WO2007102393A1 - Method for manufacturing electromagnetic wave shielding film and electromagnetic wave shielding film - Google Patents

Abstract

This invention provides a method for manufacturing an electromagnetic wave shielding film with high productivity, and an electromagnetic wave shielding film having a high electromagnetic wave shielding function, an excellent antireflection function, and a high near infrared light absorption function. The electromagnetic wave shielding film can be manufactured by a method characterized by comprising providing an original plate for an electromagnetic wave shielding film, comprising a layer containing photosensitive silver halide particles provided on a support, exposing and developing the original plate to form a meshy metal part, and then coating a layer having an antireflection function.

Description

 Specification

 Method for manufacturing electromagnetic shielding film, and electromagnetic shielding film

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to a method for producing an electromagnetic wave shielding film that shields electromagnetic waves generated from electronic equipment such as a mobile phone, a microwave oven, a CRT, and a flat panel display, and an electromagnetic wave shielding film obtained by the production method.

 Background art

 In recent years, there is an increasing need to reduce electromagnetic interference (EMI) due to increased use of electronic devices. It has been pointed out that EMI can cause malfunctions and failures of electronic and electrical equipment, as well as harm the human body. For this reason, electronic devices are required to keep the intensity of electromagnetic wave emission within the standards or regulations.

 [0003] Particularly, a plasma display panel (PDP) generates electromagnetic waves in principle because it is based on the principle that a rare gas is made into a plasma state to emit ultraviolet rays and phosphors emit light with this light beam. In addition, near infrared rays are also emitted at this time, so that malfunction of operation elements such as a remote controller is caused.

 [0004] The electromagnetic wave shielding ability can be simply expressed by the surface resistance value, and the translucent electromagnetic wave shielding film for PDP is required to be 10 Ω or less. In consumer plasma televisions using PDP, 2 It is more necessary to set the impedance to Ω or less, and it is desirable that the conductivity is extremely high, preferably 0.2 Ω or less.

In order to achieve such high electromagnetic shielding properties, several methods have been proposed so far. For example, when an infrared absorbing film is applied to a glass plate baked with a metal mesh having a high aperture ratio, the manufacturing method of the metal mesh baking is complicated and complicated, and skill is required for production. In addition, there is a problem that it takes a long process time. Since the developed silver obtained from the halogenated silver particles is metallic silver, it is conceivable to prepare a metallic silver mesh by a manufacturing method applying photographic development. When a photosensitive material having a layer containing silver halide silver particles is exposed in a mesh shape and developed, a conductive metal silver portion in which silver particles are gathered in a mesh shape is formed (see, for example, Patent Document 1). [0006] Other functions required for the PDP include an antireflection layer for preventing reflection of outside light, a near infrared absorption layer for shielding near infrared rays, and a color tone correcting layer for correcting color balance. However, since each functional filter has been produced separately and pasted together, the manufacturing process is complicated, complicated and requires skill in production, and takes a long time. There was a point.

 [0007] Therefore, studies have been made to solve this problem by integrating the above functional layers on a single support.

 [0008] However, since the physical and chemical properties and characteristics of each functional layer are different, simple integration may cause functional degradation or a heavy load on the manufacturing process. I understood that.

 [0009] For example, a layer containing silver halide grains needs to have a high ratio of silver to a binder in order to increase the conductivity of the formed mesh pattern, so that there are large restrictions on coating conditions. The antireflection layer can be applied using a non-aqueous organic solvent, and the near-infrared shielding layer has been tried to be dispersed in a hydrophobic plasticizer (see, for example, Patent Document 2). In other words, it is difficult to make it close to the layers it contains, which is a factor that reduces productivity.

 Patent Document 1: Japanese Patent Application Laid-Open No. 2004-221564

 Patent Document 2: JP 2005-099820 A

 Disclosure of the invention

 Problems to be solved by the invention

An object of the present invention is to provide an electromagnetic shielding film having high productivity, a method for producing an electromagnetic shielding film, a high electromagnetic shielding function produced by the production method, an excellent antireflection function, and a high near infrared absorption function. A film is provided.

 Means for solving the problem

The above object of the present invention is achieved by the following configuration.

[0012] 1. An anti-reflective function is obtained after forming a mesh-like metal part by exposing and developing an original plate for an electromagnetic wave shielding film in which a layer containing photosensitive halogen silver halide particles is provided on a support. A method for producing an electromagnetic wave shielding film, comprising coating and forming a layer having the same. [0013] 2. The method for producing an electromagnetic wave shielding film as described in 1 above, wherein the layer having an antireflection function is formed on a back surface of a support having a layer having an electromagnetic wave shielding function.

 [0014] 3. The method for producing an electromagnetic wave shielding film as described in 1 or 2 above, wherein the layer having an antireflection function comprises a plurality of light-transmitting layers containing inorganic fine particles and having different refractive indexes.

 [0015] 4. The layer according to any one of the above items 1 to 3, wherein the layer containing the photosensitive silver halide grains is provided after providing a layer having a near-infrared absorbing function on a support. The manufacturing method of electromagnetic wave shielding film of description.

 [0016] 5. The electromagnetic wave according to any one of 1 to 4, wherein the layer containing the photosensitive silver halide grains is provided simultaneously with a layer having a near-infrared absorbing function on a support. A method for producing a wave shielding film.

 [0017] 6. The above-mentioned layer characterized in that the layer containing photosensitive silver halide grains and the layer having a near infrared absorption function are formed by simultaneous multi-layer coating by a slide hopper type coating device or a slide type curtain coating device. Method for producing electromagnetic wave shielding film according to 4 or 5

[0018] 7. The method for producing an electromagnetic wave shielding film as described in any one of 1 to 6, wherein the layer having an antireflection function is formed by successive multilayer coating using a slot type coating device.

 [0019] 8. After exposing and developing the original plate for an electromagnetic wave shielding film provided with the layer containing the photosensitive halogen silver halide particles, the substrate is further subjected to physical development processing and Z or tacking treatment, 8. The method for producing an electromagnetic wave shielding film as described in any one of 1 to 7 above, wherein a metal layer having an electromagnetic wave shielding function is formed, and then a layer having an antireflection function is formed by coating.

 [0020] 9. An electromagnetic wave shielding film produced by the method for producing an electromagnetic wave shielding film as described in any one of 1 to 8 above.

 The invention's effect

[0021] By the method for producing an electromagnetic wave shielding film of the present invention, the electromagnetic wave shielding film having high electromagnetic wave shielding properties and high near-infrared ray absorption properties and further having an excellent antireflection function. Could be provided.

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0022] In the method for producing an electromagnetic wave shielding film of the present invention, a mesh-shaped metal part is formed by exposing and developing an original plate for an electromagnetic wave shielding film in which a layer containing photosensitive silver halide particles is provided on a support. After the formation, a layer having an antireflection function is formed by coating.

 In the present invention, in order to exhibit an electromagnetic wave shielding function, a layer containing silver halide grains (halogenated silver grain containing layer) is provided on the support. The halogen-containing silver particle-containing layer can contain a binder, an activator and the like in addition to the halogen-containing silver particles.

 [0024] Examples of the halogen silver halide grains used in the present invention include inorganic silver halide grains such as halogen silver and organic halogen silver grains such as silver behenate, but it is easy to obtain conductive metal silver. It is preferable to use inorganic halogen silver. As the silver halide preferably used in the present invention, for example, silver halide mainly composed of AgCl, AgBr, and Agl is preferably used, and fine particles with high sensitivity are preferable in order to obtain highly conductive metal silver. Silver halides mainly composed of AgBr containing iodine or AgCl containing bromine are preferably used.

 [0025] When the silver halide grains are developed into metallic silver grains, electricity flows from the grains to the grains, and the contact area needs to be as large as possible. For that purpose, the smaller the particle size, the better. However, the small particles aggregate to form a large lump, and the contact area immediately decreases, so there is an optimum particle size.

 [0026] The average grain size of the silver halide is preferably 1 to 1000 nm (l μm) in terms of a sphere equivalent diameter 1 to 1 and more preferably LOOnm. In addition, the sphere equivalent diameter of silver halide grains is the diameter of grains having the same volume and a spherical shape. The size of the halogenated silver particles is the temperature, pAg, particle size control agent, for example, 1-Ferru 5 mercaptotetrazole, 2 mercaptobenzimidazole, benztriazole, tetrazaindene compounds, at the time of preparing the halogenated silver particles. In addition, nucleic acid derivatives, thioether compounds, and the like can be used in appropriate combinations.

[0027] The shape of the silver halide grains is not particularly limited. For example, the shape is spherical, cubic, or flat (6 (Square plate, triangle plate, quadrilateral plate, etc.), octahedron, and tetrahedron. In order to increase sensitivity, tabular grains having an aspect ratio of 2 or more, 4 or more, 8 or more, and 16 or less can be preferably used. The particle size distribution may be wide or narrow, but a narrow distribution is preferable in order to obtain high conductivity and increase the aperture ratio. The monodispersity known in the photographic industry is preferably 100 or less, and more preferably 30 or less. From the viewpoint of facilitating the flow of electricity, the larger the contact area between the generated particles, the better the shape of the particles.The flatter and the larger the aspect ratio, the better, but the larger the aspect ratio, the better the concentration. Aspect ratio exists.

 [0028] The halogenated silver 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 for obtaining a high-contrast emulsion. In particular, transition metal ions such as rhodium ions, ruthenium ions, and iridium ions are preferably used because the difference between the exposed portion and the unexposed portion tends to occur clearly when a metallic silver image is formed. Transition metal ions represented by rhodium ions and iridium ions can also be compounds having various ligands. Examples of such ligands include cyanide ions, halogen ions, thiocyanate ions, nitrosyl ions, water, and hydroxide ions. Specific examples of the compound include potassium bromate rhodate and potassium iridate.

In the present invention, the content of rhodium compound and Z or iridium compound contained in halogenated silver is 10- ^{ω to} ιο— ² moles relative to the number of moles of silver in the silver halide. Z mode, it is preferable Lumpur is Ag tool 10- ⁹ ~:! LO- and even more preferably is ³ mol / mol Ag / ,.

[0030] In addition, in the present invention, silver halides containing Pd ions, Pt ions, Pd metals, and Z or Pt metals can also be preferably used. Pd and Pt are uniformly distributed in the silver halide grains, but it is preferable that they are contained in the vicinity of the surface layer of the silver halide grains. Contact to the present invention, Te, content of Pd ion and / or Pd metal contained in the silver halide is a 10- ⁶ to 0.1 mol Z mol Ag with respect to the number of moles of silver in the silver halide More preferably, it is 0.01 to 0.3 mol Z mol Ag.

[0031] In the present invention, chemical sensitization performed on a photographic emulsion can be performed to further improve sensitivity. As chemical sensitization, for example, noble metal sensitization such as gold, palladium, platinum sensitization, Chalcogen sensitization such as io sensitization by inorganic thio or organic thio compounds, reduction sensitization such as sodium chloride, hydrazine and the like can be used.

 [0032] Chemically sensitized halogen silver halide grains can be spectrally sensitized. Preferred examples of the spectral sensitizing dye include cyanine, force nolevocyanin, dicanolevoyanine, complex cyanine, hemisyanine, styryl dye, merocyanine, complex merocyanine, and holopolar monochromator. The spectral sensitizing dyes used can be used alone or in combination.

 [0033] Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. For these dyes, any of nuclei usually used in cyanine dyes can be used as the basic heterocyclic nuclei. 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; Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, namely indolenine nucleus, benzindolene nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselena Such as sol nucleus, benzimidazole nucleus, quinoline nucleus. These nuclei may be substituted on carbon atoms. Merocyanine dyes or complex merocyanine dyes have pyrazoline mononuclear nuclei, thiohydantoin nuclei, 2 thoxazolidine 2,4 dione nuclei, thiazolidine 2,4 dione nuclei, rhodanine nuclei as nuclei having a ketomethylene structure. 5 to 6-membered heterocyclic nuclei such as thiobarbituric acid nuclei can be applied.

 It is preferable to use near-infrared sensitizing dyes when using near-infrared lasers in the exposure of silver and silver particles. These dyes can be referred to JP-A-2000-347343, JP-A-2004-037711 and JP-A-2005-134710. Particularly preferred specific examples are shown below.

[0034] [Chemical 1]

[0035] These sensitizing dyes may be used alone or in combination.

 A combination of sensitizing dyes is often used for the purpose of supersensitization.

[0036] In order to incorporate these sensitizing dyes in a silver halide silver emulsion, they may be dispersed directly in the emulsion, or water, methanol, propanol, methyl mouthsolve, 2, 2, 3, It may be dissolved in a solvent such as 3-tetrafluoropropanol alone or in a mixed solvent and added to the L agent. Also, as described in Japanese Patent Publication Nos. 44-23389, 44-27555, 57-22 089, etc., an acid or base is allowed to coexist to form an aqueous solution, or US Pat. No. 3,822,135. No. 4, 4, 006, 025, etc. An aqueous solution or a colloidal dispersion in the presence of a surfactant such as sodium zensulfonate may be added to the emulsion. Further, after dissolving in a substantially non-miscible solvent such as phenoxyethanol, water or a hydrophilic colloid dispersion may be added to the emulsion. As described in JP-A-53-102733 and JP-A-58-105141, the dispersion may be directly dispersed in an lyophilic colloid and the dispersion may be added to the emulsion.

 [0037] In the present invention, the electromagnetic wave shielding film has an antireflection layer on the same support.

 The antireflection layer may be formed on a layer having a mesh-like metal part formed by exposing and developing a layer containing silver halide grains, but an antireflection layer is provided on the back side of the support. It is preferable. It has been found that the adhesive strength of the antireflection layer is increased by the surface treatment on the back side, and that the antireflection layer cannot be sufficiently smooth when formed on a layer having a mesh-like metal part. It depends.

 [0038] The layer having an antireflection function according to the present invention preferably comprises a high refractive index layer, a medium refractive index layer, and a low refractive index containing inorganic fine particles that are preferably composed of a plurality of light transmissive layers having different refractive indexes. More preferably, the rate layer force is also configured. The layers having different refractive indexes are adjusted according to the kind of inorganic fine particles contained therein, the particle diameter, the amount added, the kind of resin binder, and the like.

 [0039] The refractive index of the high refractive index layer is preferably 1.55-2.30, more preferably 1.57-2.20. The refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the base film and the refractive index of the high refractive index layer. The refractive index of the medium refractive index layer is preferably 1.55 to L80. The refractive index of the low refractive index layer is preferably 1.46 or less, particularly 1.3 to 1.45.

 [0040] The thickness of each layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and even more preferably 30ηπ! Most preferred is ~ 0.2 m.

 [0041] The haze of the metal oxide layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the metal oxide layer is preferably 3H or more in terms of lead writing hardness of 1 kg load, and most preferably 4H or more. When the metal oxide layer is formed by coating, it preferably contains inorganic fine particles and a binder polymer.

[0042] The inorganic fine particles used in the metal oxide layer such as the medium refractive index layer or the high refractive index layer are bent. Fracture power i. 80-2. 80 power is preferred, 1. 90-2. 80 power ^ more preferred! /,. The mass average diameter of the primary particles of the inorganic fine particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm.

[0043] The mass average diameter of the inorganic fine particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, and even more preferably 10 to 100 nm. 10 to 80 nm It is most preferable to be. If the average particle size of the inorganic fine particles is 20-30 nm or more, it is measured by a light scattering method, and if it is 20-30 nm or less, it is measured by an electron micrograph. The specific surface area of the inorganic fine particles, a measured value by the BET method, it is further preferable that a 10 to 400 m ² / g is preferred instrument ² 0~200m 2 / g instrument 30 to 150 m ² / g Most preferably.

 [0044] The inorganic fine particles are particles formed from a metal oxide. Examples of metal oxides or sulfates include titanium dioxide (eg, rutile, mixed crystals of rutile Z anatase, anatase, amorphous structure), tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide. 2um and so on. Of these, titanium dioxide, tin oxide and indium oxide are particularly preferred. The inorganic fine particles are mainly composed of oxides of these metals and can further contain other elements. The main component means the component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

 [0045] The inorganic fine particles may be surface-treated! The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alcohols, stearic acid, silane coupling agents and titanate coupling agents. Of these, a silane coupling agent is most preferable. It may be processed by combining two or more kinds of surface treatments.

 [0046] The shape of the inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a layer shape, a spindle shape, or an indefinite shape. Two or more types of inorganic fine particles may be used in combination in the metal oxide layer.

[0047] The proportion of inorganic fine particles in the metal oxide layer is preferably 5 to 90% by volume. The amount is preferably 10 to 65% by volume, more preferably 20 to 55% by volume.

[0048] The inorganic fine particles are used in a coating solution for forming a metal oxide layer in a state of dispersion in a medium. As the dispersion solvent for the inorganic fine particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C.

 [0049] Specific examples of the dispersion solvent include water, alcohol (for example, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester ( For example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, propyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), aromatic hydrocarbons ( For example, benzene, toluene, xylene), amide (for example, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (for example, jetyl ether, dioxane, tetrahydrated furan), ether alcohol (for example, 1- Methoxy-2-propanol) It is below. Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferred! /.

[0050] The inorganic fine particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (for example, a bead mill with a pin), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high speed impeller mill are particularly preferred. In addition, preliminary dispersion processing may be performed. Examples of a disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an etastruder.

 [0051] The metal oxide layer preferably uses a polymer having a crosslinked structure (hereinafter also referred to as "crosslinked polymer") as a binder polymer. Examples of the crosslinked polymer include crosslinked polymers such as a polymer having a saturated hydrocarbon chain such as polyolefin (hereinafter collectively referred to as “polyolefin”), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. Among them, a polyolefin crosslinked product, which is preferably a crosslinked product of polyolefin, polyether, and polyurethane, and a crosslinked product of polyolefin, more preferably a crosslinked product of polyether, is most preferable.

[0052] Further, it is more preferable that the crosslinked polymer has a ionic group. There are no key-on groups It has a function of maintaining the dispersed state of the fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film. The anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but may be bonded to the main chain as a side chain via the linking group. Is preferred.

[0053] The refractive index of the low refractive index layer used in the present invention is preferably 1.46 or less, particularly 1.3 to 1.

 The low refractive index layer can be formed by a sol-gel method using silicon alkoxide as the coating composition. Alternatively, a low refractive index layer can be formed by using fluorine resin. In particular, it is preferably composed of a cured material of a thermosetting or ionizing radiation curable fluorine-containing resin and ultrafine particles of silicon oxide. Silicon oxide ultrafine particles are composite particles having porous particles described later and a coating layer provided on the surface of the porous particles, or hollow particles filled with a solvent, gas, or porous substance inside. It is preferable.

 [0054] It is preferable that the dynamic friction coefficient of the cured product is 0.02-0.2, and the pure water contact angle is preferably 90 to 130 °. Examples of the curable fluorine-containing resin include perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane), fluorine-containing copolymer. And a compound (having a monomer having a crosslinkable group and a fluorine-containing monomer as structural units). Specific examples of the fluorine-containing monomer unit include, for example, hexafluoroethylene, hexafluoropropylene, tetrafluoroethylene, fluoroolefins (for example, bi-lidene fluoride perfluoro-2, 2 —Dimethyl-1,3-diquinol, fluoroethylene, etc.), fluorinated alkyl ester derivatives of (meth) acrylic acid (eg, Biscote 6FM (Osaka Organic Chemical), M-2020 (Daikin), etc.), fluorinated butyl ether Etc. The monomer having a crosslinkable group has a carboxyl group, amino group, hydroxyl group, sulfonic acid group, etc. in addition to a (meth) atrelate monomer having a crosslinkable functional group in the molecule in advance, such as glycidyl methacrylate.

(Meth) acrylate monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.). JP-A-10-25388 and JP-A-10-147739 describe that a crosslinked structure can be introduced after copolymerization. [0055] Further, it is possible to use a copolymer with a monomer having no fluorine atom, which is only a polymer having the above-mentioned fluorine-containing monomer as a structural unit. There are no particular limitations on the monomer units that can be used in combination, for example, acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate), methacrylate esters (methyl methacrylate, methyl methacrylate). Acid ethyl, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, dibutylbenzene, _a -methylstyrene, butruluene, etc.), acrylamides (N-t-butylacrylamide, N-cyclohexene) Xylatylamide, etc.), methacrylamides, acrylonitrile derivatives, etc., olefins (ethylene, propylene, isoprene, vinylidene chloride, butyl chloride, etc.), butyl ethers (methylvinyl ether, etc.), vinyl esters (vinyl acetate, propion) Vinyl acid It can be mentioned cinnamic acid vinyl Le etc.).

 [0056] The fluorine-containing resin used for forming the low refractive index layer is preferably added with silicon oxide fine particles in order to improve scratch resistance. The amount added is adjusted by the balance between refractive index and scratch resistance. Silica silicate fine particles can be added to the coating composition as it is silica sol dispersed in a commercially available organic solvent, and there are some! /, Which can be used by dispersing various commercially available silica powders in an organic solvent. it can.

 [0057] In the present invention, after forming a mesh-like metal part by exposing and developing an original plate for electromagnetic wave shielding film provided with a layer containing photosensitive halogen silver halide grains, antireflection is performed. A layer having a function is formed by coating. That is, we have found an important causal relationship regarding which of the layer having the mesh-like metal portion and the layer having the antireflection function should be formed first, and have arrived at the present invention.

 First, contrary to the present invention, when a layer having an antireflection function is first formed on a support and then a layer containing photosensitive silver halide grains is provided on the support, a layer having an antireflection function is provided. It was found that some of the inorganic fine particles contained in the film fall off and contaminate the coating production process to form a layer containing photosensitive silver halide grains, which can cause spot failure in the coating stripe o

Second, contrary to the present invention, a layer having an antireflection function is first formed on a support by coating, and then exposed to an electromagnetic wave shielding film master provided with a layer containing photosensitive silver halide grains. It has been found that when a mesh-like metal part is formed by development processing, the antireflection function is significantly reduced, the haze value is increased and the translucency is lowered, or spot-like defects are generated. . This is because the inorganic fine particles, particularly silicon oxide fine particles contained in the layer having an antireflection function are dissolved in the alkaline environment of the developing solution, or the dispersion stability of the inorganic fine particles is lowered to cause aggregation. This is presumed to occur.

 [0059] Thirdly, as described above, since the antireflection layer is generally applied using a non-aqueous organic solvent for the constituent material, charging of the support must be avoided in the application process. I have to. For this reason, it is necessary not only to have grounding equipment and explosion-proof measures, but also to apply at low speed. If a layer having a mesh-like metal portion is provided in advance as in the present invention, the support can be prevented from being charged almost at all, so that high-speed coating is possible.

 [0060] In the electromagnetic wave shielding film of the present invention, it is preferable to enhance the photographic gradation of the layer containing the halogenated silver particles. As such a method, there is a method of narrowing the particle size distribution of halogenated silver particles, and it is known to use a hydrazine compound or a tetrazolium compound as a high contrast agent for plate making. A hydrazine compound is a compound having an NHNH- group, and a typical one is represented by the following general formula.

[0061] 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. As a preferable substituent, a linear or branched alkyl group (preferably having a carbon number of 1 To 20 methyl group, ethyl group, isopropyl group, n-dodecyl group, etc.), alkoxy group (preferably methoxy group having 2 to 21 carbon atoms, ethoxy group etc.), aliphatic isylamino group (preferably 2 to 21 carbon atoms) In addition to these, for example, substituted or unsubstituted aromatic rings such as —CONH—, —O—, and the like, can be mentioned, such as acetylamino groups, heptylamino groups, and the like. , -SO NH-,-NHCONH-,-CH CHN-, etc.

 twenty two

 Including those bonded by a group. V is a hydrogen atom or 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, pyro group) Group).

 [0062] The 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 halogenated silver particle layer, in the hydrophilic colloid layer adjacent to the halogenated silver particle layer, or in another hydrophilic colloid layer. Particularly preferred hydrazine compounds are listed below.

 [0063] (H— 1): 1-trifluoromethyl carbole— 2— {[4— (3-n-butylureido) phenol]} hydrazine

 (H-2): 1-trifluoromethyl carboyl 2— {4— [2— (2, 4 di-tert-pentylphenoxy) butyramide] phenol} hydrazine

 (H— 3): 1— (2, 2, 6, 6-tetramethylpiperidyl mono 4-aminooxalyl) one 2— {4 one [2- (2, 4-di-tert pentylphenoxy) Butyramide] phenol} hydrazine

(H-4): 1-(2, 2, 6, 6-tetramethylpiveridyl 4-aminooxalyl) 2— {4- [2— (2, 4-di-t-pentylphenoxy) Butylamide] Phenolsulfonamide Phenol} hydrazine

 (H— 5): 1— (2, 2, 6, 6-tetramethylpiperidyl 4-aminooxalyl) 1 2-— (4-— (3-— (4--black mouth ferru) 4-- feu-lou 3-thiabutanamide) benzenesulfonamide) phenol) hydrazine

 (H-6): 1- (2, 2, 6, 6-tetramethylpiperidyl 1-amino-oxalyl) 1 2— (4— (3 thia 6, 9, 12, 15- tetraoxatricosane Amide) Benzenesulfonamide) Ferhydrazine

 (11 7): 1— (1-Methylenecarborpyridium) -2- (4- (3-Chaer 6, 9, 1 2, 15-Tetraoxatricosanamide) benzenesulfonamide) phenylhydrazine chloride .

 [0064] The hydrazine compound is particularly preferably one in which a sulfonamidophenol group is substituted as the T group and a trifluoromethyl group is substituted as the V group. The oxalyl group bonded to hydrazine is particularly preferably a piperidylamino group, although it may be substituted. Specific examples of tetrazolium compounds are shown below.

[0065] (T-1): 2, 3 Di (p-methylphenol) 5 phenol tetrazolium chloride (τ--2): 2, 3 -Di (Ρ--ethyl chloride)-1 5 tetratetrazolium chloride

(τ- -3): 2, 3, 5 Tri —P Methylphenol tetrazolium chloride

 (τ- -4): 2, 3-diphenyl-nyl 5- (p-methoxyphenyl) tetrazolium chloride

(τ- -5): 2, 3 — Di (ο—methylphenol) 1—Fuel tetrazolium chloride

(τ- -6): 2, 3, 5 Tri —P-methoxyphenyltetrazolium chloride

 (τ- -7): 2, 3 — Di (0-methylphenol) -5-phenoltetrazolium chloride

(τ- -8): 2, 3 — Di (m_-methylphenol) 5-5-tetratetrazolium chloride

(τ- -9): 2, 3, 5 Tri-p ethoxymethylphenol tetrazolium chloride.

 [0066] These can be used with reference to the description in JP-B-5-58175, and in some cases, they can be used in combination with hydrazine compounds.

 [0067] When hydrazine is used as a thickening agent, an amine compound or a pyridine compound is used to enhance the reduction action of hydrazine. A representative amine compound can be represented by the following general formula containing at least one nitrogen atom.

 [0068] R—N (Z) —Q, R—N (Z) —L—N (W) —Q

 R, Q, Z, and W in the formula represent an alkyl group having 2 to 30 carbon atoms that may be substituted. Further, these alkyl group chains may be bonded by a heteroatom such as nitrogen, sulfur, or oxygen. R and Z, or Q and W may form a saturated and unsaturated ring with each other. L represents a divalent linking group. This linking group may contain a hetero atom such as sulfur, oxygen, and nitrogen. The linking group of L can have 1 to 200 carbon atoms, 1 to 30 sulfur atoms, 1 to 20 nitrogen atoms and 1 to 40 oxygen atoms. Flower ,. Specific examples of these amine compounds are shown below.

 (A- 1): Jetylaminoethanol

 (A- 2): Dimethylamino-1

 (A- -3): 2 Propanediol

 (A- -4): 5 Amino-1 pentano

 (A- -5): Jetenoreamine

 (A- -6): Methylamine

(A— -7): Triethylamine (A-8): Dipropylamine

 (A-9): 3-Dimethyleno-amino-prono-no-nore

 (A-10 1 Dimethylamino 2-propanol

 (A-11 Bis (dimethylaminotetraethoxy) thioether

 (A-12 Bis (jetylaminopentaethoxy) thioether

 (A- 13 Bis (piperidinotetraethoxy) thioether

 (A-14 Bis (piberidinoethoxyethyl) thioether

 (A-15 Bis (-pecotinediethoxy) thioether

 (A-16 Bis (disyanethinoleaminodiethoxy) etherole

 (A-17 Bis (diethoxyethylaminotetraethoxy) ether

 (A-18 5-Dibutylaminoethylcarbamoyl benzotriazole

 (A- 19 5 Morpholinoethylcarbamoylbenzotriazole

 (A-20 5— (2 Methylimidazole-2 Ethylene) Force Rubamoylbenzotriazo Inore

 (A-21): 5 Dimethylaminoethylureylene benzotriazole

 (A-22): 5 Jetylaminoethylureylene benzotriazole

 (A-23): 1-Getinoreamino 2- (6 aminopurine) ethane

 (A-24): 1 (dimethylaminoethyl) 5 mercaptotetrazole

 (A-25): 1-Piberidinoethyl 5 Mercaptotetrazole

 (A- 26): 1-Dimethylamino-5 Mercaptotetrazole

 (A-27): 2 mercapto-5 dimethylaminoethylthiothiadiazole (A-28): 1 mercapto-2 morpholinoethane.

 [0070] The amine compound that promotes the reducing action of the hydrazine compound includes at least one piperidine ring or pyrrolidine ring, at least one thioether bond, and at least two ether bonds in the molecule. Is particularly preferred.

[0071] As compounds that promote the reduction action of hydrazine, pyridinium compounds and phosphonium compounds are used in addition to amine compounds. Since the oum compound is positively charged, it adsorbs to the negatively charged silver halide particles and removes it from the developing agent during development. It is considered that high contrast is promoted by promoting electron injection. As preferred pyridinium compounds, reference can be made to the bispyridium compounds described in JP-A-5-53231 and JP-A-6-242534. Particularly preferred pyridinium compounds are those that are linked at the 1- or 4-position of the pyridinium to form a bispyridium! To salt! For example, in addition to chlorine ions and bromine ions as halogen ions, boron tetrafluoride ions and perchlorate ions are preferred, but chlorine ions or boron tetrafluoride ions are preferred! / ,. Preferred U and bispyridium compounds are shown below.

 (B- 1): 1, 1 'Dimethyl-4, 4'--Bibiridinum dichloride

 (B-2): 1, 1'-dibenzyl-4,4 'bibilidinium dichloride

 (B- 3): 1, 1 'Huge Petit Lou 4, 4' Bibilidinum Dichloride

 (B- 4): 1, 1 'Zee η-octyl 4, 4' bibilidinum dichloride

(B-5): 4, 'Dimethyl-1, 1'--Bibiridinum dichloride

 (B- 6): 4, '-Benzyl- 1, \' Bibilidinum dichloride

 (B- 7): 4, '--Geheptinolay 1, \' Bibilidinum dichloride

 (B-8): 4, 'Zee η-octyl 1, 1' bibilidinum dichloride

(B-9): Bis (4,4′-diacetamido--1,1′-tetramethylenepyridinum) dichloride.

 [0073] Although the hydrazine compound acts on the high-concentration contrast, the contrast of the legs is insufficient, and as an attempt to improve this, an oxidized form of the developing agent produced during development is used. You can use this technique. The presence of a redox compound that reacts with the oxidized oxidant of the developing agent increases the sharpness of the image by releasing an inhibitor that suppresses the strength of the compound. Oxidation of the developing agent is generated by the progress of development and is related to the reduction rate of the particles. It is preferable to use a good chemical sensitizer because this effect can be enhanced by forming a development nucleus having a high reduction rate with a chemical sensitizer. Using redox compounds sharpens the edges of the image, reducing the grain spacing and reducing the resistance of silver metal lines.

[0074] Redox compounds have hydroquinones, catechols, naphthohydroquinones, aminophenols, virazolidones, hydrazines, reductones, etc. as redox groups. . Preferred redox compounds are compounds having an NHNH group as a redox group, and those represented by the following general formula are typical.

[0075] T-NHNHCO-V- (Time) PUG

 T-NHNHCOCO-V- (Time) PUG

 In the formula, T and V represent a group having the same meaning as the hydrazine compound. PUG represents a photographically useful group, for example, 5-troindazole, 4-troindazole, 1-phenoltetrazole, 1- (3-sulfophenol) tetrazole, 5-trobenztriazole, 4 --- trobenzotriazole , 5--troimidazole, 4--troimidazole and the like. What are these development-inhibiting compounds? 《1? «1--0--directly through a heteroatom such as 3 at the 0 site, or further through an alkylene, phenylene, aralkylene, or aryl group represented by (Time) It can be connected through N or S heteroatoms. In addition, a hydroquinone compound having a ballast group into which development inhibitory groups such as triazole, indazole, imidazole, thiazole and thiadiaol are introduced can be used.

 [0076] For example, 2- (dodecylethylene oxide) thiopropionic acid amide-5- (5-troindazole-2-yl) hydroquinone, 2- (stearylamide) 5-(1-fertetrazol-5thio) hydroquinone, 2— (2,4 di-t-amylphenopropionic acid amide) —5— (5-trotriazole-2-yl) hydroquinone, 2 dodecylthio—5 1 (2 mercaptothiadiazole-5 thio) hydroquinone, etc. Can be mentioned. N represents 1 or 0. The redox compound can be synthesized with reference to the description in US Pat. No. 4,269,929.

 [0077] Particularly preferred are the redox compounds listed below.

 [0078] -1): 1- (4-Troindazole- 2-Lucal Ball)-2-{[4- (3-11 Butylureido) -Fail]} Hydrazine

 (R-2): 1 (5-troindazol-2-yllucol) -2-2- {4- [2- (2,4-di-tert-pentylphenoxy) butyramide] phenol} hydrazine

 (R—3): 1— (4-trotriazole-2-yl-carbol) —2— {4- (2- (2, 4-di-tert-pentylphenoxy) butyramide] phenol } Hydrazine

(R—4): 1— (4-Troimidazole 2- 2-Lucol Ball) -2— {4 1 [2— (2, 4-Di-t-pentylphenoxy) butyramide] phenolsulfonamidephenol} hydrazine

 (R-5): 1- (1 Sulphophenyltetrazole-4-Methyloxazole) -2-{3-[1-Fel //-p Chloroform methanethioglycinamide phenol] sulfo Namidephenol} hydrazine

 (R-6): 1- (4-troindazol-2-yllucol) -2-{[4 (Otachirutetraethylene oxide) thioglycinamide file sulfonamide file]} hydrazine.

[0079] Hidorajini匕合thereof, Amini匕合thereof, pyrid - © beam compounds, Tetorazoriumu compound and TOLEDO box compound Shi preferred is to 1 X 10- ⁶ ~5 X 10- ² molar content per mole of silver halide ingredients particularly 1 X 10- ⁴ ~2 X 10- ² mol is preferred. It is easy to increase the degree of contrast γ to 6 or more by adjusting the amount of applied force of these compounds. γ can be further adjusted by the monodispersity of the emulsion, the amount of rhodium used, chemical sensitization, and the like. Here, γ is the density difference with respect to the difference between the exposure amounts giving the densities of 0.1 and 3.0.

 [0080] 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 as a solution of an organic solvent that is miscible with water, such as alcohols, esters, and ketones, to a halogenated silver particle solution or a hydrophilic colloid solution. do it. Further, when it is not soluble in these organic solvents, it can be added as fine particles having a size of 0.01 to 10 m by a ball mill, sand mill, jet mill or the like. As the fine particle dispersion method, a solid dispersion technique of a dye as a photographic additive can be preferably applied. For example, a desired particle size can be obtained by using a disperser such as a ball mill, a planetary rotating ball mill, a vibrating ball mill, or a jet mill. When a surfactant is used during dispersion, stability after dispersion can be improved.

 [0081] In the silver halide grain-containing layer according to the present invention, the silver halide grains are uniformly dispersed and the silver halide grains are supported on the support, and the silver halide grain-containing layer and the support are supported. A binder can be used for the purpose of ensuring the adhesion of the resin.

[0082] The binder that can be used in the present invention is not particularly limited, and the water-insoluble polymer is not limited. The ability to use both a polymer and a water-soluble polymer From the viewpoint of improving developability, it is preferable to use a water-soluble polymer. In the present invention, it is advantageous to use gelatin as a binder, but if necessary, gelatin derivatives, gelatin and other high molecular weight graft polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, single or A hydrophilic colloid such as a synthetic hydrophilic polymer such as a copolymer can also be used. The amount of the binder in the layer containing the silver halide silver particles is not particularly limited, and an optimum value can be used from the viewpoints of coating properties, film properties, electromagnetic wave shielding performance, and the like.

 [0083] From the viewpoint of forming a developed silver network and increasing the conductivity of the film after development, in the present invention, the AgZ binder volume ratio is set higher than that of a normal photographic silver halide silver photographic material. The binder content in the particle-containing layer is preferably 0.2 to: LOO in terms of AgZ binder volume ratio, more preferably 0.3 to 30, and 0.3. It is more preferable to be ~ 10! / ヽ.

 In the present invention, a layer containing a near-infrared absorbing dye is provided for the purpose of shielding near-infrared rays. This near-infrared absorbing dye is used together with fine particles of water-dispersible thermoplastic resin or phosphate ester, in order to increase its near-infrared shielding effect, increase dispersion or dissolution stability, and increase stability over time. We have found that it is preferable to disperse in an aqueous gelatin solution.

 [0085] The water-dispersible thermoplastic resin used in the present invention is a thermoplastic resin coated at a drying temperature so that a film can be formed by heating and drying on a support. The drying temperature is usually between room temperature and about 100 ° C, and drying is performed at a temperature in this range.

 [0086] The water-dispersible thermoplastic resin used in the present invention is treated as a synonym for latex because it handles a resin that is stably dispersed in an aqueous medium. Latex refers to a white milky liquid that can also be used to absorb forces such as rubber wrinkles, but since the advent of emulsion polymers, polymeric substances, including aqueous dispersions of synthetic polymers, have been incorporated into aqueous media. Those that are stably dispersed are now called latus status, so this designation is used!

[0087] Examples of the water-dispersible thermoplastic resin include polysalt-vinylidene, salt-syl-vinylidene-acrylic acid copolymer, salt-syl-vinylidene-taconic acid copolymer, sodium polyacrylate, polyethylene Oxide, acrylic acid amide-acrylic acid ester copolymer, styrene Water maleic acid copolymer, acrylonitrile butadiene copolymer, vinyl chloride-vinyl acetate copolymer, and monomers containing carboxylic acid groups such as acrylic acid, methacrylic acid, itaconic acid and maleic acid, or dimethylacrylamide Examples thereof include a styrene butadiene copolymer and a styrene monoisoprene copolymer using a small amount of one or a plurality of monomers having a sulfonic acid group such as propane sulfonic acid and styrene sulfonic acid group.

 [0088] The above latex is widely used as a binder for aqueous coating, and among them, a latex that improves water resistance is preferable as a binder. The amount of latus used for the purpose of obtaining water resistance as a binder is a power determined in consideration of applicability. The point of moisture resistance The amount used is preferably as high as possible. 50% or more to the total binder mass 100% 80% or more and 100% or less are more preferred. Such a rosin can also be marketed.

 [0089] For example, styrene resin is an industry standard product number of styrene-butadiene copolymer,

 Various brands such as # 1500, # 1502, # 1507, # 1712, # 1778, Sumitomo SBR Latex (Sumitomo Chemical Co., Ltd.), JSR Latex (Nippon Synthetic Rubber Co., Ltd.), Nipol Latex (Nippon Zeon Corporation) )) Can be used. The styrene-butadiene copolymer preferably has a styrene / butadiene copolymer ratio (mass) force of S10Z90 to 90Z10, more preferably 20Z80 to 60Z40. A high styrene latex having a ratio of 60 to 40 to 90 to 10 is preferably used in combination with a low styrene content and (10 to 90 to 70) resin in order to increase the scratch resistance and physical strength of the photosensitive layer. . The mixing ratio (mass) is preferably in the range of 20-80-80-20.

 [0090] Examples of high styrene latex include JSR0051 and 0061 (Nippon Synthetic Rubber Co., Ltd.) and Nipol 2001, 2057, 2007 (Nippon Zeon Co., Ltd.). It can be used. Latexes with a low styrene content include those commonly used other than those listed above as the high styrene latex, and include JSR # 1500, # 1502, # 1507, # 1712, and # 1778.

[0091] In addition, acrylic latex generally known as acrylic resin, such as Nipol AR31, AR32 or Hycar 4021 (V, trade name of Nippon Zeon Co., Ltd.) can be used. [0092] As the above-described acrylic resin, a polymer or copolymer using the following acrylate monomer as a raw material can also be used. In the following, the (meth) atalyloyl group is used in the meaning of an atalyloyl group or a methallyloyl group. Monomers having one (meth) atallyloyl group in the molecule include methacrylic acid esters of methyl alcohol, methyl acrylate, ethyl acrylate, ethyl acrylate, Acrylate esters of aliphatic alcohols such as acrylate, butyl acrylate and octyl acrylate, acrylate esters of alicyclic alcohol such as cyclohexyl acrylate and cyclohexyl methyl acrylate, cyclohexyl methacrylate Acrylates containing aromatic groups such as methacrylic acid esters of alicyclic alcohols such as acrylate, cyclohexylmethyl methacrylate, phenol acrylate, 4-propyl acrylate, benzyl acrylate, benzyl methacrylate Acid ester, phenol methacrylate, 4-chloro Methacrylic acid esters containing aromatic groups such as ethyl metatalylate and benzyl metatalylate, acrylic acid or methacrylic acid hydroxy such as 2-hydroxyethyl atylate, 2-hydroxyethyl metatalylate There are alkyl esters and the like.

 [0093] Monomers having two or more (meth) atalyloyl groups in the molecule include ethylene glycol diatalate, propylene glycol diatalate, diethylene glycol diatalate, 1,3 diacryloxy-2-propanol polyethylene glycol diatalate. Acrylic acid diesters such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3 dimethacryloxy-2-propanol and other methacrylic acid diesters, glycerin tritalylate, trimethylol Acrylic acid triesters such as propane tritalylate, methacrylic acid such as glycerin trimetatalylate, trimethylolpropane trimetatalylate There are acid triesterol.

[0094] As styrene resin, styrene monomers such as methyl styrene, ethyl styrene, propylene styrene, butyl styrene, hexyl styrene, heptyl styrene, otachinol styrene, dimethyl styrene, trimethyl styrene, jetyl styrene, triethyl styrene Halogenostyrene monomers such as styrene styrene monomer, fluorostyrene, chlorostyrene, bromostyrene, styrene styrene, dibutyl styrene, Using monomers, acetyl styrene monomers, methoxy styrene monomers, etc., alone or copolymerized with other monomers.

 [0095] Examples of bur resin include butyl pyridine, butyl pyrrolidone, bulur rubazole, butyl acetate, acrylonitrile, butyl chloride, butyl bromide, salt vinylidene, odorous vinylidene, and the like as monomers. Alternatively, it contains berylene or the like as a structural unit. Moreover, a monomer having two or more vinyl groups in the molecule may be included as a structural unit. Examples thereof include conjugated genomers such as dibutylbenzene, butadiene, and black-opened plane, isoprene adipate divininole, divinyl sulfone, triethylene glycol divinyl ether, 1,4-cyclohexane dimethanol dibule ether, and the like.

[0096] These monomers can be emulsion-polymerized as described above. As the water-soluble polymerization initiator used in this emulsion polymerization, any one can be selected. Examples thereof include 2, 2′-azobis (2 methylpropionamidine) dihydrochloride, 4, 4 ′ azobis (4 Shianoyoshi). Herbic acid), 2, 2'-azobis [2- (2-imidazoline-2-yl) propane] dihydrochloride, 2,2'-azobis [2-(5-methyl-2-imidazoline-2-yl) propane] 2 And hydrochloride, 2,2′-azobisisobutyramide dihydrate, and the like. The amount of the water-soluble polymerization initiator is from 001 to 0.5 mole _^0/0 preferably 0. for all the monomers.

[0097] The dispersant used in the emulsion polymerization is appropriately used to stabilize the system. Examples of the dispersion stabilizer or dispersant include polybulal alcohol, polybulurpyrrolidone, polyacrylamide, polymethacrylamide, hydroxyalkyl acrylate polymer, hydroxyalkyl methacrylate polymer, polyacrylic acid or a salt thereof, polymethacrylic acid or Its salt, ethylene acrylic acid copolymer or its salt, ethylene-methacrylic acid copolymer or its salt, ethylene maleic acid copolymer or its salt, styrene attalic acid copolymer or its salt, styrene-methacrylic acid copolymer Polymer or salt thereof, polyethyleneimine, polyalkylene glycol, polyalkylene oxide, methylolated polyamide, water-soluble melamine resin, water-soluble phenol resin, water-soluble urea resin, casein, gelatin, canoleboximethylol Norerozu, methylcarbamoyl Roh receptacle Honoré Rose, hydroxy § Honoré Kino receptacle Honoré low's, carboxymethyl starch, cationic starch, dextrin, alginic acid or a salt thereof, carrageenan, Jierangamu, locust bean gum, gum arabic, tragacanth Gum, dalcomannan, zalepmannan, guar gum, plant mucus, etc. are used alone or as a mixture of two or more.

[0098] The dispersant is preferably used in an amount of 0.01 to 20% by mass based on the total amount of monomers to be used or the total amount of rosin to be dispersed. Furthermore, the surfactant used in the emulsion polymerization is not particularly limited as long as it does not adversely affect the polymerization reaction, and is a cation surfactant, cationic surfactant, zwitterionic surfactant or nonionic surfactant. Any surfactant can be used.

[0099] For example, sodium alkylbenzenesulfonate, sodium salt of higher alcohol sulfate ester, higher α-year-old lefine sulfone salt sodium salt, higher fatty acid salt, higher alkylphenol alkylene oxide sulfonate sodium salt, higher alkylamine salt, Higher alkyl trimethylammonium salts, higher alkyl pyridinium salts, higher acyl aminomethyl rupyridium salts, higher acyloxymethyl pyridinium salts, Ν, Ν—dipolyoxyethylene-Ν—higher grades Alkylamine salts, higher alkyl polyethylene polyamine salts, trimethyl higher alkyl alkyl phosphate salts, trimethyl higher alkyl benzylammodium salts, higher alcohol ethylene oxide adducts, higher alkyl phenol ethylene oxide adducts, higher fatty acid ethylene oxides Adducts, higher alkylamine ethylene oxide adducts, higher fatty acid amide ethylene oxide adducts, glycerin higher fatty acid esters, pentaerythritol higher fatty acid esters, higher fatty acid esters of sorbitol and sorbitan (or their ethylene oxide adducts) Sucrose higher fatty acid ester, higher alkyl ether of polyol, higher fatty acid amide of alkanolamine, amino acid type amphoteric activator, betaine type amphoteric activator, and the like, or a mixture of ^two or more thereof.

 [0100] The surfactant is based on the total amount of the monomers used or the total amount of the resin to be dispersed.

 It is preferable to use 01 to 20% by mass.

 [0101] The water-dispersible thermoplastic resin according to the present invention is preferably used together with gelatin at a mixing mass ratio of 1: 2 to 10: 1. When used in combination with gelatin, it becomes possible to simultaneously coat the halogen-containing silver particle-containing layer, and the productivity is remarkably improved. If the mass ratio of gelatin used is large, the deterioration of moisture resistance will be large and the coating will not be uniform.

[0102] When used with gelatin, phosphate ester compound is used instead of water-dispersible thermoplastic resin The product can be used by dispersing fine particles in gelatin.

 [0103] The average particle size of the phosphoric acid ester compound is ΙΟηπ! Dispersing the phosphoric acid ester compound in an ester organic solvent such as ethyl acetate, adding a nonionic or ionic surfactant, and dispersing it in gelatin. can do. As the non-ionic or ionic surfactant used here, a surfactant of the type used for emulsion polymerization of water-dispersible thermoplastic resin can be applied. In order to improve the dispersibility, a highly efficient homogenizer, ultrasonic dispersion, supersonic jet dispersion, etc. can be used to disperse as fine particles.

 [0104] Examples of the phosphoric acid ester compound include those obtained by esterifying phosphoric acid with an aliphatic alcohol, aromatic alcohol, or mixed alcohol thereof, and condensed esters obtained by condensing two or more dialkyl or diaryl phosphoric acid esters. be able to. Specific examples include trioctyl phosphate ester, tridodecyl phosphate ester, triphenyl phosphate ester, tricresyl phosphate ester, tri p-methylphenyl phosphate ester, and the like.

[0105] Specific examples of near-infrared absorbing dyes include polymethine series, phthalocyanine series, naphthalocyanine series, metal complex series, aminium series, imonium series, dimonium series, anthraquinone series, dithiol metal complex series, naphthoquinone series, indole phenol , Azo and triarylmethane compounds.

 [0106] Near-infrared absorptivity is required for optical filters for PDP mainly for heat ray absorption and noise prevention of electronic devices. For this purpose, a metal complex-based, amino-based, phthalocyanine-based, naphthalocyanine-based, dimethyl-containing pigment having a maximum absorption wavelength of 750-: LlOOnm is preferred. Of these, a sulfur system and a smutium compound system are particularly preferable.

 [0107] The absorption maximum of a conventionally known nickel dithiol complex compound or fluorinated phthalocyanine compound is 700 to 900 nm, and in practical use, it usually absorbs in a longer wavelength region than the above compound. An effective near-infrared absorption effect can be obtained by using in combination with an aminium-based compound having a maximum, particularly a diimonium-based compound.

Specific examples of imonium compounds that can be used in the present invention are shown below. [0109] (1- 1): N, N, N ′, N ′ —tetrakis (4 di-n-butylaminophenol) -1,4-benzoquinone bis (immo-hexafluoroantimony) acid)

 (1-2): N, N, N ', N' —tetrakis (4 di-n-butylaminophenol) -1,4 benzoquinone bis (imum-perchloric acid)

 (1-3): N, N, N ', N' — Tetrakis (4 di-amylaminophenol) — 1, 4 Benzoquinone bis (immo-hexafluoroantimonic acid)

 (1-4): N, N, N ′, N ′ —tetrakis (4 di-n-propylaminophenol) -1,4-benzoquinone bis (immo-hexafluoroantimonic acid) )

 (1-5): N, N, Ν ', N' —tetrakis (4 di-η-hexylaminophenol) -1,4-benzoquinone bis (immo-hexafluoroantimonic acid)

 (1-6): Ν, Ν, Ν ', N' —tetrakis (4 di-iso propylaminophenol) -1,4-benzoquinone bis (immo-hexafluoroantimonic acid)

 (1-7): N, N, Ν ', N' —tetrakis (4 di-η-pentylaminophenol) -1,4-benzoquinone bis (immo-hexafluoroantimony) Acid)

 (1-8): Ν, Ν, Ν ', N' —tetrakis (4 dimethylaminophenol) -1,4 benzoquinone monobis (imum hexafnoreo oral antimonic acid).

[0110] As the near-infrared absorbing dye in the present invention, dimo-um compounds are IRG-022, IRG-040 (these are trade names manufactured by Nippon Gyaku Co., Ltd.), nickel dithiol complex compounds, SIR—128, SIR—130, SIR—132, SIR—159, SIR—152, SIR—162 (these are trade names manufactured by Mitsui Engineering Co., Ltd.), phthalocyanine compounds are IR-10, IR — Commercially available products such as 12 (above, Nippon Shokubai Co., Ltd. trade name) can be used.

[0111] The near-infrared absorbing dyes are alcohol solvents such as methanol, ethanol and isopropanol, ketone solvents such as acetone, methyl ethyl ketone and methyl butyl ketone, organic solvents such as dimethyl sulfoxide, dimethylformamide, dimethyl ether and toluene. It is preferable to use it as a fine particle having an average particle size of 0.01 to 10; ζ ΐη by using a micronizing machine described later. The optical density is a maximum wavelength from 0.05 to 3. It is preferably used in the range of 0 concentration. [0112] When a colorant having near infrared absorption ability is contained in the color tone correction layer, any one of the above dyes may be contained, or two or more kinds may be contained. It is preferable to use UV absorbers to avoid deterioration of near-infrared absorbing dyes by UV rays.

 As the ultraviolet absorber, known ultraviolet absorbers such as salicylic acid compounds, benzophenone compounds, benzotriazole compounds, S triazine compounds, and cyclic imino ester compounds 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.

 [0114] As a preferred specific example,

 (U— 1): 2 -— (2-Hydroxy —3, 5 di α cuminole) 2Η Benzotriazonore

(U 2): 5 Chloro-2- (2-hydroxy-3-t-butyl-5-methylphenol) 2H benzotriazolene,

 (U 3): 5 Chloro-2- (2 —hydroxy-3,5 di-t-butylphenyl) 2H—benzotriazolone

 (U—4): 5 Chloro-2- (2-hydroxy-3, 5 G α cumino lefenore) 2Η— Benzotriazolene

 (U 5): 5 Chloro 2— (2-hydroxy 1 3-a-cumino 1-t-octino lefe- nore) 2H-benzotriazonore

 (U-6): 2-(3— t-Butyl-2 hydroxy-5- (2 isooctyloxycarbo-ruethyl) phenol) 5 black 2H benzotriazole

 (U-7): 5 Trifluoromethyl mono 2- (2-hydroxy mono 3-a-tamyl mono 5-t-octylphenol) 2H-benzotriazole

 (U-8): 5 Trifluoromethyl 2- (2-hydroxy-1-5-t-octylphenol) 2H-benzotriazolole

 (U-9): 5 trifluoromethyl-1- (2-hydroxy-1,3,5-di-tert-octylphenol 2-nole) 2H-benzotriazonole

(U—10): 5 Trifluoromethyl 2- (2-Hydroxy 3-3-a-Tamil 5- 5-t Tilphenol) — 2H-benzotriazole

 (U— 11): 2, 4 Bis (4 biphenyl) 6— (2 Hydroxy 4-octyloxycarboxylethylideneoxyphenyl) s Triazine

 (U-12): 2, 4 Bis (2, 4 Dimethinolephenol) 1 6- [2 Hydroxy 4- (3-Noxyloxy * 1 2 Hydroxypropyloxy) 5 α-Tamilphenyl] — s Triazine, (* indicates a mixture of octyloxy, nonyloxy and decyloxy groups)

 (U-13): 2, 4, 6 Tris (2-hydroxy-4-isooctyloxycarbo-isopropylideneoxyphenyl) —s-triazine

 (U—14): Hydroxyphenolone 2 ァ Benzotriazolene

 (U— 15): 2— (2 Hydroxy-5-methylphenol) 2Η Benzotriazole (U— 16): 2— (3,5 Di-tert-butyl-2-hydroxyphenol) 2H Benzotriazole is there.

 [0115] In the method for producing an electromagnetic wave shielding film of the present invention, it is preferable to provide a layer containing photosensitive halogen silver halide grains after providing a layer having a near infrared absorption function on a support. Or it is preferable to provide simultaneously the layer which has a near-infrared absorption function, and the layer containing a photosensitive halogenated silver particle on a support body.

 [0116] This is because, since the silver Z binder volume ratio of the layer containing the photosensitive silver halide grains of the present invention is high, the coating stability is low in the usual method, and thus low speed coating is unavoidable. If it is on a layer having a near-infrared absorbing function, the coating stability of the layer containing the photosensitive silver halide grains is improved, and it has been found that high-speed coating is possible.

[0117] When a layer having a near-infrared absorbing function and a layer containing photosensitive halogen-silver particles are simultaneously laminated in a multilayer system, the silver Z binder volume ratio of the layer containing photosensitive halogen-silver particles is considerably high. Moreover, it is also the force which discovered that high-speed application | coating was possible. Furthermore, when the support, the layer having a near infrared absorption function, and the layer containing the photosensitive halogen silver halide particles are close to or adjacent to each other, the halation irradiation in the case where the exposure is performed with a near infrared laser beam or the like. This is preferable because a mesh pattern having a sharper fine line force can be formed. [0118] In the present invention, as the support, for example, a cellulose ester film, a polyester film, a polycarbonate film, a polyarylate film, a polysulfonate (including polyethersulfone) film, polyethylene terephthalate, polyethylene Polyester film such as phthalate, polyethylene film, polypropylene film, cellophane, cenorelose diacetate vinylome, cenorelose acetate butyrate film, poly (vinylidene chloride) film, polyvulcoalcohol film, ethylene vulcoal film, syndicate Otactic polystyrene film, polycarbonate film, norbornene resin film, polymethylpentene film, polyetherketone film It is possible to use a film, a polyether ketone imide film, a polyamide film, a fluorine resin film, a nylon film, a polymethyl methacrylate film or an acrylic film.

 Of these, cellulose triacetate film, polycarbonate film, polysulfone (including polyethersulfone) and polyethylene terephthalate film are preferably used.

 [0120] In the present invention, it is particularly preferable to use a cellulose ester film as the support from the viewpoints of transparency, isotropicity, adhesiveness, and the like.

 [0121] When the electromagnetic wave shielding film of the present invention is used for a display screen of a display, high transparency is required. Therefore, it is desirable that the support itself has high transparency. In this case, the average transmittance of the plastic film or glass plate in the entire visible light region is preferably 85 to: LOO%, more preferably 90 to: LOO%. In the present invention, as the color tone regulator, a plastic film or glass plate colored to such an extent that the object of the present invention is not hindered can be used.

 [0122] In the present invention, the average transmittance in the visible light region is obtained by integrating the transmittances of the visible light castle obtained by measuring the transmittance in the visible light region from 400 to 700 nm at least every 5 nm. Defined as the average value.

 [0123] In the present invention, an embodiment in which the average transmittance in the visible light region is 85% or more is preferable, more preferably 88% or more, and still more preferably 90% or more.

[0124] The thickness of the support used in the present invention is not particularly limited. From the viewpoint of sex, it is preferably 5 to 200 m, more preferably 30 to 150 / ζ πι.

 [0125] The support used in the present invention may be subjected to a hydrophilic treatment on the surface, or an undercoat layer or the like may be applied to various supports before applying a halogenated silver layer or the like, if necessary. I prefer that.

 [0126] Various methods are conventionally known as a method for applying a halogenated silver particle layer, a near infrared absorbing dye layer, and an antireflection layer in the present invention. For example, dip coating method, blade coating method, air knife coating method, wire bar coating method, gravure coating method, reverse roll coating method, slot type coating method, slide hopper coating method, slot type curtain coating method, slide type curtain coating method Laws are known. And in these coating methods, in order to obtain a uniform dry film thickness with high accuracy in the width direction of the substrate, pay attention to the coating film thickness accuracy and uniformity during coating (after coating and before drying), Applying.

 [0127] Among these coating methods, a coating apparatus having a flow rate regulation die is particularly capable of high-speed, thin-film, high-precision, multi-layer simultaneous coating, and photographic photosensitive material, ink jet recording material, It is widely used as a coating device for magnetic recording materials.

 [0128] In the present invention, it is preferable to use a coating apparatus having a flow rate regulating die. In particular, the slide hopper type coating device and the slide type curtain coating device can be used for simultaneous multi-layer coating, and the productivity can be significantly improved by simultaneously coating the layers containing halogen silver and silver particles and the layer containing near-infrared absorbing dye. It becomes possible.

 [0129] For the antireflection layer, the simultaneous application of multiple layers is difficult as the composition of the coating solution, so the slot type coating apparatus is most suitable. The slot-type coating device is also a coating device having a die, and high-precision coating can be performed by using this method.

[0130] In the case of a slide hopper coating apparatus, the coating liquid sent to the die from the liquid feeding pump enters a liquid pool called a pocket extending in the width direction, and this force also has a uniform thickness in the coating width direction. Thus, the liquid is pushed out of the narrow slit, flows down the slide surface, forms a coating liquid reservoir called a bead between the slide surface tip and the continuously running support, and the coating is performed through this bead. By overlaying different liquids on the slide surface, simultaneous multi-layer coating becomes possible. A pressure reducing chamber is provided at the bottom of the bead for bead stabilization. The negative pressure is maintained so as to be formed constantly.

 [0131] In the case of a slide type curtain coating apparatus, similarly, the slide surface flows down with a uniform thickness in the coating width direction, and a curtain-like liquid film is formed between the edge guides provided at both ends of the slide surface. The free-falling curtain-like liquid film collides with a continuously running support to form a coating layer. In the case of a slide-type curtain coating device, simultaneous multi-layer coating can be performed by stacking different liquids on the slide surface.

 [0132] In the case of a slot-type coating device, the coating liquid force slit force extruded with a uniform film thickness in the width direction is pushed out, and a bead is formed directly with the traveling support, and the coating is performed via this bead. Is done. In the case of a slot-type coating device, a decompression chamber is installed below the bead as needed to stabilize the bead.

 [0133] After being coated by these coating apparatuses, the coating solution may be dried by various drying methods and then wound up, or may be directly transported to the next step.

 In the present invention, the silver halide grain-containing layer provided on the support is exposed in order to form a conductive pattern by the development / reinforcement process described later. As the light source used for the exposure, for example, an embodiment using a strong ultraviolet ray or near infrared ray, which includes light such as visible light and ultraviolet light, and radiation such as electron beam and X-ray, is preferable. Further, a light source having a wavelength distribution may be used for the exposure, or a light source having a narrow wavelength distribution may be used.

 [0135] As the visible light, various light emitters that emit light in the spectral region are used as necessary. For example, a red light emitter, a green light emitter, or a blue light emitter may be used alone or in combination. The spectral region is not limited to the above-mentioned red, green, and blue, and phosphors that emit light in the yellow, orange, purple, or infrared region are also used. In addition, mercury lamp g-line and mercury lamp i-line are also used.

[0136] In the present invention, exposure can be performed using various laser beams. For example, the exposure in the present invention includes a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) that combines a solid state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. A scanning exposure method using monochromatic high-density light can be preferably used, and a KrF excimer laser, an ArF excimer laser, an F laser, or the like can also be used. In order to make the system compact and rapid, 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 and quick, has a long life, and is highly stable, exposure is preferably performed using a semiconductor laser.

 [0138] As the laser light source, specifically, an ultraviolet semiconductor, a blue semiconductor laser, a green semiconductor laser, a red semiconductor laser, a near infrared laser, and the like are preferably used.

 [0139] The method of exposing the silver halide grain-containing layer to an image may be performed by surface exposure using a photomask or by scanning exposure using a laser beam. In this case, exposure methods such as surface contact exposure, near field exposure, reduced projection exposure, and reflection projection exposure may be used, such as condensing exposure using a lens or reflection exposure using a reflecting mirror. The output of the laser may be about several tens of μW to 5 W, as long as it is an amount suitable for sensitizing the silver halide.

 [0140] In the present invention, after the halogenated silver particle-containing layer is exposed, development processing is performed. In addition to hydroquinones such as hydroquinone, sodium hydroquinone sulfonate, chlorohydroquinone, etc. as developing agents, there are 1-phenol 3-virazolidone, 1-phenyl-1,4-dimethyl-1,3-virazolidone as developing agents. It can be used in combination with bisazolidone such as 1-phenyl-4-methyl-4-hydroxymethyl-3 virazolidone, 1-phenyl-4-methyl-3 virazolidone, and superadditive developing agents such as N-methylparaaminophenol sulfate. 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.

 [0141] In addition, sodium sulfite salt or potassium sulfite salt as a preservative, sodium carbonate salt or potassium carbonate salt as a buffering agent, diethanolamine, triethanolamine, or jetylamino as a development accelerator in a development processing solution. Propanediol or the like can be used as appropriate.

[0142] The development processing solution used in the development processing according to the present invention may contain an image quality improving agent for the purpose of improving the image quality. Examples of the image quality improver include nitrogen-containing heterocyclic compounds such as 1-phenol-15-mercaptotetrazole and 5-methylbenzotriazole. [0143] In the present invention, the development processing performed after exposure may include physical development before fixing! The pre-fixing physical development is a process for reinforcing developed silver by supplying silver ions other than the inside of the halogen-containing silver particles having a latent image by exposure before the fixing process described later. Indicates. As a specific method for supplying silver ions from the developing solution, for example, a method in which silver ion-silver complex ion silver nitrate is previously dissolved in the developing solution as described in the physical development described later, Alternatively, a halogenated silver solvent such as sodium thiosulfate or ammonium thiocyanate is dissolved in the developing solution, and the unexposed portion of the halogenated silver is dissolved during development, so that a halogenated silver particle having a latent image is obtained. The method of supplementing the development of this.

 [0144] In the present invention, it is preferable to use a formulation in which a silver halide solvent is preliminarily dissolved in a developing solution because a reduction in film transmittance due to the occurrence of capri in an unexposed area can be suppressed.

 [0145] In the development processing in the present invention, after the black and white development of the exposed silver halide grains, a fixing treatment is performed for the purpose of removing and stabilizing the unexposed portions of the silver halide grains.

 [0146] In the fixing process of the present invention, the fixing solution used in a photographic film or photographic paper using halogen silver halide grains can be used. The fixing solution used in the fixing process according to the present invention is a fixing agent. As sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, or the like can be used. As a hardening agent for fixing, aluminum sulfate, chromium sulfate, or the like can be used. As the preservative for the fixing agent, sodium sulfite, potassium sulfite, ascorbic acid, erythorbic acid and the like described in the developing solution can be used, and in addition, citrate, oxalic acid and the like can be used.

 [0147] In the washing water used in the present invention, N-methyl-isothiazole-3-one, N-methyl-isothiazol-5-chloro-3-one, N-methyl-isothiazole- 4,5-Dichloro-3-one, 2-Nitroe 2-Bromue 3-hydroxypropanol, 2-Methyl-4-chlorophenol, hydrogen peroxide, etc. can be used.

[0148] In the present invention, it is preferable to perform the intensifying process in order to assist the contact between the developed silvers formed by the above-described developing process and increase the conductivity. In the present invention, the auxiliary treatment The term `` process '' refers to a process of increasing the conductivity by supplying a conductive material source not contained in the silver halide photosensitive material from the outside during the development process or after the process. As a specific method, For example, physical development or plating treatment can be exemplified.

 [0149] Physical development is 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, as is well known in the photographic art. You can do this.

[0150] In the present invention, the case where the developed silver where the development start point of physical development is only the latent image nucleus becomes the physical development start point is also defined as physical development, and this can be preferably used.

 [0151] In the present invention, various conventionally known plating methods can be used for the plating treatment used as the intensifying treatment. For example, electrolytic plating and electroless plating are carried out singly or in combination. Can do. Among these, electrolytic plating with excellent selectivity for plating metal, adjustment of plating speed, and plating strength can be preferably used in the present invention. In the case of non-wireless contact, there is an advantage that uneven contact due to current distribution unevenness does not occur. As a metal that can be used for plating, for example, copper, nickel, conoleto, tin, silver, gold, platinum, and other various alloys can be used. It is particularly preferable to use a copper electrolytic plating from the viewpoint of relatively easy plating and high conductivity.

 [0152] The intensifying process can be performed at any time during development, after development, before fixing, or after fixing process. However, from the viewpoint of maintaining high transparency of the film, after the fixing process. Preferred is the mode of implementation.

[0153] In the present invention, it is preferable to carry out the oxidation treatment after the development treatment or the intensification treatment. Oxidation treatment allows unnecessary metal components to be ionized and dissolved and removed, and the transmittance of the film can be further increased.

[0154] In the present invention, in order to impart high translucency, high !, and electromagnetic wave shielding performance, a lattice-like fine line pattern is drawn by exposure, and then subjected to development processing or the like to conduct electricity. An embodiment in which a sex mesh pattern is formed is preferable. The conductive metal portion preferably has a line width of 20 m or less and a line interval of 50 m or more. Conductive metal parts such as earth connections For purposes, the line width may have a portion wider than 20 m. From the viewpoint of making the image inconspicuous, it is preferable that the line width of the conductive metal portion is less than 18 m.

More preferably less than 14 m, more preferably less than 14 m, even more preferably less than 7 m, most preferably less than 7 m. Further, the thickness of the wire is preferably from 0.05 to 30 111, more preferably from 0.1 to 20 111, and more preferably from 0.1 to LO / z m force S.

 [0155] In the present invention, it is preferable that the visible light transmittance of a portion without a fine line in the lattice-like mesh pattern is 70% or more in order to impart high transparency and high! Electromagnetic wave shielding performance. 80% or more is more preferable, and 90% or more is particularly preferable. In measurement, it is necessary to make the measurement parameter sufficiently larger than the mesh pattern pitch described above, and it is preferable to measure at least 100 times larger than the mesh area of the mesh.

 [0156] The conductive metal part of the present invention has an aperture ratio of preferably 85% or higher, more preferably 90% or higher, and more preferably 95% or higher from the viewpoint of visible light transmittance. Is most preferred. The aperture ratio is the percentage of the mesh without fine lines. For example, the aperture ratio of a square mesh with a line width of 10 μm and a pitch of 200 μm is 90%. In addition, the visible light transmittance of the opening (the portion without the thin line) is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more.

 Example

 [0157] Hereinafter, the present invention will be described in more detail with reference to examples of the present invention. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

 [0158] Example 1

 << Preparation of a solution containing silver halide grains >>

An emulsion containing 10 g of gelatin per 100 g of silver in an aqueous medium and containing silver iodobromide grains (1 = 2.5 mol%) having an average equivalent sphere diameter of 0.044 / zm was prepared. At this time, the mass ratio of silver Z gelatin was 10Z1 (silver Z gelatin volume ratio 1.3), and a gelatin-treated low molecular weight gelatin having an average molecular weight of 40,000 was used. [0159] Further, bromide rhodium potassium and potassium chloride iridium acid This emulsion was added to a concentration force S 10- ⁷ (mol / mol Ag), Rh and Ir ions bromide grains Doped. Adding sodium palladium chloride acid to the emulsion, further Harogeni匕銀per mole 10- ⁴ moles after gold-sulfur sensitization, the following sensitizing dye SD- 1 using chloroauric acid and Chio sodium sulfate After addition and spectral sensitization, hydrazine (H-2) and an accelerator amine compound (A-10) were added as a thickening agent.

[0160] Using a slide hopper type coating device on a polyethylene terephthalate (PET) film that had been primed on both sides so that the silver coating amount would be 10 g / m ² (gelatin coating amount lg / m ² ) .

 [0161] [Chemical 2]

[0162] 《Exposure Z development processing》

 Using an image setter that gives a lattice-like mesh pattern with a line Z space of 10 μm / 195 μm, the sample 101 was obtained using a laser beam with an oscillation wavelength of 440 nm (manufactured by Nichia Corporation). After performing mesh exposure using a blue semiconductor laser diode), development is performed at 25 ° C for 60 seconds using the following developer, and fixing treatment is further performed at 25 ° C for 120 seconds using the following fixer. And then washed with water. In the obtained sample 101, a mesh-like lattice pattern as a metallic silver image was formed.

 [0163] (Developer composition)

 Hydroquinone 30g

 1-phenyl 1,3,3-dimethylpyrazolidone 1.5 g

 Potassium bromide 3. Og

 Sodium sulfite 50g

 Potassium hydroxide 30g

Boric acid 10g N-n-Butyljetanolamine 15g Water was added to 1L, and the pH was adjusted to 10.20.

[0164] (Fixing solution composition)

 Ammonium thiosulfate 72.5% aqueous solution 240ml

 Sodium sulfite 17g

 Sodium acetate trihydrate 6.5 g

 Boric acid 6. Og

 Sodium citrate dihydrate 2. Og

 Acetic acid 90% aqueous solution 13.6ml

 Sulfuric acid 50% aqueous solution 4.7 g

 Aluminum sulfate (AI O equivalent content 8.1% WZV aqueous solution) 26.5g

 twenty three

 Water was added to 1L and the pH was adjusted to 5.0.

[0165] On the back side of the sample 101 on which the developed mesh-like metal lattice pattern was formed, a solution having the following composition was sequentially applied in a multilayer manner using a slot-type coating device in the order of the middle refractive layer, the high refractive layer, and the low refractive layer. did. The coating thickness after drying of each layer was adjusted to 80 nm, 70 nm, and 95 nm in order. In this way, an electromagnetic wave shielding film sample 101 having an antireflection layer was produced.

 [0166] <Preparation of antireflection layer Z coating>

 <Preparation of titanium diacid titanium dispersion>

 Titanium dioxide (primary particle mass average particle size: 50 nm, refractive index: 2.70) 30 parts by mass, cation diatalate monomer (PM21, Nippon Kayaku Co., Ltd.) 4.5 parts by mass, Cationic methacrylate monomer (DMAEA, manufactured by Kojin Co., Ltd.) 0.3 parts by mass and 65.2 parts by mass of methyl ethyl ketone were dispersed by a sand grinder to prepare a titanium dioxide diacid dispersion.

[0167] (Preparation of coating solution for medium refractive index layer)

Cyclohexanone 151. 9 g and methyl ethyl ketone 37. Og, photopolymerization initiator (Irgacure 907, manufactured by Ciba-Gaigi Co., Ltd.) 0.14 g and photosensitizer (Cacure 1 DETX, Nippon Yakuhin Co., Ltd.) (Made) 0.04g was melt | dissolved. In addition, the above titanium dioxide dispersion 6. lg and a mixture of dipentaerythritol pentaatalylate and dipentaerythritol hexaatalylate (DPHA, Nippon Kayaku Co., Ltd.) 2.Add 4 g, stir at room temperature for 30 minutes, and then filter through a polypropylene filter with a pore size of 0.4 μm to prepare a coating solution for the medium refractive index layer .

 [0168] (Preparation of coating solution for high refractive index layer)

 Cyclohexanone 1152. 8g and methyl ethyl ketone 37.2g, photopolymerization initiator (ILGACURE 907, manufactured by Ciba-Gaigi Co., Ltd.) 0.06g and photosensitizer (CACURE I DETX, Nippon Kayaku Co., Ltd.) (Made) 0.02g was melt | dissolved. In addition, the ratio of the above titanium dioxide dispersion and the mixture of dipentaerythritol pentaatalylate and dipentaerythritol hexaatalylate (D PHA, Nippon Kayaku Co., Ltd.) increased the ratio of titanium dioxide dispersion to increase the refractive index. The amount was adjusted so as to be the refractive index of the refractive index layer, stirred at room temperature for 30 minutes, and then filtered through a polypropylene filter having a pore diameter of 0.4 m to prepare a coating solution for a high refractive index layer.

 [0169] (Preparation of coating solution for low refractive index layer)

 200g silica dispersion of silica fine particles with an average particle size of 15nm (methanol silica sol, manufactured by Nissan Chemical Co., Ltd.) 3g silane coupling agent (KBM-503, Shin-Etsu Silicone Co., Ltd.) 3g and 0.1MZL hydrochloric acid 2g In addition, the mixture was stirred at room temperature for 5 hours and then allowed to stand at room temperature for 3 days to prepare a dispersion of silica-coupled silica fine particles. To 35.04 g of the dispersion, 58.35 g of isopropyl alcohol and 39.34 g of diacetone alcohol were added. In addition, photopolymerization initiator (Irgacure 907, manufactured by Ciba-Gaigi Co., Ltd.) 1.02 g and photosensitizer (Cacure 1 DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.51 g were dissolved in 772.85 g of isopropyl alcohol. Further, 25.6 g of a mixture of dipentaerythritol pentaatarylate and dipentaerythritol hexatatalylate (DPHA, Nippon Kayaku Co., Ltd.) was added and dissolved. 67.23 g of the resulting solution was added to the above dispersion, a mixture of isopropyl alcohol and diacetone alcohol. The mixture was stirred for 20 minutes at room temperature and filtered through a polypropylene filter having a pore size of 0.4 m to prepare a coating solution for a low refractive index layer.

[0170] Next, as a comparative example, a sample 102 was manufactured in the order of application opposite to that of the sample 101. That is, on the polyethylene terephthalate (PET) film that has been subjected to undercoating, the antireflection layer is successively applied by a slot type coating apparatus and dried, and then the silver halide grain-containing layer is slid to the opposite side of the support. Coating was performed using a hopper type coating apparatus, and exposure and development processes were performed to form an electromagnetic wave shielding layer having a mesh-like metal lattice pattern. in this way Thus, an electromagnetic wave shielding film sample 102 having an antireflection layer was produced.

[0171] << Evaluation >>

 Each sample prepared by the above method was evaluated for electromagnetic wave attenuation effect, transparency, and spot failure on the film surface by the following method.

[0172] (Electromagnetic wave attenuation effect)

 After development, the silver image area was heated with an infrared pulsed semiconductor laser (Frankfurt, pulse width 10 msec) with a wavelength of 800 to 870 nm and an output of 50 W. The electromagnetic wave attenuation effect was measured by the Kansai Electronics Industry Promotion Center (KEC method). ), The electromagnetic wave attenuation effect was measured, and the electromagnetic wave attenuation effect (dB) at 100 MHz was compared.

[0173] (Transparency)

 The transparency was evaluated by a visual relative evaluation, which was evaluated according to three levels: good, slightly cloudy, and clear cloudy.

[0174] (Spot failure)

 The number of spot failures on the film surface as a product was evaluated by the number of visual observations per 10 cm2. Evaluation criteria were as follows.

[0175] ◎: Very good 0

 Y: Good 1-2

 Δ: Practically acceptable level 3-4

 X: 5-8 pieces that are impractical.

 [0176] (Evaluation of antireflection properties)

 Place a sample horizontally on a desk, and set a parok fluorescent lamp (3-wavelength emission type) FL40SS .ELWZ37 type 37WX 2 sets on a 3m-high ceiling as one set. A set was placed. The evaluator sat on a desk chair and evaluated the relative rank of the fluorescent lamps reflected on the sample on the desk as follows.

[0177] ○: Reflection of a nearby fluorescent lamp is a little worrisome.

 △: I'm worried about the reflection of distant fluorescent lights

 X: I'm worried about the reflection of fluorescent lights.

[0178] (Application speed limit) When coating the coating solution containing silver halide particles, change the coating speed to determine the upper limit speed (mZ) at which coating unevenness (mainly unevenness) occurs and the uniformity of the coated surface is impaired. It was.

 [0179] (Other)

 In addition, the findings found in the preparation of the sample are shown.

[0180] [Table 1]

[0181] A slight crack was observed in the antireflection layer of Sample 102.

[0182] From the above results, a mesh metal part was formed in the production of the electromagnetic shielding film.

 Later, by applying the coating layer in the order of antireflection function, the antireflection layer is excellent in transparency, is highly resistant to spot failures, has high antireflection properties, and does not generate cracks. Recognize.

[0183] Further, as a result of measuring the charge amount of the support in the transport state immediately before applying the antireflection layer,

 Compared to sample 102, sample 101 had a smaller charge and grounding was found to be effective. It turns out that it is the outstanding manufacturing method which can reduce the load to a production process.

[0184] Example 2

 《Preparation of near-infrared absorbing dye coating solution 1》

0. A 5 L three-necked flask was charged with 300 g of deionized water, 25 g of methyl methacrylate (MMA), 25 g of styrene, 45 g of ethyl acrylate (EA), 5 g of hydroxyethyl methacrylate HHEMA, and 250 mg of ammonium persulfate. The mixture was stirred at 100 ° C for 3 hours while bubbling with nitrogen to obtain an acrylic resin (AC) aqueous dispersion. After completion of the reaction, lOOmg of hydroquinone was added to obtain a thermoplastic resin aqueous dispersion. [0185] To this dispersion, an immonium-based near-infrared absorbing dye (I 2) in a fine solid state dispersion of lOOnm or less was added, and after stirring for 1 hour, a 2% by weight aqueous solution of gelatin was further added, and a near-infrared absorbing dye. The coating solution was 1.

 [0186] The near-infrared absorbing dye was dispersed with a planetary ball mill (partially stabilized zirconium) manufactured by Ito. 100 ml of water, 10 g of near-infrared absorbing dye (I 2), and beads (5 mm diameter) were operated in 30 ml at room temperature in a 200 ml container to prepare a dispersion with an average particle diameter of lOOnm.

 [0187] << Preparation of near-infrared absorbing dye coating liquid 2 >>

Phosphate - gelatin dispersion, tri cresyl phosphate ester 4g in gelatin aqueous solution (4 wt _^0/0) of 50 ml, 50 ml of acetic acid Echiru, surfactant (condensate of polyethylene glycol lauryl alcohol polymerization degree 10) 0.2 g was added and ultrasonically dispersed. To this dispersion, a near-infrared absorbing dye coating liquid 2 was prepared by adding a solid near-infrared absorbing dye (1-2) in a fine particle solid dispersion of lOOnm or less.

 [0188] The near-infrared absorbing dye was dispersed in the same manner as in the preparation of the near-infrared absorbing dye coating solution 1.

[0189] As the support, the same undercoated polyethylene terephthalate film as in Example 1 was used, and the amount of the immo-based near-infrared dye (1-2) was 0.

Thus, near-infrared absorbing dye coating solutions 1 and 2 were applied using a slide hopper type coating device, respectively, to obtain samples 201 and 202.

[0190] On the near-infrared absorbing layers of Samples 201 and 202, the same halogen-silver particle-containing coating solution as in Example 1 was applied so that the silver coating amount was lOgZm ² (gelatin coating amount lgZm ² ).

 [0191] Next, the near-infrared absorbing dye coating solutions 1 and 2 and the same silver halide particle-containing coating solution as in Example 1 were used, using a slide hopper type coating device, and the lower layer was a near-infrared absorbing dye layer, Samples 203 and 204 were prepared by simultaneous multilayer coating so that the upper layer was a layer containing a silver halide silver particle.

[0192] Samples 201 to 204 were exposed and developed in the same manner as in Example 1 to form a mesh-like metal lattice pattern. Then, a coating solution for the antireflection layer was prepared in the same manner as in Example 1, and applied to the back side of the support in the same amount as in Example 1. [0193] On the same undercoated polyethylene terephthalate film as in Example 1, the same halogen-silver particle-containing coating solution as in Example 1 was made to have a silver coating amount force S _10g Zm ² (gelatin coating amount lg Zm ² ). After applying to the sample and exposing and developing in the same manner as in Example 1 to form a mesh-like metal lattice pattern, the above-mentioned near-infrared absorbing dye coating solutions 1 and 2 are applied to the sample, respectively. 205 and 206 were produced. Then, a coating solution for the antireflection layer was prepared in the same manner as in Example 1, and coated on the back side of the support in the same amount as in Example 1.

 [0194] << Evaluation >>

 Each sample produced by the above method was evaluated in the same manner as in Example 1.

[0195] (Near-infrared dye layer stability over time)

Evaluation of stability over time was expressed as the percentage of deterioration of the absorption maximum after standing for 200 hours at a temperature of 70 ° C and a relative humidity of 90%. Table 2 shows the contents of the fabricated samples and the evaluated performance results. Light resistance deterioration test using Suga Test Instruments Co., Ltd. Super Xenon Weather Meter SX75, 50% relative humidity, and evaluated the rate of absorption degradation of irradiation intensity 50WZm ^2, 100 hours after the test. The smaller the value, the higher the stability.

[0196] (Others)

 In addition, the findings found in the preparation of the sample are shown.

[0197] [Table 2]

[0198] In Samples 205 and 206, coating unevenness of the near-infrared absorbing dye-containing layer slightly occurred. It is inferred that this is due to the unevenness of the mesh pattern in the lower layer.

[0199] From the above results, in the production of the electromagnetic wave shielding film, after providing a layer having a near-infrared absorption function, a layer provided with a layer containing photosensitive silver halide particles, or near-infrared absorption. By providing a layer having a light-absorbing function and a layer containing photosensitive silver halide silver particles by simultaneous multi-layer coating, not only the electromagnetic wave attenuation effect, transparency of the antireflection layer and spot failure, but also high-speed coating can be achieved. This is an excellent manufacturing method that is possible and has no problems in applicability of the near-infrared dye layer.

 [0200] Example 3

An aqueous gelatin solution was added to the coating solution containing the halogenated silver particles in Samples 203 and 204 of Example 2, and the silver coating amount was 1. Og / m ² and the gelatin coating amount was 0.2 g / m ² (silver / Samples 301 and 302 were prepared in the same manner except that the gelatin volume ratio was 0.64). After the exposure and development processes were performed in the same manner as in Example 1, the following physical development was performed continuously. The solution was subjected to physical development at 25 ° C. for 5 minutes and then washed with water. Then, the following copper plating solution was subjected to electrolytic plating at 2.5 AZcm ² at 25 ° C. for 5 minutes and washed with water.

 [0202] (Physical developer)

 800ml pure water

 Quenic acid 5g

 Hydroquinone 7g

 Silver nitrate 3g

 Add water to bring the total volume to 1 liter.

 [0203] (Copper plating solution)

 125 g of copper sulfate

 85g sulfuric acid

 Polyethylene glycol 0.lg

 1M hydrochloric acid 2.Oml

 Add water to bring the total volume to 1 liter.

 [0204] After drying, in the same manner as in Example 1, an antireflection layer was applied to the back side of the support in the same amount as in Example 1.

[0205] As a result of performing the same evaluation as in Example 2, samples 301 and 302 subjected to intensifying treatment such as physical development and tacking are excellent electromagnetic shielding films satisfying all the evaluation items. This shows that the production method of the present invention is excellent.

 [0206] Example 4

 In the same manner except that the sensitizing dye (SD-1) in the halogen silver halide grains in Sample 101 of Example 1 and Sample 301 of Example 3 was replaced with a near-infrared sensitizing dye (S-1), Samples 401 and 402 were prepared. In the exposure, the same operation was performed except that near-infrared semiconductor laser light having an oscillation wavelength of 8 lOnm was used to produce an electromagnetic wave shielding film.

[0207] When the metal mesh was examined with an electron microscope, sharp thin lines were reproduced in the sample 402. As a result, the silver halide grains were sensitized in the near-infrared, showed near-infrared photosensitivity, and an electromagnetic wave shielding film master having a near-infrared absorbing dye layer in the near layer was irradiated with near-infrared laser light. When the mesh pattern was exposed, it was found that a particularly excellent electromagnetic shielding film could be produced.

Claims

The scope of the claims

 [1] A layer having an antireflection function after forming a mesh-like metal part by exposing and developing an original plate for an electromagnetic wave shielding film provided with a layer containing photosensitive silver halide grains on a support. A method for producing an electromagnetic wave shielding film, characterized by coating and forming.

 [2] The method for producing an electromagnetic wave shielding film according to [1], wherein the layer having an antireflection function is applied and formed on the back side of a support having a layer having a mesh-like metal part.

 [3] The electromagnetic wave shielding according to claim 1 or 2, wherein the layer having an antireflection function is composed of a plurality of light-transmitting layers containing inorganic fine particles and having different refractive indexes. A method for producing a film.

 [4] The method according to any one of claims 1 to 3, wherein the layer containing the photosensitive halogen silver halide grains is provided after providing a layer having a near infrared absorption function on a support.

2. A method for producing an electromagnetic wave shielding film according to item 1.

[5] The method according to any one of claims 1 to 4, wherein the layer containing the photosensitive halogen silver halide grains is provided on the support simultaneously with the layer having a near infrared absorption function. The manufacturing method of the electromagnetic wave shielding film of description.

[6] The layer including the photosensitive halogen silver halide particles and the layer having a near-infrared absorption function are formed by simultaneous multi-layer coating by a slide hopper type coating device or a slide type curtain coating device. 6. A method for producing an electromagnetic wave shielding film according to item 4 or 5.

 [7] The electromagnetic wave shielding film according to any one of [1] to [6], wherein the layer having an antireflection function is formed by successive multilayer coating using a slot type coating device. Irum manufacturing method.

[8] After exposing and developing the original plate for an electromagnetic wave shielding film provided with a layer containing the photosensitive halogen silver halide particles, the substrate is further subjected to physical development processing and Z or staking processing to form a mesh-shaped electromagnetic wave. The method for producing an electromagnetic wave shielding film according to any one of claims 1 to 7, wherein a metal layer having a shielding function is formed and then a layer having an antireflection function is applied and formed. . An electromagnetic wave shielding film produced by the method for producing an electromagnetic wave shielding film according to any one of claims 1 to 8.