JP5131268B2 - Transparent film having conductive metal pattern and method for producing the same - Google Patents

Description

  The present invention relates to a transparent film having a conductive metal pattern that can be suitably used in various fields such as a liquid crystal display element, an organic light emitting element, an inorganic electroluminescent element, a solar cell, an electromagnetic wave shield, and a touch panel, and a method for producing the same.

  A transparent film having a conductive metal pattern is used for a liquid crystal display, an electroluminescence display, a plasma display, an electrochromic display, a transparent electrode such as a solar cell, a touch panel, and electronic paper, and an electromagnetic shielding material.

  For example, a transparent film having a conductive metal pattern is used as an electromagnetic wave shielding material that can achieve both high electromagnetic wave shielding performance and transmittance, and various methods have been proposed as an implementation means thereof (for example, Patent Document 1). -3)). However, in any case, the manufacturing method is complicated, the technology is insufficient from the viewpoint of continuous productivity for mass production, and improvement has been desired. In addition, among electromagnetic wave shielding films using conductive metal patterns, the method of producing a conductive pattern using exposure to photosensitive silver halide and a development process is easy to form and inexpensive. It is disclosed as a useful method capable of producing a large amount of transparent electromagnetic wave shielding material. As one of them, an electromagnetic wave shielding material using a silver salt diffusion transfer method is known (for example, refer to Patent Documents 4 and 5). In the diffusion transfer method, physical development nuclei are uniformly formed on a substrate in advance. As a result, an unnecessary catalyst remains in the non-conductive portion, and the permeability is easily lost. Further, since the diffusion phenomenon of silver ions or silver complexes is used for development, sharpness is likely to deteriorate, and an improvement thereof is desired. It was.

  As another method utilizing the exposure and development process for photosensitive silver halide, the silver halide emulsion layer is exposed and developed to directly form developed silver, which is then used as a catalyst for plating and the like. An electromagnetic wave shielding material in which a conductive pattern is produced is known (for example, see Patent Documents 6 to 8). In these materials, a binder is used to hold the photosensitive silver halide emulsion on the support. However, it is preferable that the Ag / binder ratio is as high as possible in order to increase the conductivity.

  As described above, a method for producing a transparent film having a conductive metal pattern using a photosensitive material having photosensitive silver halide grains is known, and some of them have begun to be put into practical use.

  However, a transparent film having such a highly transparent conductive metal pattern is used for a flat display panel such as a plasma display panel or used for an office window glass. It is expected that what is on the other side is clearly visible. However, there is a phenomenon in which the visibility of the image is lowered due to the optical action of the conductive metal pattern provided on the support, the layer containing the conductive pattern, or the support used in the conductive pattern, and improvement thereof is desired. It was.

As a factor of the decrease in visibility, surface reflection and scattering of external light by a transparent film having a conductive metal pattern, generation of moire by a conductive metal pattern, and the like can be mentioned.
In addition, when a transparent film having a conductive metal pattern is observed under a three-wavelength fluorescent lamp, the light reflected on the support surface interferes with the light reflected on the film surface, and subtle film thickness unevenness results in rainbow-colored unevenness ( Hereinafter, the interference unevenness may be observed), and such interference unevenness also causes a decrease in visibility.

  In display panel materials, it is known that similar rainbow-colored unevenness (interference unevenness) is observed when a hard coat layer of an antireflection film is produced. On the other hand, Patent Document 10 discloses an improvement technique such as using a solvent that swells or dissolves the base material.

However, this technique is a technique for preventing iridescent unevenness caused by the high refractive index of the hard coat layer of the antireflection film, and it is not known whether it is effective for a transparent film having a conductive metal pattern. In addition, it is difficult to give irregularities to the base material because haze increases. In the case of biaxially stretched polyester, the solvent for swelling or dissolving the base material has problems such as many agents having problems in the working environment.
JP-A-5-327274 JP-A-11-170421 Japanese Patent Laid-Open No. 2003-23290 JP 2004-172041 A JP 2005-183059 A JP 2004-221564 A JP 2004-221565 A WO 01/51276 pamphlet JP-A-8-197670 JP 2003-131007 A

  The present invention has been made in view of the above-mentioned problems, and the object thereof is a conductive metal pattern having high transparency and excellent visibility during image observation through a transparent film having a conductive metal pattern. It is providing the transparent film which has these, and its manufacturing method.

  Therefore, as a result of intensive studies on the transparent film having the conductive metal pattern, the present inventors have found that the transparent film having the conductive metal pattern has an absolute reflectance in the visible region and a support having an easy-adhesive layer used therefor. It has been found that a transparent film having a conductive metal pattern excellent in improvement in visibility during image observation through a transparent film having a conductive metal pattern can be obtained by appropriately controlling the absolute reflectance of a single substance.

  That is, the object of the present invention is achieved by a transparent film having the following conductive metal pattern.

  1. In a transparent film having a conductive metal pattern formed by forming a pattern with a conductive metal on a support having an easy adhesion layer, the absolute value of the absolute reflectance in the visible region is the absolute value of the single support having the easy adhesion layer. A transparent film having a conductive metal pattern characterized by not exceeding a maximum value of reflectance.

  2. In a transparent film having a conductive metal pattern formed by forming a pattern with a conductive metal on a support having an easy-adhesion layer, the maximum absolute reflectance of the visible region on the conductive pattern forming surface side is opposite. 2. The transparent film having a conductive metal pattern according to 1 above, which is smaller than the maximum absolute reflectance on the side.

  3. In a transparent film having a conductive metal pattern formed by forming a pattern with a conductive metal on a support having an easy-adhesion layer, the layer imparting the function of reducing the reflectance is a pattern forming layer with a conductive metal and the support. The transparent film having the conductive metal pattern according to 1 or 2, wherein the transparent film is present between the two.

  4). In a transparent film having a conductive metal pattern formed by forming a pattern with a conductive metal on a support having an easy-adhesion layer, the maximum absolute reflectance of the visible region on the conductive pattern forming surface side is opposite. 2. The transparent film having a conductive metal pattern as described in 1 above, wherein the transparent film has a larger absolute reflectance on the side.

  5). In a transparent film having a conductive metal pattern formed by forming a pattern with a conductive metal on a support having an easy-adhesion layer, the layer imparting the function of decreasing the reflectance is opposite to the pattern forming layer with the conductive metal. The transparent film having the conductive metal pattern according to 1 or 4, wherein the transparent film is provided on the conductive film.

  6). 6. The transparent film having a conductive metal pattern according to any one of 1 to 5, wherein the transparent film having the conductive metal pattern has two or less maximum absorptions of absolute reflectance in the visible region. .

  7). The difference between the maximum value and the minimum value of the absolute reflectance in the visible region of the transparent film having the conductive metal pattern is the difference between the maximum value and the minimum value of the absolute reflectance in the visible region of the single support having the easy-adhesion layer. The transparent film having a conductive metal pattern according to any one of 1 to 6 above, wherein the transparent film is 2 times or less.

  8). The difference between the maximum value and the minimum value of the absolute reflectance in the visible region of the transparent film having the conductive metal pattern is within 30% of the maximum value, according to any one of 1 to 7 above. A transparent film having a conductive metal pattern.

  9. 9. The conductive metal pattern of the transparent film having the conductive metal pattern is patterned so as to selectively shield an electromagnetic wave having a specific frequency. A transparent film having a conductive metal pattern.

  10. 10. A method for producing a transparent film having a conductive metal pattern according to any one of 1 to 9, wherein a silver halide emulsion-containing layer containing at least a photosensitive silver halide and a binder is formed on a support. A method for producing a transparent film having a conductive metal pattern, wherein the photosensitive material having a development process is performed after exposure.

  11. The support is a biaxially stretched polyester, and the layer imparting the above-described reflectance lowering function is provided adjacent to the biaxially stretched polyester, and the refractive index of the layer imparting the reflectance decreasing function is 1.57. It is 1.63 to 1.63, The transparent film which has the electroconductive metal pattern of said 3 or 5 characterized by the above-mentioned.

  12 12. The transparent film having a conductive metal pattern as described in 3 or 11 above, wherein the layer imparting the function of reducing the reflectivity contains a metal oxide sol.

  13. 13. The transparent film having a conductive metal pattern as described in 12 above, wherein the metal oxide is a tin oxide sol or a cerium oxide sol.

  According to the present invention, there are provided a transparent film having a conductive metal pattern that has high transparency and further improved visibility during image observation through a transparent film having a conductive metal pattern, and a method for producing the same. be able to.

It is a figure which shows some examples of the electromagnetic wave reflective surface which has an antenna element pattern. It is a schematic diagram showing arrangement | positioning of the evaluation apparatus of an attenuation factor.

  The transparent film having a conductive metal pattern of the present invention is a transparent film having a conductive metal pattern formed by forming a pattern with a conductive metal on a support having an easy adhesion layer. The maximum value does not exceed the maximum absolute reflectance of a single support having an easy-adhesion layer. The absolute reflectance of a single support having an easy-adhesion layer here refers to the absolute reflectance of the surface of the support having the easy-adhesion layer on the side where the conductive metal pattern is formed.

  Hereinafter, the present invention will be described in detail.

  In the present invention, the visible region refers to a wavelength region from 400 nm to 700 nm, and the absolute reflectance of the electromagnetic wave shielding film of the film in this region is, for example, using a device such as Photo FE-3000 (manufactured by Otsuka Electronics Co., Ltd.). Can be measured.

  In measurement, it is necessary to prevent the measurement aperture from covering the metal pattern, or the measurement aperture should be sufficiently larger than the above metal pattern, and at least 100 times larger than the area of the metal pattern. Set aperture and measure.

  The absolute reflectance of a single support having an easy-adhesion layer is preferably measured before the formation of a layer containing a pattern made of a conductive metal, but can be measured in a small area even after the metal pattern is formed. In the case where the absolute reflectance of the support portion having an easy-adhesion layer is obtained or the entire surface is coated, an acid / alkali or organic solvent is appropriately used to provide the support portion on the support. This can be determined by measuring after removing the constituent layers.

  In the present invention, there is no particular limitation on the means for satisfying the requirement of the present invention that the maximum value of the absolute reflectance in the visible region does not exceed the maximum value of the absolute reflectance of the support alone, for example, pattern formation by a conductive metal Layer, or a method of appropriately adjusting the refractive index and thickness of the binder resin used for the easy-adhesion layer and the protective layer, or a pattern forming layer made of a conductive metal, or a binder resin used for the easy-adhesion layer and the protective layer Alternatively, a method of appropriately adding compounds having different refractive indexes, a method of changing the smoothness of the surface of the transparent film having a conductive metal pattern, and adjusting the reflectance as appropriate can be used.

  Above all, by providing a reflectance-reducing functional layer on at least one layer that forms the easy-adhesion layer, and adjusting the refractive index of this reflectance-reducing functional layer, the maximum absolute reflectance in the visible region is supported with the easy-adhesion layer. From the viewpoint that it is easy to form a transparent film having a conductive metal pattern that minimizes adverse effects on the film surface and has low haze and high transparency, so as not to exceed the maximum absolute reflectance of a single body This is a particularly preferred embodiment of the present invention. In addition, the aspect in which this reflectance fall functional layer serves as the pattern formation layer by an electroconductive metal and the easily bonding layer of a support body is preferable. The refractive index n3 of the reflectance-reducing functional layer is preferably an intermediate refractive index between the refractive index n1 of the pattern forming layer made of a conductive metal and the refractive index n2 of the support, and particularly preferably between n1 and n2. Of 10 to 90%, and more preferably 20 to 80% of the value.

  Further, the film thickness of the reflectance lowering functional layer is not particularly limited, but in order to bring out the effect of the present invention to a higher degree, it is 0.2 to 2 times the film thickness of the pattern forming layer made of a conductive metal. The aspect which is a film thickness is preferable, More preferably, it is an aspect made into the film thickness of 0.5 to 1.5 times. Further, from the viewpoint of improving the coating uniformity, the thickness of the reflectance-reducing functional layer is preferably 400 nm or less, and more preferably 200 nm or less. In addition, this reflectance fall functional layer may be comprised from the several layer.

  As the binder preferably used in the reflectance lowering functional layer, for example, gelatin, gelatin derivatives, gelatin and other polymer graft polymers, various latexes, aqueous polymer solutions, and the like can be preferably used. Examples of water-soluble polymers include vinyl alcohol polymers such as polyvinyl alcohol, water-soluble polyesters, etc., and examples of latexes include acrylic-styrene polymer latex, styrene-diolefin polymer latex, and vinylidene chloride. A polymer latex or a polyurethane-based polymer latex can be exemplified, and among them, a latex obtained by polymerizing an ethylenically unsaturated monomer is preferable from the viewpoint of easily improving the adhesion improving function.

  Ethylenically unsaturated monomers include acrylic esters (eg, methyl acrylate, ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, iso-nonyl acrylate, n-dodecyl acrylate, t -Butyl acrylate, phenyl acrylate, 2-naphthyl acrylate, etc.), methacrylic acid esters (for example, n-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, iso-nonyl methacrylate, n-dodecyl methacrylate methyl methacrylate, ethyl methacrylate) 2-hydroxyethyl methacrylate, benzyl methacrylate, 2-hydroxypropyl methacrylate, phenyl Acrylate, cyclohexyl methacrylate, cresyl methacrylate, 4-chlorobenzyl methacrylate, ethylene glycol dimethacrylate, etc.), vinyl esters (eg, vinyl benzoate, pivaloyloxyethylene, etc.), acrylamides (eg, acrylamide, methylacrylamide, Ethylacrylamide, propylacrylamide, butylacrylamide, t-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, diacetoneacrylamide Etc.), Methacryl Amides (eg, methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, t-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylamino Ethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, etc.), styrenes (for example, styrene, methyl styrene, dimethyl styrene, trimethylene styrene, ethyl styrene, isopropyl styrene, chlorostyrene, Methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene Vinyl benzoic acid methyl ester), divinylbenzene, acrylonitrile, methacrylonitrile, N- vinylpyrrolidone, N- vinyl oxazolidone, vinylidene chloride, mention may be made of phenyl vinyl ketone. These monomers may be used alone or in combination of two or more.

  Further, at least one of the ethylenically unsaturated monomers is preferably a monomer having an epoxy group or a monomer having an active methylene group, more preferably a monomer having an epoxy group and a monomer having an active methylene group are used in combination. It is. Examples of the monomer having an epoxy group include glycidyl methacrylate and glycidyl acrylate. Examples of the ethylenically unsaturated monomer having an active methylene group include 2-acetoacetoxyethyl methacrylate, 2-acetoacetoxyethyl acrylate, 2- Acetoacetamidoethyl methacrylate and the like can be used.

  As the water-soluble polymer used at the time of polymerization, most water-soluble natural polymers and water-soluble synthetic polymers having a water-soluble anionic group, cationic group or nonionic group in the molecular structure can be used. As a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphoric acid or a salt thereof, a tertiary amine or an ammonium salt as a cationic group, and a nonionic group as a hydroxyl group, an amide group, a methoxy group, an alkylene oxide group Are preferably an oxyethylene group or a heteroatom ring such as a pyrrolidone group. Among the water-soluble synthetic polymers, anionic or nonionic ones are preferable, and anionic polymers are particularly preferable. More preferred are polymers having a sulfonate, and a polystyrene sulfonic acid copolymer, a sulfonated product of isoprene-styrene copolymer, and a copolyester having 5-sulfoisophthalic acid as a copolymerization component are more preferred. Two or more water-soluble polymers may be used in combination.

  The latex used in the reflectance-reducing functional layer can be produced by an emulsion polymerization method. For example, water is used as a dispersion medium, and the monomer is 10 to 50% by mass with respect to water and 0.05 to 5% by mass with respect to the monomer. % Polymerization initiator and 0.1 to 20% by mass of a dispersant, and the mixture is polymerized with stirring at about 30 to 100 ° C., preferably 60 to 90 ° C. for 3 to 8 hours. Conditions such as the amount of monomer, amount of polymerization initiator, reaction temperature, reaction time and the like can be widely changed.

As the polymerization initiator, water-soluble peroxides (for example, potassium persulfate, ammonium persulfate, etc.), water-soluble azo compounds (for example, 2,2′-azobis (2-aminodipropane) hydrochloride, etc.) or these A redox polymerization initiator combined with a reducing agent such as Fe ²⁺ salt or sodium bisulfite can be used.

  Various latexes having an average particle diameter of about 0.02 to 0.8 μm can be used, and any latex having an average particle diameter of 0.05 to 2.0 μm can be preferably used.

Moreover, the aspect which adjusts a refractive index by adding a metal oxide to a reflectance fall functional layer is especially preferable. The high refractive index material is preferably a relatively high refractive index agent having a refractive index exceeding 1.7. Examples of such a high refractive index material include metal oxides such as tin oxide, cerium oxide, titanium oxide, yttrium oxide, lanthanum oxide, niobium oxide, and zirconium oxide. However, since the haze of the film is increased when the particle diameter exceeds 100 nm, the primary particle diameter is preferably 0.5 to 100 nm, more preferably 0.5 to 10 nm. Most preferably, it is 0.5-5 nm. As the agent for achieving such a particle size, the aforementioned metal oxide sol can be preferably used. Of these, tin oxide sol and cerium oxide sol are preferable.
The metal oxide sol can be produced by a known method. For example, the method described in Japanese Patent Publication No. 35-6616 is used for a tin oxide sol, and the method described in JP-A-5-13211 1 is used for a cerium oxide sol. it can.

  The above metal oxide sol is commercially available from Taki Chemical Co., Ltd. as the Niedral series, the Cerames series, and the functional oxide sol series, and such materials can be used.

  In the present invention, the absolute reflectance of the transparent film having the conductive metal pattern is such that the maximum absolute reflectance in the visible region on the conductive pattern forming surface side is smaller than the maximum absolute reflectance on the opposite surface side. It can be preferably used. When the transparent film having this conductive metal pattern is used by being attached to a substrate such as glass, it is visible when the opposite side of the conductive pattern forming surface is attached to the substrate with an adhesive or the like. This is a particularly preferable embodiment.

  In the present invention, an aspect in which the maximum absolute reflectance in the visible region on the conductive pattern forming surface side is larger than the maximum absolute reflectance on the opposite surface side can also be preferably used. When the transparent film having the conductive metal pattern is attached to a substrate such as glass, the visibility is improved when the conductive pattern forming surface is attached to the substrate with an adhesive or the like. This is a particularly preferred embodiment.

  In the transparent film having the conductive metal pattern of the present invention, an embodiment in which the absolute absorption of the absolute reflectance in the visible region is 2 or less is particularly preferable. A transparent film having a conductive metal pattern with less reflection color unevenness by making the maximum absorption of the absolute reflectance in the visible region less than 2 so that the reflectance change becomes gentle when the viewing angle of the film is changed. It becomes possible to provide.

  Further, in the transparent film having the conductive metal pattern of the present invention, the difference between the maximum value and the minimum value of the absolute reflectance in the visible region of the transparent film having the conductive metal pattern is different from that of the support alone having the easy adhesion layer. An aspect in which the difference between the maximum value and the minimum value of the absolute reflectance in the visible region is twice or less is preferable because the effect of the present invention is enhanced, and an aspect in which it is particularly preferably 1 time or less.

  Furthermore, in the transparent film having the conductive metal pattern of the present invention, a mode in which the difference between the maximum and minimum absolute reflectance values in the visible region is preferably within 30% of the maximum value, particularly preferably within 20%. It is an aspect to make. These are all effective for reducing uneven reflection color during film viewing. For example, a transparent film having a conductive metal pattern was viewed under a light source having a discontinuous emission spectrum such as a three-wavelength fluorescent lamp. Even in this case, it is possible to provide a transparent film having a conductive metal pattern with little uneven reflection color.

  In the transparent film having a conductive metal pattern of the present invention, an aspect in which the maximum absolute reflectance in the visible region does not exceed 0.075 is preferable, and an aspect in which the absolute value is 0.06 or less has a significant improvement in visibility. This is a particularly preferred embodiment.

The method for producing a transparent film having a conductive metal pattern of the present invention is not particularly limited. For example, a method using an ink jet technique, a method using a printing technique, a method using a silver halide photosensitive material, and the like. Can be mentioned. Moreover, the method of forming a random conductive metal pattern spontaneously as described in Japanese translations of PCT publication No. 2005-530005 gazette can also be utilized. As a method using an inkjet technique, for example, a liquid discharge head having a nozzle with an internal diameter of 0.5 to 30 μm for discharging a charged liquid onto a support having an easy-adhesion layer, and supplying a solution into the nozzle A method of forming by electroless plating after applying a plating catalyst ink in a desired pattern using a liquid discharge device comprising a supply means for supplying and a discharge voltage applying means for applying a discharge voltage to the solution in the nozzle, or A liquid discharge head having a nozzle having an internal diameter of 0.5 to 30 μm for discharging a charged liquid on the transparent film substrate, supply means for supplying the solution into the nozzle, and discharge voltage to the solution in the nozzle And applying a metal fine particle-containing ink in a desired pattern using a liquid discharge device equipped with a discharge voltage applying means for applying a metal ion or metal A method of applying an ink containing a complex ion and a reducing agent in a desired pattern, or a method of applying a metal ion or metal complex ion-containing ink and a reducing agent-containing ink in a desired pattern from different nozzles can be used.
The following is a photosensitive material having a layer comprising a photosensitive silver halide and a binder as a particularly useful method that allows easy formation of a pattern and that can produce a transparent film having a conductive metal pattern in large quantities at low cost. Next, a method for performing development processing will be described.

[Silver halide emulsion-containing layer]
In the present invention, a photosensitive silver halide and a silver halide emulsion-containing layer containing a binder, which will be described later, are provided on the support. In addition to this, the silver halide emulsion-containing layer includes a hardener and a high contrast. Agents, activators and the like.

In the present invention, the content of the photosensitive silver halide is preferably aspect in terms of silver is less than ^{0.05g / m 2 ~3g / m 2} , particularly preferably 0.3 g / m ² in terms of silver is ~ 1 g / In this embodiment, it is less than m ² . When the photosensitive silver halide content is less than 0.05 g / m ² , it is difficult to obtain sufficient electromagnetic wave shielding performance. This is presumed to be because the amount of developed silver nuclei serving as a catalyst for physical development or metal plating treatment described later becomes insufficient and it becomes difficult to form an effective conductive mesh. In addition, when the photosensitive silver halide content is 3 g / m ² or more, the amount of silver halide relative to the binder is relatively large, so that the coating tends to become brittle and maintain sufficient coating strength. It becomes difficult.

  When the amount of the binder is increased in order to maintain the physical properties of the film, the distance between the grains of the photosensitive silver halide grains is increased, so that it becomes difficult to form a developed silver network, and it is difficult to form an effective conductive mesh, Durability against changes in temperature and humidity is also insufficient, making it difficult to obtain the effects of the present invention.

In the present invention, the amount of the binder of the light-sensitive material is 10 mg / m ^{2 to} 0.2 g / m ² , which is a particularly preferable embodiment from the viewpoint of achieving both conductivity and film properties. When the amount of the binder is less than 10 mg / m ^2, the amount of silver halide relative to the binder is relatively large, so that the coating tends to become brittle and it is difficult to maintain sufficient coating strength. In addition, when the amount of the binder is more than 0.1 g / m ² , the distance between the photosensitive silver halide grains is increased, so that it is difficult to form a developed silver network, and it is difficult to form an effective conductive mesh. In addition, the durability against changes in temperature and humidity becomes insufficient, and the effects of the present invention cannot be obtained.

[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 metallic silver having good conductivity, fine particles having high sensitivity are preferable, and silver iodobromide particles are preferably used. When a large amount of iodine is contained, the sensitivity is high and the particles can be made fine.

  In order to reduce the surface specific resistance after silver halide grains are developed to become metallic silver grains and effectively shield electromagnetic waves, the contact area between 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 the silver halide grains is preferably 0.01 to 0.5 μm, more preferably 0.03 to 0.3 μm, in terms of a sphere equivalent diameter. In addition, the sphere equivalent diameter of silver halide grains represents the diameter of grains having the same volume and having a spherical shape. 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, an embodiment in which the value obtained by dividing the coating silver amount (g / m ² ) by the particle size (μm) is 6 to 25 is preferable. When a large amount of photosensitive silver halide having a relatively small particle size is used, this value tends to be larger than 25. In this case, the silver halide grains slip off from the coating at the edge when the film is cut. It tends to be easier. Further, when a small amount of photosensitive silver halide having a relatively large particle size is used, this value tends to be smaller than 6, and in this case, the number of photosensitive silver halide grains in a unit area is reduced, so that the conductivity is reduced. This is because it tends to decrease.

  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. In order to increase the sensitivity, tabular grains having an aspect ratio of 2 or more, 4 or more, and further 8 to 16 can be preferably used. 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 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 is preferably 10 ⁻¹⁰ to 10 ⁻² mol / mol Ag per mol of silver halide, and is preferably 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, in order to further improve the sensitivity, chemical sensitization performed in a photographic emulsion can be performed. 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 emulsion, they may be dispersed directly in the emulsion, or water, methanol, propanol, methyl cellosolve, 2,2,3,3-tetrafluoro A solvent such as propanol may be added alone or in a mixed solvent and added to the emulsion. Further, as described in JP-B-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, 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, it may be dispersed directly in a hydrophilic colloid and the dispersion may be added to the emulsion.

(binder)
In the silver halide emulsion-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 the adhesion between the silver halide 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.

(UV absorber)
In the present invention, it is preferable to use an ultraviolet absorber in order to avoid deterioration of the electromagnetic wave shielding film due to ultraviolet rays.

  As the ultraviolet absorber, known ultraviolet absorbers such as salicylic acid compounds, benzophenone compounds, benzotriazole compounds, S-triazine compounds, cyclic imino ester compounds and the like can be preferably used. Of these, benzophenone compounds, benzotriazole compounds, and cyclic imino ester compounds are preferred. As what is blended with the polyester, a cyclic imino ester compound is particularly preferable. There are no particular restrictions on the layer to which these UV absorbers are added, but from the viewpoint of preventing deterioration of the binder used in the silver halide emulsion-containing layer due to UV rays, it can be added directly to the silver halide emulsion-containing layer or halogenated. An embodiment in which the layer is provided closer to outside light than the silver emulsion-containing layer is preferable. When added to a silver halide emulsion-containing layer or a layer adjacent thereto, preferred ultraviolet absorbers include benzotriazoles, for example, represented by the general formula [III-3] described in JP-A-1-250944. Compounds represented by the general formula [III] described in JP-A No. 64-66646, UV-1L to UV-27L described in JP-A No. 63-187240, and JP-A No. 4-1633 A compound represented by the general formula [I], a compound represented by the general formulas (I) and (II) described in JP-A-5-165144, and the like are preferably used. These ultraviolet absorbers are used in high-boiling organic solvents represented by phthalates such as dioctyl phthalate, di-i-decyl phthalate, and dibutyl phthalate, and phosphate esters such as tricresyl phosphate and trioctyl phosphate. An embodiment in which it is added in a dispersed form is preferably used. Moreover, the aspect which adds these ultraviolet absorbers directly to a support body is also used preferably, In this case, the aspect as described, for example in Japanese translations of PCT publication No. 2004-531611 can also be used preferably.

[High contrast agent]
In the present invention, in order to draw a conductive pattern with clear edges, it is preferable that the photosensitive material has a high contrast. As the method, a method of increasing the silver chloride content to narrow the particle size distribution, or hydrazine It is preferable to use a compound or a tetrazolium compound as a contrast enhancer. The hydrazine compound is a compound having a —NHNH— group, and a typical one is represented by the following general formula (1).

General formula (1) T-NHNHCO-V, T-NHNHCOCO-V
In the formula, each T represents an optionally substituted aryl group or heterocyclic group. The aryl group represented by T includes a benzene ring or a naphthalene ring, and this ring may have a substituent, and as a preferable substituent, a linear or branched alkyl group (preferably having 1 to 20 carbon atoms). Methyl group, ethyl group, isopropyl group, n-dodecyl group, etc.), alkoxy group (preferably C2-C21 methoxy group, ethoxy group, etc.), aliphatic acylamino group (preferably C2-C21 alkyl group) An acetylamino group, a heptylamino group, etc.), an aromatic acylamino group, and the like. In addition to these, for example, a substituted or unsubstituted aromatic ring as described above is -CONH-, -O-,- Also included are those bonded by a linking group such as SO ₂ NH—, —NHCONH—, —CH ₂ CH═N—, and the like. V represents a hydrogen atom, an optionally substituted alkyl group (methyl group, ethyl group, butyl, trifluoromethyl group, etc.), aryl group (phenyl group, naphthyl group), heterocyclic group (pyridyl group, piperidyl group, pyrrolidyl group) , Furanyl group, thiophene group, pyrrole group and the like).

  The above-mentioned hydrazine compound can be synthesized with reference to the description in US Pat. No. 4,269,929. The hydrazine compound can be contained in the silver halide grain-containing layer, in the hydrophilic colloid layer adjacent to the silver halide grain-containing layer, or in another hydrophilic colloid layer.

Particularly preferred hydrazine compounds are listed below.
(H-1): 1-trifluoromethylcarbonyl-2-{[4- (3-n-butylureido) phenyl]} hydrazine (H-2): 1-trifluoromethylcarbonyl-2- {4- [ 2- (2,4-di-tert-pentylphenoxy) butyramide] phenyl} hydrazine (H-3): 1- (2,2,6,6-tetramethylpiperidyl-4-amino-oxalyl) -2- { 4- [2- (2,4-di-tert-pentylphenoxy) butyramide] phenyl} hydrazine (H-4): 1- (2,2,6,6-tetramethylpiperidyl-4-amino-oxalyl)- 2- {4- [2- (2,4-di-tert-pentylphenoxy) butyramide] phenylsulfonamidophenyl} hydrazine (H-5): 1- (2,2,6,6-tetramethyl Peridyl-4-amino-oxalyl) -2- (4- (3- (4-chlorophenyl-4-phenyl-3-thia-butanamide) benzenesulfonamido) phenyl) hydrazine (H-6): 1- (2, 2,6,6-tetramethylpiperidyl-4-amino-oxalyl) -2- (4- (3-thia-6,9,12,15-tetraoxatricosanamide) benzenesulfonamido) phenylhydrazine (H- 7): 1- (1-Methylenecarbonylpyridinium) -2- (4- (3-thia-6,9,12,15-tetraoxatricosanamide) benzenesulfonamido) phenylhydrazine chloride.

  When hydrazine is used as the thickening agent, an amine compound or a pyridine compound can be preferably used in order to enhance the reducing action of hydrazine. As the amine compound that promotes the reducing action of the hydrazine compound, it is particularly preferable that the molecule has at least one piperidine ring or pyrrolidine ring, at least one thioether bond, and at least two ether bonds.

  In addition to the above-described amine compounds, pyridinium compounds and phosphonium compounds can also be preferably used as compounds that promote the reduction action of hydrazine. Since onium compounds are positively charged, they are adsorbed on silver halide grains that are negatively charged and promote electron injection from the developing agent at the time of development, thereby promoting high contrast. It has been. As preferred pyridinium compounds, reference can be made to bispyridinium compounds disclosed in JP-A-5-53231 and 6-242534. Particularly preferred pyridinium compounds are those in which a bispyridinium body is formed by linking at the 1-position or 4-position of pyridinium. In the salt, as the halogen anion, chlorine ion, bromine ion and the like are preferable, and other examples include boron tetrafluoride ion and perchlorate ion, and chlorine ion or boron tetrafluoride ion is preferable.

The hydrazine compound, amine compound, pyridinium compound, and tetrazolium compound are preferably contained in an amount of 1 × 10 ^{−6 to} 5 × 10 ⁻² mol per mol of silver halide, particularly 1 × 10 ⁻⁴ to 2 × 10 ⁻² mol. Is preferred. It is easy to adjust the addition amount of these compounds to increase the degree of contrast γ to 6 or more.

  These compounds are used by being added to a layer containing halogenated particles or another hydrophilic colloid layer. If it is water-soluble, add it to an aqueous solution, and if it is water-insoluble, add it to a silver halide grain solution or hydrophilic colloid solution as a solution of an organic solvent miscible with water such as alcohols, esters, and ketones. Good. Moreover, when it does not melt | dissolve in these organic solvents, it can add with a ball mill, a sand mill, a jet mill, etc. and it can be made into 0.01-10 micrometers microparticles | fine-particles. As the fine particle dispersion method, a technique of solid dispersion of a dye as a photographic additive can be preferably applied. For example, a desired particle size can be obtained using a dispersing machine such as a ball mill, a planetary rotating ball mill, a vibrating ball mill, or a jet mill. When a surfactant is used at the time of dispersion, stability after dispersion can be improved.

[Support]
In the present invention, as a support, for example, a cellulose ester film, a polyester film, a polycarbonate film, a polyarylate film, a polysulfone (including polyether sulfone) film, a polyester film such as polyethylene terephthalate, polyethylene naphthalate, Polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film, polymethyl Pentene film, polyetherketone film, polyether Ton imide film, a polyamide film, a fluororesin film, a nylon film, a polymethyl methacrylate film or an acrylic film or the like. In addition to these plastic films, quartz glass, soda glass, and the like can be used.

  Of these, cellulose triacetate film, polycarbonate film, polysulfone (including polyethersulfone) and polyethylene terephthalate film are preferably used. The biaxially stretched polyester support (film) is transparent and has an appropriate strength even in a thin film, and therefore is particularly effective for the base material of such a film, and is most preferably a biaxially stretched polyethylene terephthalate film. .

  When the transparent film having the conductive metal pattern of the present invention is used for a display screen of a display, high transparency is required, and therefore it is desirable that the support itself has high transparency. In this case, the average transmittance of the entire visible light region of the plastic film or glass plate is preferably 85 to 100%, more preferably 90 to 100%. Moreover, in this invention, what colored the said plastic film or glass plate to the extent which does not interfere with the objective of this invention can also be used as a color tone regulator.

  In the present invention, the average transmittance in the visible light region is the average value obtained by integrating the transmittances in the visible light region obtained by measuring the transmittance in the visible light region from 400 to 700 nm at least every 5 nm. Defined as

  In measurement, the measurement aperture needs to be sufficiently larger than the mesh pattern described above, and is obtained by measuring at least 100 times larger than the mesh area of the mesh.

  Although there is no restriction | limiting in particular in the thickness of the support body used for this invention, It is preferable that it is 5-200 micrometers from a viewpoint of the maintenance of a transmittance | permeability, and a handleability, and it is further more preferable that it is 30-150 micrometers.

[Easily adhesive layer]
Next, the easily bonding layer used for this invention is demonstrated. The easy adhesion layer used in the present invention is a layer provided between the support and the conductive metal pattern forming layer in order to ensure the adhesion between the support and the conductive metal pattern. A multi-layer structure having more than one layer may be used. The easy-adhesion layer contains a resin (binder) for achieving adhesiveness, and when it functions as a refractive index reduction layer, it contains at least a material (refractive index adjusting agent) for obtaining a desired refractive index. As the resin, a binder or the like preferably used for the above-described reflectance lowering functional layer can be used.

  The easy-adhesion layer used in the present invention can be formed by coating and drying on a plastic film using a generally well-known coating method.

  Examples of coating methods that can be used include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, or US Pat. No. 2,681,294. Examples include the extrusion coating method using the described hopper. In addition, as required, U.S. Pat. Nos. 2,761,791, 3,508,947, 2,941,898, and 3,526,528, Harasaki A method of simultaneously applying two or more layers described in Yuji's “Coating Engineering”, page 253 (published by Asakura Shoten in 1973) can also be used. Drying conditions are generally 100 to 200 ° C. and about 10 seconds to 10 minutes.

  In applying the coating liquid for the easy adhesion layer onto the support, the support can be pretreated. Pretreatment includes chemical treatment, alkali treatment, mixed acid treatment, mechanical surface-roughening treatment, corona discharge treatment, ultraviolet treatment, high-frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, ozone treatment, and other surface activation treatments. Can be mentioned.

  When providing the easy-adhesion layer according to the present invention on the support, it can be provided before or after stretching during the formation of the polyester film, but it is not necessary to consider the stretchability of the easy-adhesion layer. Is easy.

  A surfactant, swelling agent, matting agent, antihalation dye, pigment, antifoggant, preservative, etc. may be added to the coating solution as necessary.

〔exposure〕
In the light-sensitive material having a silver halide emulsion-containing layer according to the present invention, the light-sensitive material is exposed in order to form a conductive pattern by development / compensation processing described later. Examples of the light source used for exposure include light such as visible light and ultraviolet light, radiation such as electron beam and X-ray, and ultraviolet light or near infrared light is preferably used. Further, a light source having a wavelength distribution may be used for exposure, and a light source having a narrow wavelength distribution may be used.

  Various light emitters that emit light in the spectral region are used as necessary for visible light. 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. 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 quick, 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, quick, long-life, and highly stable, exposure is preferably performed using a semiconductor laser.

  Specifically, as the laser light source, an ultraviolet semiconductor, a blue semiconductor laser, a green semiconductor laser, a red semiconductor laser, a near infrared laser, or the like is preferably used.

  The method for exposing the silver halide emulsion-containing layer in the form of an image may be performed by surface exposure using a photomask or by scanning exposure using a laser beam. At this time, condensing exposure using a lens or reflection exposure using a reflecting mirror may be used, and exposure methods such as surface contact exposure, near field exposure, reduced projection exposure, and reflection projection exposure can be used. The output of the laser used for the exposure varies depending on the sensitivity of the silver halide grains, the exposure speed, and the optical system of the apparatus.

[Development processing]
In the present invention, after the photosensitive material is exposed, development processing is performed. The development process is preferably a so-called black-and-white development process that does not contain a color developing agent.

  As the developing solution, in addition to hydroquinones such as hydroquinone, sodium hydroquinonesulfonate, chlorohydroquinone and the like as developing agents, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1- Use in combination with pyrazolidones such as phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone and superadditive developing agents such as N-methylparaaminophenol sulfate. Can do. 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.

  In addition, sodium sulfite or potassium sulfite as a preservative, sodium carbonate or potassium carbonate as a buffer, diethanolamine, triethanolamine, diethylaminopropanediol or the like as a development accelerator can be appropriately used in the developing solution.

  The development processing solution used in the development processing can contain an image quality improver 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 present invention, it is preferable that the development processing performed after exposure includes physical development before fixing. The term “physical development before fixing” as used herein refers to a process in which silver ions are supplied from outside the silver halide grains having a latent image by exposure to reinforce developed silver before performing a fixing process described later. As a specific method for supplying silver ions from the developing solution, for example, a method of dissolving silver nitrate or the like in advance in a developing solution and dissolving silver ions, or sodium thiosulfate in the developing solution, Examples include a method in which a silver halide solvent such as ammonium thiocyanate is dissolved, unexposed silver halide is dissolved during development, and development of silver halide grains having a latent image is supplemented.

  In the present invention, it is preferable to use a formulation in which a silver halide solvent is preliminarily dissolved in a developer because a reduction in the transmittance of the film due to fogging in unexposed areas can be suppressed.

  In the development processing in the present invention, after the development of the exposed silver halide grains, fixing processing is performed for the purpose of removing and stabilizing the 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 fixing agent preservative, sodium sulfite, potassium sulfite, ascorbic acid, erythorbic acid and the like described in the developing solution can be used, and citric acid, oxalic acid, and the like can be used.

  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.

[Reinforcement processing]
In the present invention, in order to assist the contact between the developed silvers formed by the above-described development process, and to increase the conductivity, it is preferable to perform a reinforcement process. In the present invention, the intensifying process refers to a process in which a conductive substance source not previously contained in the photosensitive material is supplied from the outside during or after the development process to increase the conductivity. Examples thereof include physical development or plating treatment. Physical development can be performed by immersing a photosensitive material containing a silver halide emulsion having a latent image in a processing solution containing silver ions or silver complex ions and a reducing agent. In the present invention, physical development is defined not only when the development start point of physical development is the latent image nucleus but also when developed silver is the physical development start point, and this can be preferably used.

  In the present invention, various conventionally known plating methods can be used for the plating treatment. For example, electrolytic plating and electroless plating can be performed alone or in combination. Among them, it is possible to preferably use electrolytic plating that has high plating efficiency and is less likely to cause a decrease in transmittance due to plating adhesion to unnecessary portions. As metals that can be used for electrolytic plating, for example, copper, nickel, cobalt, tin, silver, gold, platinum, and other various alloys can be used, but the plating process is relatively easy and has high conductivity. From the viewpoint of easy obtaining, it is particularly preferable to use electrolytic copper plating.

  The intensifying process can be performed during development, at any timing after development and before fixing, and after the fixing process, but it is preferably performed after the fixing process from the viewpoint of maintaining high transparency of the film.

  In the present invention, an embodiment in which the amount of metal applied by physical development or metal plating is 10 to 100 times in terms of mass with respect to developed silver obtained by exposing and developing the photosensitive material is preferable. This value can be obtained by quantifying the metal contained in the photosensitive material by, for example, fluorescent X-ray analysis before and after performing physical development or metal plating. When the amount of metal applied by physical development or metal plating is less than 10 times in terms of mass relative to developed silver obtained by exposing and developing a photosensitive material, the conductivity tends to be slightly reduced. If it is larger than 100 times, the transmittance tends to decrease due to metal deposition on unnecessary portions other than the conductive pattern portion.

  In the present invention, the description of physical development or metal plating means performing at least one of physical development or plating treatment, and means that both physical development and metal plating may be included, In the present invention, it is preferable to perform both physical development and metal plating.

[Oxidation treatment]
In the present invention, it is preferable to carry out an oxidation treatment after the development treatment, physical development or plating treatment. 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 treating with an aqueous solution containing a peroxide such as a hypohalite, a halogenate, or an organic peroxide can be used. The oxidation process is preferably performed after the development process and before the plating process because the transmittance can be improved efficiently in a short time, and particularly preferably after the physical development. This is the mode to be performed.

(Blackening treatment)
In the present invention, from the viewpoint of preventing external light reflection on the film surface, it is preferable to perform a blackening treatment after completion of the metal plating treatment. When a transparent film having such a blackened conductive metal pattern is used for a display such as a PDP, for example, contrast reduction due to reflection of external light can be reduced, and the color tone of the screen when not in use can be increased to black. It is preferable because the quality can be maintained. The blackening treatment method is not particularly limited, and known methods can be used alone or in combination as appropriate. For example, when the outermost surface of the conductive pattern is made of metallic copper, a method of oxidizing by immersing in an aqueous solution containing sodium chlorite, sodium hydroxide, or trisodium phosphate, or copper pyrophosphate or pyrophosphoric acid A method of blackening by immersion in an aqueous solution containing potassium and ammonia and performing electrolytic plating can be preferably used. If the outermost layer of the conductive pattern is made of a nickel-phosphorus alloy coating, immerse it in an acidic blackening solution containing copper (II) chloride or copper (II) sulfate, nickel chloride or nickel sulfate, and hydrochloric acid. The method to do can be used preferably.

  In addition to the above-described method, the blackening treatment can be performed by a method of finely roughening the surface. However, from the viewpoint of maintaining high conductivity, oxidation is more effective than finer roughening of the surface. A blackening treatment method is preferred.

[Configuration of electromagnetic shielding layer]
In the present invention, in order to provide high translucency and high electromagnetic wave shielding performance, it is possible to form a conductive metal pattern by drawing a lattice-like fine line pattern by exposure and then performing development processing or the like. preferable. The conductive metal part pattern is preferably an orthogonal mesh pattern, preferably having a line width of 20 μm or less and a line interval of 50 μm or more. The conductive metal portion may have a portion whose line width is wider than 20 μm for the purpose of ground connection or the like. Further, from the viewpoint of making the image inconspicuous, the line width of the conductive metal portion is preferably less than 18 μm, more preferably less than 15 μm, further preferably less than 14 μm, still more preferably less than 10 μm, and most preferably less than 7 μm.

  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 90% or more from the viewpoint of visible light transmittance. The aperture ratio is the ratio of the portion without fine lines forming the mesh to the whole. For example, the aperture ratio of a square lattice mesh having a line width of 10 μm and a pitch of 200 μm is 90%.

  In the present invention, it is also preferable to provide a photosensitive silver halide emulsion layer on both sides of a support having an easy-adhesion layer and to form a conductive pattern on each. In this case, it is preferable that the silver halide emulsion coated on each surface has sensitivity at different wavelengths by spectral sensitization or the like. By giving sensitivity to different wavelengths on the front and back surfaces, it is possible to produce different conductive patterns on each surface, for example, to selectively shield against electromagnetic waves of different frequencies on the front and back surfaces. It is also possible to form a conductive pattern. Specific examples include those described in Japanese Patent Application No. 2006-156998.

[Functional layers other than electromagnetic shielding layers]
When the transparent film having a conductive metal pattern of the present invention is used in combination with an optical filter for a plasma display panel (PDP), for example, it is a layer containing a near-infrared absorbing dye under the silver halide grain layer. It is also preferable to provide a certain near infrared absorption layer. In some cases, the near-infrared absorbing layer may be provided on the opposite side of the support to the silver halide grain layer side, or may be provided on both the silver halide grain layer side and the opposite side. A near infrared absorption layer can be provided between the silver halide grain layer containing silver halide and the support, or a near infrared absorption layer can be provided on the opposite side of the support as viewed from the silver halide grain layer. The former is preferred because it can be applied simultaneously with one side of the support.

  Specific examples of near-infrared absorbing dyes include polymethine, phthalocyanine, naphthalocyanine, metal complex, aminium, imonium, diimonium, anthraquinone, dithiol metal complex, naphthoquinone, indolephenol, azo And triallylmethane-based compounds. The PDP optical filter is required to have near-infrared absorptivity mainly for absorption of heat rays and noise prevention of electronic devices. For this purpose, a dye having a near-infrared absorbing ability having a maximum absorption wavelength of 750 to 1100 nm is preferable, and a metal complex, aminium, phthalocyanine, naphthalocyanine, diimonium, and squalium compound are particularly preferable.

  As a near-infrared absorbing dye, diimonium compounds are IRG-022, IRG-040 (above, trade names manufactured by Nippon Kayaku Co., Ltd.), nickel dithiol complex compounds are SIR-128, SIR-130, SIR-132, SIR. -159, SIR-152, SIR-162 (above, trade names manufactured by Mitsui Chemicals, Inc.), and phthalocyanine compounds use commercially available products such as IR-10, IR-12 (above, trade names of Nippon Shokubai Co., Ltd.). can do.

  The near-infrared absorbing dye may be used after being dissolved in an organic solvent such as alcohol solvents such as methanol, ethanol and isopropanol, ketone solvents such as acetone, methyl ethyl ketone and methyl butyl ketone, dimethylsulfoxide, dimethylformamide, dimethyl ether and toluene. It is preferable to apply fine particles having an average particle size of 0.01 to 10 μm with a fine particle machine, and it is preferable to use an optical density in the range of 0.05 to 3.0 at the maximum wavelength.

  In addition, when making the color tone correction | amendment layer contain the pigment | dye which has a near-infrared absorptivity, you may contain any 1 type among said pigment | dye, and may contain 2 or more types.

  When the transparent film having the conductive metal pattern of the present invention is used in combination with, for example, an optical filter for a plasma display panel (PDP), in order to prevent a decrease in color reproducibility due to emission of neon gas emission lines used in the PDP. As a countermeasure, an embodiment containing a dye that absorbs light at around 595 nm is preferable. Specific examples of the dye that absorbs such a specific wavelength include, for example, azo, condensed azo, phthalocyanine, anthraquinone, indigo, perinone, perylene, dioxazine, quinacridone, methine, Well-known organic pigments and organic dyes such as isoindolinone-based, quinophthalone-based, pyrrole-based, thioindigo-based, and metal complex-based materials, and inorganic pigments may be mentioned. Among these, phthalocyanine-based and anthraquinone-based dyes are particularly preferably used because of good weather resistance.

  When the transparent film having the conductive metal pattern of the present invention is used for the purpose of protecting a display screen or the like, it is preferable to provide an antireflection layer. As the antireflection layer, inorganic materials such as metal oxides, fluorides, silicides, borides, carbides, nitrides, sulfides, etc., can be used by vacuum deposition, sputtering, ion plating, ion beam assist, etc. A method of laminating a thin film in a layer or a multilayer, a method of laminating a resin having a different refractive index such as an acrylic resin or a fluororesin into a single layer or a multilayer can be used.

  In the transparent film having a conductive metal pattern of the present invention, when the antireflection layer is formed on the opposite side of the film having the support, the antireflection layer is first formed. After forming, a mode in which a protective film is bonded and then a conductive pattern layer is formed is preferable. When the antireflection layer is formed after the conductive pattern is formed first, the efficiency of the plasma treatment and corona treatment performed to improve the adhesion between the antireflection layer and the support tends to be reduced. The embodiment in which the layer is formed first is preferred. In addition, when the antireflection layer is formed first, from the viewpoint of preventing the layer from being deteriorated by development, plating treatment, or the like, a mode in which a conductive pattern layer is formed after pasting a protective film in advance is preferable. .

  As the protective film used in the present invention, a commercially available protective film can be used. From the viewpoint of facilitating coating of a photosensitive silver halide emulsion layer for forming a conductive pattern, the film is used. Is preferably 10 to 100 μm, particularly preferably 20 to 60 μm. If the thickness is less than 10 μm, the rigidity of the film is remarkably reduced, so that the work efficiency of the protection film is likely to be lowered. If the thickness is more than 100 μm, a failure such as a winding reel tends to occur when the film is wound. is there.

  Although there is no restriction | limiting in particular in the kind of adhesive used for a protective film, The thing which does not damage an antireflection film at the time of peeling, without altering an antireflection film is used preferably. From such a viewpoint, an acrylic or silicone adhesive is preferably used. Moreover, as the adhesive force, what is 0.08-0.6N / 25mm is used preferably.

[Adhesive]
In the present invention, in order to attach a transparent film having a conductive metal pattern having a water-soluble binder to a transparent substrate, the pressure-sensitive adhesive that can be used should be highly transparent and have an appropriate adhesive force. Although there is no particular limitation, acrylic adhesives, rubber adhesives, silicon adhesives, and the like can be preferably used. Among these, from the viewpoint of excellent transparency, adhesiveness, and heat resistance, an embodiment in which it is used by being bonded to a transparent substrate via an acrylic pressure-sensitive adhesive is preferably used.

  An acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive obtained by copolymerizing a polar monomer component with an acrylic acid alkyl ester as a main component, and the copolymerization ratio of the polar monomer component is acrylic acid-based. Preferably it is 0.1-20 mass parts per 100 mass parts of alkyl ester components, More preferably, it is 0.5-15 mass parts, More preferably, about 1-10 mass parts is preferable.

  Examples of acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, The carbon number of the alkyl group, such as heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate or dodecyl (meth) acrylate, Acrylic acid alkyl ester or methacrylic acid alkyl ester of about 1 to 12 is preferably used. Two or more of these may be used in combination.

  As the polar monomer, a compound having a reactive group with a curing agent is used, and the type thereof is not particularly limited, but in general, those having a hydroxyl group or a carboxyl group are preferable. For example, acrylic ester, methacrylic acid Examples thereof include carboxyl group-containing acrylic monomers such as esters, and specific compounds include hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Acrylic acid polar monomers such as amino group-containing (meth) acrylic acid ester monomers such as acrylic acid ester monomers, N, N-dimethylaminoethyl acrylate, Nt-butylaminoethyl acrylate, etc. Alternatively, maleic acid or the like is preferably used. These may be used in combination of two or more as required.

[Curing agent]
In order to perform intramolecular crosslinking or intermolecular crosslinking of the pressure-sensitive adhesive component, it is preferable to use a curing agent. The curing agent is appropriately selected and used depending on the type of the pressure-sensitive adhesive monomer. Polyisocyanate compounds such as aromatic diisocyanates such as adducts, melamine compounds such as butyl etherified styrene melamine and trimethylol melamine, diamine compounds such as hexamethylene diamine and triethyl diamine, bisphenol A / epichlorohydrin, polyethylene glycol diglycidyl ether, trimethylol Epoxy such as propane triglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylenediamine Compounds, urea resin-based compound, aluminum chloride, ferric chloride, aluminum sulfate, metal salts such as copper acetate or the like is used.

  In this invention, the aspect in which an acrylic adhesive contains an epoxy-type hardening | curing agent is used preferably. Epoxy curing agents are generally highly reactive with the carboxyl groups of acrylic pressure-sensitive adhesives, and may further strengthen the bond between the transparent film having a conductive metal pattern including gelatin having a carboxyl group and the pressure-sensitive adhesive. It is considered possible, and even when stored in a high temperature / high humidity environment for a long period of time, the adhesion of the film is unlikely to deteriorate, and the discoloration of developed silver can be reduced. The mechanism for reducing the degree of discoloration is not clear, but it is presumed that the effect of outside air is reduced by the effect of improving the adhesion.

  The amount of the curing agent is usually 0.001 to 10 parts by mass, preferably 0.005 to 5 parts by mass, and more preferably about 0.01 to 3 parts by mass per 100 parts by mass of the acrylic resin.

Since the transparent film having a conductive metal pattern obtained in the present invention has good visibility, it can be suitably used as a translucent electromagnetic shielding material. Moreover, as various conductive wiring materials such as circuit wiring, it can be preferably used as a flexible transparent surface electrode. For example, it is preferably used as a transparent electrode for organic EL, inorganic EL display, lighting, various electronic papers, solar cells, etc. it can.
In particular, the transparent film having a conductive metal pattern of the present invention is suitably used as a light-transmitting electromagnetic shielding material used in a plasma display panel or an electromagnetic shielding material requiring transparency and frequency selectivity such as a window and a window. be able to.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
(Preparation of Support Base 1 with Easy Adhesive Layer)
A corona discharge treatment of 12 W · min / m ² is applied to both sides of a 100 μm biaxially stretched PET support, and the easy-adhesion layer coating solution B-1 is applied to a dry film thickness of 0.1 μm, and 12 W is applied thereon. -The corona discharge process of min / m < ² > was performed and the easily bonding layer coating liquid B-2 was apply | coated so that it might become a dry film thickness of 0.06 micrometer.

<Easily adhesive layer coating solution B-1>
Copolymer latex liquid (solid content 30%) of butyl acrylate 30% by mass, t-butyl acrylate 20% by mass, styrene 25% by mass, 2-hydroxyethyl acrylate 25% by mass 50 g
Compound (UL-1) 0.2g
Hexamethylene-1,6-bis (ethyleneurea) 0.05g
Finish with water 1000ml
<Easily adhesive layer coating solution 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

A tin oxide sol (SnO ₂ sol synthesized by the method described in Example 1 of Japanese Patent Publication No. 35-6616) is heated and concentrated to the easy-adhesion layer coating solution B-1 so that the solid content concentration is 10% by mass. After that, the bases Base2 and Base3 having an easy-adhesion layer were produced in the same manner as in the production of Base1, except that the pH was adjusted to 10 with ammonia water).

Base 2: A tin oxide sol was added so that the coating amount was 80 mg / m ² .

Base 3: A tin oxide sol was added so that the coating amount was 160 mg / m ² .

(Preparation of EMP-1)
The following (A1 solution) and (B1 solution) were simultaneously added to 1 liter of a 0.5% gelatin aqueous solution kept at 35 ° C. while controlling the silver potential (EAg) = 85 mV and pH = 5.8, and the following ( C1 solution) and (D1 solution) were simultaneously added while controlling EAg = 85 mV and pH = 5.8. At this time, the silver potential was controlled using a 10% potassium bromide aqueous solution, and the pH was controlled using acetic acid or a sodium hydroxide aqueous solution.

(A1 solution)
Potassium bromide 104g
Potassium iodide 3.0g
1300ml with water
(B1 solution)
150 g silver nitrate
1360ml with water
(C1 liquid)
310g of potassium bromide
Potassium hexachloroiridium (IV) 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium iodide 10 g
4000ml with water
(D1 solution)
480 g of silver nitrate
4200ml with water
After the addition, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.04 μm and a coefficient of variation in particle size distribution. A 0.13 silver halide emulsion EMP-1 was obtained.

(Preparation of EMP-2 to EMP-3)
In the preparation of EMP-1, the average particle size was 0.07 μm in the same manner except that the temperature at the time of addition of (A1 solution) and (B1 solution) and the addition of (C1 solution) and (D1 solution) was 40 ° C. The silver halide emulsion EMP-2 having a variation coefficient of 0.14 in the grain size distribution and a silver halide emulsion EMP having an average grain diameter of 0.12 μm and a variation coefficient of the grain size distribution of 0.13 by slowing the addition rate -3 was obtained.

(Preparation of EM-1)
The EMP-1 was subjected to chemical sensitization at 40 ° C. for 80 minutes using 2.0 mg of sodium thiosulfate per mole of silver halide, and 4-hydroxy-6-methyl-1,3,3 after completion of chemical sensitization. 500 mg of 3a, 7-tetrazaindene (TAI) was added per mole of silver halide to obtain a silver halide emulsion EM-1.

(Preparation of EM-2 to EM-3)
In the preparation of EM-1, the silver halide emulsion was changed from EMP-1 to EMP-2 and EMP-3, and the addition amount of sodium thiosulfate and TAI was adjusted in proportion to the total surface area of the silver halide grains. Otherwise, silver halide emulsions EM-2 and EM-3 were obtained in the same manner.

(Production of photosensitive materials 101 to 109)
As described above, the silver halide emulsions EM-1 to EM-3 prepared as described above are applied to the bases Base1 to Base3 on which the easy-adhesion layer has been applied so that the coated silver amount as shown in Table 1 is obtained. After coating, the photosensitive materials 101 to 109 were produced by drying. In the preparation of each photosensitive material, a hardener (H-1: tetrakis (vinylsulfonylmethyl) methane) was added at a ratio of 50 mg per 1 g of gelatin. Further, as a coating aid, a surfactant (SU-2: di (2-ethylhexyl) sulfosuccinate / sodium) was added to adjust the surface tension. In each photosensitive material, the amount of gelatin was adjusted so that the mass ratio of silver to gelatin was 5.0. The mass ratio of silver and gelatin referred to here is a value obtained by dividing the mass of silver equivalent to the silver halide applied by the mass of gelatin applied. The amount is shown as a value obtained by converting the amount of the silver halide emulsion used into equimolar silver.

(Production of transparent films S101 to S109 having conductive metal patterns)
The photosensitive materials 101 to 109 manufactured as described above are exposed using an ultraviolet lamp through a lattice-shaped photomask having a line width of 8 μm and a line-to-line spacing of 300 μm. After developing for 60 seconds at 25 ° C. using the solution (DEV-1), fixing processing was performed for 120 seconds at 25 ° C. using the following fixing solution (FIX-1), followed by washing with water. Furthermore, physical development was performed at 25 ° C. for 300 seconds using the following physical developer (PD-1), followed by washing with water. Then, the electrolytic copper plating process was performed at 25 degreeC using the plating solution (EPL-1), and the transparent films S101-S109 which have an electroconductive metal pattern were produced.

(Preparation of transparent films S110 to S114 having a conductive metal pattern)
The following Pd fine particle dispersion is diluted with a pure water / propylene glycol monomethyl acetate mixed solvent on a base material Base 2 having an easy-adhesion layer using a known electrostatic inkjet printer having an inner diameter of the tip of the nozzle of 10 μm. CAT-1) is applied, a mesh pattern having a width of 10 μm and an interval of 240 μm is produced, and subsequently subjected to electroless copper plating at 45 ° C. using the following electroless plating solution (PL-2) to conduct electricity. A conductive metal pattern was formed. Further, 5% by mass of dimethyl sulfoxide was added to Baytron PH510 (manufactured by HC Starck) which is a dispersion of conductive polymer compound-containing liquid EDOT: PSS = 1: 2.5 on the produced conductive metal pattern. By applying the added liquid so that the dry film thickness becomes 130 nm, a transparent film S110 having a conductive metal pattern was produced.

Base 4: A transparent film S111 having a conductive metal pattern was prepared in the same manner as S105 except that tin oxide sol was added to the easy-adhesion layer coating solution B-1 so that the coating amount was 40 mg / m ² .

Base5: Commercially available cerium oxide sol (manufactured by Taki Chemical Co., Nidral P-10, solid content 10% by mass) instead of tin oxide sol was applied to the easy-adhesion layer coating solution B-1 so that the coating amount was 40 mg / m ^2. A transparent film S112 having a conductive metal pattern was produced in the same manner as S105 except for the addition.

Base 6: Commercially available cerium oxide sol (manufactured by Taki Chemical Co., Nidral P-10, solid content 10% by mass) instead of tin oxide sol was applied to the easy-adhesion layer coating solution B-1 so that the coating amount was 60 mg / m ^2. A transparent film S113 having a conductive metal pattern was produced in the same manner as S105 except for the addition.

Base 7: Commercially available cerium oxide sol (manufactured by Taki Chemical Co., Nidral P-10, solid content 10% by mass) instead of tin oxide sol was applied to the easy-adhesion layer coating solution B-1 so that the coating amount was 80 mg / m ^2. A transparent film S114 having a conductive metal pattern was produced in the same manner as S105 except for the addition.

(DEV-1: Developer)
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: Fixer)
750 ml of pure water
Sodium thiosulfate 250g
Anhydrous sodium sulfite 15g
Glacial acetic acid 15ml
Potash alum 15g
Add water to make the total volume 1 liter (PD-1: physical developer)
800ml of pure water
Citric acid 5g
Hydroquinone 7g
Silver nitrate 3g
Add water to bring the total volume to 1 liter.

(EPL-1: Electrolytic plating solution)
Copper sulfate (pentahydrate) 200g
50g of sulfuric acid
Add water to bring the total volume to 1 liter.
(CAT-1: Pd catalyst solution)
Soluble palladium salt (Pd ²⁺ concentration 1.0 g / l) 20% by mass
Isopropyl alcohol 12% by mass
Glycerin 20% by mass
2-Methyl-2,4-pentanediol 5% by mass
1,3-butanediol 3% by mass
Ion exchange water 40% by mass
(PL-2: Electroless copper plating solution)
Copper sulfate 0.04 mol Formaldehyde (37%) 0.08 mol Sodium hydroxide 0.10 mol Triethanolamine 0.05 mol Polyethylene glycol 100 ppm
Add water to bring the total volume to 1 liter.

(Measurement of absolute reflectance of transparent film having support having conductive layer and conductive metal pattern)
With respect to the bases Base1 to Base7 having the easy-adhesion layer produced as described above and the transparent films S101 to S114 having the conductive metal pattern, each reflection spectrum was measured using FE-3000 (manufactured by Otsuka Electronics Co., Ltd.). did. In the measurement of the reflection spectrum, a small amount of immersion oil A (manufactured by Nikon) was dropped on a slide glass having a thickness of 1.3 mm, and the measurement sample was attached so that the back surface of the measurement sample was in close contact with the slide glass. The measurement was performed. Moreover, in the transparent film which has an electroconductive metal pattern, it measured avoiding the part of a metal mesh. In this way, the absolute reflectance from a wavelength of 400 nm to 700 nm is obtained, the maximum reflectance of the support in this wavelength range is obtained as Rb (max), and the minimum reflectance is obtained as Rb (min). The maximum reflectance of the transparent film was determined as Rm (max) and the minimum reflectance was determined as Rm (min), and the respective differences Rb (max-min) and Rm (max-min) were determined. Furthermore, the ratio of each difference, Rm (max-min) / Rb (max-min), was determined as Ratio. Also, the number of maximum or minimum points of the spectrum in this wavelength range was read. The results are also shown in Table 1.

(Evaluation of transparent films S101 to S114 having conductive metal pattern)
For each of the transparent films S101 to S114 having the conductive metal pattern obtained as described above, the sample is placed on the print on which the image and text characters are printed so that the base surface is located below. The visibility (sharpness, transparency, contrast) of images and text characters was observed while changing the viewpoint, and the appearance was evaluated.

  This evaluation was performed by 20 subjects, and the total score was obtained. The evaluation raw points are as follows, and 1 to 5 points are assigned to each sample. The larger the total points, the better the visibility.

Evaluation score 5: Sharpness, transparency and contrast are high and very easy to see 3: It is clear that any of sharpness, transparency and contrast is slightly inferior, but at a level that does not matter.

    1: It is understood that any one of sharpness, transparency, and contrast is slightly inferior, and is a level to be worried about.

(Interference unevenness)
For each of the transparent films S101 to S114 having a conductive metal pattern, the back surface was painted black by black spraying, and then the sample was placed on a horizontal table, and a three-wavelength fluorescent lamp (Purook fluorescent lamp FLR40S-EX-DM Matsushita Electric) The degree of occurrence of interference unevenness was visually evaluated according to the following criteria.

○: Interference unevenness is not seen at all ○ △: Interference unevenness is hardly understood Δ: Interference unevenness is slightly visible but there is no problem Δ ×: Interference unevenness is seen ×: Interference unevenness is clearly seen ××: Strong interference unevenness is observed.

(Refractive index)
Further, the refractive index of the easily adjustable refractive index adjusting layer in contact with the support was measured by the following method.

  The support is subjected to corona discharge treatment, and when the easy-adhesion layer coating solution B1 is applied, the refractive index evaluation table sample is cut out, and for each sample, the analysis attached to the device is performed from the measurement result of the spectral reflectance of the spectrophotometer. The refractive index of the easily adhesive layer was determined using software. The spectrophotometer uses a U-4000 type (manufactured by Hitachi, Ltd.), and the back side of the measurement side of the sample is light-absorbed with a black spray to prevent reflection of light on the back side, and the regular reflection of 5 degrees The reflectance in the visible light region (400 to 700 nm) was measured under the conditions.

From the results in Table 1, it can be seen that Samples S101, S104 to S108, and S110 to S114 that satisfy the requirements of the present invention have the effect of the present invention that is excellent in visibility. Among them, the difference between the maximum and minimum absolute reflectance in the visible region of a transparent film having a conductive metal pattern is within 30% of the maximum, and the maximum absolute reflectance in the visible region is 2 or less. Some have more favorable results. In addition, a layer that imparts the reflectance lowering function is provided adjacent to the biaxially stretched polyester, and the refractive index of the layer that imparts the reflectance lowering function is 1.57 to 1.63. It can be seen that interference is less visible even under a wavelength fluorescent lamp, and the visibility is more excellent.

Example 2
An adhesive is applied to the transparent films S101 to S109 having the conductive metal pattern produced in Example 1, and the surface opposite to the conductive metal pattern forming surface is attached to glass to each of the optical filter samples S201 to S201. S209 was prepared and observed and evaluated in the same manner as in Example 1. The results are shown in Table 2.

  From the results in Table 2, it can be seen that Samples S101 and S104 to S108 that satisfy the requirements of the present invention can achieve the effect of the present invention that is excellent in visibility even when the optical filter is attached to glass.

Example 3
Of the easy-adhesion layers of the PET support used in the preparation of the sample S101 of Example 1, the easy-adhesion layer on the base surface opposite to the conductive metal pattern forming surface is the same as the easy-adhesion layer used for the production in Base3. A transparent film S301 having a conductive metal pattern was produced in the same manner except that the constitution was adopted. In S301 produced in this way, an adhesive was applied to the conductive metal pattern forming surface, and an optical filter in which the conductive metal pattern forming surface side was attached to glass was produced. The same evaluation as in Example 1 was performed. When implemented, the evaluation score was 80 points. Moreover, the evaluation score when an adhesive was applied to the surface opposite to the conductive metal pattern forming surface and affixed to glass was 70 points. From this result, a transparent film having a conductive metal pattern in which the maximum absolute reflectance of the visible region on the conductive metal pattern forming surface side is larger than the maximum absolute reflectance on the opposite surface side is used as a substrate such as glass. Even when pasted and used, the effect of the present invention that is excellent in visibility is obtained, and when the conductive pattern forming surface is pasted to a substrate with an adhesive or the like, the effect of improving visibility is high, especially It turns out that it is a preferable aspect.

Example 4
Next, except that the antenna pattern was exposed using an ultraviolet lamp through a photomask formed so that the unit length of the linear antenna elements was 79 mm, the line width was 40 μm, and the distance between the linear antenna elements was 300 μm. A selective electromagnetic wave shielding film was produced in the same manner as in the transparent films S101 to S109 having the conductive metal pattern of Example 1, and the reflection characteristics in the 2G band (1.90 GHz; wavelength 158 mm) were confirmed.

  In addition, as an evaluation method of reflection characteristics, the attenuation rate was evaluated by the following method. FIG. 2 is a schematic diagram showing the arrangement of the attenuation rate evaluation apparatus. A vector network analyzer (HP, 8150B) is connected to a pair of dielectric lenses 1 and 2 installed facing each other, and the produced selective electromagnetic wave shielding film sample is placed between them. Attenuation at a frequency of 1.90 GHz (wavelength: 158 mm) Confirmed by rate (dB).

Claims (13)

In a transparent film having a conductive metal pattern formed by forming a pattern with a conductive metal on a support having an easy adhesion layer, the absolute value of the absolute reflectance in the visible region is the absolute value of the single support having the easy adhesion layer. A transparent film having a conductive metal pattern characterized by not exceeding a maximum value of reflectance. In a transparent film having a conductive metal pattern formed by forming a pattern with a conductive metal on a support having an easy-adhesion layer, the maximum absolute reflectance of the visible region on the conductive pattern forming surface side is opposite. The transparent film having a conductive metal pattern according to claim 1, wherein the transparent film has a smaller absolute reflectance on the side than the maximum value. In a transparent film having a conductive metal pattern formed by forming a pattern with a conductive metal on a support having an easy-adhesion layer, the layer imparting the function of reducing the reflectance is a pattern forming layer with a conductive metal and the support. The transparent film having a conductive metal pattern according to claim 1 or 2, wherein the transparent film exists between the two. In a transparent film having a conductive metal pattern formed by forming a pattern with a conductive metal on a support having an easy-adhesion layer, the maximum absolute reflectance of the visible region on the conductive pattern forming surface side is opposite. The transparent film having a conductive metal pattern according to claim 1, wherein the transparent film has a larger absolute reflectance on the side than the maximum value. In a transparent film having a conductive metal pattern formed by forming a pattern with a conductive metal on a support having an easy-adhesion layer, the layer imparting the function of decreasing the reflectance is opposite to the pattern forming layer with the conductive metal. The transparent film having a conductive metal pattern according to claim 1 or 4, wherein the transparent film is provided on the conductive film. The conductive property according to any one of claims 1 to 5, wherein the transparent film having the conductive metal pattern has two or less maximum absorptions of absolute reflectance in the visible region. A transparent film having a metal pattern. The difference between the maximum value and the minimum value of the absolute reflectance in the visible region of the transparent film having the conductive metal pattern is the difference between the maximum value and the minimum value of the absolute reflectance in the visible region of the single support having the easy-adhesion layer. It is 2 times or less, The transparent film which has an electroconductive metal pattern of any one of Claims 1-6 characterized by the above-mentioned. The difference between the maximum value and the minimum value of the absolute reflectance in the visible region of the transparent film having the conductive metal pattern is within 30% of the maximum value. A transparent film having the conductive metal pattern according to any one of the above items. 9. The conductive film according to claim 1, wherein the conductive metal pattern of the transparent film having the conductive metal pattern is patterned so as to selectively shield an electromagnetic wave having a specific frequency. A transparent film having the conductive metal pattern according to claim 1. A method for producing a transparent film having a conductive metal pattern according to any one of claims 1 to 9, wherein the halogen contains at least photosensitive silver halide and a binder on a support. A method for producing a transparent film having a conductive metal pattern, wherein the photosensitive material having a silver halide emulsion-containing layer is subjected to development after exposure. The support is a biaxially stretched polyester, and the layer imparting the above-described reflectance lowering function is provided adjacent to the biaxially stretched polyester, and the refractive index of the layer imparting the reflectance decreasing function is 1.57. The transparent film having a conductive metal pattern according to claim 3 or 5, wherein the transparent film has a thickness of 1.63 to 1.63. The transparent film having a conductive metal pattern according to claim 3 or 11, wherein the layer imparting the function of reducing the reflectance contains a metal oxide sol. The transparent film having a conductive metal pattern according to claim 12, wherein the metal oxide is a tin oxide sol or a cerium oxide sol.