JP5298491B2 - Transparent conductive film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive film suitable for a flexible transparent electrode which has little loss even in a large area, has no problem in color of the conductive film, and is strong in bending and has a high resistance against a corrosive gas such as NOx and SOx. <P>SOLUTION: The transparent conductive film has a conductive pattern containing silver and a transparent conductive membrane consisting of a conductive polymer compound adjoined on it from a transparent film substrate side on the transparent film substrate. The conductive pattern is formed by installing a layer containing silver halide particles on the transparent film substrate and by forming a metal silver portion of a desired pattern by applying exposure and development processing with a desired pattern, and further, by applying a physical development processing. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a transparent conductive film used for a flexible transparent electrode for a large area. More specifically, the loss is small even in a large area, the color of the film is not a problem, and the film is resistant to bending. The present invention relates to a transparent conductive film suitable for a flexible transparent electrode, which has high resistance to corrosive gases such as SOx.

  Transparent conductive films are used for liquid crystal displays, electroluminescence displays, plasma displays, electrochromic displays, transparent electrodes such as solar cells and touch panels, and electromagnetic shielding materials. As a transparent conductive film widely applied, an indium-tin composite oxide (ITO) is deposited on at least one surface of a transparent film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) by vacuum deposition or This is a method of forming a film by a dry process such as a sputtering method (for example, see Patent Document 1). However, a method of forming ITO by a dry process such as a vacuum evaporation method or a sputtering method has a problem that a high temperature is required for film formation or a film formation cost is high. In addition, an ITO film formed by a coating film formation method also requires a high temperature for film formation, and its conductivity depends on the degree of dispersion of ITO, and the haze value is not low. Further, in any of the production methods, the ITO film is weak against bending of the film, and there is a problem that the conductivity is impaired due to cracks.

  On the other hand, a transparent conductive film in which a conductive polymer is formed on a transparent film has been proposed. A transparent conductive layer formed of a conductive polymer has flexibility in the film itself, and thus hardly causes problems such as cracks, but it has been difficult to obtain conductivity equivalent to that of an ITO film.

  Furthermore, in the case of an electrode having a large area, the length of the electrode becomes long and its resistance value becomes a problem. For example, an electromotive force obtained with a solar cell or the like is lost due to a voltage drop at the electrode portion. Even ITO with superior conductivity is insufficient in conductivity for a large area.

  In addition, conductive mesh films are known as electromagnetic shielding for plasma televisions. For example, copper plating is performed after a copper thin film is processed by an etching process using a photolithography method or after a plating catalyst is pattern printed by a printing method. The method of doing is known.

  Furthermore, a technique for combining such a conductive mesh and a transparent conductive film such as ITO is known (for example, see Patent Documents 2 to 6). However, in the case of combination with ITO, the above-mentioned problem caused by ITO becomes a problem as it is. As for the conductive mesh portion, coloring is a problem when copper is used. In addition, it is also known that blackening treatment is performed as a method for improving copper coloring. However, not only is the treatment complicated, but also the adhesiveness is deteriorated. There is no problem because the internal electron transfer becomes a point, but when used in combination with a conductive film, the blackening treatment causes a loss due to the resistance of the contact portion between the mesh and the conductive film and the work function of the blackening treatment portion Sometimes.

  Further, although a silver mesh not plated with copper is also described in Patent Document 5, for example, further studies have revealed that the silver mesh has poor resistance to NOx, SOx, etc., and the conductivity is deteriorated. It was.

  In Patent Document 5, a conductive material including a conductive pattern material and a transparent conductive film produced by exposing and developing a photosensitive material having a silver salt-containing layer, and further performing physical development and / or plating. A translucent conductive sheet characterized by having a surface, and further, the translucent conductive film has a transparent metal oxide and / or organic conductive film and a mesh metal thin wire There is a disclosure of electroluminescent elements.

However, Patent Document 5 discloses bending resistance, which is the subject of the present invention, and the inclusion of silver frees the blackening treatment to reduce the interface loss with the conductive film, and the plating treatment frees the silver. It is suggested that the resistance to corrosive gases such as NOx and SOx deteriorates when the problem of the color of plated metals such as copper is solved by containing selenium, and that such performance improvement by the conductive polymer compound is suggested. Not.
JP 2003-115220 A Japanese Patent Laid-Open No. 11-184385 JP-A-11-160532 Japanese Patent Laid-Open No. 11-204986 JP 2006-352073 A Japanese Patent Laid-Open No. 9-147639

  The purpose of the present invention is to provide a flexible transparent electrode that has a small loss even in a large area, is not problematic in the color of the conductive film, is strong against bending, and has high resistance to corrosive gases such as NOx and SOx. The object is to provide a suitable conductive film.

  In order to solve the above-mentioned problems of the present invention, a conductive pattern containing silver and a transparent conductive film made of a conductive polymer compound are provided on the side close to the substrate without using a photolithography method using copper or a copper plating process. It is important to provide them adjacent to each other in this order, and more specifically, this is achieved by the following configuration.

1. A transparent conductive material in which a conductive pattern containing silver and a transparent conductive film made of a conductive polymer compound are adjacently provided on the transparent film substrate from the side close to the transparent film substrate. In the film, the conductive pattern is provided with a layer containing silver halide grains on the transparent film substrate, and exposed and developed with the desired pattern to form a metallic silver portion of the desired pattern. Formed by further physical development processing ,
The conductive polymer compound is a polyethylenedioxythiophene-based or polyaniline-based conductive polymer compound,
Amount with the binder in the layer containing said silver halide grains is at 0.05 g / m ² or more 0.25 g / m ² or less,
A transparent conductive film , wherein the Ag / binder ratio in the layer containing the silver halide grains before exposure is 0.3 to 0.8 in volume ratio .

2 . The silver halide grains are silver chlorobromide grains, the silver chloride content is 55 mol% or more and 95 mol% or less, and the silver bromide content is 5 mol% or more and 45 mol% or less. 2. The transparent conductive film according to 1 above.

  According to the present invention, a flexible transparent electrode that has a small loss even in a large area, has no problem with the color of the conductive film, is resistant to bending, and has high resistance to corrosive gases such as NOx and SOx. A suitable conductive film can be provided.

  The present invention will be described in more detail.

  As a result of intensive studies in view of the above problems, the present inventors have found that a transparent conductive film composed of a conductive pattern containing silver and a conductive polymer compound on a transparent film substrate from the side close to the substrate. In order, the conductive pattern and the transparent conductive film are provided adjacent to each other, the conductive pattern is provided with a layer containing silver halide grains on a transparent film substrate, and is exposed and developed with a desired pattern. By forming a metal silver portion of a desired pattern and further by physical development processing, the loss is small even in a large area, the color of the conductive film is not a problem, and it is bent It has been found that a flexible conductive film that is strong and has high resistance to corrosive gases such as NOx and SOx can be obtained, and the present invention has been achieved.

  Hereinafter, the best mode for carrying out the present invention will be described, but the present invention is not limited thereto.

(Conductive pattern)
In the conductive pattern containing silver of the present invention, 70% or more of the conductive constituent components are preferably silver, and more preferably 90% or more are silver. By using silver as the main component, it is possible to prevent the mesh portion from being colored without having a harmful blackening treatment when used in combination with the conductive film. There are no particular restrictions on the pattern shape, but for example, a mesh consisting of geometric figures combining triangles, squares, rectangles, rhombuses, parallelograms, trapezoids, etc., (positive) hexagons, (positive) octagons, etc. Pattern can be raised.

  The conductive pattern preferably has a conductivity of 50Ω / □ or less, and most preferably 10Ω / □ or less, as a single film without using a transparent conductive film composed of a conductive polymer compound. In the conductive pattern exceeding 50Ω / □, the effect of improving the conductivity with respect to the transparent conductive film alone made of the conductive polymer compound is small.

  As a method for forming such a conductive pattern, a layer containing silver halide grains is provided, and a metal silver portion having a desired pattern is formed by exposing and developing with a desired pattern, followed by further physical development processing. Use the method. By this method, it is possible to easily form a metal silver portion having a desired pattern, and the transmittance does not decrease due to thickening of the intersection, which is a problem in the printing method or the like. Furthermore, by the method of physical development treatment, it becomes possible to form a dense silver line without using an additional copper plating treatment in which the post-heating treatment or coloring which deteriorates the smoothness of the transparent base material becomes a problem. Conductivity can be ensured.

(Conductive polymer compound)
In the present invention, a transparent conductive film made of a conductive polymer compound is provided on the side far from the substrate adjacent to the above-described conductive pattern.

  Thereby, even if it is a large area, it can be set as a surface electrode with few losses, and can be set as a conductive film strong against bending compared with inorganic type electrically conductive films, such as ITO. Furthermore, the resistance to corrosive gases such as NOx and SOx of the conductive pattern whose main component is silver can also be improved. This improvement effect was particularly remarkable when the conductive polymer compound was polyaniline-based. Polyaniline-based conductive polymer compounds are generally known to have a rust-preventing action, but such effects may also work effectively in the present invention.

  Next, the conductive polymer in the present invention will be described.

  The conductive polymer is not particularly limited, and polypyrrole, polyindole, polycarbazole, polythiophene (including basic polythiophene, the same applies hereinafter), polyaniline, polyacetylene, polyfuran, polyparaphenylene vinylene, polyazulene A chain conductive polymer such as polyparaphenylene, polyparaphenylene sulfide, polyisothianaphthene, and polythiazyl, and a polyacene conductive polymer can also be used. Of these, polyethylenedioxythiophene and polyaniline are preferable from the viewpoint of conductivity, transparency, and the like, and polyaniline-based conductive polymers are most preferable in view of the above-described resistance to corrosive gas.

Moreover, in this invention, in order to raise the electroconductivity of the said conductive polymer more, it is preferable to perform a doping process. As a dopant for the conductive polymer, for example, a sulfonic acid having a hydrocarbon group having 6 to 30 carbon atoms (hereinafter also referred to as “long-chain sulfonic acid”) or a polymer thereof (for example, polystyrene sulfonic acid), halogen Lewis acid, proton acid, transition metal halide, transition metal compound, alkali metal, alkaline earth metal, MClO ₄ (M = Li ⁺ , Na ⁺ ), R ₄ N ⁺ (R = CH ₃ , C ₄ H ₉ , C ₅ H ₁₁ ), or R ₄ P ⁺ (R═CH ₃ , C ₄ H ₉ , C ₅ H ₁₁ ). Of these, the long-chain sulfonic acid is preferable.

Examples of the long chain sulfonic acid include dinonyl naphthalene disulfonic acid, dinonyl naphthalene sulfonic acid, and dodecylbenzene sulfonic acid. Examples of the halogen include Cl ₂ , Br ₂ , I ₂ , ICl ₃ , IBr, IF _{5 and the} like. Examples of the Lewis acid include PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BCl ₃ , BBr ₃ , SO ₃ , and GaCl ₃ . Examples of the protonic acid include HF, HCl, HNO ₃ , H ₂ SO ₄ , HBF ₄ , HClO ₄ , FSO ₃ H, ClSO ₃ H, CF ₃ SO ₃ H, and the like. The transition metal _{halide, NbF 5, TaF 5, MoF} 5, WF 5, RuF 5, BiF 5, TiCl 4, ZrCl 4, MoCl 5, MoCl 3, WCl 5, FeCl 3, TeCl 4, SnCl 4, SeCl ₄ , FeBr ₃ , SnI _{5 and the} like. The transition metal _{compound, AgClO 4, AgBF 4, La} (NO 3) 3, Sm (NO 3) 3 and the like. Examples of the alkali metal include Li, Na, K, Rb, and Cs. Examples of the alkaline earth metal include Be, Mg, Ca, Sc, and Ba.

The dopant for the conductive polymer may be introduced into fullerenes such as hydrogenated fullerene, hydroxylated fullerene, and sulfonated fullerene. In the transparent conductive material and the transparent conductive element of the present invention, the dopant is preferably contained in an amount of 0.001 part by mass or more with respect to 100 parts by mass of the conductive polymer. Furthermore, it is more preferable that 0.5 mass part or more is contained. The transparent conductive film of the present embodiment includes a long-chain sulfonic acid, a polymer of long-chain sulfonic acid (for example, polystyrene sulfonic acid), halogen, Lewis acid, proton acid, transition metal halide, transition metal compound, alkali Both at least one dopant selected from the group consisting of metals, alkaline earth metals, MClO ₄ , R ₄ N ⁺ , and R ₄ P ⁺ and fullerenes may be included.

The transparent conductive film of the present invention has 2nd. A water-soluble organic compound may be contained as a dopant. There is no restriction | limiting in particular in the water-soluble organic compound which can be used by this invention, It can select suitably from well-known things, For example, an oxygen containing compound is mentioned suitably. The oxygen-containing compound is not particularly limited as long as it contains oxygen, and examples thereof include a hydroxyl group-containing compound, a carbonyl group-containing compound, an ether group-containing compound, and a sulfoxide group-containing compound. Examples of the hydroxyl group-containing compound include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, and glycerin. Among these, ethylene glycol and diethylene glycol are preferable. Examples of the carbonyl group-containing compound include isophorone, propylene carbonate, cyclohexanone, and γ-butyrolactone. Examples of the ether group-containing compound include diethylene glycol monoethyl ether. Examples of the sulfoxide group-containing compound include dimethyl sulfoxide. These may be used alone or in combination of two or more, but it is particularly preferable to use at least one selected from dimethyl sulfoxide, ethylene glycol, and diethylene glycol.
In the transparent conductive material and the transparent conductive element of the present invention, the 2nd. The content of the dopant is preferably 0.001 parts by mass or more, more preferably 0.01 to 50 parts by mass, and particularly preferably 0.01 to 10 parts by mass.

[Transparent film substrate]
A plastic film can be used as the transparent film substrate used in the present invention.

  Examples of the raw material for the plastic film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene, and cyclic olefin resins, polyvinyl chloride, and polychlorinated chloride. Use vinyl resins such as vinylidene, polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC), etc. Can do.

  Of these, a biaxially stretched polyethylene terephthalate film, an acrylic resin film, and a triacetylcellulose film are preferable, and a biaxially stretched polyethylene terephthalate film is most preferable in terms of transparency, heat resistance, ease of handling, and cost.

  The transparent film substrate is preferably provided with a surface treatment or an easy-adhesion layer in order to ensure wettability and adhesion of the coating solution. Conventionally known techniques can be used for the surface treatment and the easy-adhesion layer, but when the transparent film substrate is a biaxially stretched polyethylene terephthalate film, the refractive index of the easy-adhesion layer adjacent to the film is 1.57-1. By setting it to 63, the interface reflection between the film substrate and the easy adhesion layer can be reduced and the transmittance can be improved, which is more preferable. As a method for adjusting the refractive index, the refractive index can be prepared by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin. The easy-adhesion layer may be a single layer, but in order to improve the adhesiveness, it may be composed of two or more layers.

  In the present invention, the transparent film substrate means a material having a transmittance of 85% or more, preferably 90% or more.

[Silver halide grain containing layer]
In the silver halide grain-containing layer according to the present invention, the silver halide grains are uniformly dispersed, and the silver halide grains are supported on the support to ensure adhesion between the silver halide grain emulsion-containing layer and the support. A binder is used for the purpose. The binder that can be used in the present invention is not particularly limited, and any of a water-insoluble polymer and a water-soluble polymer can be used. From the viewpoint of improving developability, it is preferable to use a water-soluble polymer.

  In the light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder, but if necessary, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, simple substances. Hydrophilic colloids such as synthetic hydrophilic polymer materials such as mono- or copolymers can also be used.

  In the present invention, a photosensitive silver halide grain and a silver halide grain-containing layer containing a binder, which will be described later, are provided on a transparent film substrate. Agents, contrast enhancers, activators, and the like.

  In the present invention, the silver / binder volume ratio of the silver halide grains in the photosensitive silver halide grain-containing layer before exposure is preferably 0.3 or more and 0.8 or less, and is 0.4 or more and 0.7 or less. Most preferably it is. If it is less than 0.3, it will be difficult to obtain sufficient conductivity even if physical development is carried out, and if it is more than 0.8, the binder will not be able to hold silver halide grains sufficiently, and the coating solution In the case of silver halide grains, aggregation of silver halide grains occurs, and after pattern formation, pattern retention is poor and pattern peeling occurs, which is not preferable.

In the present invention, the amount per the photosensitive silver halide grain-containing layer binder amount is preferably not 0.05 g / m ² or more 0.25 g / m ² or less. It is difficult to obtain 0.05 g / m ² less than a sufficient conductivity, developed silver particles are present many that do not contribute to the conductivity on the side closer to the substrate of 0.25 g / m ² larger than the pattern portion (Estimated because the exposure light is attenuated on the side closer to the substrate or physical development is less likely to occur) When compared with the same conductive film, the haze increases, The binder film shrinks / extends and tends to cause curling, which is not preferable.

[Silver halide grains]
The composition of the silver halide grains used in the present invention has an arbitrary halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. However, in order to obtain the effect of the present invention, the composition of the silver halide grains is silver chlorobromide, the silver chloride content is 55 mol% or more, and the silver bromide content is 5 To 45 mol%, more preferably the silver chloride content is 70 mol% or more, and the silver bromide content is 10 to 30 mol%. If the silver chloride is less than 55 mol%, it is difficult to obtain a silver concentration suitable for physical development in terms of sensitivity and contrast, and if the silver bromide is less than 5 mol%, the filament structure of the developed silver does not spread. Since the distance between the silver particles is increased and physical development is not successful, it is difficult to obtain desirable conductivity.

  In order to reduce the surface specific resistance after the silver halide grains are developed into metal silver grains, the contact area between the developed silver grains needs to be as large as possible. For this purpose, a smaller silver halide grain size is better to increase the surface area ratio, but too small grains tend to agglomerate into large agglomerates, in which case the contact area will be reduced, so there is an optimum grain size. To do. In the present invention, the average grain size of silver halide grains is preferably from 0.01 to 0.5 μm, more preferably from 0.03 to 0.3 μm, in terms of cubic equivalent diameter. The cubic equivalent diameter of silver halide grains represents the length of one side when a volume equal to the volume of each grain is converted into a cube. The average grain size of silver halide grains is the temperature at the time of preparation of silver halide grains, pAg, pH, addition rate of silver ion solution and halogen solution, grain size control agent (for example, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, benztriazole, tetrazaindene compounds, nucleic acid derivatives, thioether compounds, etc.) can be appropriately combined and controlled.

  In the present invention, the shape of the silver halide grains is not particularly limited, and for example, spherical, cubic, flat plate (hexagonal flat plate, triangular flat plate, tetragonal flat plate, etc.), octahedron, tetrahedron It can be in various shapes such as shapes. The particle size distribution is not particularly limited, but a narrow distribution is preferable from the viewpoint of enhancing the transparency while sharply reproducing the outline of the pattern and maintaining high conductivity during pattern formation by exposure. The particle size distribution of the silver halide grains used in the light-sensitive material according to the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less. Here, the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R
(In the formula, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)
The silver halide grains used in the present invention may further contain other elements. For example, in a photographic emulsion, it is also useful to dope metal ions used to obtain a high-contrast emulsion. In particular, Group 8-10 metal ions such as iron ion, rhodium ion, ruthenium ion and iridium ion are preferably used because the difference between the exposed portion and the unexposed portion tends to be clearly generated when the metal silver image is generated.

  These metal ions can be added to the silver halide grain emulsion in the form of a salt or a complex salt. Transition metal ions represented by rhodium ions and iridium ions can also be compounds having various ligands. Examples of such a ligand include cyanide ions, halogen ions, thiocyanate ions, nitrosyl ions, water, hydroxide ions, and the like. Specific examples of the compound include potassium bromide rhodate and potassium iridate.

In the present invention, the content of the metal ion compound contained in the silver halide grains, per mol of silver halide is preferably 10 ^-10 to 10 ^-2 mol / mol Ag, 10 ^-9 to 10 More preferably, it is ⁻³ mol / mol Ag.

  In order for silver halide grains to contain the above-described metal ions, the metal compound is subjected to physical ripening before formation of silver halide grains, during formation of silver halide grains, after formation of silver halide grains, etc. What is necessary is just to add in the arbitrary places in a process. Moreover, in addition, the solution of a heavy metal compound can be continuously performed over the whole or a part of particle formation process.

  In the present invention, it is preferable to perform chemical sensitization performed on a photographic emulsion in order to improve sensitivity. As chemical sensitization, for example, noble metal sensitization such as gold, palladium and platinum sensitization, chalcogen sensitization such as sulfur sensitization with inorganic sulfur or organic sulfur compounds, reduction sensitization such as tin chloride and hydrazine, etc. are used. be able to.

  The silver halide grains are preferably subjected to spectral sensitization. Preferred spectral sensitizing dyes include cyanine, carbocyanine, dicarbocyanine, complex cyanine, hemicyanine, styryl dye, merocyanine, complex merocyanine, holopolar dye, and the like. Can be used alone or in combination.

  Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. For these dyes, any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic ring nucleus. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei, and these Nucleus fused with aromatic hydrocarbon ring, ie, indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus Quinoline nuclei and the like. These nuclei may be substituted on carbon atoms.

  The merocyanine dye or the complex merocyanine dye includes a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and a rhodanine nucleus as a nucleus having a ketomethylene structure. A 5- to 6-membered heterocyclic nucleus such as a thiobarbituric acid nucleus can be applied.

  These sensitizing dyes may be used alone or in combination. A combination of sensitizing dyes is often used for the purpose of supersensitization.

  In order to incorporate these sensitizing dyes in a silver halide grain emulsion, they may be dispersed directly in the emulsion, or water, methanol, propanol, methyl cellosolve, 2,2,3,3-tetra A solvent such as fluoropropanol may be dissolved alone or in a mixed solvent and added to the emulsion. Further, as described in JP-B Nos. 44-23389, 44-27555, 57-22089, etc., an acid or a base is allowed to coexist to form an aqueous solution, US Pat. No. 3,822,135, As described in US Pat. No. 4,006,025 and the like, an aqueous solution or colloidal dispersion prepared by coexisting a surfactant such as sodium dodecylbenzenesulfonate may be added to the emulsion. Further, after dissolving in a substantially immiscible solvent such as phenoxyethanol, water or a hydrophilic colloid dispersion may be added to the emulsion. As described in JP-A Nos. 53-102733 and 58-105141, the dispersion may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion.

〔exposure〕
In the present invention, the silver salt-containing layer provided on the support is exposed so that a desired conductive metal pattern is obtained.

  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.

  Examples of the light source include scanning exposure using a cathode ray (CRT). The cathode ray tube exposure apparatus is simpler and more compact and less expensive than an apparatus using a laser. Also, the adjustment of the optical axis and color is easy. As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. For example, one or more of a red light emitter, a green light emitter, and a blue light emitter are mixed and 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.

In the present invention, exposure can be performed using various laser beams. For example, a monochromatic high-density light 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 nonlinear laser and a solid state laser using a semiconductor laser as an excitation light source was used. A scanning exposure method can be preferably used, and a KrF excimer laser, an ArF excimer laser, an F ₂ laser, or the like can also be used. In order to make the system compact and inexpensive, the exposure is 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 preferable to perform exposure using a semiconductor laser.

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. About 530 nm green laser, wavelength about 685 nm red semiconductor laser (Hitachi type No. HL6738MG), wavelength about 650 nm red semiconductor laser (wavelength converted by LiNbO ₃ SHG crystal with waveguide inversion domain structure) Hitachi type No. HL6501MG) is preferably used.

  The method for exposing the silver salt-containing layer in a pattern may be performed by surface exposure using a photomask or by scanning exposure using a laser beam. At this time, refractive exposure using a lens or reflection exposure using a reflecting mirror may be used, and exposure methods such as contact exposure, proximity exposure, reduced projection exposure, and reflection projection exposure can be used.

[Chemical development]
In the present invention, after the photosensitive material is exposed, chemical development processing (also simply referred to as “chemical development”) is performed. The chemical development process is preferably a so-called black and white development process that does not contain a color developing agent.

  As a chemical developing solution, in addition to hydroquinones such as hydroquinone, sodium hydroquinone sulfonate, chlorohydroquinone and the like as developing agents, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1 -Pyrazolidones such as phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and 1-phenyl-4-methyl-3-pyrazolidone and superadditive developing agents such as N-methylparaaminophenol sulfate be able to. Further, it is preferable to use a reductone compound such as ascorbic acid or isoascorbic acid in combination with the superadditive developing agent without using hydroquinone.

  Further, sodium sulfite salt or potassium sulfite salt as a preservative, sodium carbonate salt or potassium carbonate salt as a buffering agent, diethanolamine, triethanolamine, diethylaminopropanediol or the like as a development accelerator can be appropriately used in the chemical developing solution.

  The development processing solution used in the chemical development processing can contain an image quality improving agent for the purpose of improving the image quality. Examples of the image quality improver include nitrogen-containing heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole and 5-methylbenzotriazole.

  In the chemical development processing in the present invention, after the chemical development, fixing processing is performed for the purpose of removing and stabilizing unexposed silver halide grains. For the fixing treatment in the present invention, a fixer formulation used for photographic films, photographic papers and the like using silver halide grains can be used. The fixing solution used in the fixing process may use sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, or the like as a fixing agent. Aluminum sulfate, chromium sulfate, or the like can be used as a hardener for fixing. As the preservative for the fixing agent, sodium sulfite, potassium sulfite, ascorbic acid, erythorbic acid and the like described in the chemical developing solution can be used, and citric acid, oxalic acid and the like can be used.

  Furthermore, it is preferable to perform a water washing treatment after the fixing treatment. The washing water used in the present invention includes N-methyl-isothiazol-3-one, N-methyl-isothiazol-5-chloro-3-one, and N-methyl-isothiazole-4,5 as antifungal agents. -Dichloro-3-one, 2-nitro-2-bromo-3-hydroxypropanol, 2-methyl-4-chlorophenol, hydrogen peroxide and the like can be used.

[Physical development processing]
In the present invention, a physical development process (also simply referred to as “physical development”) is performed after the chemical development process in order to impart a preferable conductivity to a conductive pattern whose main component is silver. In the present invention, “physical development processing” refers to newly developed silver ions supplied from the outside in addition to developed silver produced from silver halide grains in a photosensitive material by chemical development processing, and is generated by chemical development processing. This refers to the process of reinforcing developed silver. As a specific method for supplying silver ions from the physical development processing solution, for example, a method in which silver nitrate or the like is dissolved in advance in the physical development processing solution, or silver ions are dissolved, or in the physical development processing solution, A method for enhancing development of silver halide grains having a latent image by dissolving a silver halide solvent such as sodium thiosulfate, ammonium thiocyanate, etc., and dissolving silver halide grains in an unexposed area during development. In the present invention, the former is preferable.

  In the present invention, further additional plating treatment and blackening treatment performed after plating as used in the prior art are not performed.

[Oxidation treatment]
In the present invention, oxidation treatment may be performed after chemical development processing and / or after physical development processing. By the oxidation treatment, unnecessary metal components can be ionized and dissolved and removed, and the transmittance of the film can be further increased.

  As the treatment liquid used for the oxidation treatment, for example, a treatment method using an aqueous solution containing Fe (III) ions, or hydrogen peroxide, persulfate, perborate, perphosphate, percarbonate, perhalogenate. A treatment solution containing a conventionally known oxidant such as a method of treatment using an aqueous solution containing a peroxide such as hypohalite, halogenate, or organic peroxide can be used. The oxidation treatment may be performed at any timing from the end of the chemical development process to the end of the physical development process, but is preferably performed after the end of the physical development process.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

(Underdrawn PET film support)
A biaxially stretched PET support of 100 μm is subjected to a corona discharge treatment of 12 W · min / m ^{2, and} an undercoating solution B-1 is applied to each surface to a dry film thickness of 0.1 μm. Then, a corona discharge treatment of 12 W · min / m ² was performed on the B-1 dry film on each surface, and the undercoating liquid B-2 was applied so as to have a dry film thickness of 0.06 μm. Thereafter, heat treatment was performed at 120 ° C. for 1.5 minutes to obtain an underdrawn PET film support.

<Undercoat coating liquid B-1>
Copolymer latex liquid of 20 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate and 40 parts by mass of butyl acrylate (solid content: 30%) 50 g
SnO ₂ sol (A) 440g
Compound (UL-1) 0.2g
Finish with water 1000ml
<Undercoat coating liquid B-2>
10g gelatin
Compound (UL-1) 0.2g
Compound (UL-2) 0.2g
Silica particles (average particle size 3μm) 0.1g
Hardener (UL-3) 1g
Finish with water 1000ml

SnO ₂ sol (A)
(Synthesis example of SnO ₂ sol (A))
65 g of SnCl ₄ .5H ₂ O was dissolved in 2000 ml of distilled water to obtain a homogeneous solution, which was then boiled to obtain a precipitate. The produced precipitate is taken out by decantation and washed with distilled water many times. Silver nitrate is added dropwise to distilled water in which the precipitate has been washed, and after confirming that there is no reaction of chlorine ions, distilled water is added to the washed precipitate to make a total volume of 2000 ml. To this, 40 ml of 30% aqueous ammonia was added and heated to obtain a uniform sol. Further, while adding ammonia water, the solution was concentrated by heating until the solid content concentration of SnO ₂ reached 8.3% by mass to obtain SnO ₂ sol (A).

[Preparation of silver halide fine grain emulsion 1]
The following solution A was kept at 34 ° C. in a reaction vessel, and the pH was adjusted to 2.95 using nitric acid (concentration 6%) while stirring at high speed using a mixing and stirring device described in JP-A-62-2160128. It was adjusted. Subsequently, the following solution B and the following solution C were added at a constant flow rate over 8 minutes and 6 seconds using the double jet method. After completion of the addition, the pH was adjusted to 5.90 using sodium carbonate (concentration 5%), and then the following solution D and solution E were added.

(Solution A)
Alkali-treated inert gelatin (average molecular weight 100,000) 18.7g
Sodium chloride 0.31g
Solution I (below) 1.59ml
Pure water 1246ml
(Solution B)
169.9g of silver nitrate
Nitric acid (concentration 6%) 5.89ml
Finish to 317.1 ml with pure water (Solution C)
Alkali-treated inert gelatin (average molecular weight 100,000) 5.66 g
Sodium chloride 58.8g
13.3 g of potassium bromide
Solution I (below) 0.85ml
Solution II (below) 2.72 ml
Finish to 317.1 ml with pure water (Solution D)
2-Methyl-4hydroxy-1,3,3a, 7-tetraazaindene 0.56 g
112.1 ml of pure water
(Solution E)
Alkali-treated inert gelatin (average molecular weight 100,000) 3.96 g
Solution I (below) 0.40ml
128.5 ml of pure water
(Solution I)
Surfactant: 10% by weight methanol solution of polyisopropylene polyethylene oxydisuccinate sodium salt (Solution II)
10% by weight aqueous solution of rhodium hexachloride complex After the above operation is completed, desalting and water washing are performed using a flocculation method at 40 ° C. according to a conventional method. The pH was adjusted to 5.90 at 40 ° C., and finally a silver chlorobromide cubic grain emulsion containing 10 mol% of silver bromide and having an average grain size of 0.09 μm and a coefficient of variation of 10% was obtained.

(Solution F)
Alkali-treated inert gelatin (average molecular weight 100,000) 16.5g
Pure water 139.8ml
The silver halide emulsion was subjected to chemical sensitization at 40 ° C. for 80 minutes using 20 mg of sodium thiosulfate per mole of silver halide, and 4-hydroxy-6-methyl-1,3, after completion of chemical sensitization. 500 mg of 3a, 7-tetrazaindene (TAI) per 1 mol of silver halide and 150 mg of 1-phenyl-5-mercaptotetrazole per 1 mol of silver halide were added to obtain silver halide emulsion EM-1. In this silver halide emulsion EM-1, the volume ratio of silver halide grains to gelatin (silver halide grains / gelatin) was 0.625. Further, a hardening agent (H-1: tetrakis (vinylsulfonylmethyl) methane) was added at a ratio of 200 mg per 1 g of gelatin, and a surfactant (SU-2: sulfosuccinate disulfate) was applied as a coating aid. (2-ethylhexyl) .sodium) was added to adjust the surface tension. The coating solution thus obtained was applied on one surface of the above-mentioned easily adhesive polyester film support so that the amount of gelatin applied was as described in Table 1, followed by curing at 50 ° C. for 24 hours.

  The film produced as described above is exposed using an ultraviolet lamp through a grid-like photomask having a line width of 6 μm and a distance between lines of 244 μm, and the following developer (DEV-1) Then, development processing was performed at 25 ° C. for 60 seconds, and then fixing processing was performed at 25 ° C. for 120 seconds using the following fixing solution (FIX-1). Further, physical development was performed at 25 ° C. for 10 minutes using the following physical developer (PDEV-1), followed by washing with water and drying.

(DEV-1)
500 ml of pure water
Metol 2g
80 g of anhydrous sodium sulfite
Hydroquinone 4g
4g borax
Sodium thiosulfate 10g
Potassium bromide 0.5g
Add water to bring the total volume to 1 liter (FIX-1)
750 ml of pure water
Sodium thiosulfate 250g
Anhydrous sodium sulfite 15g
Glacial acetic acid 15ml
Potash alum 15g
Add water to bring the total volume to 1 liter (PDEV-1)
The following A liquid and B liquid are mixed immediately before processing (A liquid).
400ml of pure water
Citric acid 10g
Disodium hydrogen phosphate 1g
Ammonia water (28% aqueous solution) 1.2ml
Hydroquinone 3g
(Liquid B)
10 ml of pure water
0.4 g of silver nitrate
(Washing treatment and drying treatment)
The washing process was performed with tap water for 10 minutes. Moreover, the drying process was dried until it became a dry state using drying air (50 degreeC).

(Transparent conductive film)
Using a conductive polyaniline dispersion ORMECON D1033 (manufactured by Olmecon, Germany) containing a sulfonic acid-based dopant as a conductive polymer compound, it was applied on a silver mesh prepared to have a dry film thickness of 130 nm. A transparent conductive film 101 of the present invention was produced.

  Similarly, except that the AgBr / AgCl ratio, the Ag / binder ratio, and the amount with the binder were changed as shown in Table 1, the transparent conductive films 102 to 117 of the present invention were further converted into PEDOT: PSS as the conductive polymer compound. = 1: 2.5 The transparent conductive film of the present invention was prepared in the same manner as the transparent conductive film 101 except that Baytron PH510 (manufactured by HC Starck) was added to 5% by mass of dimethyl sulfoxide. A film 118 was produced.

  Further, a transparent conductive film 119 of the present invention was produced in the same manner as the transparent conductive film 101 except that a conductive polyaniline dispersion ORMECON NXC001X (made by Olmecon, Germany) was used as the conductive polymer compound.

(Comparative sample)
The following samples were prepared as comparative samples.

Sample 201: Sample without applying conductive polymer compound after physical development of sample 101 Sample 202: Without a silver halide emulsion layer on an easily-adhered support, ORMECON D1033 (manufactured by Olmecon, Germany) Applied Sample Specimen 203; After physical development of Sample 101, the following plating solution (PL-1) was used for electrolytic copper plating treatment at 25 ° C. for 5 minutes, and then ORMECON D1033 (manufactured by Olmecon, Germany) was applied. Sample Sample 204; After plating of Sample 203, after applying blackening treatment at 80 ° C. for 1 minute using the following blackening solution (BK-1), ORMECON D1033 (made by Olmecon, Germany) is applied. Sample 205; Sample obtained by depositing ITO film instead of ORMECON D1033 (manufactured by Olmecon, Germany) of Sample 101 (PL-1)
1000ml of pure water
200 g of copper sulfate
50g of sulfuric acid
(BK-1)
1000ml of pure water
Sodium chlorite 31g
Sodium hydroxide 15g
Trisodium phosphate 12g
The following evaluation was performed for each sample. The results are shown in Table 1.

(Measurement of surface resistivity)
The surface resistivity was measured using a resistivity meter (Loresta GP (MCP-T610 type): manufactured by Dia Instruments Co., Ltd.). In addition, about the sample of this invention, the surface specific resistance was measured also about the sample after physical development before apply | coating a conductive polymer compound.

× 100Ω / □ or more △ × 50Ω / □ or more and less than 100Ω / □ △ 30Ω / □ or more and less than 50Ω / □ ○ △ 10Ω / □ or more and less than 30Ω / □ ○ Less than 10Ω / □.

(Measurement of transmittance)
The transmittance was measured using a spectrophotometer (Hitachi spectrophotometer U-3210: manufactured by Hitachi, Ltd.).

○ 80% or more ○ △ 75% or more and less than 80% △ 70% or more and less than 75% △ × 65% or more and less than 70% × less than 65%.

(Bending resistance)
A sample cut out to 10 cm × 10 cm was rounded into a cylindrical shape with a diameter of 3 cm, and it was repeatedly pushed with a finger 10 times so that the cross-section had a shape of ∞, and it was confirmed whether cracks occurred.

○ No generation × Crack generation (gas resistance)
JIS C0048 Environmental Test Method -Electric / Electronic- Mixed Gas Flow Corrosion Test The surface specific resistance of samples stored in a gas environment for 10 days was compared before and after storage in accordance with Test Method 4. See Table 2 for details of storage conditions.
Surface specific resistance value after storage rises to 10 times or more compared with before storage Δ × 5 times or more and less than 10 times Δ 3 times or more and less than 5 times ○ Δ 2 times or more and less than 3 times ○ Set to less than 2 times.

(Haze)
Evaluation was performed by using Tokyo Denshoku TURBIDITY METER T-2600DA.

○ Less than 2% ○ △ 2% or more and less than 3% △ 3% or more and less than 5% △ × 5% or more and less than 8% × 8% or more.

(Coloring)
The sample was observed visually.

× You can clearly see the color of the mesh ○ I don't care about the color of the mesh.

(Adhesiveness)
Use a razor blade to cut 10 × 10 = 100 square mesh cuts at an angle of 45 ° to the mesh at 1 mm × 1 mm. Nitto Denko's cellophane tape no. No. 29 was attached, and the number of remaining pieces when it was peeled strongly was counted.

○ 90 or more ○ △ 70 or more and less than 90 △ 50 or more and less than 70 △ × 30 or more and less than 50 × less than 30

(curl)
When the sample was cut out at 3.5 cm × 15 cm and left at 23 ° C. in each environment of 20% RH and 80% RH for 3 hours, the state of curling was observed.

○ No curl in any environment △ Slightly curl but no problem in handling × Strong curl occurs.

  As shown in Table 1, satisfactory values were obtained for the surface resistivity, which is an index of electromagnetic wave shielding ability, in all the samples. However, in the present invention, the transparency which is very important for the display front filter is high in the present invention. A translucent conductive film with high quality and high transmittance was obtained, but in the comparative example, adhesion of dirt was recognized, and not only was it seen as unevenness, but also a satisfactory transmittance was obtained with low transmittance. I couldn't.

Claims (2)

A transparent conductive material in which a conductive pattern containing silver and a transparent conductive film made of a conductive polymer compound are adjacently provided on the transparent film substrate from the side close to the transparent film substrate. In the film, the conductive pattern is provided with a layer containing silver halide grains on the transparent film substrate, and exposed and developed with the desired pattern to form a metallic silver portion of the desired pattern. Formed by further physical development processing ,
The conductive polymer compound is a polyethylenedioxythiophene-based or polyaniline-based conductive polymer compound,
Amount with the binder in the layer containing said silver halide grains is at 0.05 g / m ² or more 0.25 g / m ² or less,
A transparent conductive film , wherein the Ag / binder ratio in the layer containing the silver halide grains before exposure is 0.3 to 0.8 in volume ratio . The silver halide grains are silver chlorobromide grains, the silver chloride content is 55 mol% or more and 95 mol% or less, and the silver bromide content is 5 mol% or more and 45 mol% or less. The transparent conductive film according to claim 1 .