include epoxy acrylate, urethane acrylate,
Polyester acrylate, polyfunctional acrylate, polyether acrylate, silicon acrylate, polybutadiene acrylate, unsaturated polyester / styrene, polyene / thiol, polystyryl methacrylate, UV curing lacquer and the like are preferably used. Examples of electron beam curable resins include epoxy acrylate, urethane acrylate, polyester acrylate, polyfunctional acrylate, polyether acrylate, silicon acrylate, polybutadiene acrylate, unsaturated polyester / styrene, polyene / thiol, polystyryl methacrylate, and UV curable lacquer. 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, urea resin, acrylic resin and the like are preferably used. Paints include cellulose derivative paints such as nitrocellulose lacquer, acrylic lacquer and acetylcellulose lacquer, alkyd resin paint, amino alkyd resin paint, guanamine resin paint, vinyl chloride resin paint, butyral resin paint, styrene / butadiene resin paint, heat Curable acrylic resin paint, epoxy resin paint, unsaturated polyester paint, polyurethane resin paint, silicon resin paint and the like are preferably used.

The thickness of the transparent protective layer 6 is usually 1 μm to 1
00 μm is desirable, preferably 5 μm to 50 μm, and more preferably 10 μm to 30 μm. In addition, the transparent protective layer 6 may be provided on the transparent substrate 2 on the side where the transparent conductive film 3 is not provided to improve the light transmittance and protect the transparent substrate 2.

As a method for forming the transparent protective layer 6, a usual coating method and / or a laminating method can be used. Preferred methods are a printing method such as a screen printing method, a bar coating method, a spray coating method, a roll coating method and the like. The coating method and the like are exemplified. The transparent protective layer 6 also protects the transparent conductive film 3. However, when it is formed before the formation of the electrode 5, the transparent protective layer 6 also plays the role of determining the position where the electrode 5 is to be formed, and the transparent surface. It is also possible to significantly improve the work efficiency of manufacturing the heater.

As the electrode 5, any electrode having conductivity can be used. As preferable electrodes, 1) conductive resin, 2) conductive resin and metal foil, 3)
Examples of the electrode layer include a conductive resin and a metal plating layer, 4) a metal plating layer, and the like.

As the conductive resin used for the electrode 5, a resin such as polypyrrole having conductivity itself, silver paste, copper paste, silver-copper paste or other metal powder of silver or copper, or carbon black. Examples thereof include those in which carbon is mixed alone or a mixture is mixed with a resin. Examples of the metal foil include metal foils such as copper foil and nickel foil. Examples of the metal plating layer include nickel, copper, and other metal layers that can normally be plated. These can be used alone or as a laminated or mixed layer to form the electrode 5. The conductive resin layer may be provided by a normal printing method or the like. When a metal foil is used, for example, an adhesive may be provided on one surface of the metal foil to adhere it to the conductive resin layer, and the conductive resin may be provided on the surface not coated with the adhesive. The metal plating layer may be formed by a method selected from wet processes such as electroplating, electroless plating, and direct plating.

The thickness of the electrode 5 may be such that the transparent conductive film can flow an electric current enough to function as a heat generating surface, but is preferably 0.1 μm or more, and more preferably 0.
It is 5 to 100 μm, more preferably 1 to 50 μm, and most preferably 5 to 20 μm.

When the electrode 5 includes a forming process by the plating method, the plating metal may reach any part of the transparent conductive film 3 or the component of the transparent conductive film 3 and the plating metal are mixed. It may be. That is, when the transparent conductive film 3 is a multi-layered body, when the plated metal reaches the metal oxide and / or the nitride, which is the transparent thin film component, it further penetrates into the metal layer and the metal, which is the transparent thin film 3 component below the metal layer. It may reach up to the oxide and / or nitride or the transparent substrate 2. In addition, plated metal and metal oxides and nitrides and /
Alternatively, the metal components of the metal layer may be present in a state of being at least partially mixed. As long as a current flows from the electrode 5 to the transparent conductive film 3 and the heat generating surface can generate heat, the electrode 5 and the transparent conductive film 3 may be in any state.

The transparent protective plastic member 7 protects at least the cross section of the transparent conductive film 3 from contaminants and prevents corrosion, and any transparent plastic member having such an action can be used without limitation. . Further, it is desirable that the transparent protective plastic member 7 is a member that exerts mechanical protection of the electrode 5 and the transparent protective layer 6 and chemical protection other than the above. As the transparent protective plastic member 7, a member having a light transmittance at a wavelength of 550 nm of desirably 60% or more, preferably 70%, more preferably 80% or more is used. The transparent protective plastic member 7 can be formed by laminating a plastic film of the same kind as that actually used as the transparent substrate 2 with an adhesive, or the same kind as that actually used as the transparent protective layer 6. They may be used, or they may be formed by applying an organic substance such as polyester, polyolefin, or acrylic resin, or a silicone-based hard coat agent. Moreover, you may use the silica sol agent etc. which have the same function.

The transparent protective plastic member 7 may be formed by hardening a liquid material, or may be formed by laminating film-shaped or sheet-shaped members. For example, a resin liquefied using a liquid resin component or solvent,
At least the transparent conductive film 3 of the end surface of the transparent sheet heater
It can also be formed by coating, spraying, or immersing a part or all of the end surface thereof including the cross-section, and curing it by heating, drying, UV irradiation, or the like. Further, for example, it is a suitable method to form a film-shaped or sheet-shaped transparent plastic member by thermocompression bonding with or without an adhesive layer. For example, a single-layer or multi-layer film or sheet made of a material containing at least one kind selected from the group of the materials exemplified above as the material forming the transparent substrate 2 and the transparent protective layer 6 can be preferably used. In addition, the transparent protective plastic member 7 is a liquid crystal encapsulant of ultraviolet curing type such as modified acrylate or the like, thermosetting type of epoxy sealing agent or the like, or curing type combined with ultraviolet heating such as a mixture thereof, epoxy resin, urethane resin or phenol. Sealant made of resin, silicone resin, silicone epoxy resin, DPA epoxy resin, etc., architectural sealant made of polysulfide-based, acrylic-based, acrylic urethane-based, butyl rubber-based, SBR-based, etc., corrosion prevention of the peripheral edge of the mirror Edge coatings and sealing agents used for, or other acrylic ester resins such as polymethylmethacrylate,
Acrylic resin such as polyacrylonitrile or polymethacrylonitrile, polyolefin resin such as polyethylene or polypropylene, silicon resin such as polymer obtained from ethyl silicate, polyester resin, melamine resin, fluorocarbon resin, organic resin such as phenol resin, etc. Any material can be applied as long as it has transparency. Further, depending on the purpose, several kinds of resins or substances may be mixed or laminated and used from the above compounds. Further, a transparent plastic containing or coated with an anticorrosive agent described later can also be used as the transparent protective plastic member 7.

The thickness of the portion of the transparent protective plastic member 7 that covers at least the cross section of the transparent conductive film 3 is usually 0.5 to
The thickness is about 200 μm, preferably 1 to 50 μm, and more preferably 5 to 30 μm. Further, the transparent protective plastic member 7 is in the form of a film or sheet, and for example, as shown in FIG.
In the case of a suitable example laminated on 5 ', the thickness of the laminated part is usually 1 μm to 200 μm, preferably 2 μm.
m to 100 μm, and more preferably 5 to 50 μm. Further, when a transparent protective plastic film 9 is further laminated on the transparent protective plastic member 7 as shown in, for example, FIG. 5, the thickness of the film 9 is usually 1 μm to 2 mm, and preferably 5 μm to 2 mm. It is 500 μm, more preferably 10 to 200 μm, and most preferably 50 to 150 μm. As the transparent protective plastic film 9, the same material as the transparent protective plastic member 7 can be used as appropriate.

A plastic film having a moisture-proof layer or a gas barrier layer on one or both sides can also be used as the transparent protective plastic member 7. This moisture-proof layer or gas barrier layer is, for example, a group consisting of metal oxides, metal nitrides, metal nitride oxides, metal nitride hydrides, metal carbides and transparent polymers exemplified as the transparent thin film forming the transparent conductive film 3. It is a single layer or a multi-layer laminate of one kind of thin film selected from the above or two or more kinds thereof. The multilayer laminate is
You may comprise combining 1 type of single layer.

The metal oxide constituting the moisture-proof layer or the gas barrier layer is prepared by decomposing polysilazane, or a silane derivative such as tetramethyldisiloxane or hexaethyldisiloxane in the presence of oxygen in a chemical-plasma-type. A silicon oxide film formed by deposition (CPD) is given as an example, but any other substance or one formed by another method can be used as long as it has a similar function. The thickness of each of the metal oxide layer, the metal nitride layer, the metal oxynitride layer, the metal hydronitride layer, and the metal carbide layer is usually 0.3 nm to 500 nm, preferably 1 nm to 100 nm. , More preferably 5 nm
80 nm, most preferably 5 nm to 60 nm.

As the transparent polymer constituting the moisture-proof layer or the gas barrier layer, UV curable resin, electron beam curable resin,
Examples thereof include thermosetting resins. In particular, urethane resin,
Epoxy resin, acrylic resin, acrylic ester resin, phenoxy ether cross-linking resin, melamine resin, phenol resin, silicone resin, xylene resin, guanamine resin, diallyl phthalate resin, vinyl ester resin, polyimide, maleic acid resin, unsaturated polyester resin , At least one selected from the group consisting of alkyd resins, and copolymers or mixtures thereof.

More specifically, the UV curable resin, electron beam curable resin and thermosetting resin will be exemplified. As the UV curable resin, epoxy acrylate, urethane acrylate, polyester acrylate, polyfunctional acrylate, polyether acrylate and silicone can be used. Acrylates, polybutadiene acrylates, unsaturated polyesters / styrenes, polyenes / thiols, polystyrylmethacrylates, UV curable lacquers, copolymers and mixtures of these are preferably used. As electron beam curable resin,
Epoxy acrylate, urethane acrylate, polyester acrylate, polyfunctional acrylate, polyether acrylate, silicon acrylate, polybutadiene acrylate, unsaturated polyester / styrene, polyene / thiol, polystyryl methacrylate, UV
Hardened lacquers and their copolymers and mixtures are preferably used. 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, an acrylic resin, a silicon resin, an alkyd resin, and a copolymer or mixture thereof are preferably used.

In order to improve the moisture resistance of the transparent polymer,
Polypropylene, polyethylene, polyolefin such as ethylene-propylene copolymer, polyester, polyamide, ionomer, polyvinyl acetate, ethylene-vinyl acetate copolymer, acrylic resin such as acrylic acid ester and methacrylic acid ester, polyvinyl acetal, phenol , Modified epoxy resin, copolymers or mixtures thereof may be used. Further, a mixture of a thermosetting resin and a UV curing resin may be used as a curing resin, or a mixture of different types of resins may be used.

In order to improve the gas barrier property of the transparent polymer, at least one of the acrylonitrile component, the vinyl alcohol component, the vinyl butyral component, the cellulosic component, the aramid component, the vinyl halide and the vinylidene halide component is added to 60 parts. You may use the polymer (air-permeable resin) containing it by mol% or more, or a mixture thereof. Examples of the acrylonitrile component polymer include polyacrylonitrile and polyacrylonitrile-butadiene copolymer. Examples of the vinyl alcohol component polymer include polyvinyl alcohol and the like. As the vinyl butyral component polymer, polyvinyl butyral,
Examples thereof include a mixture of polyvinyl butyral and an epoxy resin. As the vinylidene halide component polymer,
PVDC (polyvinylidene chloride), PVDC-VC copolymer, PVDC-acrylonitrile copolymer, PVDC
-Acrylic ester copolymer, multi-component copolymer containing several monomers copolymerizable with vinylidene chloride, PTFE
(Polytetrafluoroethylene) and the like. Examples of the vinyl halide component include monofluoroethylene trifluoride and the like.

An anchor coat may be provided on the transparent substrate 2 before coating the gas permeable resin for improving the gas barrier property as described above. As the transparent polymer anchor coating agent, at least one selected from the group consisting of polyurethane, polyamide, polyethyleneimine, amorphous polyester, hydrophilic polyester, ionic polymer complex, alkyl titanate resin, copolymers or mixtures thereof. Is preferred.

The anchor coat layer, the cured resin layer, the gas permeable resin layer for improving the gas barrier property, and the thermoplastic resin layer each have a thickness of usually 0.5 to 200 μm.
The thickness is about m, preferably 1 to 50 μm, and more preferably 5 to 30 μm.

When a plastic film or sheet is used as the transparent protective plastic member 7, an ordinary transparent adhesive or adhesive can be used. As this adhesive, an acrylic pressure-sensitive adhesive or a cyanoacrylate-based reactive adhesive is desirable. When a transparent protective plastic film with an adhesive in which an adhesive layer is provided on the transparent protective plastic film is used, any adhesive can be used as long as the transparent substrate 2 or the like can be bonded as desired, Even such an adhesive can be used for bonding other than the heat generating part. Examples of these adhesives include [pressure-sensitive adhesive (adhesive)] acrylic type, [solvent type adhesive] vinyl acetate resin type, chloroprene rubber type, nitrile rubber type, cellulose type, multi-liquid mixture type, etc. [Emulsion type adhesive] α-olefin type, cured vinyl acetate resin type, vinyl acetate resin type, vinyl acetate-acrylic type,
Acrylic copolymer type, vinyl-urethane type, epoxy type, vinylidene chloride type, vinyl chloride type, non-aqueous emulsion type, powder emulsion type, synthetic rubber latex type, etc. [Chemical reaction adhesive] cyanoacrylate type, epoxy type , Polyurethane resin type, [hot melt type adhesive] EVA type, polyamide type, polyester type and the like. In addition, urea resin,
Melamine resin, phenol resin, resorcinol resin,
An adhesive using an α-olefin resin, an epoxy resin, a polyurethane, an acrylic resin, a methacrylic resin, or a derivative resin or a copolymer thereof can also be used. Further, an ultraviolet curable adhesive, an electron beam curable adhesive, a thermosetting adhesive, or the like can also be used.

In some cases, a coupling agent such as a silane coupling agent may be used for the transparent substrate 2 and the transparent protective plastic member 7 to improve the adhesive strength. Examples of silane coupling agents include vinyltrichlorosilane, vinylethoxysilane, vinyl-tris-
(Β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl)-
γ-aminopropyltrimethoxysilane, N (dimethoxymethylsilylpropyl) ethylenediamine, N- (trimethoxysilylpropyl) -ethylenediamine and the like can be mentioned.

As described with reference to FIGS. 14 to 18, when the anticorrosion treatment is performed by using the anticorrosion agent, the anticorrosion agent is selected from the group consisting of 1) benzotriazole, indazole, imidazole, and their derivatives. One or more active ingredients selected, 2) one or more active ingredients selected from the group consisting of amino acids, amino acid esters, alkali metal salts of amino acids, ammonia, and amine salts; 3) mercaptans or derived therefrom. Active ingredient of molecules in close relationship, 4) Active ingredient consisting of copper chelate compound, 5) Mixture of 1) to 4) above, or 6) Mixture of third ingredient in mixture of 1) to 4) above. ,
Corrosion inhibitors consisting of are preferred. When copper is used as the material of the electrode 5, it is particularly effective to use amino acids, benzotriazoles or amino acids and benzotriazoles in combination to prevent corrosion of the electrodes from the end faces.

The benzotriazoles used for the anticorrosion treatment are 1,2,3-benzotriazole and its derivatives, for example, 2-alkylated benzotriazole such as 2-methylbenzotriazole, 2-phenylbenzotriazole. 5,6-methylbenzotriazole,
5-benzotriazolecarboxylic acid, halogenated benzotriazole, hydroxybenzotriazole, dodecylbenzotriazole, carboxybenzotriazole, and ester of carboxybenzotriazole, for example, ester of methyl, ethyl, isopropyl, butyl, hexyl, octyl, dodecyl or the like. Soluble salts and the like.

The indazoles used for anticorrosion treatment are
4-chloroindazole, 4-nitroindazole, 4
-Chloro-5-nitroindazole, 5-nitro-3-
Examples include methylindazole, 4,6-dinitro-5,7-dimethylindazole, and 5,7-dinitro-6-methylindazole.

The imidazoles used for anticorrosion treatment are
Alkylimidazoles such as 2-octylimidazole, 2-undecylimidazole, and 2-heptandecylimidazole.

Amino acids used for anticorrosion treatment include neutral amino acids, basic amino acids, acidic amino acids, sulfur-containing amino acids, aromatic amino acids and different amino acids that can react with copper and copper-based metals to form complex compounds. Includes nodal cyclic amino acids. Examples of preferred amino acids include glycine, alanine, valine, leucine, disuloisin, leucine, serine, arginine, glutamine, glutamic acid, aspartic acid, cysteine, methionine, phenylalanine,
Examples include histidine, oxyproline, hydroxyprotein, and the like, and esters thereof, and those having high hydrophilicity are particularly desirable. Here, the alcohol component of the ester preferably has 8 or less carbon atoms, and may be a saturated or unsaturated hydrocarbon group such as methyl, ethyl, propyl, benzyl, amyl and octyl.

The mercaptans used for anticorrosion treatment are
It also includes molecules having a close relationship derived from mercaptans such as disulfide and thiol ester, for example, mercaptoacetic acid, 3-mercaptopropionic acid, 1-mercaptoundecylic acid, thiophenol, phenyldisulfide, N- ( 2-hydroxymethyl) mercaptoacetamide, 2,2′-dimercaptodiethyl ether, 2,2′-dimercaptodiethylthioether,
1,2-ethanedithiol, 3-mercaptopropyltrimethoxysilane, glycol bis (3-mercaptopropionate), trimethylolpropane tris (3-
Mercaptopropionate), glycol dimercaptoacetate and the like.

The copper chelate compound used for the anticorrosion treatment is mainly an organic copper chelate compound, and includes acetylacetone copper, trifluoroacetylacetone copper, ethylenediamine copper, phthalocyanine copper, hemocyanin, ethylenediaminetetraacetate copper, dimethyldithiocarbamate copper and diethyl. Examples thereof include copper dithiocarbamate and copper hydroxyquinoline. Further, organic acid copper salts such as copper citrate, copper tartrate, copper lactate, and copper acetate can also be used equivalently.

In the case where the organic protective layer 32 containing an anticorrosive is provided on at least the cross section of the transparent conductive film 3 to prevent corrosion (FIG. 16).
Etc.), as the organic component of the organic protective layer 32, those exemplified above as the transparent protective plastic member 7 can be preferably used. Further, the materials exemplified above as the transparent substrate 2 and the transparent protective film 6 can also be preferably used. When a resin layer, a paint or a sealant is used as the organic protective layer 32 containing the anticorrosive, the thickness thereof is not particularly limited, but is usually 1 μm.
m-1,000 μm, preferably 5 μm-500
μm, and more preferably 10 μm to 200 μm.

When an adhesive layer containing an anticorrosive agent is provided on at least the cross section of the transparent conductive film 3 to prevent corrosion, the adhesive layer is the above-mentioned adhesive used for adhering the transparent protective plastic member 7 and the transparent substrate 2. Agents and the like can be used.

When the cross section of the transparent conductive film 3 is treated with an anticorrosion agent to form the anticorrosion component layer 31 (FIG. 14, etc.), as a method of incorporating the anticorrosion effective component, a conventionally well-known method is used. It can be adopted without limitation. That is, at least a part of the end surface of the transparent sheet heater including the cross section of the transparent conductive film 3 or the entire end surface thereof, the anticorrosion component (benzotriazoles, indazoles, etc.) dissolved in a suitable solvent.
Imidazoles, amino acids, mercaptans, copper chelate compounds, etc.), spraying with a spray gun, or dipping the cross section in such a solvent. When the anticorrosive component has sublimability, the object of the present invention can also be achieved by subjecting the cross section of the transparent planar heater to contact treatment with the compound heated to an appropriate temperature. The state of being in contact with or entering the surface or the inside of the cross section is referred to as containing, and the object of the present invention is sufficiently achieved by this. In addition, after mixing the anticorrosion component with the resin component, or after mixing the anticorrosion component with the resin using a solvent, at least a part of the end face of the transparent sheet heater including the cross section of the transparent conductive film 3 or the entire end face thereof. It is also possible to form the organic protective layer 32 containing a corrosion inhibitor by applying, spraying, or immersing it, and curing it by heating, drying, UV irradiation, or the like. Further, a polymer film or sheet provided with an adhesive layer containing a corrosion-preventing component,
At least the transparent conductive film 3 of the end surface of the transparent sheet heater
It is also possible to form an adhesive layer containing an anticorrosion agent by bonding the adhesive layer to a part including the cross section or the entire end surface so that the adhesive layer contacts.

The concentration of the anticorrosion component is preferably as high as possible from the viewpoint of anticorrosion function. However, when a corrosion inhibitor is contained in the organic protective layer or the adhesive layer, the concentration of the corrosion inhibitor is preferably 20% by weight or less, and preferably 10% by weight or less, with respect to the amount of solid components such as resin. Is particularly preferred. When the anticorrosive agent is dissolved in a solvent or the like to directly perform anticorrosion treatment on the cross section, the solution concentration is preferably 5% by weight or less, more preferably 3% by weight or less.

The transparent protective plastic member 7 described above
Alternatively, the anticorrosion treatment using the anticorrosion agent is performed on at least a cross section such as a cut surface of the transparent conductive film 3. In particular, the transparent conductive film 3
When includes a metal thin film layer containing at least silver and / or copper as a main component, it is desirable to perform at least on the cross section of the metal thin film layer. Of course, it does not matter if it is performed on the peripheral edge portion including the other cross-sectional portion and the end surface of the transparent sheet heater. Further, it is a desirable mode to perform anticorrosion treatment on the cross section of the electrode 5 and the cross section of the transparent protective layer 6. On the end face of the transparent sheet heater of the present invention, examples of the portion subjected to anticorrosion treatment include a part of the cross section of the transparent conductive film 3, the whole cross section of the transparent conductive film 3, and a part of the peripheral edge portion of the heater. , The entire peripheral edge portion of the heater, the cross section of the transparent conductive film 3 and a part of the peripheral edge portion of the heater, the cross section of the transparent conductive film 3 and the entire peripheral edge portion of the heater, and the like. More specifically, examples of the anticorrosion treated portion include (i) a metal thin film layer of the transparent conductive film 3.
(ii) Transparent thin film layer / metal thin film layer of transparent conductive film 3, (iii) Transparent thin film layer / metal thin film layer / transparent thin film layer of transparent conductive film 3, (i
v) transparent protective layer 6 / transparent thin film layer of transparent conductive film 3 / metal thin film layer / transparent thin film layer / transparent substrate 2, (v) transparent protective plastic film 9 / adhesive layer / transparent protective layer 6 / transparent conductive film 3 Transparent thin film layer / metal thin film layer / transparent thin film layer / transparent substrate 2 / adhesive layer / separator 11, etc. Further, a laminate of a plurality of metal thin film layers and transparent thin film layers of the transparent conductive film 3 can be applied.

Eyelets 14 are attached to the electrodes 5 of the transparent sheet heater 1.
When the metal fitting 13 is attached to the electrode 5 and the electric wire is attached to the electrode 5 by soldering or the like, the metal fitting 13 may be anywhere on the electrode 5, but is preferably provided on the electrode connecting portion 5a. Electrode 5 of heater 1
The transparent substrate 2 not only on the top but also on the side opposite to the metal electrode
It may be provided on the above, and may be physically fixed to the transparent planar heater of the present invention with an eyelet 14 or the like, and may be electrically connected to the electrode 5 (FIG. 3 and the like). Further, it may be provided on both surfaces of the transparent planar heater on the electrode 5 and the transparent substrate 2 on the opposite side to electrically connect with the electrode and stabilize the metal fitting 13. Also, it is installed on the adhesive layer or the separator 11,
The electrodes may be electrically connected. Also, eyelet 1
It is also possible to use the one having the function of 4 and the metal fitting 13 integrated, and the fitting for connecting the external electrode to the electrode 13
It is also possible to turn on the electric power by using a crocodile or the like without providing.

When the transparent sheet heater is adhered to the support, an adhesive layer may be provided on the surface of the transparent substrate 2 or the transparent protective plastic member 7. When the transparent protective plastic member 7 is not provided on the main surface of the heater, the transparent protective layer 6,
The adhesive layer may be provided at a desired position such as the surface of part or all of the electrode 5. As this adhesive layer, a general transparent pressure-sensitive adhesive or adhesive can be used. Examples of preferable adhesives include acrylic pressure-sensitive adhesives and cyanoacrylate-based reactive adhesives. The adhesive may be applied at the time of use, pressure-bonded to a support (for example, a liquid crystal display), and fixed to a transparent heater. In addition, when the adhesive layer is provided on the transparent planar heater in advance, the adhesive surface may be laminated with the separator 11 (release sheet) as needed (FIG. 6 and the like), and the adhesive may be used when the product is transported or stored. It is desirable to keep the surfaces from sticking.
As the separator 11, in addition to release paper that is normally used,
Polyethylene, polypropylene film, polyester film and the like can be used. The thickness of the separator is usually 1 μm to 200 μm, and preferably 2
μm to 100 μm, more preferably 5 μm to 5
0 μm.

Next, a method for manufacturing the durable transparent sheet heater of the present invention will be described. The manufacturing method of the present invention is a method for manufacturing the above-described transparent planar heater of the present invention,
The method is characterized by including a step of performing anticorrosion treatment on a cross section, a peripheral edge portion and the like of the transparent conductive film. Typical aspects of this manufacturing method are as follows.

In the first aspect, the first step of providing the transparent protective layer on the surface corresponding to the heat generating surface of the transparent conductive film laminated on the main surface of the transparent substrate, and the transparent protective plastic member are A second step of providing a resist in a region of the transparent conductive film corresponding to a portion to be provided, a third step of providing the first electrode and the second electrode, a fourth step of removing the resist, and A fifth step of removing the transparent conductive film,
A method of manufacturing a transparent planar heater, which includes a sixth step of covering at least a cross section of the transparent conductive film and a peripheral edge portion of the heater with the transparent protective plastic member, and a seventh step of removing an unnecessary portion.

A second aspect is a first step of preliminarily producing a transparent sheet heater in which the cross section of the transparent conductive film is not covered with a transparent protective plastic member, and the cross section of the transparent conductive film.
And a second step of covering the peripheral edge portion and both main surfaces of the heater with a transparent protective plastic member.

Next, a preferred embodiment of the method for producing a durable transparent sheet heater of the present invention will be described.

(1) First, of the transparent conductive film 3 provided on the transparent substrate 2, a portion other than the transparent conductive film 3 covered with the transparent protective layer 6 and the electrode 5 is removed by etching or the like to form a transparent surface. A heater original fabric is produced. Using this raw material of the heater, a transparent planar heater is obtained according to the following methods (1-1) to (1-6).

(1-1) Transparent protective layer 6 of the raw material of the heater
A transparent protective plastic member 7 is provided on the entire side surface. Next, the transparent substrate 2 is separated at the joint portion where the transparent conductive film 3 is removed and covered with the transparent protective plastic member 7. As a result, a transparent flat heater in which the cross section and the peripheral edge portion of the transparent conductive film 3 are covered with the transparent protective plastic member 7 is completed. The external electrode connecting metal fitting 13 is attached to a part of the electrode of the produced transparent sheet heater with an eyelet 14 to form a transparent sheet heater.

(1-2) The transparent protective plastic member 7 is provided on the surface of the raw material of the heater except the area corresponding to the external electrode connection of the electrode 5. Next, the transparent substrate 2 is separated in the same manner as in the above method (1-1) to obtain a finished transparent planar heater. Attach the external electrode connecting metal fitting 13 with the eyelet 14 to the electrode portion of the produced transparent planar heater that is not covered with the transparent protective plastic member 7.
Use a transparent sheet heater.

(1-3) Transparent conductive film 3 of heater raw material
The transparent protective plastic member 7 is fitted to the side, and the transparent substrate 2
The transparent protective plastic member 7 and the transparent substrate 2 are thermocompression-bonded in the area where the transparent conductive film 3 is removed. Next, the transparent substrate 2
The transparent conductive film 3 is removed and separated at the joint portion covered with the transparent protective plastic member 7, and at least the cross section and the peripheral edge portion of the transparent conductive film 3 are covered with the transparent protective plastic member 7. To do. The external electrode connecting fitting 13 is attached with an eyelet 14 to the electrode portion covered with the transparent protective plastic film 7 of the produced transparent sheet heater to obtain a transparent sheet heater.

(1-4) As a region for external electrode connection,
The transparent protective plastic member 7 having a hole formed in a portion corresponding to the electrode region is aligned with the transparent conductive film 3 side of the heater material such that the hole overlaps the electrode region, and the transparent conductive film 3 of the transparent substrate 2 is removed. The transparent protective plastic member 7 and the transparent substrate 3 are thermocompression-bonded in the formed area. Next, the above method (1-
In the same manner as 3), the transparent sheet heater is separated from the raw material of the heater, and at least the cross section and the peripheral edge portion of the transparent conductive film 3 are covered with the transparent protective plastic member 7. The external electrode connecting metal fitting 13 is attached by an eyelet 14 to the electrode portion of the produced transparent sheet heater which is not covered with the transparent protective plastic film 7 to obtain a transparent sheet heater.

(1-5) Transparent conductive film 3 of the raw material of the heater
On the side, transparent protective plastic member 7 with adhesive or adhesive
Then, the transparent planar heater in which at least the cross section and the peripheral edge portion of the transparent conductive film 3 are covered with the transparent protective plastic member 7 is separated from the raw material of the heater in the same manner as in the above method (1-3). To do. Transparent protective plastic film 7 with adhesive or pressure sensitive adhesive for the produced transparent sheet heater
The external electrode connecting metal fitting 13 is attached to the electrode portion covered with with an eyelet 14 to form a transparent planar heater.

(1-6) A transparent protective plastic member 7 with an adhesive or a pressure sensitive adhesive, which is provided with a hole in a portion corresponding to the external electrode connecting region, which overlaps with the electrode region, is arranged so that the hole overlaps with the electrode region. The transparent conductive film 3 side of the original fabric is aligned and adhered. Next, in the same manner as in the above method (1-3), the transparent sheet heater is separated from the raw material of the heater to obtain a transparent sheet heater in which at least the cross section and the peripheral edge portion of the transparent conductive film 3 are covered with the transparent protective plastic member 7. Transparent protective plastic film 7 with adhesive or pressure sensitive adhesive for the produced transparent sheet heater
The external electrode connecting metal fitting 13 is attached to the electrode portion not covered with with an eyelet 14 to form a transparent planar heater. here,
Further, another transparent protective plastic film (which may be provided with an adhesive layer) may be provided on at least the transparent protective plastic 7.

(2) The transparent heating layer with transparent protective layer 6 and the electrode portion are cut out from the transparent planar heater consisting of the heating surface with transparent protective layer 6 and the electrode provided on the transparent conductive film 3, and the transparent planar heater raw material is obtained. To do. Using this heater blank,
A transparent planar heater is obtained according to the methods of -1) to (2-4).

(2-1) Transparent conductive film 3 of the original heater
The transparent protective plastic member 7 is fitted to the side, another transparent protective plastic member is also fitted to the opposite surface, and thermocompression-bonded around the heater raw material, and the heater raw material is covered with the transparent protective plastic member. Use as a heater. The external electrode connecting metal fitting 13 is attached with an eyelet 14 to the electrode portion of the produced transparent sheet heater which is not covered with the transparent protective plastic member to obtain a transparent sheet heater.

(2-2) As a region for connecting external electrodes, a transparent protective plastic member 7 having a hole formed in a portion corresponding to the electrode region is formed so that the hole overlaps with the electrode region, and the transparent conductive film 3 side of the raw material of the heater. Align with another transparent protective plastic member with no holes on the opposite side,
The area around the raw material of the heater is thermocompression bonded to form a transparent sheet heater in which the raw material of the heater is covered with a transparent protective plastic member.
The external electrode connecting metal fitting 13 is attached with an eyelet 14 to the electrode portion of the produced transparent sheet heater which is not covered with the transparent protective plastic member to obtain a transparent sheet heater.

(2-3) Transparent conductive film 3 of the original heater
On the side, transparent protective plastic member 7 with adhesive or adhesive
Next, another transparent protective plastic member is placed on the opposite surface, and the entire surface or the peripheral portion is pressure-bonded to obtain a transparent planar heater in which the raw material of the heater is covered with the transparent protective plastic member. Another transparent protective plastic member with an adhesive or an adhesive may be used on the surface opposite to the transparent conductive film 3 side. The external electrode connecting metal fitting 13 is attached with an eyelet 14 to the electrode portion of the produced transparent sheet heater which is not covered with the transparent protective plastic member to obtain a transparent sheet heater.

(2-4) As a region for external electrode connection,
A transparent protective plastic member 7 with an adhesive or a pressure sensitive adhesive, which is provided with a hole in a corresponding portion overlapping the electrode region, is aligned with the transparent conductive film 3 side of the raw heater so that the hole overlaps the electrode region.
Next, another transparent protective plastic member having no holes is attached to the surface on the opposite side and pressure-bonded to obtain a transparent sheet heater in which the raw material of the heater is covered with the transparent protective plastic member. A transparent protective plastic film with an adhesive or a pressure-sensitive adhesive may be used on the surface opposite to the transparent conductive film 3 side. An external electrode connecting fitting 13 is attached with an eyelet 14 to the electrode portion of the produced transparent sheet heater which is not covered with the transparent protective plastic film to obtain a transparent sheet heater.

However, the present invention is not limited to the manufacturing method,
For example, a bag-shaped transparent protective plastic film or an adhesive-attached transparent protective plastic film can be used as the member 7. Further, a method used when the light emitting surface is covered with a moisture-proof film to protect the light emitting surface by EL (electroluminescence) can also be used. In addition to the above methods, various methods in which the transparent conductive film 3 can be covered and protected by, for example, a transparent plastic film, a transparent plastic film with an adhesive or a pressure-sensitive adhesive can be applied. In the manufacturing method of the present invention, even if the unnecessary transparent conductive film 3 is not removed and remains, the conductive component is immobilized or stabilized by the alkali or other solvent, and the cross section due to moisture or the like is generated. Also, as long as the erosion of the transparent conductive film from the peripheral edge portion is prevented, unnecessary transparent conductive film may remain.

Next, a preferred example of the method for producing the durable transparent planar heater of the present invention will be specifically described with reference to FIGS. 19 to 26, (a) is a schematic plan view and (b) is a schematic sectional view thereof.

First, as shown in FIG. 19, the transparent conductive film 3 is formed on one surface of the transparent substrate 2 to form a transparent conductive substrate. Next, as shown in FIG. 20, the transparent protective layer 6 is formed by printing on the pattern of the surface corresponding to the heat generating surface of the transparent conductive film 3. The surface corresponding to the heat generating surface means the electrodes 5 to be formed later facing each other,
Areas where the transparent conductive film 3 is heated by being sandwiched by 5 ', for example, an area to be joined with the transparent substrate 2 and a transparent protective plastic member 7 to be formed later, an electrode 5 to be formed later.
It is a region excluding the formation region and other plating electrode portions.

Next, as shown in FIG. 21, the transparent protective layer 6
Then, a resist 40 for plating is applied by printing in a desired pattern. The pattern of the resist 40 is such that the electrodes 5 and 5'formation-scheduled regions to be opposed to each other to be formed later are openings, and the region to be joined to the transparent substrate 2 and the transparent protective plastic member 7 to be formed later is transparent. Protective layer 6
In addition, it covers other parts that do not require plating.
Next, as shown in FIG. 22, a metal plating layer 41 is formed by plating. Next, as shown in FIG. 23, an unnecessary portion of the transparent conductive film 3, that is, the transparent protective layer 6 and the electrode 5 is formed.
The transparent conductive film 3 other than the region in which is formed is removed.

Next, as shown in FIG. 24, a transparent protective plastic member is formed so as to cover the upper surfaces of the electrode 5 and the transparent protective layer 6 and the cross sections of the transparent conductive film 3 and the electrode 5 and to be bonded to the transparent substrate 2. Form 7.

Next, as shown in FIG. 25 (enlarged view), each transparent flat heater is cut by die cutting. In this die-cutting, the area of the transparent substrate 2 from which the transparent conductive film 3 has been removed and the transparent protective plastic member 7 are separated from each other, and at the same time, eyelet holes 42 and 42 'are formed. Next, as shown in FIG. 26, the external connection fittings 13 and 13 'are provided using the eyelets 14 and 14'. In this way, the transparent conductive film 3 and the electrode 5 are formed by the transparent protective plastic member 7.
The transparent planar heater of the present invention having a corrosion-resistant cross section is obtained.

29 and 30 are schematic plan views showing an example of a transparent conductive film having a predetermined pattern. This transparent heater with a pattern can be produced by forming a transparent protective plastic member according to the operation of FIGS.

Further, instead of the eyelet method, FIG.
(B), you may use the connection tool as shown in FIG.
The external connection fittings shown in FIGS. 27A and 27B are fittings provided with two opposed flat plates. The electrode part can be sandwiched between the two flat plates and fixed to the electrode part by mechanical pressure, mechanical pressure and heating, or mechanical pressure and resistance welding. You may make a hole with this metal fitting so that the wire can pass through (Fig. 27).
(B), FIG. 28). When the wire is passed through the hole, the stranded wire can be fixed to the fitting for connection by soldering. FIG.
The external connection fitting shown in FIG. 8 is a connecting tool similar to the connecting tool shown in FIG. 27.

Although the resist 40 is used in the manufacturing method of the present invention exemplified above, any resist can be used as this resist as long as it is a commonly used resist. For example, alkali peeling type and solvent peeling type etching resists, plating resists, filling inks, solder resists, active resists are preferable. That is, cyclized rubber, negative photoresist based on polycinnamic acid, and photoresist such as phenol and cresol, positive photoresist based on novolac resin, melamine resin-based, epoxy resin-based, imide-modified photoresist Examples thereof include heat-curable solder resists such as UV curable solder resists such as radical polymerization type and cationic polymerization type, and dry film resists.
Further, a positive X-ray resist based on a methacrylate copolymer or the like, a negative X-ray resist based on an acrylate or the like, or a positive electron based on a methacrylate or a copolymer thereof or the like. An electron beam resist such as a line resist, a negative type electron beam resist such as a photoresist type, a silicone resin type, an epoxy polymer type, or a polycioxane type can also be used.

[0107]

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

Example 1 On a polyethylene terephthalate (PET) film having a visible light transmittance of 89% and a thickness of 100 μm, silver (thickness 10 nm) / copper (thickness 1 nm) /
Silicon nitride (thickness 30 nm) / indium oxide (thickness 6
A laminated film of 0 nm) was deposited by a reactive DC magnetron sputtering method to form a transparent conductive film. The visible light transmittance of the obtained transparent conductive film was 76%, and the surface resistance was 7Ω / □. On the obtained transparent conductive film, an ultraviolet-curable transparent urethane acrylate (Mitsubishi Rayon Co., Ltd.) is used except for the area where the transparent substrate and the transparent protective plastic member are to be joined, the heater electrode formation area and the plating electrode section. Made, product name Diamond Beam UK
-6074) was applied and cured to form a transparent protective layer having a thickness of 10 μm. Next, a resist was provided in a region where the transparent substrate and the transparent protective plastic member were to be joined. Then the pH
Electroplating was performed in a nickel sulfamate plating bath of 4.5 to form a nickel film having a thickness of 5 μm, which was used as a plated metal layer. Furthermore, after removing the resist by immersing it in a 1% KOH aqueous solution, it was immersed in an 8% hydrochloric acid solution to remove an unnecessary conductive film. The size of the electrode is 125 mm (length) x 4 m
m (width), and the distance between the electrodes was 90 mm.

Further, a transparent urethane acrylate (Diabeam UK-6074) having a thickness of 20 μm was provided, leaving a region corresponding to the connection portion with the external electrode, to form a transparent protective plastic member. Next, after separating the transparent substrate region from which the transparent conductive film is removed and the transparent protective plastic member at the joint, the metal fitting is connected to the region corresponding to the external electrode where the transparent protective plastic member is not provided with an eyelet. Was attached, and a transparent sheet heater in which the cross section of the transparent conductive film and the heat generating surface side including the peripheral edge portion were covered with a transparent protective plastic member as shown in FIGS. Then, a pressure sensitive adhesive layer (adhesive layer) with a separator (release sheet) was provided on the transparent substrate side to complete a transparent planar heater. The resistance between both electrodes of this transparent sheet heater was 5Ω.

The separator of the transparent sheet heater was peeled off and attached to a glass plate, and the transparent sheet heater was put together with the glass plate in a thermostat at -20 ° C.
When the voltage was applied, the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C.
Next, when it was immersed in 1N hydrochloric acid for 1 hour, there was no change in the end surface. Further, a high temperature and high humidity test was carried out at 85 ° C. × 95%, but after 2,000 hours, no change was observed on the end faces. After that, 13 V was applied between the electrodes, and the distribution of heat generation after 1 minute from energization was examined using an infrared thermometer (product name Avio manufactured by Nippon Avionics Co., Ltd.) (hereinafter referred to as heat generation test). . In this heat generation test, the transparent sheet heater generated heat without abnormality.

Example 2 Visible Light Transmittance 89%, 10
Silicon nitride (thickness 50
nm) / silver (thickness 10 nm) / silicon oxynitride (thickness 60)
(nm) was deposited by a reactive DC magnetron sputtering method to form a transparent conductive film. On the obtained transparent conductive film, the same UV-curable transparent material as that used in Example 1 except for the joining planned region of the transparent substrate and the transparent protective plastic member, the heater electrode forming region and the plating electrode. Urethane acrylate was applied and cured to form a transparent protective layer having a thickness of 10 μm. Next, a resist was provided in a region where the transparent substrate and the transparent protective plastic member were to be joined. After that, a conductive paste (phenol resin binder) containing a copper filler is applied to the electrode formation region and held at 150 ° C. for 30 minutes.
conductive layer of μm thickness (resistivity ^{6 × 10 - 5 Ω · cm} ) was provided. Then, the transparent conductive layer is washed with a hydrochloric acid solution of PH = 2, further washed with water, and then electroplated in a pH 1 alkanol sulfonic acid bath to form a solder layer made of a tin-lead alloy having a thickness of about 5 μm to form a metal electrode. And Further, after removing the resist in the same manner as in Example 1, the transparent transparent conductive film was immersed in an 8% hydrochloric acid solution to remove the unnecessary transparent conductive film, thus completing the raw material of the transparent planar heater.

Next, a 25 μm PET film provided with an adhesive layer made of polyester of 8 μm was laid so that the heat generating surface side and the adhesive layer faced each other, and the region where the transparent conductive film of the transparent substrate was removed and the overlapping region of the PET film. At 100 ° C for 3
Hold for 0 seconds to join.

The transparent substrate region from which the transparent conductive film is removed and P
After separating at the joint with the transparent protective plastic film made of ET film, attach the external electrode connecting metal fitting to the electrode part with eyelets, and the transparent protective plastic film is on the heating surface side including the cross section and peripheral edge of the transparent conductive film. A covered transparent sheet heater was prepared. The size of the metal electrode is 25m
m (length) x 4 mm (width), distance between electrodes is 90 m
m. The resistance between both electrodes was 5Ω.

When this transparent sheet 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. Next, add 1N hydrochloric acid to 1
After immersion for a time, there was no change in the end faces. Again 85
A high temperature and high humidity test was conducted at ℃ × 95%, but after 2,000 hours, no change was observed on the end faces. After that, a heat generation test was conducted, but heat was generated without any abnormality.

Example 3 Visible Light Transmittance 89%, 10
On a 0 μm thick PET film, a laminated film of indium oxide (thickness 40 nm) / silver (thickness 10 nm) / indium oxide (thickness 60 nm) was deposited by a reactive DC magnetron sputtering method to form a transparent conductive film. Formed. On the obtained transparent conductive film, a region to be joined between the transparent substrate and the transparent protective plastic member, a heater electrode formation region portion, and a plating electrode portion were removed except for Example 1.
The same UV-curable transparent urethane acrylate as that used in 1. was applied and cured to form a transparent protective layer having a thickness of 10 μm. Next, a resist was provided in a region where the transparent substrate and the transparent protective plastic member were to be joined. Next, a conductive paste containing a silver filler in the electrode formation region (acrylic resin binder: manufactured by Mitsui Toatsu Chemicals, Inc., trade name MSP-
600F) is applied and held at 140 ° C for 30 minutes, then 10μ
conductive layer of m thickness (resistivity ^{6 × 10 - 5 Ω · cm} ) was provided. Further, a 25 μm copper foil provided with an adhesive layer on one surface was adhered on the copper foil via the adhesive layer. Further, apply the conductive paste (acrylic resin binder) on the copper foil,
After 30 minutes hold at 140 ° C., the conductive layer of 10μm thickness (resistivity ^{6 × 10 - 5 Ω · cm} ) and is provided, and an electrode. Then, unnecessary portions were cut off to prepare a raw material of a transparent planar heater in which the transparent conductive film was not protected.

Next, an OPP (stretched polypropylene) film having a hole formed in a region corresponding to the connection with the external electrode was laminated so that the hole was aligned with the electrode of the transparent sheet heater.
Further, an OPP film having no holes was overlaid on the transparent substrate side, the OPP films were thermocompression bonded to each other around the raw material of the transparent planar heater, and unnecessary portions were separated to complete the transparent planar heater.

When this transparent sheet 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. Next, add 1N hydrochloric acid to 1
After immersion for a time, there was no change in the end faces. Again 85
A high temperature and high humidity test was conducted at ℃ × 95%, but after 2,000 hours, no change was observed on the end faces. After that, a heat generation test was conducted, and heat was generated without any abnormality.

Example 4 Visible Light Transmittance 89%, 10
On a 0 μm thick PET film, silicon nitride (thickness 30
nm) / titanium (thickness 1 nm) / silver containing 15% gold (thickness 10 nm) / silicon nitride (thickness 30 nm) / indium oxide (thickness 30 nm) by a reactive RF ion plating method. Deposited to form a transparent conductive film. The visible light transmittance of the obtained transparent conductive film was 74%, and the surface resistance was 7Ω / □. Hereinafter, a transparent planar heater was produced in the same manner as in Example 1. Next, when it was immersed in 1N hydrochloric acid for 1 hour, there was no change in the end surface. Further, a high temperature and high humidity test was performed at 85 ° C. × 95%, but after 2,000 hours, no change was observed on the end faces. After that, a heat generation test was conducted, but heat was generated without any abnormality.

<Example 5> A thermosetting polyurethane layer (thickness: 10 nm, manufactured by Mitsui Toatsu Chemicals Inc., trade name: Olester UD101N), polyvinyl alcohol, on one side of a polycarbonate (PC) film having a thickness of 100 μm. Layers (thickness 8 nm) were sequentially laminated. Further, a thermosetting silicone resin (thickness 20 μm: manufactured by Toray Dow Corning Silicone Co., Ltd., trade name SR2410) is applied to prevent moisture,
A gas barrier film was prepared. ASTM-D14
According to No. 34, the oxygen permeability of this film was measured and found to be 0.5 cc · m ⁻² · day ⁻¹ . Furthermore, the oxygen transmission rate at a relative humidity of 100% is ASTM-
When measured according to D3985, 0.6 cc ・ m ^-2・
It was less than day ^-1 . Next, ASTM-E96 (38
The water vapor permeability was measured at 90 ° C. and 90% RH, and it was 0.2 g · m ⁻² · day ⁻¹ . This moisture resistance,
25 adhesive on the transparent substrate of gas barrier film
It was provided with a thickness of μm and was attached to the heat generating surface side of the original sheet of the transparent sheet heater produced in Example 2. After separating the transparent substrate area from which the transparent conductive film is removed and the transparent protective plastic member, separate the external electrode connecting metal fittings with the eyelets on the electrode part, and heat the cross section of the transparent conductive film and the peripheral edge heat. A transparent planar heater whose surface side was covered with transparent protective plastic was produced.

When this transparent sheet heater was put 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. Also, 85 ℃ × 95
A high temperature and high humidity test was conducted in%, but after 1,000 hours, no change was observed on the end face. After that, a heat generation test was conducted, but heat was generated without any abnormality.

<Embodiment 6> A transparent conductive film of 10Ω / □ IT was used.
A transparent planar heater was produced in the same manner as in Example 2 except that O (indium tin oxide) was used. Next, 1N
When immersed in hydrochloric acid for 1 hour, there was no change in the end faces.

Comparative Example 1 A transparent planar heater was prepared under the same conditions as those prepared in Example 1 except that the transparent protective plastic member was not provided, and when immersed in 1N hydrochloric acid for 1 hour, spotted spots were formed on the end faces. There was discoloration and the end face was partially peeled off. In addition, a high temperature and high humidity test at 85 ° C. × 95% was performed, but after 500 hours, spot-like discoloration appeared on the end surface, and 5
After 00 hours, spot-like discoloration proceeded even to the vicinity of the central part, and it could not be used as a transparent planar heater.

Comparative Example 2 A transparent planar heater was prepared under the same conditions as those prepared in Example 3 except that the transparent protective plastic member was not provided, and a high temperature and high humidity test at 85 ° C. × 95% was conducted. However, after 500 hours, spot-like discoloration appeared on the end face, and spot-like discoloration proceeded in some places, and it became impossible to use as a heater.

<Comparative Example 3> A transparent sheet heater was produced under the same conditions as those produced in Example 4 except that the transparent protective plastic member was not provided, and when immersed in 1N hydrochloric acid for 1 hour, spotted spots were formed on the end faces. There was discoloration and the end face was partially peeled off.

Comparative Example 4 A transparent sheet heater was produced under the same conditions as those produced in Example 6 except that the transparent protective plastic member was not provided. Next, when it was immersed in 1N hydrochloric acid for 1 hour, a part of the transparent conductive film on the end face portion of the transparent planar heater was dissolved and disappeared.

Example 7 Visible Light Transmittance 89%, 10
On a 0 μm thick PET film, silicon nitride (thickness 30
nm) / silver (thickness 10 nm) / copper (thickness 1 nm) / silicon nitride (thickness 10 nm) / indium oxide (thickness 60 n)
The laminated film of m) was deposited by the reactive RF magnetron sputtering method to form a transparent conductive film. The visible light transmittance of the obtained transparent conductive film is 7
The surface resistance was 4% and the surface resistance was 7Ω / □. On the obtained laminated film, the same UV-curable transparent urethane acrylate as that used in Example 1 was applied and cured except for the plating electrode part and the heater electrode formation region part, and the thickness was 10 μm.
m transparent protective layer was formed. Next, a conductive paste containing copper fillers in the electrode formation area part (phenolic binder) was applied, after 30 minute hold at 160 ° C., the conductive layer of 10μm thickness (resistivity ^{6 × 10 - 5 Ω · cm} ) of Provided.
Then, electroplating is performed in a nickel sulfamate plating bath having a pH of 4.5 to form a nickel film having a thickness of 5 μm,
The plated metal layer was used. The size of the electrodes was 125 mm (length) × 4 mm (width), and the distance between the electrodes was 90 mm. Further, a PET film having a thickness of 25 μm with an adhesive having a thickness of 20 μm was laminated while leaving the electrode connection portion to form a transparent protective plastic member. Then, an adhesive layer with a separator (release sheet) was provided on the transparent substrate side to complete a transparent sheet heater. 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 a glass plate. The 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 1 minute. That is, the temperature rise is 22 ° C
Met.

Next, a modified vinyl acetate resin containing 5% by weight of 1,2,3-benzotriazole was applied to the end surface (cut surface) of the transparent sheet heater to a thickness of 5 μm, and the temperature was set to 110 ° C.
It was held for 5 minutes to form an organic protective layer containing a corrosion inhibitor.

When this was immersed in 1N hydrochloric acid for 1 hour,
There was no change in the end faces. Further, a high temperature and high humidity test was performed at 85 ° C. × 95%, but after 2,000 hours, no change was observed on the end faces. After that, a heat generation test was carried out, and it was confirmed that heat generation occurred without any problem.

Example 8 Visible Light Transmittance 89%, 10
Silicon nitride (thickness 50n on 0μm thick PET film)
m) / silver (thickness 10 nm) / silicon oxynitride (thickness 60 n)
The laminated film of m) was deposited by the reactive RF magnetron sputtering method to form a transparent conductive film. The same UV-curable transparent urethane acrylate as that used in Example 1 was applied and cured on the heat-generating surface area for a heater on the obtained laminated film to form a first transparent protective layer.

[0131] Thereafter, a conductive paste containing copper fillers in the electrode formation area part (phenolic binder) was applied, after 30 minute hold at 0.99 ° C., 10 [mu] m conductive layer having a thickness (resistivity 6 × 10 ^{- 5} Ω · cm ) Is provided. Then, the conductive layer is washed with an acid solution of PH = 2, further washed with water, and then pH 1
Electroplating in the alkanol sulfonic acid bath of
A solder layer made of a tin-lead alloy having a thickness of about 5 μm was formed to obtain a metal electrode. The size of the metal electrode is 25 mm (length)
× 4 mm (width), the distance between the electrodes was 90 mm.
The resistance between both electrodes was 5Ω. This transparent sheet heater is placed in a constant temperature bath at -20 ° C and left to stand, and then 13 V
When the voltage was applied, the surface temperature rose to + 2 ° C in 1 minute. That is, the temperature rise was 22 ° C.

An edge coating clear (Eton 2100, manufactured by Kawakami Paint Co., Ltd.) was applied to the peripheral edge portion of the transparent sheet heater and dried to obtain an organic material protective layer containing a corrosion inhibitor having a thickness of 50 μm.

A high temperature and high humidity test at 85 ° C. × 95% was conducted on this transparent sheet heater, but there was no change even after 1000 hours. Further, a heat generation test was conducted thereafter, and it was confirmed that there was no problem.

Example 9 Visible Light Transmittance 89%, 10
A transparent conductive film was formed by depositing a laminated film of indium oxide (thickness 40 nm) / silver (thickness 10 nm) / indium oxide (thickness 60 nm) on a PET film having a thickness of 0 μm by a reactive RF magnetron sputtering method. Was formed. On the obtained laminated film, the same UV-curable transparent urethane acrylate as that used in Example 1 was applied and cured except for the plating electrode part and the heater electrode formation region part, and a transparent protective layer having a thickness of 10 μm. Was formed. Next, a conductive paste (acrylic resin binder) containing a silver filler is applied to the electrode formation region, and 140
After holding at 30 ° C for 30 minutes, a conductive layer with a thickness of 10 µm (specific resistance 6 x
10 ^{- 5} Ω · cm) and the provided. Then, a copper foil provided with an adhesive on one surface was adhered on it via an adhesive layer. Further, the conductive paste (acrylic resin binder) is coated on the copper foil, after 30 minute hold at 140 ° C., the conductive layer of 10μm thickness (resistivity ^{6 × 10 - 5 Ω · cm} ) is provided and an electrode did. Further, a PET film having a thickness of 20 μm and having a pressure-sensitive adhesive and having a thickness of 25 μm was laminated to form a transparent protective plastic layer, leaving the electrode connection portion.

Next, Loctite 350 (modified acrylate), which is an ultraviolet-curable sealing sealant, is applied to the peripheral edge portion of the transparent sheet heater and dried to form an organic protective layer containing a corrosion inhibitor having a thickness of 50 μm. It was

When this was immersed in 1N hydrochloric acid for 1 hour, there was no change in the peripheral edge portion. Also, 85 ℃ × 95
A high temperature and high humidity test was conducted in%, but no change was observed on the end face after 1000 hours. After that, a heat generation test was carried out, and it was confirmed that heat generation occurred without any problem.

Example 10 Visible Light Transmittance 89%, 1
Silver (10 nm thick) on a PET film with a thickness of 00 μm
/ Cu (thickness 1 nm) / silicon nitride (thickness 40 nm) / indium oxide (thickness 60 nm) is deposited by a reactive RF magnetron sputtering method,
A transparent conductive film was formed. The transparent conductive film thus obtained has a visible light transmittance of 76% and a surface resistance of 7Ω / □.
Met. On the obtained laminated film, the same UV-curable transparent epoxy acrylate as used in Example 1 was applied and cured except for the plating electrode portion and the heater electrode formation region portion, and a transparent protective layer having a thickness of 10 μm was formed. Formed.
Next, electroplating was performed in a nickel sulfamate plating bath having a pH of 4.5 to form a nickel film having a thickness of 5 μm, which was used as a plated metal layer. The size of the electrode is 125 mm (length) ×
The width was 4 mm and the distance between the electrodes was 90 mm. The resistance between both electrodes was 5Ω.

When this transparent sheet 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.

Next, 5 1,2,3 benzotriazole was added.
The modified vinyl acetate resin containing 5% by weight was applied to the cross section of the transparent sheet heater in a thickness of 5 μm and kept at 110 ° C. for 5 minutes to provide an organic protective layer containing a corrosion inhibitor.

When this was immersed in 1N hydrochloric acid for 1 hour,
There was no change in the end faces. In addition, a high temperature and high humidity test was performed at 85 ° C. × 95%, but after 1,000 hours, no change was observed on the end faces. After that, a heat generation test was carried out, and it was confirmed that heat generation occurred without any problem.

<Comparative Example 5> A transparent planar heater produced in the same manner as in Example 7 was subjected to 1N without corrosive treatment.
When immersed in hydrochloric acid for 1 hour, there was spot-like discoloration on the end face, and the end face was partially peeled off.

<Comparative Example 6> The transparent flat heater produced in the same manner as in Example 8 was subjected to an anti-corrosion treatment, and the end surface thereof was changed to 85.
A high temperature and high humidity test was conducted at ℃ × 95%, but after 500 hours, spot-like discoloration appeared on the end face, and after 1,000 hours, spot-like discoloration entered into the vicinity of the center, and the transparent surface It can no longer be used as a heater.

<Comparative Example 7> A transparent planar heater produced in the same manner as in Example 9 was treated with 1N without corrosive treatment.
When immersed in hydrochloric acid for 1 hour, there was spot-like discoloration on the end face, and the end face was partially peeled off.

Example 11 On a PET film having a visible light transmittance of 89% and a thickness of 100 μm, silver (thickness: 10 n
m) / copper (thickness 1 nm) / silicon nitride (thickness 30 nm)
A laminated film made of / indium oxide (thickness 60 nm) was deposited by a reactive DC magnetron sputtering method using a metal target to form a transparent conductive film. The visible light transmittance of the obtained transparent conductive film is 7
The surface resistance was 6% and the surface resistance was 7Ω / □. On the obtained transparent conductive film, the solvent is used except for the region to be joined with the transparent substrate and the anticorrosion layer, the region other than the patterned conductive film on the heating surface, the electrode forming region for the heater and the electrode for plating. A UV-curable transparent urethane acrylate of a mold was applied and cured to form a transparent protective layer having a predetermined pattern and a thickness of 10 μm. Next, a resist was provided in a region where the transparent substrate and the anticorrosion layer were to be joined. Then, electroplating was performed in a nickel sulfamate plating bath having a pH of 4.5 to form a nickel film having a thickness of 5 μm, which was used as an electrode. In addition, the resist is 1% KO
After immersing in an aqueous solution of H and removing it, immersing in an 8% hydrochloric acid solution to form a conductive film having a predetermined pattern with a conductive film line width at the central portion of 200 μm, and removing unnecessary conductive film (Fig. 30).

The size of the electrode is 125 mm (length) x 4 m
m (width) and the distance between the electrodes was 90 mm. In addition, leaving the area corresponding to the connection part with the external electrode in the electrode 2
An anticorrosion layer was formed of transparent urethane acrylate having a thickness of 0 μm.

After the transparent substrate region from which the transparent conductive film is removed and the corrosion-resistant layer are separated from each other, a connecting metal fitting is resistance-welded to a region corresponding to a connection portion to an external electrode on which no corrosion-resistant layer is provided. It was heat-fused and attached to the electrode with.

Then, a pressure sensitive adhesive layer (adhesive layer) with a separator (release sheet) was provided on the transparent substrate side to complete a transparent sheet heater with connecting terminals.

The resistance between both electrodes of the formed transparent sheet heater was 5Ω. Peel off the separator of the transparent sheet heater to which the power supply wire is connected by soldering to the metal fittings and attach it to the glass plate. Then, put this transparent sheet heater together with the glass plate in a constant temperature bath at -20 ° C and leave it there. 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. The temperature distribution within the heating surface was ± 1 ° C, which was uniform.

Next, when immersed in 1N hydrochloric acid for 1 hour,
There was no change in the end faces. A high temperature and high humidity test was performed at 85 ° C. × 95%, but after 1,000 hours, no change was observed on the end faces. After that, a heat generation test was conducted, and heat was generated without any abnormality.

[0150]

According to the present invention described above, the durability against contaminants such as moisture is improved and the environmental stability is excellent,
A transparent planar heater having high reliability and high light transmittance and a method for manufacturing the same can be provided.

[Brief description of drawings]

FIG. 1 is a schematic plan view of a preferred example of the present invention.

FIG. 2 is a schematic cross-sectional view taken along the line A-A ′ in FIG.

3A and 3B are schematic cross-sectional views taken along the line BB ′ of FIG. 1.

4 is a schematic perspective view of FIG. 1. FIG.

5 is a schematic cross-sectional view taken along the line AA ′ in FIG. 1 to show another example.

FIG. 6 is a schematic cross-sectional view taken along the line AA ′ in FIG. 1 to show another example.

FIG. 7 is a schematic plan view of another preferred example of the present invention.

FIG. 8 is a schematic cross-sectional view taken along the line C-C ′ of FIG.

9 is a schematic cross-sectional view taken along the line AA ′ of FIG. 1 to show another example.

FIG. 10 is a schematic cross-sectional view taken along the line D-D ′ of FIG.

FIG. 11 is a schematic cross-sectional view taken along the line DD ′ of FIG. 1 to show another example.

FIG. 12 is a schematic cross-sectional view showing a preferable example in which the transparent planar heater of the present invention is attached to a support, in particular.

FIG. 13 is a schematic plan view of a preferred example of the present invention.

FIG. 14 is a schematic cross-sectional view taken along the line A-A ′ in FIG.

FIG. 15 is a schematic perspective view of FIG.

FIG. 16 is a schematic cross-sectional view taken along the line AA ′ in FIG. 13 to show another example.

FIG. 17 is a schematic cross-sectional view taken along the line AA ′ of FIG. 13 to show another example.

FIG. 18 is a schematic cross-sectional view taken along the line AA ′ of FIG. 13 to show another example.

FIG. 19 is a diagram illustrating a step in the method for manufacturing a transparent planar heater of the present invention, (a) is a schematic plan view,
(B) is the typical cross section.

FIG. 20 is a diagram illustrating steps in the method for manufacturing a transparent sheet heater of the present invention, in which (a) is a schematic plan view,
(B) is the typical cross section.

FIG. 21 is a diagram illustrating the steps in the method for manufacturing a transparent planar heater of the present invention, in which (a) is a schematic plan view,
(B) is the typical cross section.

FIG. 22 is a view illustrating steps in the method for manufacturing a transparent sheet heater of the present invention, (a) is a schematic plan view,
(B) is the typical cross section.

FIG. 23 is a diagram illustrating the steps in the method for manufacturing a transparent planar heater of the present invention, (a) is a schematic plan view,
(B) is the typical cross section.

FIG. 24 is a diagram illustrating the steps in the method for producing a transparent planar heater of the present invention, in which (a) is a schematic plan view,
(B) is the typical cross section.

FIG. 25 is a view illustrating steps in the method for manufacturing a transparent sheet heater of the present invention, (a) is a schematic plan view,
(B) is the typical cross section.

FIG. 26 is a diagram illustrating the steps in the method for producing a transparent sheet heater of the present invention, in which (a) is a schematic plan view,
(B) is the typical cross section.

27 (a) and (b) are schematic perspective views showing other examples of the external connection fittings.

FIG. 28 is a schematic perspective view showing another example of the external connection fitting.

FIG. 29 is a schematic plan view illustrating a transparent planar heater of the present invention having a transparent conductive film having a desired pattern shape.

FIG. 30 is a schematic plan view illustrating a transparent planar heater of the present invention having a transparent conductive film having a desired pattern shape.

FIG. 31 is a schematic cross-sectional view illustrating a conventional transparent sheet heater.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent planar heater 2 Transparent substrate 3 Transparent conductive film 5, 5'electrode 5a, 5a 'connecting part 5b, 5b' conductive resin layer 5c, 5c 'plated metal layer 6 transparent protective layer 7 transparent protective plastic member 8 adhesive layer 9 Transparent protective plastic film 10 Adhesive layer 11 Separator 12, 12 'Hole 13, 13' External connection metal fitting 14, 14 'Eyelet 15 Polarizing plate (P) 16 Polarizing plate (Q) 17 Liquid crystal display element 18 Backlight 31 Corrosion-proof component Layer 32 Resin layer containing anticorrosion component 40 Resist 41 Metal plating layer 42 Hole 51 Transparent substrate 52 Transparent conductive film 53, 53 'Electrode 54 Transparent protective layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuichiro Harada 2-1-1, Tangodori, Minami-ku, Nagoya, Aichi Prefecture Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Yoshihiro Sakai 2-chome, Tangodori, Minami-ku, Aichi Prefecture 1 Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Toshihiro Hyakudo 3-5 Kasumigaseki, Chiyoda-ku, Tokyo Inside Mitsui Toatsu Chemical Co., Ltd. (72) Akemi Nakajima 2 Tango Dori, Minami-ku, Nagoya-shi, Aichi Prefecture 1-chome Mitsui Toatsu Chemical Co., Ltd.

Claims (17)

[Claims] 1. A transparent substrate, a transparent conductive film laminated on the transparent substrate, a first electrode extending on a first end portion of the transparent conductive film, and a relative distance from the first end portion. A transparent planar heater comprising: a second electrode extending on a facing second end portion; and a transparent protective layer laminated on a portion of the transparent conductive film where no electrode is formed, A transparent sheet heater, wherein the cross section of the conductive film is subjected to anticorrosion treatment. 2. The transparent sheet heater according to claim 1, wherein the transparent conductive film has a predetermined pattern and functions as a heat generating surface of the transparent sheet heater. 3. The transparent planar heater according to claim 1, wherein the cross section of the electrode and the cross section of the transparent protective layer are subjected to anticorrosion treatment. 4. The transparent surface according to claim 1, wherein the transparent conductive film includes at least one layer each of a transparent thin film and a metal thin film containing at least one selected from the group consisting of silver and copper as a main component. Shaped heater. 5. The transparent thin film is a single layer of a material selected from the group consisting of metal oxides, metal nitrides, metal oxynitrides, metal nitrides and metal carbides, or a laminate composed of two or more layers. The transparent sheet heater according to claim 4. 6. The metal thin film is a first metal thin film (A).
And a second metal thin film (B) and are laminated from the transparent substrate side like AB, BAB, or BA. The first metal thin film (A) is (i) silver and A single layer or laminate of at least one metal selected from the group (a1) consisting of copper, (ii) a group (a2) consisting of at least one metal selected from the group (a1), and palladium, platinum and gold A single layer or a laminate of an alloy thin film with at least one metal selected, or (iii) at least one metal selected from the group (a1) and at least one metal selected from the group (a2) The second metal thin film (B) is a single layer or a laminated body of a mixture thin film composed of: (iv) copper, nickel, tin, indium, titanium, palladium, aluminum, chromium, silicon, tungsten, vanadium, zinc. , Tan A single layer or a laminate of at least one metal selected from the group (b1) consisting of aluminum, gold, platinum and cobalt, (v) a single layer of an alloy thin film of at least one metal selected from the group (b1). The transparent planar heater according to claim 4, which is a laminated body, or (vi) a single layer or laminated body of a mixture thin film composed of at least one metal selected from the group (b1). 7. The transparent sheet heater according to claim 1, wherein the anticorrosion treatment of the cross section of the transparent conductive film is performed by providing a transparent protective plastic member. 8. The transparent sheet heater according to claim 7, wherein the transparent protective plastic member is a transparent protective plastic film or sheet. 9. The transparent planar heater according to claim 7, wherein the transparent protective plastic member is provided via an adhesive layer. 10. The transparent planar heater according to claim 7, wherein the transparent protective plastic member is provided on the entire end surface of the heater. 11. The anticorrosion treatment of the cross section of the transparent conductive film comprises:
The transparent sheet heater according to claim 1 or 2, which is formed by using an anticorrosive agent. 12. The anticorrosive agent is 1) one or more active ingredients selected from the group consisting of benzotriazole, indazole, imidazole, and derivatives thereof, 2) amino acids, amino acid esters, alkali metal salts of amino acids, One or more active ingredients selected from the group consisting of ammonia and amine salts, 3) active ingredients of mercaptan or molecules closely related thereto derived from them, 4) active ingredients of copper chelate compounds, 5) the above 1) to 4), or 6) the mixture of 1) to 4) containing a third component,
The transparent sheet heater according to claim 11, which comprises: 13. The transparent planar heater according to claim 12, wherein an organic protective layer containing an anticorrosive agent comprising any of the components 1) to 6) is provided on at least a cross section of the transparent conductive film. 14. The transparent planar heater according to claim 12, wherein an adhesive layer containing a corrosion inhibitor composed of any of the components 1) to 6) is provided on at least a cross section of the transparent conductive film. 15. A transparent substrate, a transparent conductive film laminated on the transparent substrate, a first electrode extending on a first end portion of the transparent conductive film, and a relative distance from the first end portion. In a method for producing a transparent planar heater, comprising: a second electrode extending on a facing second end portion; and a transparent protective layer laminated on a portion of the transparent conductive film where no electrode is formed. A method for manufacturing a transparent sheet heater, comprising a step of subjecting a cross section of the transparent conductive film to an anticorrosion treatment. 16. A first step of providing the transparent protective layer on a surface corresponding to a heat generating surface of the transparent conductive film laminated on one main surface of the transparent substrate, and a step of providing a transparent protective plastic member. A second step of providing a resist in a corresponding region of the transparent conductive film, a third step of providing the first electrode and a second electrode, and a fourth step of removing the resist,
A fifth step of removing the unnecessary transparent conductive film, a sixth step of covering at least the cross section of the transparent conductive film and the peripheral edge portion of the heater with the transparent protective plastic member, and a seventh step of removing the unnecessary portion. A method for manufacturing a transparent sheet heater including: 17. A first step of preliminarily producing a transparent planar heater in which a cross section of the transparent conductive film is not covered with a transparent protective plastic member, a cross section of the transparent conductive film, and a peripheral edge portion of the heater, The method for producing a transparent planar heater according to claim 15, further comprising a second step of covering both main surfaces with a transparent protective plastic member.