JP2008077879A - Transparent flexible film heater and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent flexible film heater having a high heat generation property, high transparency and excellent visibility at the same time, and having, in a pattern-like form, a current-carrying heat-generating metal thin wire in a transparent layer; and a manufacturing method of the transparent flexible film heater capable of easily forming a pattern, and of inexpensively manufacturing the transparent flexible film heaters in large numbers. <P>SOLUTION: This transparent flexible film heater is a heating element having a substantially transparent conductive metal pattern structure on a transparent flexible support body, and satisfies expression (1): 0.1≤E<SP>2</SP>/(L×R)≤2.0 when it is assumed that a distance between application electrodes of the heating element, resistance between electrodes of the heating element and a power voltage are L (cm), R(Ω) and E (v), respectively. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a transparent flexible film heater excellent in visibility and heat generation and a method for producing the same.

Conventionally, as a transparent flexible film heater, one in which a metal oxide conductive material such as ITO or tin oxide is attached to a plastic base such as PET by a method such as sputtering is known (Patent Documents 1 to 3). Since these are large in resistance, when the size is increased, the total resistance value becomes large, so that a high voltage power source is required. For this reason, these transparent flexible film heaters have limitations such as a practical size limit and a high voltage circuit such as a step-up transformer.
JP-A 64-38990 JP-A-6-333881 JP-A-6-283260

  The object of the present invention is to provide a transparent flexible heat-generating film that exhibits high heat generation (high temperature rise ΔT, high heat generation efficiency, high durability) even with a low-voltage power source such as a battery, especially a large-sized transparent flexible film. It is to provide a heater and a manufacturing method thereof.

As a result of extensive research, the present inventors have found that a heating element having a substantially transparent conductive metal pattern structure and a transparent flexible film heater satisfying the following relational expression is suitable for the required size and power supply voltage. It was found that high exothermicity was developed. The term “substantially transparent” as used herein means that the light transmittance at 500 nm is 70% or more, and does not cause observational damage when viewed through the film.
That is, the objective of this invention is achieved by the following transparent flexible film heater and its manufacturing method.

(1) A heating element having a substantially transparent conductive metal pattern structure on a transparent flexible support, and the distance between the electrodes applied to the heating element is L (cm), and the resistance between the electrodes of the heating element Is a transparent flexible film heater characterized by satisfying the following formula (1) where R (Ω) is the power supply voltage and E (v) is the power supply voltage.
0.1 ≦ E ² /(L×R)≦2.0 Formula (1)
(2) The heating element having the conductive metal pattern structure has a pattern structure including a conductive metal portion made of a fine metal wire having a line width of 50 μm or less and a light-transmitting portion surrounded by the fine wire portion. The transparent flexible film heater as described in (1) above,
(3) The transparent flexible film heater according to (2) above, wherein the line width of the fine metal wire portion is 25 μm or less.
(4) The transparent flexible film heater according to the above (2) or (3), wherein the line width of the thin metal wire portion is 0.4 μm or more and 50 μm or less.
(5) The above-mentioned (2), wherein the line width of the fine metal wire portion is 0.4 μm or more and 50 μm or less, and the ratio of the light transmitting portion / total film area is 70 to 99.9%. The transparent flexible film heater according to any one of (1) to (4).
(6) In any one of the above (1) to (5), the pattern structure is a quadrilateral (including square and rhombus) mesh, hexagonal mesh, parallel straight line pattern, parallel wave line pattern, or parallel zigzag pattern. The transparent flexible film heater as described.
(7) The heating element having the conductive metal pattern structure exposes and develops a silver salt-containing layer containing photosensitive silver halide provided on a support, and thereby a metallic silver portion and light transmittance The transparent flexible film heater according to any one of the above (1) to (6), wherein the transparent flexible film heater is formed by performing a consolidation treatment after forming the portion.
(8) The heating element having the conductive metal pattern structure exposes and develops a silver salt-containing layer containing a photosensitive silver halide provided on the support, thereby developing a metallic silver portion and a light transmitting property. The metal silver part is formed by carrying conductive metal particles by subjecting the metal part to physical development and / or plating treatment, (1) to (1) above (7) The transparent flexible film heater in any one of.
(9) The heating element having the conductive metal pattern structure exposes and develops a silver salt-containing layer containing a photosensitive silver halide provided on the support, thereby developing a metallic silver portion and a light transmitting property. And the metal part is subjected to physical development and / or plating treatment to carry conductive metal particles on the metal silver part and then compacted, (7) ) Or the transparent flexible film heater according to (8).

(10) The transparent flexible film heater according to any one of (7) to (9), wherein the silver halide is mainly composed of silver bromide.
(11) The transparent flexible film heater as described in any one of (7) to (10) above, wherein an Ag / binder volume ratio in the silver salt-containing layer is 1/4 or more.
(12) The transparent flexible film heater according to any one of (7) to (10) above, wherein an Ag / binder volume ratio in the silver salt-containing layer is ½ or more.
(13) The transparent flexible film heater as described in any one of (7) to (12) above, wherein an average spherical equivalent diameter of silver halide contained in the silver salt-containing layer is 0.1 to 100 nm. .
(14) The transparent flexible film heater according to any one of (7) to (13), wherein the exposure is performed by a scanning exposure method using a laser beam.
(15) The transparent flexible film heater as described in any one of (7) to (14) above, wherein the exposure is performed through a photomask.
(16) The transparent flexible film heater as described in any one of (7) to (15) above, wherein the developer used in the development treatment of the silver salt-containing layer contains an image quality improver.
(17) The transparent flexible film heater according to (16), wherein the image quality improver is a nitrogen-containing heterocyclic compound.
(18) The transparent flexible film heater as described in any one of (7) to (17) above, wherein the developer used in the development treatment of the silver salt-containing layer is a lith developer.
(19) The mass of the metallic silver contained in the exposed area after the development treatment is a content of 50% by mass or more based on the mass of silver contained in the exposed area before the exposure. The transparent flexible film heater according to any one of (7) to (18) above.
(20) The transparent flexible film heater as described in (8) above, wherein the plating treatment is performed by electroless plating.
(21) The transparent flexible film heater as described in (8) above, wherein the plating treatment is performed by electrolytic plating.
(22) The transparent flexible film heater according to any one of (8), (20), and (21), wherein the plating treatment is performed by electroless plating and subsequent electrolytic plating.
(23) The transparent flexible film heater as described in (20) or (22) above, wherein the electroless plating is electroless copper plating.
(24) The transparent flexible film heater as described in any one of (7) to (23) above, wherein the gradation after the development processing of the silver salt-containing layer exceeds 4.0.
(25) The transparent flexible film heater according to any one of (1) to (24), wherein the surface of the conductive metal portion is further blackened.
(26) The transparent flexible film heater as described in any one of (1) to (25) above, wherein the light-transmitting part does not have a physical development nucleus.
(27) The surface resistance of the transparent flexible film heater after the physical development and / or plating treatment and / or consolidation treatment is 100Ω / sq or less, and the transmittance of the light transmissive part is 95% or more. The transparent flexible film heater according to any one of (1) to (26) above,
(28) The surface resistance of the transparent flexible film heater after the physical development and / or plating treatment and / or consolidation treatment is 0.1 to 50Ω / sq, and the transmittance of the light transmissive portion is 95% or more. The transparent flexible film heater as described in (26) above, wherein

(29) The transparent flexible film heater as described in any one of (1) to (28) above, wherein the mass of silver is 50% by mass or more based on the total mass of the metal components contained in the conductive metal part. .
(30) The total mass of silver, copper, and palladium with respect to the total mass of the metal component contained in the conductive metal part is 80% by mass or more, and any one of (1) to (29) above The transparent flexible film heater as described.
(31) The transparent flexible film heater as described in any one of (1) to (30) above, wherein the opening ratio of the conductive metal portion is 85% or more.
(32) The above characterized in that the layer composed of conductive metal particles carried on the conductive metal part has a thickness of 0.1 μm or more and less than 30 μm and a surface resistance value of 100Ω / sq or less. The transparent flexible film heater according to any one of 1) to (31).
(33) The transparent flexible film heater as described in any one of (1) to (32) above, wherein the support is made of a plastic film having a thickness of 8 to 200 μm.
(34) The plastic film constituting the support is polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyvinyl chloride, polyvinylidene chloride, polyvinyl butyral, polyamide, polyether, polysulfone, polyethersulfone, polycarbonate, (33) above, characterized in that it is a polyolefin such as polyarylate, polyetherimide, polyetherketone, polyetheretherketone, EVA, polycarbonate, triacetylcellulose (TAC), acrylic resin, polyimide, or aramid. The transparent flexible film heater as described.
(35) The transparent flexible film heater as described in any one of (1) to (34) above, wherein the light transmissive portion has a transmittance of 95% or more.
(36) The transparent flexible film heater as described in any one of (1) to (35) above, wherein a transmittance of the light transmissive portion is 98% or more.
(37) A silver salt-containing layer containing photosensitive silver halide provided on a support is exposed and developed to form a metallic silver portion and a light-transmitting portion, and then subjected to a compaction treatment to conduct electricity. A heating element having a conductive metal pattern structure is formed. The method for producing a transparent flexible film heater according to (1).
(38) A silver salt-containing layer containing photosensitive silver halide provided on the support is exposed and developed to form a metallic silver part and a light-transmitting part, and the metallic part is physically developed. And / or forming a heating element having a conductive metal pattern structure by carrying conductive metal particles on the metal silver portion by plating, and manufacturing the transparent flexible film heater according to (1) Method.

The transparent flexible film heater and the method for producing the same of the present invention have the following effects and utilities.
1) Free patterning is possible by changing the exposure pattern.
2) The energization resistance value can be easily adjusted by changing the post-processing conditions such as exposure line width, exposure pattern, physical development, and plating, or changing the silver halide emulsion coating amount.
3) The specific resistance value can be easily changed by changing the Ag ratio in the coating or the compaction conditions.
In particular, the transparent flexible film heater of the present invention has excellent visibility and heat generation, when the light passing through the transparent flexible film heater is observed, the presence of an electric heating element such as a thin metal wire pattern is not recognized or at least not bothered. It has sex.
Another advantage of the present invention is that it can be manufactured by exposing and developing a silver salt material, particularly a silver halide photographic light-sensitive material, and if necessary, can be produced by adding a plating process, a physical development process or a consolidation process. And can be supplied by a method capable of mass production.

Below, the transparent flexible film heater of this invention and its manufacturing method are demonstrated in detail.
In the present specification, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.

As described above, the transparent flexible film heater of the present invention is excellent in translucency, energization heat generation and visibility. In particular, it is characterized by high heat generation even under disadvantageous conditions such as large size and low voltage power supply.
The transparent flexible film heater of the present invention is a heating element having a substantially transparent conductive metal pattern structure on a transparent flexible support, and the distance between applied electrodes of the heating element is L (cm). When the resistance between the body electrodes is R (Ω) and the power supply voltage is E (v), the following equation (1) is satisfied.
0.1 ≦ E ² /(L×R)≦2.0 Formula (1)
If E ² / (L × R) represented by the formula (1) is less than 0.1, sufficient heat generation cannot be obtained at a low voltage, and if it exceeds 2.0, the heat generation efficiency tends to decrease. E ² / (L × R) is preferably 0.2 to 1.5.
The heating element having the conductive metal pattern structure preferably includes a conductive metal portion made of a fine metal wire having a line width of 50 μm or less and a light transmissive portion surrounded by the fine wire portion. The line width of the fine metal wire portion is 50 μm or less, preferably 25 μm or less. With this line width, the right eye cannot recognize the fine metal wire at a clear vision distance. Therefore, the presence of the energization heating element is not recognized and does not become an obstacle during observation. In addition, if the line width of the metal thin wire portion is 0.4 μm or more, preferably 0.7 μm or more, the scattered light and diffracted light derived from the fine structure of the thin wire are reduced, so that the visibility is further improved.
Furthermore, in order to make translucency, energization exothermicity, and visibility mutually excellent, in addition to the requirements related to the fine line width, it is necessary to satisfy both of translucency and energization exotherm. Although the line width of the fine metal wire portion is 0.4 μm or more and 50 μm or less, the ratio of the light transmitting portion / total film area is preferably 70 to 99.9%. A more preferable light transmitting part / total film area ratio is 85 to 99.9%.
In the present invention, as practical energization exothermic property, the equilibrium temperature at the time of continuous energization is 28 ° C. or more, and the glass transition temperature of the support used + 70 ° C. or less (at the time of energization heating at room temperature). preferable. More preferably, the equilibrium reaching temperature is 30 ° C. or higher, and the glass transition temperature of the support to be used + 50 ° C. or lower (same as above).
In order to adjust to the above preferable temperature range, it is necessary that the resistance value be in an appropriate range. However, since developed silver is generally a rough structure with a filament structure, physical development and electroless plating are described later. Alternatively, it is preferable to thicken the metal portion with an electroplating treatment and using developed silver as a core. As another method, it is preferable to increase the density of the metal part by subjecting the developed silver to a consolidation process, to reduce the resistance value and to improve the heat generation property. It is also preferable to subject the developed silver to further compaction by performing physical development. Particularly preferred is an embodiment in which the consolidation treatment is performed and the plating treatment is not performed.
The consolidation process (smoothing process) is preferably performed by a calendar roll device. A calendar roll usually consists of a pair or a plurality of opposed rolls. As a roll used for the calendar process, a plastic roll such as epoxy, polyimide, polyamide, polyimide amide, or a metal roll is used. In particular, when coating with a double-sided emulsion, it is preferable to treat with metal rolls. The linear pressure is preferably 1960 N / cm (200 kg / cm) or more, and more preferably 2940 N / cm (300 kg / cm) or more.

In addition to the above-described method using a silver halide photographic light-sensitive material, the heating element having a translucent conductive metal pattern structure is provided with a copper foil, that is, a copper metal thin film on a support, and the surface thereof is patterned. It can also be manufactured by a method of forming a conductive metal part by etching.
Moreover, the method of forming the electroconductive metal part formed by performing copper plating on the metal fine particle distribute | arranged to pattern structure form by printing can also be used.
Furthermore, the pattern structure may be formed by a screen printing plate or a gravure printing plate. The printed metal pattern is subjected to metal plating such as copper plating to produce a conductive heating element.

  A method for producing a translucent conductive heating element using a silver halide photographic light-sensitive material, which is a particularly preferable embodiment (resistance value and specific resistance value can be easily changed) of the present invention, will be described below.

In a preferred embodiment of the translucent conductive heating element of the present invention, a photosensitive material having an emulsion layer containing a photosensitive silver halide salt is exposed on a support and subjected to a development treatment to correspond to the exposure. Or, conversely, it can be manufactured by forming a metallic silver portion and a light transmitting portion, respectively. Further, in order to adjust the resistance, the metal silver portion may be subjected to physical development and / or plating treatment so that a conductive metal is supported on the metal silver portion, and / or the metal silver portion may be consolidated.
The method for forming a translucent conductive heating element of the present invention includes the following three forms depending on the photosensitive material and the form of development processing.
(1) An embodiment in which a photosensitive silver halide black-and-white photosensitive material not containing physical development nuclei is chemically developed or thermally developed to form a metallic silver portion on the photosensitive material.
(2) An embodiment in which a photosensitive silver halide black-and-white photosensitive material containing physical development nuclei in a silver halide emulsion layer is dissolved and physically developed to form a metallic silver portion on the photosensitive material.
(3) A photosensitive silver halide black-and-white photosensitive material that does not contain physical development nuclei and an image-receiving sheet having a non-photosensitive layer that contains physical development nuclei are overlaid and diffused and transferred to develop a metallic silver portion on the non-photosensitive image-receiving sheet. Form formed on top.
The aspect (1) is an integrated black-and-white development type, and a light-transmitting conductive film is formed on a photosensitive material. The obtained developed silver is chemically developed silver or heat developed silver, and is highly active in the subsequent plating or physical development process in that it is a filament with a high specific surface.
In the aspect (2), the light-transmitting conductive film is formed on the photosensitive material by dissolving silver halide grains close to the physical development nucleus and depositing on the development nucleus in the exposed portion. This is also an integrated black-and-white development type. Although the developing action is precipitation on physical development nuclei, it is highly active, but developed silver has a spherical shape with a small specific surface.
In the aspect (3), the light-transmitting conductive film is formed on the image receiving sheet by dissolving and diffusing the silver halide grains in the unexposed area and depositing on the development nuclei on the image receiving sheet. This is a so-called separate type in which the image receiving sheet is peeled off from the photosensitive material.
In any embodiment, either negative development processing or reversal development processing can be selected (in the case of the diffusion transfer system, negative development processing is possible by using an auto-positive type photosensitive material as the photosensitive material). .
The chemical development, thermal development, dissolution physical development, and diffusion transfer development mentioned here have the same meanings as are commonly used in the industry, and are general textbooks of photographic chemistry such as Shinichi Kikuchi, “Photochemistry” (Kyoritsu Publishing) (Published in 1955), C.I. E. K. It is described in "The Theory of Photographic Processes, 4th ed." Edited by Mees (Mcmillan, 1977). Although this case is an invention related to liquid processing, it can also be referred to a technique of applying a thermal development method as a development method. For example, JP-A Nos. 2004-184893, 2004-334077, 2005-010752, Japanese Patent Application Nos. 2004-244080, and 2004-085655 can be applied.

<Photosensitive material>
[Support]
As a support for the photosensitive material used in the present invention, a flexible plastic film can be used.
Examples of the plastic film material include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyvinyl chloride, polyvinylidene chloride, polyvinyl butyral, polyamide, polyether, polysulfone, polyethersulfone, polycarbonate, and polyarylate. Polyolefins such as polyetherimide, polyetherketone, polyetheretherketone, EVA, polycarbonate, triacetylcellulose (TAC), acrylic resin, polyimide, or aramid can be used.
In the present invention, a polyethylene terephthalate film is suitable as the plastic film from the viewpoint of transparency, heat resistance, ease of handling, and cost, but it is appropriately selected depending on the necessity of heat resistance and thermoplasticity.
The plastic film in the present invention can be used as a single layer, but can also be used as a multilayer film in which two or more layers are combined.

[Protective layer]
The photosensitive material used may be provided with a protective layer on the emulsion layer described later. In the present invention, the “protective layer” means a layer made of a binder such as gelatin or a high molecular polymer, and is formed in an emulsion layer having photosensitivity in order to exhibit an effect of preventing scratches and improving mechanical properties. The protective layer is preferably not provided for the plating treatment, and even if it is provided, it is preferably thin. The thickness is preferably 0.2 μm or less. The formation method of the coating method of the said protective layer is not specifically limited, A well-known coating method can be selected suitably.

  The halogen element contained in the silver halide may be any of chlorine, bromine, iodine and fluorine, or a combination thereof. For example, silver halide mainly composed of AgCl, AgBr, and AgI is preferably used, and silver halide mainly composed of AgBr or AgCl is preferably used. Silver chlorobromide, silver iodochlorobromide and silver iodobromide are also preferably used. More preferred are silver chlorobromide, silver bromide, silver iodochlorobromide and silver iodobromide, and most preferred are silver chlorobromide and silver iodochlorobromide containing 50 mol% or more of silver chloride. Used.

Silver halide is in the form of solid grains. From the viewpoint of image quality of the patterned metallic silver layer formed after exposure and development, the average grain size of silver halide is 0.1 to 1000 nm in terms of sphere equivalent diameter ( 1 μm) is preferred, 0.1 to 100 nm is more preferred, and 1 to 50 nm is even more preferred.
Incidentally, the sphere equivalent diameter of silver halide grains is the diameter of grains having the same volume and a spherical shape.

The silver halide emulsion used in the present invention may contain a metal belonging to Group VIII or Group VIIB. In particular, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, an iron compound, an osmium compound or the like in order to obtain a gradation of 4 or more or to achieve low fog.
For high sensitivity, doping with a metal hexacyanide complex such as K ₄ [Fe (CN) ₆ ], K ₄ [Ru (CN) ₆ ] or K ₃ [Cr (CN) ₆ ] is advantageous. Done.

A water-soluble rhodium compound can be used as the rhodium compound. Examples of the water-soluble rhodium compound include a rhodium halide (III) compound, a hexachlororhodium (III) complex salt, a pentachloroacorodium complex salt, a tetrachlorodiacolodium complex salt, a hexabromorhodium (III) complex salt, and a hexaamine rhodium (III). ) Complex salt, trizalatodium (III) complex salt, K ₃ Rh ₂ Br _{9 and the} like.

Examples of the iridium compound include hexachloroiridium complex salts such as K ₂ IrCl ₆ and K ₃ IrCl ₆ , hexabromoiridium complex salts, hexaammineiridium complex salts, and pentachloronitrosyliridium complex salts.
Examples of the ruthenium compound include hexachlororuthenium, pentachloronitrosylruthenium, K ₄ [Ru (CN) ₆ ] and the like.
Examples of the iron compound include potassium hexacyanoferrate (II) and ferrous thiocyanate.

  Ruthenium and osmium can be added in the form of water-soluble complex salts described in JP-A-63-2042, JP-A-1-2855941, JP-A-2-20852, JP-A-2-20855, and the like. preferable.

The amount of these compounds added is preferably 10 ⁻¹⁰ to 10 ⁻² mol / mol Ag per mol of silver halide, more preferably 10 ⁻⁹ to 10 ⁻³ mol / mol Ag.

In addition, in the present invention, silver halide containing Pd (II) ions and / or Pd metal can also be preferably used. Pd may be uniformly distributed in the silver halide grains, but is preferably contained in the vicinity of the surface layer of the silver halide grains. Here, Pd “contains in the vicinity of the surface layer of the silver halide grains” means that the Pd content is higher than the other layers within 50 nm in the depth direction from the surface of the silver halide grains. means.
Such silver halide grains can be prepared by adding Pd during the formation of silver halide grains. After adding silver ions and halogen ions to 50% or more of the total addition amount, Pd Is preferably added. It is also preferred that Pd (II) ions be present in the surface layer of the silver halide by a method such as addition at the time of post-ripening.
The Pd-containing silver halide grains increase the speed of physical development and electroless plating, increase the production efficiency of a desired transparent flexible film heater, and contribute to the reduction of production costs. Pd is well known and used as an electroless plating catalyst. However, in the present invention, Pd can be unevenly distributed on the surface layer of silver halide grains, so that extremely expensive Pd can be saved. is there.

In the present invention, the content of Pd ions and / or Pd metals contained in the silver halide is preferably 10 ^{−4 to} 0.5 mol / mol Ag with respect to the number of moles of silver in the silver halide. More preferably, it is 0.01 to 0.3 mol / mol Ag.
Examples of the Pd compound to be used include PdCl ₄ and Na ₂ PdCl ₄ .

  In the present invention, in order to further improve the sensitivity as an optical sensor, chemical sensitization performed with a photographic emulsion can be performed. As the chemical sensitization method, sulfur sensitization, selenium sensitization, chalcogen sensitization such as tellurium sensitization, noble metal sensitization such as gold sensitization, reduction sensitization and the like can be used. These are used alone or in combination. When the above chemical sensitization methods are used in combination, for example, sulfur sensitization method and gold sensitization method, sulfur sensitization method and selenium sensitization method and gold sensitization method, sulfur sensitization method and tellurium sensitization. A combination of a method and a gold sensitization method is preferable.

The sulfur sensitization is usually performed by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a predetermined time. As the sulfur sensitizer, known compounds can be used. For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. Can be used. Preferred sulfur compounds are thiosulfate and thiourea compounds. The amount of sulfur sensitizer added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, and is 10 ⁻⁷ to 10 ⁻² mol per mol of silver halide. Preferably, it is 10 ^<-5 > ^-10 <^-3> mol.

  A known selenium compound can be used as the selenium sensitizer used for the selenium sensitization. That is, the selenium sensitization is usually carried out by adding unstable and / or non-labile selenium compounds and stirring the emulsion at a high temperature of 40 ° C. or higher for a predetermined time. As the unstable selenium compound, compounds described in JP-B-44-15748, JP-A-43-13489, JP-A-4-109240, JP-A-4-324855 and the like can be used. In particular, it is preferable to use compounds represented by general formulas (VIII) and (IX) in JP-A-4-324855.

  The tellurium sensitizer used for the tellurium sensitizer is a compound that generates silver telluride presumed to be a sensitization nucleus on the surface or inside of a silver halide grain. The silver telluride formation rate in the silver halide emulsion can be tested by the method described in JP-A-5-313284. Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211, No. 1,121,496, No. 1,295,462, No. 1,396,696, Canadian Patent No. 800,958, JP-A-4-204640 No. 4-271341, No. 4-3333043, No. 5-303157, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.), P. 635 (1980). 1102 (1979), 645 (1979), Journal of Chemical Society Parkin Transaction (J. Ch.) m.Soc.Perkin.Trans.) 1, pp. 2191 (1980), S. Compounds described in The Chemistry of Organic Selenium and Tellunium Compounds, Volume 1 (1986), Volume 2 (1987), edited by S. Patai, The Chemistry of Organic Selenium and Tellurium Companies Can be used. In particular, compounds represented by general formulas (II), (III) and (IV) in JP-A-5-313284 are preferred.

The amount of selenium sensitizer and tellurium sensitizer that can be used in the present invention varies depending on the silver halide grains used, chemical ripening conditions, and the like, but is generally 10 ⁻⁸ to 10 ⁻² per mole of silver halide. A mole, preferably about 10 ⁻⁷ to 10 ⁻³ mole is used. The conditions for chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

Examples of the noble metal sensitizer include gold, platinum, palladium, iridium and the like, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used for gold sensitization include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, thioglucose gold (I), and thiomannose gold (I). About 10 ⁻⁷ to 10 ⁻² mol per mol of silver halide. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of silver halide grain formation or physical ripening.

  In the present invention, reduction sensitization can be used. As the reduction sensitizer, stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used. A thiosulfonic acid compound may be added to the silver halide emulsion by the method described in European Patent Publication (EP) 293917. The silver halide emulsion used in the preparation of the light-sensitive material used in the present invention may be only one type, or two or more types (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, Combinations of different chemical sensitization conditions and different sensitivities) may be used. In particular, in order to obtain high contrast, as described in JP-A-6-324426, it is preferable to apply an emulsion with higher sensitivity as it is closer to the support.

<Binder>
In the emulsion layer, a binder can be used for the purpose of uniformly dispersing silver salt grains and assisting the adhesion between the emulsion layer and the support. In the present invention, as the binder, both water-insoluble polymers and water-soluble polymers can be used as binders, but it is preferable to use water-soluble polymers.
Examples of the binder include polysaccharides such as gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch, cellulose and derivatives thereof, polyethylene oxide, polysaccharides, polyvinylamine, chitosan, polylysine, polyacrylic acid, polyacrylic acid, and the like. Examples include alginic acid, polyhyaluronic acid, and carboxycellulose. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group.

  The content of the binder contained in the emulsion layer is preferably adjusted so that the Ag / binder volume ratio in the silver salt-containing layer is 1/4 or more, and is adjusted to be 1/2 or more. Is more preferable.

<Solvent>
The solvent used for forming the emulsion layer is not particularly limited. For example, water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, sulfoxides such as dimethyl sulfoxide, etc. , Esters such as ethyl acetate, ethers, etc.), ionic liquids, and mixed solvents thereof.
The content of the solvent used in the emulsion layer of the present invention is in the range of 30 to 90% by mass and in the range of 50 to 80% by mass with respect to the total mass of silver salt, binder and the like contained in the emulsion layer. Preferably there is.

Next, each step of producing a transparent flexible film heater using a photosensitive material will be described.
[exposure]
Exposure to a photosensitive material having a silver salt-containing layer on the support is performed. The exposure can be performed using electromagnetic waves. Examples of the electromagnetic wave include light such as visible light and ultraviolet light, and radiation such as X-rays. Furthermore, a light source having a wavelength distribution may be used for exposure, or a light source having a specific wavelength may be used.

  As the light source, various light emitters that emit light in the visible spectrum region are used as necessary. For example, any one or two or more of a red light emitter, a green light emitter, and a blue light emitter are used. The spectral region is not limited to the above red, green, and blue, and phosphors that emit light in the yellow, orange, purple, or infrared region are also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used. An ultraviolet lamp is also preferable, and g-line of a mercury lamp, i-line of a mercury lamp, etc. are also used.

As an exposure method for forming a pattern image, a surface exposure method for irradiating a photosensitive surface with uniform light through a mask pattern to form a mask pattern imagewise, and a pattern irradiation unit by scanning a beam such as a laser beam There is a scanning exposure method in which is formed on the photosensitive surface.
In the former case, each of the above-described light sources can be used, and a general-purpose tungsten lamp, a halogen lamp for producing a photographic print, an LED, a fluorescent lamp, or the like can be appropriately used. In this case, the printing exposure includes a continuous conveyance exposure method that synchronizes the speed of the exposure surface that moves with the conveyance of the photosensitive material and the mask-modulated irradiation light, and intermittent conveyance that temporarily stops conveyance and performs flash exposure. -It may be performed by any of the intermittent irradiation exposure methods.

In the latter case, the pattern image is drawn while moving the exposure beam in the direction perpendicular to the moving direction while moving the exposure surface. In order to draw a pattern image, it is appropriate to combine the main irradiation for pattern drawing and the sub-irradiation that performs intermittent irradiation only at the intersection. The main irradiation and the sub-irradiation may be performed simultaneously during one exposure surface movement, or after the main irradiation scanning exposure, the exposure surface may be moved again to perform the sub-irradiation exposure. Further, the main irradiation for drawing the intersection line pattern may be continuous beam irradiation or digital beam irradiation in which a beam having a rectangular cross section is intermittently irradiated into a figure shape for drawing.
The exposure can be performed using various laser beams. For example, the exposure in the present invention is a monochromatic light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) that combines a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. A scanning exposure method using high-density light can be preferably used, and a KrF excimer laser, ArF excimer laser, F2 laser, or the like can also be used. In order to make the system compact and inexpensive, exposure is more preferably performed using a semiconductor laser, a semiconductor laser, or a second harmonic generation light source (SHG) that combines a solid-state laser and a nonlinear optical crystal. In order to design an apparatus that is particularly compact, inexpensive, long-life, and highly stable, it is most preferable to perform exposure using a semiconductor laser.
The energy of the exposure, in the case of using the silver halide is preferably from 1 mJ / cm ² or less, more preferably 100 .mu.J / cm ² or less, more preferably 50μJ / cm ² or less.

Specifically, as a laser light source, a blue semiconductor laser with a wavelength of 430 to 460 nm (announced by Nichia Chemical at the 48th Applied Physics Related Conference in March 2001), a semiconductor laser (oscillation wavelength of about 1060 nm) is used. waveguide-like inverted domain structure about 530nm green laser taken out by wavelength conversion by the SHG crystal of LiNbO ₃ having a red semiconductor laser having a wavelength of about 685 nm (Hitachi type No.HL6738MG), red semiconductor laser having a wavelength of about 650 nm ( Hitachi type No. HL6501MG) is preferably used.

The method of exposing the silver salt-containing layer in a pattern is preferably scanning exposure using a laser beam. In particular, a capstan type laser scanning exposure apparatus described in Japanese Patent Application Laid-Open No. 2000-39677 is preferable. Further, in this capstan method, a DMD described in Japanese Patent Application Laid-Open No. 2004-1224 is optically used instead of beam scanning by rotation of a polygon mirror. It is also preferable to use for a beam scanning system.
In particular, when a long flexible film heater having a length of 3 m or more is prepared, it is preferable to perform exposure with a laser beam while conveying a photosensitive material on a curved exposure stage.

  As described later, the mesh pattern is a lattice pattern such as a triangle, a quadrangle (rhombus, square, etc.) hexagon formed by intersecting substantially parallel straight thin lines, a parallel straight line, a zigzag line, or a wavy line. For example, the structure is not particularly limited as long as a current can flow between electrodes to which a voltage is applied.

[Development processing]
In the present invention, after the emulsion layer is exposed, further development processing is performed. The development processing can be performed by a normal development processing technique used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion mask, and the like. The developer is not particularly limited, but a PQ developer, MQ developer, MAA developer, and the like can also be used. Commercially available products include, for example, CN-16, CR-56, CP45X of Fuji Photo Film Co., Ltd. Developers such as FD-3, papitol, C-41, E-6, RA-4, D-19, D-72 formulated by KODAK, or a developer included in the kit can be used. A lith developer can also be used.
As the squirrel developer, D85 or the like prescribed by KODAK can be used. In the present invention, by performing the above exposure and development treatment, a patterned metal silver portion is formed in the exposed portion, and a light transmissive portion described later is formed in the unexposed portion.

  The developer used in the development process can contain an image quality improver for the purpose of improving the image quality. Examples of the image quality improving agent include nitrogen-containing heterocyclic compounds such as benzotriazole. In addition, it is also preferable to use polyethylene glycol, particularly when a lith developer is used.

  The mass of the metallic silver contained in the exposed portion after the development treatment is preferably a content of 50% by mass or more, and 80% by mass or more with respect to the mass of silver contained in the exposed portion before exposure. More preferably. If the mass of silver contained in the exposed portion is 50% by mass or more based on the mass of silver contained in the exposed portion before exposure, it is preferable because high conductivity can be obtained.

  The gradation after development processing in the present invention is not particularly limited, but is preferably more than 4.0. When the gradation after the development processing exceeds 4.0, the conductivity of the conductive metal portion can be increased while keeping the transparency of the light transmissive portion high. Examples of means for setting the gradation to 4.0 or higher include the aforementioned doping of rhodium ions and iridium ions.

[Physical development and plating]
In the present invention, for the purpose of increasing the conductivity of the metal silver portion formed by the exposure and development processing, physical development and / or plating treatment for supporting the conductive metal particles on the metal silver portion can also be performed. . In the present invention, the conductive metal particles can be supported on the metallic silver portion by only one of physical development and plating. However, the combination of physical development and plating is used to convert the conductive metal particles to metallic silver. It can also be carried on the part.
“Physical development” in the present invention means that metal particles such as silver ions are reduced with a reducing agent on metal or metal compound nuclei to deposit metal particles. This physical phenomenon is used in instant B & W film, instant slide film, printing plate manufacturing, and the like, and the technology can be used in the present invention.
Further, the physical development may be performed simultaneously with the development processing after exposure or separately after the development processing.

In the present invention, the plating process can be performed using electroless plating (chemical reduction plating or displacement plating), electrolytic plating, or both electroless plating and electrolytic plating. For the electroless plating in the present invention, a known electroless plating technique can be used. For example, an electroless plating technique used for a printed wiring board can be used, and the electroless plating is an electroless copper plating. Preferably there is.
Chemical species contained in the electroless copper plating solution include copper sulfate, copper chloride, reducing agents, formalin, glyoxylic acid, copper ligands, EDTA, triethanolamine, etc., bath stabilization and plating Examples of the additive for improving the smoothness of the film include polyethylene glycol, yellow blood salt, and bipyridine.
In the present invention, for the purpose of improving the conductivity of the conductive metal part by adding a metal layer on the developed silver, it is electrodeposited that the electrodeposition speed is higher than that of electroless plating and physical development and the production efficiency is excellent. Electrolytic plating is particularly preferable because the selection range of the metal species to be expanded is widened. As a method for electrolytic plating, as long as electrodeposition to developed silver is performed, a known electrolytic plating method widely used for metal processing, printed wiring, and the like can be appropriately selected and used.
A preferable electrolytic plating is electrolytic copper plating, and examples of the electrolytic copper plating bath include a copper sulfate bath and a copper pyrophosphate bath.

  The plating speed at the time of plating in the present invention can be performed under moderate conditions, and high-speed plating of 5 μm / hr or more is also possible. In the plating treatment, various additives such as a ligand such as EDTA can be used from the viewpoint of improving the stability of the plating solution.

  Various organic additives may be added to the copper plating solution. Preferred organic additives include organic compounds that suppress plating reactions (plating inhibitors), organic compounds that promote plating reactions (plating accelerators), and organic compounds that flatten metal films that are electrodeposited during the plating process ( It is preferable to contain two or more selected from these, and it is particularly preferable to add all of them in combination.

As the organic compound that suppresses the plating reaction, a chain polymer having a water-soluble group is preferable. The chain polymer may be branched. The polymer may be composed of a single monomer or a copolymer of two or more monomers. The water-soluble group is preferably a hydroxyl group, a sulfate group, a sulfite group, a carboxyl group, or a phosphonic acid group, and particularly preferably a hydroxyl group. Especially as a polymer component, the polymer component which has an oxygen atom is easy to adsorb | suck to a copper plating surface, and suppresses plating reaction. It is preferable because the plating is uniformly dense because it is easily adsorbed to the outside of the hole where the plating reaction has proceeded too much and is selectively suppressed.
As the polymer component, polyalkylene glycols are preferable. In this case, the alkylene group preferably has 2 to 8 carbon atoms, more preferably 2 to 3 carbon atoms. Specifically, polyethylene glycol, polypropylene glycol, polyethylene glycol / polypropylene glycol block copolymer (pluronic) surfactant, polyethylene glycol / polypropylene glycol graft copolymer (tetronic) surfactant, glycerin ether, dialkyl A compound selected from the group consisting of ethers can be used, preferably polyethylene glycol having a molecular weight of 1000 to 10,000, more preferably 2000 to 6000, polypropylene glycol having a molecular weight of 100 to 5000, more preferably 200 to 2000, molecular weight of 1000 to 10,000. More preferably, a polyethylene glycol / polypropylene glycol block copolymer of 1500 to 4000 is mentioned, and 2000 to 60 0 polyethylene glycol is most preferred. In addition, the chain polymer which has a water-soluble group can be used 1 type or in combination of 2 or more types. The concentration of the polymer is preferably 10 to 5000 mg / L, and more preferably 50 to 2000 mg / L.

  As the compound that accelerates the plating reaction, an organic compound having a sulfur-containing group is preferable. Examples of the sulfur-containing group include sulfide groups, thiol groups (mercapto groups), sulfonic acid groups, sulfinic acid groups, and thiosulfuric acid groups. By containing an organic compound having a sulfur-containing group, the plating reaction in the recesses that are difficult to be plated is efficiently promoted to make the plating uniform and dense, and the scratch resistance, heat resistance, and the like are improved. Specific examples of the organic compound having a sulfur-containing group include a sulfoalkylsulfonic acid (alkyl group having 1 to 10 carbon atoms, preferably 2 to 4) and a salt thereof, a group consisting of a bissulfo organic compound and a dithiocarbamic acid derivative, thiol A compound selected from sulfuric acid or a salt thereof can be used, and preferred specific examples include bis (3-sulfopropyl) disulfide (SPS), sodium mercaptopropanesulfonate (MPS) and the like. In addition, it is also preferable to use the compounds listed in the 0012 column of JP-A-7-316875. In addition, you may use a sulfur type organic compound 1 type or in combination of 2 or more types. As a density | concentration of a sulfur type organic compound, 0.02-2000 mg / L is preferable and 0.1-300 mg / L is more preferable.

The copper ion concentration in the copper plating solution is preferably in the range of 150 to 300 g / L, more preferably in the range of 150 to 250 g / L, and even more preferably in terms of the mass of copper sulfate pentahydrate. The range is 180-220 g / L.
Usually, when electrolytic plating is performed, the copper ion concentration in the plating solution is often 80 to 100 g / L. However, when electrolytic plating is performed on a film having a high surface resistance as in the present invention, electrons are difficult to spread over a wide area, so that the current density per unit area is high, and the supply of electrons is performed at a copper ion concentration within a normal range. On the other hand, the supply of copper ions cannot catch up, hydrogen is generated on the film surface, and poor-quality copper plating (so-called “burn”) adheres, making it difficult to form a uniform plating film without unevenness. Therefore, in the present invention, the copper ion concentration of the plating solution is preferably set to 150 g / L or more, and the occurrence of this “burn” can be prevented and a uniform and uniform plating film can be formed.
It should be noted that the copper ion concentration of 300 g / L or less was set in a preferable range because the effect was hardly increased even when used in excess of 300 g / L, and it took a long time to dissolve. This is because of such problems.

  The acid added to the plating solution is not particularly limited as long as the pH of the plating solution is kept sufficiently low, and examples thereof include sulfuric acid, nitric acid, hydrochloric acid and the like. The pH varies depending on the acid concentration, but is preferably 3 or less, more preferably 1 or less. In addition, when an acidic copper plating solution exceeds pH 3, since it becomes easy to precipitate copper, it is unpreferable.

The current density at the cathode surface is 3 to 50 A / dm ² , preferably 5 to 20 A / dm ² .
It is preferable to stir the plating solution in the plating tank. Air agitation, pump agitation, anode agitation, film agitation, or a combination thereof may be used. For example, if air agitation, the air flow rate is 0. 0.05 to 2.00 m ³ / m ³ · min (volume in the standard state of the amount of air that flows in the unit plating layer liquid area per minute) is preferable.
The bath temperature of the copper plating solution is preferably 15 to 40 ° C, particularly preferably 20 to 35 ° C.

  The surface resistance of the transparent flexible film heater after physical development and / or plating and / or consolidation is preferably 100 Ω / sq or less, more preferably 0.1 to 50 Ω / sq.

[Oxidation treatment]
In the present invention, it is preferable to subject the metal silver portion after the development treatment and the metal portion formed by physical development and / or plating treatment to oxidation treatment. By performing the oxidation treatment, for example, when a metal is slightly deposited on the light transmissive portion, the metal can be removed and the light transmissive portion can be made almost 100% transparent.
Examples of the oxidation treatment include known methods using various oxidizing agents such as Fe (III) ion treatment. As described above, the oxidation treatment can be performed after exposure and development processing of the emulsion layer, or after physical development or plating treatment, and may be performed after development processing and after physical development or plating treatment.

  In the present invention, the metal silver portion after the exposure and development treatment can be further treated with a solution containing Pd. Pd may be a divalent palladium ion or metallic palladium. This treatment can accelerate electroless plating or physical development speed.

[Conductive metal part]
The conductive metal part of the present invention has a pattern structure. The pattern structure is not particularly limited as long as the effects of the present invention can be obtained, such as a wave shape, a linear shape, and a mesh shape. The shapes drawn by the intersecting lines of mesh metal patterns are triangles such as regular triangles, isosceles triangles and right triangles, squares such as squares, rectangles, rhombuses, parallelograms, trapezoids, (positive) hexagons, (positive) eights It is preferably a geometric figure combining (positive) n-gons such as squares, circles, ellipses, stars, etc., more preferably square (including square and rhombus) mesh, parallel straight line pattern, parallel wavy line pattern, parallel zigzag Pattern or parallel rectangular pattern. It is more preferable that the mesh shape is composed of these geometric figures. From the viewpoint of visible light transmission, if the number of (positive) n-gons is larger, the aperture ratio increases and the visible light transmission becomes more advantageous if the line width is the same.

  In order to obtain the effect of the present invention, the line width of the conductive metal portion is preferably 50 μm or less, and more preferably 25 μm or less, 5 μm or more and 25 μm or less. The line spacing is preferably 50 μm or more and 20 mm or less, more preferably 200 μm or more and 5 mm or less, and most preferably 250 μm or more and 350 μm or less.

The conductive metal portion in the present invention has an aperture ratio of preferably 85% or more, more preferably 90% or more, and most preferably 95% or more from the viewpoint of visible light transmittance. The aperture ratio is a ratio of the entire translucent portion excluding the metal portion forming the composite mesh. For example, the aperture ratio of a square lattice mesh having a line width of 15 μm and a pitch of 300 μm is 90%.
The mass of silver with respect to the total mass of the metal component contained in the conductive metal part in the present invention is preferably 50% by mass or more, and the total mass of silver, copper and palladium is preferably 80% by mass or more.
In the transparent flexible film heater of the present invention, the thickness of the layer made of conductive metal particles carried on the conductive metal portion is 0.1 μm or more and less than 30 μm, and the surface resistance value is 100Ω / sq or less. Is preferred.

[Light transmissive part]
The “light transmissive part” in the present invention means a part having transparency other than the conductive metal part in the transparent flexible film heater. As described above, the transmittance of the light-transmitting portion is 90% or more, preferably 95, as shown by the minimum transmittance in the wavelength range of 380 to 780 nm excluding the contribution of light absorption and reflection of the support. % Or more, more preferably 97% or more, even more preferably 98% or more, and most preferably 99% or more.

  It is convenient for the pattern in this invention to maintain the productivity of a transparent flexible film heater that it is continuous for 3 m or more. The greater the number of continuous patterns, the greater the effect, and it can be said that this is an excellent mode in which the loss in producing a transparent flexible film heater can be reduced. As described above, the exposure method for printing the pattern on the long roll is performed by either the method for performing uniform irradiation exposure through the pattern mask or the scanning exposure for irradiating the long roll to be transported and moved with the laser beam. You can also.

  In the present invention, the intersecting pattern of straight fine lines in which the mesh is substantially parallel means a so-called lattice pattern, and refers to a case where adjacent straight lines constituting the lattice are parallel or parallel within ± 2 °.

  As a laser beam scanning method, a method of exposing with a linear light source or a rotating polygon mirror arranged in a direction substantially perpendicular to the conveying direction is preferable. In this case, the light beam needs to be intensity-modulated by two or more values, and the straight line is patterned as a series of dots. Since the dots are continuous, the edge of the fine line of one dot is stepped, but the thickness of the fine line means the narrowest length of the constricted part.

In the present invention, the lattice pattern is preferably inclined by 30 ° to 60 ° with respect to the transport direction. More preferably, it is 40 ° to 50 °, and most preferably 43 ° to 47 °. This is because it is generally difficult to create a mask whose pattern has an inclination of about 45 ° with respect to the frame, and it tends to cause problems such as unevenness and high price. Therefore, the effect of the present invention is more remarkable for patterning by mask contact exposure type photolithography or screen printing.
The transparent flexible film heater of the present invention preferably has substantially no physical development nucleus in the light transmissive portion. Here, “substantially” means that the light transmittance is not affected.

[Transparent flexible film heater]
The thickness of the support in the transparent flexible film heater of the present invention is preferably 1 to 500 μm, and more preferably 8 to 200 μm. If it is the range of 1-500 micrometers, the transmittance | permeability of a desired visible light will be obtained and handling will also be easy.
The electrodes for applying the voltage are not particularly limited as long as at least a pair of electrodes are provided, and these electrodes have conductivity. For example, conductive resin, conductive resin + metal A night, metal plating, a conductive silver paste, metal nanoparticles, etc. are mentioned. For effective heat generation, it is necessary to reduce the contact resistance, and a lower resistance is preferable. Any of these electrodes can be formed by a known method using a known one.
The transparent flexible film heater of the present invention can be used alone or attached to an object, or can be used by being sandwiched between substrates such as glass.

  The thickness of the metallic silver portion provided on the support before physical development and / or plating can be appropriately determined according to the coating thickness of the silver salt-containing layer coating applied on the support. The thickness of the metallic silver part is preferably 30 μm or less, more preferably 20 μm or less, further preferably 0.01 to 9 μm, and most preferably 0.05 to 5 μm. The metallic silver part may be a single layer or a multilayer structure of two or more layers. When the metallic silver portion has a pattern shape and has a multilayer structure of two or more layers, different color sensitivities can be imparted so that it can be exposed to different wavelengths. Thereby, when the exposure wavelength is changed and exposed, a different pattern can be formed in each layer.

The thickness of the conductive metal portion is preferably less than 9 μm, more preferably from 0.1 μm to less than 5 μm, and even more preferably from 0.1 μm to less than 3 μm.
In the present invention, a metallic silver portion having a desired thickness is formed by controlling the coating thickness of the above-described silver salt-containing layer, and the thickness of the conductive metallic portion can be freely controlled by physical development and / or plating treatment. Therefore, even a transparent flexible film heater having a thickness of less than 5 μm, preferably less than 3 μm, can be easily formed.

  In the conventional method using etching, it was necessary to remove and discard most of the metal thin film by etching, but in the method using the silver salt photosensitive material, a pattern containing a necessary amount of conductive metal was formed. Since it can be provided on the support, it is only necessary to use the minimum amount of metal, which is advantageous from the viewpoints of reducing the manufacturing cost and the amount of metal waste.

<Peelable protective film>
The transparent flexible film heater according to the present invention can be provided with a peelable protective film.
The protective film does not necessarily have to be provided on both sides of the transparent flexible film heater.

<Blackening treatment>
To describe the configuration shown in JP-A-2003-188576 as an example, the metal foil may have a blackening layer (by a blackening treatment) on the transparent base film side, in addition to the rust prevention effect, The blackening layer can be formed by, for example, Co—Cu alloy plating, and can prevent reflection of the surface of the metal foil 11. Further, rust prevention is provided thereon. Chromate treatment may be performed by immersing in a solution containing chromic acid or dichromate as a main component and drying to form a rust-preventive coating. However, it is also possible to use a commercially available chromate-treated copper foil, etc. When not using a previously blackened metal foil, Blackening The blackened layer is formed by forming a photosensitive resin layer that can be a resist layer, which will be described later, using a composition colored in black, and after etching is completed, the resist layer is not removed. It can be formed by plating, or by a plating method that gives a black film.

  Further, as an example of the configuration including the blackening layer, the configuration described in JP-A-11-266095 may be used. In the electromagnetic wave shielding plate, for example, the first blackening layer 3a and the second blackening layer 3a that form a mesh-like conductive pattern P formed by crossing a horizontal line x and a vertical line y. The blackened layer constituting the blackened layer 3b and the like can be formed by appropriately selecting and using it based on the following concept. In the present invention, there are two methods for forming the mesh-like conductive pattern P which is the main purpose, one of which is a metal plating method and the other is an etching method. . In the present invention, the method of forming the first blackened layer 3a, the second blackened layer 3b, the materials used, and the like are different by adopting any of the above methods. That is, in the present invention, in order to form the conductive pattern P on the first blackened layer 3a, the second blackened layer 3b, etc. by a metal plating method or the like, a conductive material capable of metal plating is used. When a blackening layer is necessary, and when blackening is performed in the final process by an etching method or an electrodeposition method, a nonconductive blackening layer can be formed using a nonconductive material or the like. . The conductive blackening layer can generally be formed using a conductive metal compound, for example, a compound such as nickel (Ni), zinc (Zn), copper (Cu), etc. The blackening layer is a paste-like black polymer material, such as black ink, or a black chemical conversion material, for example, a black compound formed by chemical conversion of the metal plating surface. It can be formed using a cationic ionic polymer material such as an electrodeposition coating material. In the present invention, using the blackening layer forming method as described above, an appropriate method according to the manufacturing process in the manufacturing method of the electromagnetic wave shielding plate is selected and adopted to form the blackening layer. Can do.

  Next, as a method of providing a blackening layer, as shown in FIG. 5 of JP-A-11-266095, an insulating film that inhibits electrodeposition on the conductive substrate 11 such as a metal plate produced as described above. First, an electrodeposition substrate 14 having a mesh-like resist pattern 12 composed of the following is first immersed in an electrolytic solution such as blackened copper or blackened nickel, and then plated by a known electrochemical plating method: Then, a mesh-like second blackened layer 3b made of a blackened copper layer or a blackened nickel layer is formed. In the present invention, the black plating bath can be a black plating bath mainly composed of nickel sulfate, and a commercially available black plating bath can also be used. For example, Shimizu Corporation black plating bath (trade name, Novroi SNC, Sn-Ni alloy system), Nippon Chemical Industry Co., Ltd. black plating bath (trade name, Nikka Black, Sn-Ni alloy system) ), A black plating bath (trade name, Ebony-chrome 85 series, Cr series) manufactured by Metal Chemical Industry Co., Ltd. can be used.

  Moreover, as said black plating bath, various black plating baths, such as Zn type, Cu type, and others, can be used. Next, in the present invention, similarly, as shown in FIG. 5 of the above publication, the electrodeposition substrate 14 provided with the second blackening layer 3b is immersed in an electrolytic solution of a metal for shielding electromagnetic waves. Then, a conductive mesh pattern 4 having a desired thickness is laminated and electrodeposited at a position corresponding to the second blackening layer 3b of the electrodeposition substrate. In the above, as the material constituting the mesh-like conductive pattern 4, the metal as the above-mentioned good conductive substance can be used as the most advantageous material. Therefore, when forming the above-mentioned metal electrodeposition layer, a general-purpose metal electrolyte can be used, so there are many kinds of inexpensive metal electrolytes, and the choice suitable for the purpose is free. There is an advantage that can be done. In general, Cu is frequently used as an inexpensive good conductive metal, and in the present invention, it is useful to use Cu in accordance with the purpose. Of course, other metals are also the same. It can be used for.

Next, in the present invention, the mesh-like conductive pattern 4 need not be composed of only a single metal layer. For example, although not shown, the mesh-like conductive pattern 4 made of Cu in the above example is used. Since P is relatively soft and easily scratched, it can be a two-layer metal electrodeposition layer using a general-purpose hard metal such as Ni or Cr as its protective layer. Next, in the present invention, as shown in FIG. 5, after the mesh-like conductive pattern 4 is formed as described above, for example, the surface of the mesh-like conductive pattern 4 is subjected to chemical conversion treatment. Specifically, for example, if the conductive pattern P is made of copper (Cu), a hydrogen sulfide (H ₂ S) solution treatment is performed to change the copper surface to copper sulfide (CuS). Blackening is performed to blacken the surface of the metal electrodeposition layer constituting the mesh-like conductive pattern 4 to form the first blackening layer 3a, and the second blackening layer 3b, A mesh-like conductive pattern P is formed by sequentially layering the conductive pattern layer 4 and the first blackening layer 3a in this order. In the present invention, the copper surface blackening treatment agent can be easily produced using a sulfide-based or sulfide-based compound, and there are many types of commercially available products, for example, Product name: Copa Black CuO, CuS, Selenium Copa Black No. 65 (made by Isolate Chemical Laboratories, Inc.), trade name, Ebonol C Special (made by Meltex Co., Ltd.), etc. can be used.

[Example 1]
No plating treatment, with calendar treatment [Emulsion adjustment]
・ 1 liquid:
750 ml of water
Gelatin (phthalated gelatin) 20g
Sodium chloride 3g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
・ Two liquids 300ml
150 g silver nitrate
・ 3 liquid water 300ml
Sodium chloride 38g
Potassium bromide 32g
Hexachloroiridium (III) potassium (0.005% KCl 20% aqueous solution) 5ml
Ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) 7ml

  Potassium hexachloroiridium (III) (0.005% KCl 20% aqueous solution) and ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) used in the three liquids were dissolved in KCl 20% aqueous solution and NaCl 20% aqueous solution, respectively. And heated for 120 minutes.

To 1 liquid maintained at 38 ° C. and pH 4.5, 90% of the 2 and 3 liquids were simultaneously added over 20 minutes while stirring to form 0.16 μm core particles. Subsequently, the following 4th and 5th liquids were added over 8 minutes, and the remaining 10% of the 2nd and 3rd liquids were added over 2 minutes to grow to 0.21 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete grain formation.
・ 4 liquid water 100ml
Silver nitrate 50g
・ 5 liquid 100ml
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 5mg

Then, it washed with water by the flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C. and the pH was lowered using sulfuric acid until the silver halide precipitated. (It was in the range of pH 3.6 ± 0.2) Next, about 3 liters of the supernatant was removed (first water washing). Further, 3 liters of distilled water was added, and sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second water wash). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing / desalting process. The emulsion after water washing and desalting is adjusted to pH 6.4 and pAg 7.5, and 10 mg of sodium benzenethiosulfonate, 3 mg of benzenethiosulfinate, 15 mg of sodium thiosulfate and 10 mg of chloroauric acid are added. Was added, and 100 mg of 1,3,3a, 7-tetraazaindene as a stabilizer and 100 mg of proxel (trade name, manufactured by ICI Co., Ltd.) as a preservative were added. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain diameter of 0.22 μm and a coefficient of variation of 9% was obtained. (Finally, the emulsion had pH = 6.4, pAg = 7.5, conductivity = 40 μS / m, density = 1.2 × 10 ³ kg / m ³ , and viscosity = 60 mPa · s.)

[Preparation of coated sample 1]
A 4 wt% compound (Cpd-7) based on gelatin was added to the emulsion, and the coating solution pH was adjusted to 5.6 using citric acid. The thus adjusted emulsion layer coating solution Ag10.5g / m ² on a polyethylene terephthalate (PET), was applied so as to gelatin 0.94 g / m ² and was then dried. PET that had been previously hydrophilized was used.

  The obtained coated sample has an Ag / binder volume ratio of the emulsion layer of 1 / 0.7 and corresponds to an Ag / binder ratio of 1/4 or more preferably used in the photosensitive material for forming a conductive film of the present invention. Yes.

[Exposure and development processing]
A grid-like pattern capable of giving a developed silver image of line / space = 15 μm / 285 μm (pitch 300 μm) was exposed to the dried coating film using an image setter FT-R5055 manufactured by Dainippon Screen Co., Ltd. At this time, the exposure amount was adjusted to be optimal for each sample. The exposed sample is developed with the following developer, and further developed using a fixer (trade name: N3X-R for CN16X: manufactured by Fuji Photo Film Co., Ltd.), and then rinsed with a pure sample. Obtained.

[Developer composition]
The following compounds are contained in 1 liter of developer.
Hydroquinone 0.037mol / L
N-methylaminophenol 0.016 mol / L
Sodium metaborate 0.140 mol / L
Sodium hydroxide 0.360 mol / L
Sodium bromide 0.031 mol / L
Potassium metabisulfite 0.187 mol / L

[Calendar processing]
The sample developed as described above was calendered. The calender roll was made of a metal roll, and was smoothed by applying a linear pressure of 4900 N / cm (500 kg / cm) and passing the sample between the rollers.
The transparent flexible film heater thus produced had a surface resistance of 0.9Ω / □.

[Comparative Example 1]
A sample similar to that in Example 1 was exposed on the entire surface to prepare a sample without a mesh pattern. This is referred to as Comparative Example 1.
The obtained sample had a surface resistance of 0.09Ω / □.

[Example 2]
Preparation of sample with plating [Coating sample 2]
A coated sample 2 was prepared by further plating the comparative sample 1 prepared in Comparative Example 1 with the following plating.
[Plating treatment]
Acid cleaning 35 ° C 30 seconds Electrolytic plating 1 35 ° C 30 seconds Voltage 70V
Electrolytic plating 2 35 ℃ 30 seconds Voltage 20V
Electrolytic plating 3 35 ℃ 30 seconds Voltage 10V
Electrolytic plating 4 35 ℃ 30 seconds Voltage 5V
Rinse 1 * 35 ° C. 10 seconds Rinse 2 * 35 ° C. 10 seconds Rust prevention solution 35 ° C. 30 seconds Rinse 3 * 25 ° C. 60 seconds Rinse 4 * 25 ° C. 60 seconds Drying 50 ° C. 60 seconds * Rinse process is 1 to 2 A two-tank countercurrent system from rinse 4 to 3 was adopted.
The plating solution prescriptions for electrolytic plating 1 to 4 are the same and are shown below.
[Electrolytic plating solution 1L prescription]
・ Electrolytic copper plating solution composition (same replenisher composition)
Copper sulfate pentahydrate 75g
190g of sulfuric acid
Hydrochloric acid (35%) 0.06mL
Capper Gream PCM 5mL
(Rohm and Haas Electronic Materials Co., Ltd.)
Add pure water and add 1 L
A 0.01 mol / L aqueous solution of benzotriazole was used as a rust preventive liquid.

[Rinse solution 1L prescription (Rinse 1-6 are common)]
Deionized water (conductivity 5μS / cm or less) 1000 mL
The pH value was adjusted to 6.5. The obtained transparent flexible film heater had a surface resistance of 0.2Ω / □.

[Comparative Example 2]
No plating or calendering [Emulsion preparation]
・ 1 liquid:
750ml water
20g gelatin
Sodium chloride 3g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
・ Two liquids 300ml
150 g silver nitrate
・ 3 liquid water 300ml
Sodium chloride 38g
Potassium bromide 32g
Hexachloroiridium (III) potassium (0.005% KCl 20% aqueous solution) 5ml
Ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) 7ml

  Potassium hexachloroiridium (III) (0.005% KCl 20% aqueous solution) and ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) used in the three liquids were dissolved in KCl 20% aqueous solution and NaCl 20% aqueous solution, respectively. And heated for 120 minutes.

To 1 liquid maintained at 38 ° C. and pH 4.5, 90% of the 2 and 3 liquids were simultaneously added over 20 minutes while stirring to form 0.16 μm core particles. Subsequently, the following 4th and 5th liquids were added over 8 minutes, and the remaining 10% of the 2nd and 3rd liquids were added over 2 minutes to grow to 0.21 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete grain formation.
・ 4 liquid water 100ml
Silver nitrate 50g
・ 5 liquid 100ml
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 5mg

Then, it washed with water by the flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of anionic precipitation agent-1 shown below was added, and the pH was lowered using sulfuric acid until the silver halide was precipitated. Next, about 3 liters of the supernatant was removed (first water wash). Further, 3 liters of distilled water was added, and sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second water wash). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing / desalting process. 30 g of gelatin was added to the emulsion after washing and desalting, adjusted to pH 5.6 and pAg 7.5, 10 mg of sodium benzenethiosulfonate, 3 mg of benzenethiosulfinate, 15 mg of sodium thiosulfate and 10 mg of chloroauric acid were added. Chemical sensitization to obtain optimum sensitivity at 0 ° C., 100 mg of 1,3,3a, 7-tetraazaindene as stabilizer and 100 mg of proxel (trade name, manufactured by ICI Co., Ltd.) as preservative It was. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain diameter of 0.22 μm and a coefficient of variation of 9% was obtained. (Finally, the emulsion had pH = 5.7, pAg = 7.5, conductivity = 40 μS / m, density = 1.2 × 10 ³ kg / m ³ , and viscosity = 60 mPa · s.)

[Preparation of Comparative Application Sample 2]
A 4 wt% compound (Cpd-7) based on gelatin was added to the emulsion, and the coating solution pH was adjusted to 5.6 using citric acid. Thus the emulsion layer coating liquid prepared Ag3.4g / ^{m 2} on a polyethylene terephthalate (PET), was applied so as to gelatin 1.9 g / ^{m 2} and was then dried. PET that had been previously hydrophilized was used.
[Exposure and development processing]
A grid-like pattern capable of giving a developed silver image of line / space = 15 μm / 285 μm (pitch 300 μm) was exposed to the dried coating film using an image setter FT-R5055 manufactured by Dainippon Screen Co., Ltd. At this time, the exposure amount was adjusted to be optimal for each sample.
Using the developer (A) and fixer (B) of the following formulation for the exposed sample, using an FG-680AG automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) under the developing conditions of 35 ° C. and 30 seconds. Processed.

-Developer (A) formulation The composition per liter of the concentrated solution is shown.
Potassium hydroxide 60.0g
Diethylenetriamine / pentaacetic acid 3.0g
Potassium carbonate 90.0g
Sodium metabisulfite 105.0g
Potassium bromide 10.5g
Hydroquinone 60.0g
5-methylbenzotriazole 0.53g
4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2.3 g
3- (5-Mercaptotetrazol-1-yl) benzenesulfonic acid sodium salt
0.15g
2-Mercaptobenzimidazole-5-sulfonic acid sodium salt 0.45 g
Sodium erythorbate 9.0g
Diethylene glycol 7.5g
pH 10.79
In use, the mother liquor is diluted at a ratio of 1 part water to 2 parts of the concentrate, the pH of the mother liquor is 10.65, and the replenisher is at a ratio of 3 parts water to the 4 parts of the concentrate. The pH of the diluted replenisher was 10.62.

-Fixing liquid (B) prescription The prescription per 1 L of the concentrated liquid is shown.
360g ammonium thiosulfate
Ethylenediamine ・ tetraacetic acid ・ 2Na ・ 2 hydrate 0.09g
Sodium thiosulfate, pentahydrate 33.0g
Sodium metasulfite 57.0g
Sodium hydroxide 37.2g
Acetic acid (100%) 90.0g
Tartaric acid 8.7g
Sodium gluconate 5.1g
Aluminum sulfate 25.2g
pH 4.85
In use, it is diluted at a ratio of 2 parts of water to 1 part of the concentrated liquid. The pH of the working solution is 4.8. The replenisher used was the same diluted solution as used above, and was used at 258 ml per 1 m ^{2 of} the sensitive material.
The transparent flexible film heater thus produced had a surface resistance of 32Ω / □.
[Evaluation]
The sample obtained as described above was cut into 3.5 cm × 10 cm, and the short side as shown in FIG. 1 (application conceptual diagram of the present invention in which the electrode terminals for energization were provided at both ends of the transparent flexible film heater). Solder is attached linearly as electrodes on both sides. A constant voltage was applied between the electrodes, the surface temperature was measured with an infrared thermometer, and the temperature difference (ΔT) from before the voltage application was measured.
The results obtained are shown in the table below.

E: Power supply voltage (V)
A = E ² / (L × R)
L: Distance between electrodes (cm)
R: Resistance value (Ω)

  As is apparent from the results of the table, Examples 1 and 2 in which the calculated value A is within the range of the present invention have high heat generation efficiency and practically high temperature rise. However, in Comparative Example 2 where A is smaller than the range of the present invention, although the heat generation efficiency is high, it is understood that the temperature rise is very small and not suitable for practical use. On the other hand, it can be seen that Comparative Example 1 in which A is larger than the range of the present invention has low heat generation efficiency and is not suitable for practical use.

It is a conceptual diagram of the experimental sample structure of calorific value measurement.

Explanation of symbols

1 Electrode (solder)

Claims (38)

A heating element having a conductive metal pattern structure that is substantially transparent on a transparent flexible support, and the distance between applied electrodes of the heating element is L (cm), and the resistance between the electrodes of the heating element is R ( Ω) and a transparent flexible film heater characterized by satisfying the following formula (1) when the power supply voltage is E (v).
0.1 ≦ E ² /(L×R)≦2.0 Formula (1)   The heating element having the conductive metal pattern structure has a pattern structure including a conductive metal portion made of a fine metal wire having a line width of 50 μm or less and a light transmissive portion surrounded by the fine wire portion. The transparent flexible film heater according to claim 1.   The transparent flexible film heater according to claim 2, wherein a line width of the thin metal wire portion is 25 μm or less.   4. The transparent flexible film heater according to claim 2, wherein a line width of the thin metal wire portion is 0.4 μm or more and 50 μm or less.   The line width of the fine metal wire portion is 0.4 μm or more and 50 μm or less, and the ratio of the light transmitting portion / total film area is 70 to 99.9%. The transparent flexible film heater in any one of.   6. The transparent flexible film according to claim 1, wherein the pattern structure is a quadrilateral (including square or rhombus) mesh, a hexagonal mesh, a parallel straight line pattern, a parallel wavy pattern, or a parallel zigzag pattern. heater.   The heating element having the conductive metal pattern structure exposes a silver salt-containing layer containing photosensitive silver halide provided on a support, and develops the metal silver portion and the light transmissive portion. The transparent flexible film heater according to any one of claims 1 to 6, wherein the transparent flexible film heater is formed by a consolidation treatment after the formation.   The heating element having the conductive metal pattern structure exposes a silver salt-containing layer containing photosensitive silver halide provided on a support, and develops the metal silver portion and the light transmissive portion. 8. The method according to claim 1, wherein the metal silver portion is formed by carrying conductive metal particles by physical development and / or plating treatment of the metal portion. The transparent flexible film heater of crab.   The heating element having the conductive metal pattern structure exposes a silver salt-containing layer containing photosensitive silver halide provided on a support, and develops the metal silver portion and the light transmissive portion. 9. The method according to claim 7 or 8, wherein the metal part is formed and subjected to physical development and / or plating so that conductive metal particles are supported on the metal silver part and then compacted. The transparent flexible film heater described in 1.   The transparent flexible film heater according to any one of claims 7 to 9, wherein the silver halide is mainly composed of silver bromide.   The transparent flexible film heater according to any one of claims 7 to 10, wherein an Ag / binder volume ratio in the silver salt-containing layer is ¼ or more.   The transparent flexible film heater according to any one of claims 7 to 10, wherein an Ag / binder volume ratio in the silver salt-containing layer is ½ or more.   The transparent flexible film heater according to any one of claims 7 to 12, wherein an average spherical equivalent diameter of silver halide contained in the silver salt-containing layer is 0.1 to 100 nm.   The transparent flexible film heater according to claim 7, wherein the exposure is performed by a scanning exposure method using a laser beam.   The transparent flexible film heater according to claim 7, wherein the exposure is performed through a photomask.   The transparent flexible film heater according to any one of claims 7 to 15, wherein the developer used in the development treatment of the silver salt-containing layer contains an image quality improver.   The transparent flexible film heater according to claim 16, wherein the image quality improver is a nitrogen-containing heterocyclic compound.   The transparent flexible film heater according to any one of claims 7 to 17, wherein the developer used in the development treatment of the silver salt-containing layer is a lith developer.   The mass of the metallic silver contained in the exposed portion after the development treatment is a content of 50% by mass or more based on the mass of silver contained in the exposed portion before exposure. The transparent flexible film heater in any one of 7-18.   The transparent flexible film heater according to claim 8, wherein the plating process is performed by electroless plating.   The transparent flexible film heater according to claim 8, wherein the plating process is performed by electrolytic plating.   The transparent flexible film heater according to any one of claims 8, 20 and 21, wherein the plating is performed by electroless plating and subsequent electrolytic plating.   The transparent flexible film heater according to claim 20 or 22, wherein the electroless plating is electroless copper plating.   24. The transparent flexible film heater according to any one of claims 7 to 23, wherein a gradation after development processing of the silver salt-containing layer exceeds 4.0.   The transparent flexible film heater according to any one of claims 1 to 24, wherein the surface of the conductive metal portion is further blackened.   The transparent flexible film heater according to any one of claims 1 to 25, wherein the light-transmitting portion does not have a physical development nucleus.   The surface resistance of the transparent flexible film heater after the physical development and / or plating treatment and / or consolidation treatment is 100Ω / sq or less, and the transmittance of the light transmissive part is 95% or more. The transparent flexible film heater in any one of the said Claims 1-26.   The surface resistance of the transparent flexible film heater after the physical development and / or plating treatment and / or consolidation treatment is 0.1 to 50Ω / sq, and the transmittance of the light transmissive portion is 95% or more. 27. The transparent flexible film heater according to claim 26, characterized by the above.   29. The transparent flexible film heater according to any one of claims 1 to 28, wherein the mass of silver is 50% by mass or more with respect to the total mass of the metal component contained in the conductive metal part.   30. The transparent flexible film according to any one of claims 1 to 29, wherein the total mass of silver, copper and palladium with respect to the total mass of the metal component contained in the conductive metal part is 80% by mass or more. heater.   The transparent flexible film heater according to any one of claims 1 to 30, wherein an opening ratio of the conductive metal portion is 85% or more.   The thickness of the layer made of conductive metal particles carried on the conductive metal part is 0.1 μm or more and less than 30 μm, and the surface resistance value is 100Ω / sq or less. 31. The transparent flexible film heater according to any one of 31.   The transparent flexible film heater according to claim 1, wherein the support is made of a plastic film having a thickness of 8 to 200 μm.   The plastic film constituting the support is polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyvinyl chloride, polyvinylidene chloride, polyvinyl butyral, polyamide, polyether, polysulfone, polyethersulfone, polycarbonate, polyarylate, 34. The transparent according to claim 33, which is a polyolefin such as polyetherimide, polyetherketone, polyetheretherketone, EVA, polycarbonate, triacetylcellulose (TAC), acrylic resin, polyimide, or aramid. Flexible film heater.   The transparent flexible film heater according to any one of claims 1 to 34, wherein the light transmissive portion has a transmittance of 95% or more.   The transparent flexible film heater according to any one of claims 1 to 34, wherein the light transmissive portion has a transmittance of 98% or more.   A conductive metal pattern is formed by exposing a silver salt-containing layer containing a photosensitive silver halide provided on a support to a metal silver portion and a light-transmitting portion by exposing and developing the layer and then subjecting it to a consolidation treatment. The method for producing a transparent flexible film heater according to claim 1, wherein a heating element having a structure is formed.   A silver salt-containing layer containing a photosensitive silver halide provided on a support is exposed and developed to form a metallic silver part and a light-transmitting part, and the metallic part is physically developed and / or The method for producing a transparent flexible film heater according to claim 1, wherein a conductive element is supported on the metal silver portion by plating to form a heating element having a conductive metal pattern structure.

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