WO2008010461A1 - Transparent electromagnetic shielding film and process for producing the same - Google Patents

Abstract

A transparent electromagnetic shielding film that excels in electromagnetic wave shielding performance, having high transparency, and that excels in durability despite temperature and humidity changes. This transparent electromagnetic shielding film is one obtained by exposure and subsequent development processing of a photosensitive material having a support and, superimposed thereon, a layer containing at least photosensitive silver halide and a binder, characterized in that the content of photosensitive silver halide in the photosensitive material is from 0.05 to less than 1 g/m2 in terms of silver, and that the amount of the binder is in the range of 10 mg/m2 to 0.2 g/m2.

Description

 Specification

 Transparent electromagnetic wave shielding film and method for producing the same

 Technical field

 The present invention relates to a transparent electromagnetic wave shielding film that shields electromagnetic waves generated from electronic devices such as mobile phones, microwave ovens, CRTs, and flat panel displays, and a method for manufacturing the same.

 Background art

 [0002] In recent years, the use of electronic devices such as display devices used in mobile phones, personal computers, TVs, and the like has increased, but these electronic devices are also generally capable of emitting electromagnetic waves. As a result, it is known that so-called electromagnetic interference (EMI) occurs, such as malfunction of electronic and electrical equipment, failure, or possible harm to human body. Along with this, the need to reduce such EMI has increased, and standards or regulations regarding the intensity of electromagnetic wave emission have been established mainly in Europe and the United States, and recent electronic devices are required to meet these standards. ing.

 [0003] As a method for blocking electromagnetic waves, for example, a method using a so-called electromagnetic wave absorbing material showing high dielectric loss, conductive loss, and magnetic loss is known. However, since these materials are generally opaque, they cannot be used for equipment that requires visibility, such as CRTs, flat panel displays, or window glass, and their use has been limited. .

 [0004] As a means for achieving both electromagnetic wave shielding performance and transparency, for example, a method of forming a thin film of a conductive material such as silver on a transparent substrate by sputtering or the like is known (for example, see Patent Document 1). .)

 [0005] However, in the case of these metal thin films, it is necessary to increase the thickness of the metal thin film layer in order to provide high electromagnetic wave shielding performance. It was difficult to achieve both shielding performance and transmittance. In addition, since the sputtering method generally requires a vacuum environment, there have been problems with the viewpoint of improving productivity.

[0006] As an electromagnetic wave shielding material that can achieve both high electromagnetic wave shielding performance and transmittance, there is a material using a conductive mesh, and various methods have been proposed as an implementation means thereof (for example, See Patent Documents 2-4. ) ₀ However, both a complicated manufacturing method, the viewpoint force of continuous productivity for mass production is also the technique is insufficient, improvement has been desired. In addition, among electromagnetic wave shielding films using conductive mesh, the method of producing a conductive mesh by using exposure to photosensitive halogen silver and development processes makes it easy to form a mesh pattern. It has been published as a useful method for producing transparent electromagnetic wave shielding materials in large quantities at low cost. As one of them, an electromagnetic wave shielding material using a silver salt diffusion transfer method is known (see, for example, Patent Documents 5 and 6). As a result of the uniform coating, unnecessary catalyst remains in the non-conductive portion, impairing the permeability, and immediately using the diffusion phenomenon of silver ions or silver complexes for development, sharpness is likely to deteriorate and the improvement is improved. It was hoped.

[0007] In addition, as another method utilizing the exposure and development process of photosensitive halogen silver, exposure and development are performed on the silver halide emulsion layer. Electromagnetic wave shielding materials in which a conductive pattern is produced by performing plating or the like as a catalyst are known (see, for example, Patent Documents 7 to 9). _{0 In} these materials, a photosensitive silver halide emulsion is used as a support. The power to use a binder to hold on It is preferred to increase the AgZ binder ratio as much as possible to increase conductivity! /

 Patent Document 1: Japanese Unexamined Patent Application Publication No. 2004-179405

 Patent Document 2: JP-A-5-327274

 Patent Document 3: Japanese Patent Laid-Open No. 11-170421

 Patent Document 4: Japanese Patent Laid-Open No. 2003-23290

 Patent Document 5: Japanese Unexamined Patent Application Publication No. 2004-172041

 Patent Document 6: Japanese Patent Laid-Open No. 2005-183059

 Patent Document 7: Japanese Unexamined Patent Application Publication No. 2004-221564

 Patent Document 8: Japanese Patent Application Laid-Open No. 2004-221565

 Patent Document 9: Pamphlet of International Publication No. 01Z51276

 Disclosure of the invention

 Problems to be solved by the invention

[0008] However, when the AgZ binder ratio is kept high, the conductivity increases, but the temperature, humidity, The transparent electromagnetic wave shielding film tends to be deteriorated when used for a long period of time in an environment where the degree of change is severe, and the improvement has been desired. This is presumed to be due to deterioration of the binder held on the support when passing through various processing solutions such as development and physical development Z plating.

 [0009] The present invention has been made in view of the above problems, and its purpose is to provide a transparent electromagnetic wave shielding excellent in electromagnetic wave shielding performance, having high transparency, and having excellent durability against changes in temperature and humidity. To provide a film.

 Means for solving the problem

[0010] Therefore, the inventors of the present invention have studied the method of producing a conductive mesh using a silver halide light-sensitive material while paying attention to the halogen-silver light-sensitive material. By designing the binder to hold the substrate on the support so that the absolute amount of the binder alone is within a certain range, it maintains durability and is resistant to changes in temperature and humidity. It was found that an excellent transparent electromagnetic wave shielding film can be obtained.

 That is, the object of the present invention is achieved by the following transparent electromagnetic wave shielding film.

[0012] 1. In a transparent electromagnetic wave shielding film produced by subjecting a photosensitive material having a layer comprising at least a photosensitive silver halide silver and a binder on a support to a development process after exposure.

, The content of the photosensitive Harogeni匕銀in the photosensitive material is lgZm less than ² 0. 05G / m ² or more in terms of silver, and the amount of the binder is ² hereinafter LOmgZm ² or 0. 2GZm A transparent electromagnetic wave shielding film characterized.

[0013] 2. The transparent electromagnetic wave shielding film is subjected to physical development or metal plating after exposure and development, and the amount of metal applied by physical development or metal plating exposes and develops the photosensitive material. 2. The transparent electromagnetic wave shielding film according to 1 above, which is 10 to 100 times in terms of mass with respect to the developed silver amount obtained by the above. 3. The transparent electromagnetic wave shielding film is characterized in that a value obtained by dividing the content of silver halide (g / m ² ) by the average grain size of silver halide (μm) is 6 or more and 25 or less. 3. The transparent electromagnetic wave shielding film according to 1 or 2 above.

[0014] 4. The transparent electromagnetic wave shielding film is subjected to oxidation after exposure and development. 4. The transparent electromagnetic wave shielding film according to any one of 1 to 3 above, wherein

[0015] 5. The transparent electromagnetic wave shielding film as described in any one of 1 to 4 above, wherein the transparent electromagnetic wave shielding film is subjected to blackening treatment after exposure and development processing.

[0016] 6. The transparent electromagnetic wave shielding film as described in any one of 1 to 5 above, wherein in the transparent electromagnetic wave shielding film, photosensitive halogen silver halide particles are spectrally sensitized.

 [0017] 7. The transparent electromagnetic wave shielding film according to any one of 1 to 6, wherein the transparent electromagnetic wave shielding film has at least one ultraviolet absorbing layer.

 [0018] 8. The transparent electromagnetic wave shielding film according to any one of 1 to 7, wherein the transparent electromagnetic wave shielding film has different conductive patterns on both sides of the support of the film. Transparent electromagnetic wave shielding film.

[0019] 9. The transparent electromagnetic wave shielding film has an antireflection layer on the opposite side of the layer having the conductive pattern to the layer having the conductive pattern, and the protective film is formed after the antireflection layer is formed. 8. The transparent electromagnetic wave shielding film according to any one of 1 to 7, wherein a conductive pattern layer is formed after bonding.

[0020] 10. The method for producing a transparent electromagnetic wave shielding film according to any one of 1 to 9, wherein the developed silver obtained by exposure and development is subjected to intensification. A method for producing a transparent electromagnetic wave shielding film.

 The invention's effect

 [0021] According to the present invention, it is possible to provide a method for producing an electromagnetic wave shielding film having excellent electromagnetic wave shielding performance, high transparency, and excellent durability against changes in temperature and humidity.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0022] The transparent electromagnetic wave shielding film of the present invention comprises a photosensitive material having at least a layer composed of a photosensitive halogenated silver and a binder on a support. The content is 0.05 g / m ² or more and less than lg / m ^{2 in} terms of silver, and the amount of the binder is 1 Omg / m ² or more and 0.2 g / m ² or less.

 [0023] Hereinafter, the present invention will be described in detail.

 [Silver halide emulsion-containing layer]

 In the present invention, a silver halide emulsion-containing layer containing a light-sensitive silver halide silver and a binder, which will be described later, is provided on a support. A film agent, a hardener, an activator and the like can be contained.

In the present invention, the effect of the present invention can be obtained when the content of the photosensitive halogenated silver is 0.05 g / m ² or more and less than lg Zm ^{2 in} terms of silver. When the content of the photosensitive halogen silver is less than 0.05 gZm ² , it is difficult to obtain sufficient electromagnetic wave shielding performance. This is presumed to be because the amount of developed silver nuclei serving as a catalyst for the physical development or metal plating process described later is insufficient, and an effective conductive mesh is formed. In addition, when the photosensitive silver halide content is lgZm ² or more, the amount of halogenated silver relative to the binder is relatively large, so that the coating becomes fragile and immediately maintains sufficient coating strength. It becomes difficult.

 [0026] When the amount of the binder is increased in order to maintain the physical properties of the film, the distance between the grains of the photosensitive halogenated silver particles increases, so that a developed silver network is formed, and an effective conductive mesh is formed. At the same time, the durability against changes in temperature and humidity becomes insufficient, and it becomes difficult to obtain the effects of the present invention.

In the present invention, the effect of the present invention can be obtained when the binder amount of the light-sensitive material is 1 OmgZm ² or more and 0.2 gZm ² or less. When the amount of noinder is less than 1 Omg / m ^2, the amount of halogen silver relative to the noinder becomes relatively large, so that the film becomes fragile and it is difficult to immediately maintain a sufficient film strength. In addition, when the Noinder amount is more than 0.2 gZ m ² , the distance between the grains of the photosensitive halogen-molybdenum grains becomes large, so that a current silver network is formed, and an effective conductive mesh is formed. In addition, the durability against changes in temperature and humidity becomes insufficient, and the effects of the present invention cannot be obtained.

[0028] [Silver halide grains]

The composition of the silver halide silver grains used in the present invention is as follows: silver chloride, silver bromide, silver chlorobromide, iodine Silver bromide, silver chloroiodobromide, silver chloroiodide, etc. may have any halogen composition Force To obtain highly conductive metal silver, fine grains with high sensitivity are preferred. Silver halide grains are preferably used. If a large amount of iodine is contained, the sensitivity is high and fine particles can be obtained.

 [0029] In order to reduce the surface specific resistance of the silver halide particles after they are developed into metal silver particles and effectively block electromagnetic waves, the contact area between the developed silver particles becomes as large as possible. There is a need. For this purpose, the smaller the size of the halogen silver silver particles, the better to increase the surface area ratio, but the particles that are too small aggregate to form large agglomerates, and in that case, the contact area decreases on the contrary. Exists. In the present invention, the average grain size of the silver halide grains is preferably 0.03 to 0.3 m, more preferably 0.01 to 0.5 m in terms of a sphere equivalent diameter. The spherical equivalent diameter of a halogenated silver particle represents the diameter of a grain having a spherical shape and the same volume. The average particle size of the halogenated silver particles is the temperature, pAg, pH, addition rate of the silver ion solution and the halogen solution, the particle size control agent (for example, 1 Fe-Lu 5 mercaptotetrazole, 2 —Mercaptobenzimidazole, benztriazole, tetrazaindene compounds, nucleic acid derivatives, thioether compounds, etc.) can be combined and controlled as appropriate.

In the present invention, it is preferable that the value obtained by dividing the silver halide content (gZm ² ) by the average grain size (μm) of silver halide is 6 or more and 25 or less. When a large amount of photosensitive silver halide silver having a relatively small particle size is used, this value becomes larger than 25, and in this case, the silver halide grains slip off from the coating immediately on the edge when the film is cut. Tend to be more likely to occur. In addition, when a small amount of photosensitive silver halide is used, this value becomes smaller than 6 and, in this case, the number of photosensitive silver halide grains in the unit area decreases. This is because it tends to decrease! /.

[0031] In the present invention, the shape of the halogen silver halide grains is not particularly limited. For example, spherical, cubic, flat plate (hexagonal flat plate, triangular flat plate, quadrangular flat plate, etc.), octahedral shape, etc. It can be in various shapes such as a 14-sided shape. In order to increase the sensitivity, tabular grains having an aspect ratio of 2 or more, 4 or more, and further 8 to 16 can be preferably used. particle The size distribution is not particularly limited, but a narrow distribution is preferable from the viewpoint of enhancing the transparency while maintaining high conductivity while sharply reproducing the outline of the pattern during pattern formation by exposure. The particle size distribution of the halogen silver halide grains used in the light-sensitive material according to the present invention is preferably monodispersed halogen silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less. Here, the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

[0032] Coefficient of variation = SZR

 (In the formula, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)

The halogen silver halide grains used in the present invention may further contain other elements. For example, in a photographic emulsion, it is also useful to dope metal ions used to obtain a high contrast emulsion. In particular iron ions, rhodium ions, the first _8-10 metals ions such as ruthenium ions and Irijiu Ion preferably used because the difference between the exposed and unexposed portions in the generation of metallic silver image is likely clearly occur.

[0033] These metal ions can be added to a halogenated silver emulsion in the form of a salt complex. Transition metal ions typified by rhodium ions and iridium ions can also be compounds having various ligands. Examples of such ligands include cyanide ions, halogen ions, thiocyanate ions, nitrocinole ions, water, hydroxide ions, and the like. Specific examples of the compound include potassium bromide rhodate and potassium iridate.

[0034] Te you, the present invention, that the content of the metal Ioni匕合product contained in Harogeni匕銀are per mole of silver halide, a ^10- ω ~ 10- ² moles Z mol Ag preferred tool 10- ^9-1

0 ³ mol Z mol Ag is more preferred!

[0035] In order for silver halide grains to contain the above metal ions, the metal compound is added before the formation of silver halide grains, during the formation of halogenated silver grains, after the formation of halogenated silver grains, etc. What is necessary is just to add in the arbitrary places in each process during physical ripening. In addition, in the additive, the heavy metal compound solution can be continuously formed over a part of the particle forming process.

[0036] In the present invention, in order to further improve the sensitivity, chemical sensitization performed in a photographic emulsion is performed. You can also. Chemical sensitization includes, for example, noble metal sensitization such as gold, palladium and platinum sensitization, chalcogen sensitization such as iodo sensitization with inorganic or organic compounds, and reduction sensitization such as sodium chloride tin and hydrazine. Can be used.

 [0037] Further, it is preferable that the silver halide grains are subjected to spectral sensitization.

[0038] Preferable! / Spectral sensitizing dyes include cyanine, carbocynin, dicarboyanine, complex cyanine, hemisyanine, styryl dye, merocyanine, complex melocyanin, holopora single dye, etc., which are used in the industry. Thus, the spectral sensitizing dye can be used alone or in combination.

 [0039] Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. For these dyes, any of the nuclei commonly used in cyanine dyes can be used as the basic heterocyclic ring nucleus. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei, and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazol nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus Benzimidazole nucleus, quinolin nucleus and the like. These nuclei may be substituted on carbon atoms.

 [0040] The merocyanine dye or the complex merocyanine dye includes a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2 thoxazolidine 2,4 dione nucleus, a thiazolidine 2,4 dione nucleus, a rhodanine as a nucleus having a ketomethylene structure. 5 to 6-membered heteronuclear ring nuclei such as nucleus and thiobarbituric acid nucleus can be applied.

 [0041] These sensitizing dyes may be used alone or in combination.

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

[0042] 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. In addition, as described in Japanese Patent Publication Nos. 44-23389, 44-27555, 57-22 089, etc., an acid or a base is allowed to coexist to form an aqueous solution. 822, 135, 4, 006, 025, etc. [As described herein] Emulsions in the form of aqueous solutions or colloidal dispersions in the presence of surfactants such as sodium chloride, decenorebenzene senorephonate, etc. You may add to. Alternatively, water or a hydrophilic colloid-dispersed solution may be added to the emulsion after being dissolved in a solvent substantially immiscible with water such as phenoxyethanol. As described in JP-A-53102733 and 58-105141, the dispersion may be directly dispersed in a hydrophilic colloid and the dispersion may be added to the emulsion.

[0043] (Binder)

 In the silver halide emulsion-containing layer according to the present invention, the silver halide grains are uniformly dispersed, and the silver halide grains are supported on the support, and the adhesiveness between the silver halide emulsion-containing layer and the support. A binder is used for the purpose of ensuring the above. As the binder that can be used in the present invention, any of a water-insoluble polymer and a water-soluble polymer that are not particularly limited can be used. From the viewpoint of improving developability, a water-soluble polymer can be used. I like it.

 [0044] In the light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder.

1S If necessary, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer substances such as mono- or copolymers Can be used.

 [0045] (Ultraviolet absorber)

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

As the ultraviolet absorber, known ultraviolet absorbers such as salicylic acid compounds, benzophenone compounds, benzotriazole compounds, S triazine compounds, cyclic imino ester compounds and the like can be preferably used. Of these, benzophenone compounds, benzotriazole compounds, and cyclic imino ester compounds are preferred. As what is mix | blended with a polyester, especially a cyclic imino ester type compound is preferable. Although there is no particular limitation on the layer to which these ultraviolet absorbers are added, from the viewpoint of preventing deterioration of the binder used in the silver halide emulsion-containing layer due to ultraviolet rays, the addition to the silver halide emulsion-containing layer is difficult. Direct addition, or closer to outside light than the layer containing a halogenated silver emulsion The aspect provided in is preferable. When added to a layer containing a silver halide emulsion or a layer adjacent thereto, benzotriazoles are preferably used as ultraviolet absorbers. For example, a general formula [III 3] described in JP-A-1-250944 can be mentioned. And compounds described in Japanese Patent Publication No. 64-66646

 Compounds represented by formula [III], UV-1L to UV-27L described in JP-A-63-187240, compounds represented by general formula [I] described in JP-A-41633, JP-A-5- The compounds represented by the general formulas (1) and (II) described in Japanese Patent No. 165144 are preferably used. These ultraviolet absorbers are, for example, high boiling points represented by phthalates such as dioctyl phthalate, di-decyl phthalate, and dibutyl phthalate, and phosphate esters such as tricresyl phosphate and trioctyl phosphate. An embodiment in which it is added in a dispersed form in an organic solvent is preferably used. In addition, an embodiment in which these ultraviolet absorbers are directly added to the support is also preferably used. In this case, for example, an embodiment described in JP-T-2004-531611 can also be preferably used.

[0047] (Blackening treatment)

 In the present invention, it is preferable to perform blackening treatment from the viewpoint of preventing reflection of external light on the film surface. For example, when a transparent electromagnetic wave shielding film that has undergone such blackening treatment is used in a display such as a PDP, it is possible to reduce the decrease in contrast due to reflection of external light and to make the screen color tone black when not in use. It is preferable that it can be maintained. As the black wrinkle processing method, known methods without particular limitation can be used alone or in combination as appropriate. For example, when the outermost surface of the conductive pattern is also made of metallic copper, it can be immersed in an aqueous solution containing sodium chlorite, sodium hydroxide, or trisodium phosphate and oxidized, or copper pyrophosphate, A method of blackening by immersing in an aqueous solution containing potassium pyrophosphate and ammonia and performing electrolytic plating can be preferably used. When the outermost layer of the conductive pattern is made of a nickel-phosphorus alloy film, an acidic blackening solution containing copper (II) chloride or copper sulfate (11), nickel chloride or sulfuric acid-nickel, and hydrochloric acid. The method of immersing in can be preferably used.

[0048] In addition to the above method, black wrinkle processing is also possible by a method of roughening the surface. However, from the viewpoint of maintaining high conductivity, the blackening method using oxidation is preferred to the finer surface.

 [0049] [High contrast agent]

 In the present invention, in order to draw a conductive pattern with a clear edge, a method in which the photosensitive material is a high contrast is preferred. As a method for this, a high silver salt content is used to narrow the particle size distribution. It is preferable to use a hydrazine compound or a tetrazolium compound as a thickening agent. A hydrazine compound is a compound having an NHNH group, and a typical one is represented by the following general formula (1).

 [0050] General formula (1) T NHNHCO— V, T NHNHCOCO— V

 In the formula, each T represents an optionally substituted aryl group or heterocyclic group. The aryl group represented by T includes a benzene ring or a naphthalene ring, and this ring may have a substituent. 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) Acetylamino group, heptylamino group, etc.), aromatic isylamino groups, etc., in addition to these, for example, the substituted or unsubstituted aromatic rings as described above are —CONH—, —O—, -SO NH—, — NHCONH—, —CH CH = N—, etc.

 twenty two

 Including those bonded by a linking group. V is a hydrogen atom, an optionally substituted alkyl group (methyl group, ethyl group, butyl, trifluoromethyl group, etc.), aryl group (phenyl group, naphthyl group), heterocyclic group (pyridyl group, piperidyl group, Pyrrolidyl group, furanyl group, thiophene group, pyrrole group and the like).

 [0051] The hydrazine compound described above can be synthesized with reference to the description in US Pat. No. 4,269,929. The hydrazine compound can be contained in the halogen-containing silver particle-containing layer, in the hydrophilic colloid layer adjacent to the halogen-containing silver particle-containing layer, or in another hydrophilic colloid layer.

 [0052] Particularly preferred are the following compounds of hydrazine.

(H-1): 1-trifluoromethylcarbole 2— {[4— (3-n-butylureido) phenol]} hydrazine (H 2): l Trifluoromethyl carboru 2- {4- [2- (2, 4-Gee 61: 1; -Pentylphenoxy) butyramide] phenol} hydrazine

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

(H— 4): 1— (2, 2, 6, 6-tetramethylpiperidyl-4 amino-oxalyl) — 2— {4 1 [2- (2, 4-di tert pentylphenoxy) butyramide ] Fuelsulfonamidophenol} hydrazine

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

 (H— 6): 1— (2, 2, 6, 6-tetramethylpiperidyl— 4-amino-oxalyl) — 2— (4— (3-thia 6, 9, 12, 15-tetraoxatrico Sanamide) benzenesulfonamide) phenylhydrazine

 (H—7): 1— (1-Methylenecarbo-pyridylum) -2- (4- (3 thia 6, 9, 12, 15, 15-tetraoxatricosanamide) benzenesulfonamide) phenylhydrazine chloride ,.

 [0053] When hydrazine is used as the thickening agent, an amine compound or a pyridine compound can be preferably used in order to enhance the reducing action of hydrazine. As the amine compound that promotes the reduction action of the hydrazine compound, it is particularly preferable that the molecule has at least one piperidine ring or pyrrolidine ring, at least one thioether bond, and at least two ether bonds. .

[0054] As the compound that promotes the reducing action of hydrazine, pyridinium compounds and phosphonium compounds can be preferably used in addition to the above-mentioned amine compounds. Since the o-um compound is positively charged, it is adsorbed on the negatively charged halogen-molybdenum grains and promotes electron injection from the developing agent at the time of image formation, thereby promoting high contrast. It is thought to do. As preferred pyridinium compounds, reference can be made to the bispyridium compounds disclosed in JP-A-5-53231 and JP-A-6-242534. Particularly preferred pyridi-um compounds are those that are linked at the 1st or 4th position of the pyridium to form a bispyridumum! /, is there. As the salt, chlorine ion or bromine ion is preferred as a halogen ion, and in addition, a force such as boron tetrafluoride ion, perchlorate ion, etc. Chlorine ion or 4 fluorine boron ion is preferred.

[0055] Hidorajini匕合thereof, Amini匕合thereof, pyrid - © beam compounds, and Tetorazoriumu compound per mol of silver halide 1 X 10- ⁶ ~5 X 10- ² mol preferably tool especially 1 to contain X 10 one ⁴ ~ ² X 10- 2 mol is preferred. It is easy to adjust the addition amount of these compounds to increase the degree of contrast γ to 6 or more.

 [0056] These compounds are used by being added to a layer containing halogenated particles or another hydrophilic colloid layer. If it is water-soluble, it is added to an aqueous solution, and if it is water-insoluble, it is added to a silver halide grain solution or hydrophilic colloid solution as a solution of an organic solvent miscible with water, such as alcohols, esters, and ketones. That's fine. 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 / ζ πι by a ball mill, a sand mill, a jet mill or the like. As the fine particle dispersion method, a technique of solid dispersion of a dye as a photographic additive can be preferably applied. For example, a desired particle size can be obtained using a dispersing machine such as a ball mill, a planetary rotating ball mill, a vibrating ball mill, or a jet mill. When a surfactant is used at the time of dispersion, stability after dispersion can be improved.

 [0057] [Support]

In the present invention, as a support, for example, a cellulose ester film, a polyester film, a polycarbonate film, a polyarylate film, a polysulfone (including polyethersulfone) film, a polyester film such as polyethylene terephthalate and polyethylene naphthalate , Polyethylene film, Polypropylene film, Cellophane, Senorelose diacetate Finolem, Senorelose acetate butyrate phenolome, Polyvinylidene chloride film, Polybulol alcohol film, Ethylene butyl alcohol film, Syndiotactic polystyrene film , Polycarbonate film, norbornene resin film, polymethylpentene film, polyether ketone film, Li polyether ketone imide film, a polyamide film, a fluorine 榭脂 film, a nylon film, polymethyl methacrylate Tari acetate film or an acrylic film or the like. In addition to these plastic films, quartz glass and soda glass are also used. It is possible.

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

 [0059] In the present invention, it is particularly preferable to use a cellulose ester film or a polyester film as the support from the viewpoints of transparency, isotropicity, adhesiveness, and the like.

 [0060] When the electromagnetic wave shielding material 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 100%, more preferably 90 to: LOO%. Further, in the present invention, as the color tone adjusting agent, the plastic film or glass plate that has been colored to such an extent that the object of the present invention is not hindered is used.

 [0061] In the present invention, the average transmittance in the visible light region means that each transmittance in the visible light region determined by measuring the transmittance in the visible light region from 400 to 700 nm at least every 5 nm. The rate is defined as the average value obtained by accumulating the rates.

 [0062] For measurement, the measurement parameter must be sufficiently larger than the mesh pattern described above, and is obtained by measuring at least 100 times larger than the mesh area of the mesh.

 [0063] The thickness of the support used in the present invention is not particularly limited, but from the viewpoint of maintaining transmittance and handling, it is preferably 5 to 200 m, and preferably 30 to 150 / ζ πι. More preferably.

 [Exposure]

 In the present invention, the photosensitive material is exposed in order to form a conductive pattern by a development process described later. Examples of the light source used for exposure include light such as visible light and ultraviolet light, radiation such as electron beam and X-ray, and ultraviolet light or near infrared light is preferably used. Further, a light source having a narrow wavelength distribution may be used for exposure, or a light source having a wavelength distribution may be used.

As the visible light, various light emitters that emit light in the spectral region are used as necessary. For example, one or more of a red luminescent material, a green luminescent material, and a blue luminescent material may be used in combination. The spectral region is not limited to the above red, green, and blue, and phosphors that emit light in the yellow, orange, purple, or infrared region are also used. In addition, mercury lamp g-line, mercury lamp i-line, etc., which favor ultraviolet lamps, are also used.

[0066] In the present invention, exposure can be performed using various laser beams. For example, monochromatic high-density light such as gas laser, light emitting diode, semiconductor laser, semiconductor laser or solid-state laser using a semiconductor laser as a pumping light source and second harmonic light source (SHG) combining nonlinear optical crystal Can be used preferably, and KrF excimer laser, ArF excimer laser, F laser, etc. can also be used.

 2

 Can. In order to make the system compact and rapid, exposure should be 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. preferable. In order to design an apparatus that is particularly compact, quick, and has a long life and high stability, exposure is preferably performed using a semiconductor laser.

 [0067] 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, or the like is preferably used.

 [0068] The method for exposing the silver halide emulsion-containing layer to an image may be performed by surface exposure using a photomask or by scanning exposure using a laser beam. At this time, 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 5W, as long as it is an amount suitable for exposing silver halide.

 [Development processing]

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

[0070] In addition to hydroquinones such as rho, idroquinone, rhodium, iodoquinone sulfonic acid sodium and chlorohydroquinone as developing agents, 1-phenol 3-virazolidone, 1-phenyl as a developing agent. 1, 4, dimethyl 1, 3 pyrazolidone, 1-phenyl 1, 4-methyl 4 -It can be used in combination with virazolidones such as hydroxymethyl 3 bisazolidone, 1 phenyl 4 methyl 3 bisazolidone and superadditive developing agents such as N-methylparaaminophenol sulfate. In addition, it is preferable to use a reductone compound such as ascorbic acid or isoascorbic acid in combination with the above superadditive developing agent without using hydroquinone.

 [0071] Further, in the development processing solution, sodium sulfite and potassium sulfite as preservatives, sodium carbonate and potassium carbonate as buffers, diethanolamine, triethanolamine, and jetylamino as development accelerators. Propanediol or the like can be used as appropriate.

 [0072] The development processing solution used in the development processing can contain an image quality improving agent for the purpose of improving the image quality. Examples of the image quality improver include nitrogen-containing heterocyclic compounds such as 1-ferro-5-mercaptotetrazole and 5-methylbenzotriazole.

 In the present invention, it is preferable that the development processing performed after exposure includes physical development before fixing. The pre-fixing physical development referred to here is a process for reinforcing developed silver by supplying silver ions other than the inside of the silver halide grains having a latent image by exposure before performing the fixing process described later. Show. As a specific method for supplying silver ions from the developing solution, for example, a method in which silver nitrate or the like is dissolved in advance in the developing solution and silver ions are dissolved, or thiosulfuric acid is added in the developing solution. Examples include a method in which a halogenated silver solvent such as sodium or ammonium thiocyanate is dissolved, and unexposed silver halide is dissolved during development to assist development of silver halide grains having a latent image. It is done.

 In the present invention, the use of a formulation in which a silver halide solvent is dissolved in advance in a developer can suppress a decrease in film transmittance due to the occurrence of capri in the unexposed area. It is preferable.

[0075] In the development process of the present invention, after the development of the exposed silver halide grains, a fixing process is carried out for the purpose of removing and stabilizing the unexposed portions of the silver halide grains. Do. For the fixing treatment in the present invention, a fixer formulation used for photographic films, photographic papers and the like using silver halide grains can be used. Fixing solution used in fixing process is sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, etc. Can be used. Aluminum sulfate, chromium sulfate, etc. can be used as a hardener for fixing. As the preservative for the fixing agent, sodium sulfite, potassium sulfite, ascorbic acid, erythorbic acid, etc. described in the developing solution can be used, and in addition, citrate, oxalic acid, etc. can be used. .

 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.

 [0077] [Reinforcement processing]

 In the present invention, it is preferable to perform a helping 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 complementary processing refers to processing for improving the conductivity by supplying a conductive material source not previously contained in the photosensitive material from the outside during or after the development processing. Examples of the method include physical development or plating treatment. Physical development can be performed by immersing a photosensitive material containing a silver halide emulsion having a latent image in a processing solution containing silver ions or silver complex ions and a reducing agent. In the present invention, even when developed silver where the development start point of physical development is only the latent image nucleus becomes the physical development start point, it is defined as physical development and can be preferably used.

 In the present invention, various conventionally known plating methods can be used for the plating treatment. For example, electrolytic plating and electroless plating can be carried out singly or in combination. Among these, electroless plating that does not cause unevenness due to current distribution unevenness can be preferably used. As metals that can be used for electroless plating, for example, copper, nickel, cobalt, tin, silver, gold, platinum, and other various alloys can be used. From the viewpoint of easily obtaining conductivity, it is particularly preferable to use a copper electroless plating.

[0079] It should be noted that the intensification process can be performed at any time during development, after development, before fixing, and after fixing process, but from the viewpoint of maintaining high transparency of the film, after the fixing process. Preferred to carry out. [0080] In the present invention, it is 10 times or more and 100 times or less in terms of mass with respect to developed silver obtained by exposing and developing a metal amount-sensitive material provided by physical development or metal plating. Some embodiments are preferred. This value can be determined by quantifying the metal contained in the light-sensitive material by, for example, fluorescent X-ray analysis before and after physical development or metal plating. The amount of metal applied by physical development or metal plating

If the developed silver obtained by exposing and developing the light-sensitive material is less than 10 times in terms of mass, the conductivity tends to decrease slightly. In addition, the transmittance tends to decrease due to metal deposition on unnecessary portions other than the conductive mesh pattern portion.

 [0081] In the present invention, the description of physical development or metal plating means that at least one of physical development or plating treatment is performed, and both physical development and metal plating may be included. In the present invention, it is preferable to perform both physical development and metal plating.

 [Oxidation treatment]

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

 [0083] As the treatment liquid used for the oxidation treatment, for example, a treatment method using an aqueous solution containing Fe (III) ions, hydrogen peroxide, persulfate, perborate, perphosphate, percarbonate, Using a treatment solution containing a conventionally known oxidant, such as a method of treatment with an aqueous solution containing peroxide such as peroxygen, rogenate, hypohalite, halogenate, or organic peroxide Can. Oxidation is an aspect that is performed between the end of the development process and before the plating process. This is preferable because the transmittance can be improved efficiently in a short time, and the physical development is particularly preferable. This is a mode to be performed later.

 [Configuration of electromagnetic wave shielding layer]

In the present invention, in order to provide high translucency and high electromagnetic wave shielding performance, a conductive mesh pattern can be formed by drawing a lattice-like fine line pattern by exposure and then performing development processing or the like. preferable. The line width of the conductive metal part is 20 m or less. The interval is preferably 50 / zm or more. The conductive metal part may have a part with a line width larger than 20 m for the purpose of ground connection or the like. From the viewpoint of making the image inconspicuous, the line width of the conductive metal part is preferably less than 18 μm, less than 15 μm, more preferably less than 14 m, and even more preferably less than 10 m. The preferred value is less than 7 μm.

 [0085] The conductive metal part of the present invention has an aperture ratio of preferably 85% or more, more preferably 90% or more, and most preferably 90% or more from the viewpoint of visible light transmittance. The aperture ratio is the ratio of the portion without fine lines forming the mesh to the whole. For example, the aperture ratio of a square lattice mesh with a line width of 10 / ζ πι and a pitch of 200 μm is 90%.

 In the present invention, it is also preferable to provide a photosensitive halogen silver halide emulsion layer on both sides of the support and to form a conductive pattern on each. In this case, it is preferable that the halogen silver halide emulsion coated on each surface has a sensitivity at different wavelengths by spectral sensitization. By giving sensitivity to different wavelengths on the front and back surfaces, it becomes possible to create different conductive patterns on each surface, for example, to selectively shield against electromagnetic waves of different frequencies on the front and back surfaces. It is also possible to form a conductive pattern.

 [Functional layer other than electromagnetic wave shielding layer]

 When the electromagnetic wave shielding film of the present invention is used in combination with, for example, an optical filter for a plasma display panel (PDP), a near-infrared absorbing layer that is a layer containing a near-infrared absorbing dye under a halogenated silver particle layer. It is also preferable to set up. In some cases, the near-infrared ray absorbing layer may be provided on the opposite side of the support from the side where the halogen silver halide particle layer is present, or may be provided on both the side opposite to the halogen silver halide particle layer side. . A near-infrared absorbing layer may be provided between the silver halide grain layer containing silver halide and the support, or a near-infrared absorbing layer may be provided on the opposite side of the support as viewed from the silver halide grain layer. Yes, the former is preferred because it can be applied to one side of the support at the same time.

[0088] Specific examples of near-infrared absorbing dyes include polymethine, phthalocyanine, naphthalocyanine, metal complex, aminium, imonium, dimonium, anthraquinone, dithiol metal complex, naphthoquinone, indole phenol , Azo, tria Examples include rilmethane-based compounds. The PDP optical filter is required to have near-infrared absorptivity mainly for heat ray absorption and prevention of noise in electronic equipment. For this purpose, a metal complex, amidium, phthalocyanine, naphthalocyanine, dim-humic dye that has a maximum absorption wavelength of 750-: L lOOnm is preferred. Particularly preferred is a sulfur compound system.

 [0089] As the near-infrared absorbing dye, di-moum compounds are IRG-022, IRG-040 (the trade name of Nippon Gyaku Co., Ltd.), nickel dithiol complex compound is SIR- 128, SIR-130, SIR-132, SIR-159, SIR-152, SIR-162 (above, product names manufactured by Mitsui Chemicals Co., Ltd.), phthalocyanine compounds are IR-10, IR-12 (above Commercial products such as Nippon Shokubai Co., Ltd.) can be used.

 [0090] The near-infrared absorbing dye includes 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. As an addition amount, it is preferable to use the fine particles with an average particle size of 0.01 to 10; ζ ΐη by using a micronizing machine described later, and the optical density is 0.05 to 5 at the maximum wavelength. 3. It is preferable to use in the range of 0 concentration.

 [0091] When a colorant having a near-infrared absorbing ability is contained in the color tone correction layer, either one of the above dyes may be contained, or two or more kinds may be contained. Oh ,.

 [0092] When the electromagnetic wave shielding material of the present invention is used in combination with, for example, an optical filter for a plasma display panel (PDP), this is used to prevent a decrease in color reproducibility due to emission of neon gas used in the PDP. As a countermeasure, an embodiment containing a dye that absorbs light at around 595 nm is preferable. Specific examples of dyes that absorb such specific wavelengths include, for example, azo, condensed azo, phthalocyanine, anthraquinone, indigo, perinone, perylene, dioxazine, and quinacridone. Well-known organic pigments such as methine series, isoindolinone series, quinophthalone series, pyrrole series, thioindigo series and metal complex series, organic dyes, and inorganic pigments. Of these, phthalocyanine and anthraquinone dyes are particularly preferably used because of their good weather resistance.

[0093] When the electromagnetic wave shielding material of the present invention is used for the purpose of protecting a display screen, etc. It is preferable to provide an antireflection layer. As the antireflection layer, metal oxides, fluorides, halides, borides, carbides, nitrides, sulfides, and other inorganic materials such as vacuum deposition, sputtering, ion plating, ion beam assist, etc. A method of laminating thin films in a single layer or multiple layers, a method of laminating thin films of different refractive indexes such as acrylic resin, fluorine resin, etc. into a single layer or multiple layers can be used.

 [0094] In the present invention, an antireflection layer is formed on the opposite side of the transparent electromagnetic wave shielding film with the support of the film sandwiched between the layer having the conductive pattern! In such a case, it is preferable to form an antireflection layer first, then attach a protective film, and then form a conductive pattern layer. When the antireflection layer is formed after the conductive pattern is formed first, the efficiency of the plasma treatment and corona treatment performed to improve the adhesion between the antireflection layer and the support tends to decrease. An embodiment in which the layer is formed first is preferred. In addition, in the case where the antireflection layer is formed first, from the viewpoint of preventing the layer from being deteriorated by development, sticking processing, etc., an aspect in which the conductive pattern layer is formed after pasting a protective film in advance. Is preferred ヽ.

 [0095] The protective film used in the present invention is capable of using a commercially available protect film. A viewpoint of facilitating coating of a photosensitive silver halide emulsion layer for forming a conductive pattern. Therefore, the thickness of the film is preferably 10 m or more and 100 m or less, particularly preferably 20 μm or more and 60 μm or less. If the thickness is less than 10 μm, the film rigidity will be significantly reduced, so the work efficiency of the protection film will be reduced. If it is thicker than 100 m, troubles such as winding-up will occur when winding the film. It is because it becomes easy to do.

[0096] The type of pressure-sensitive adhesive used for the protective film is not particularly limited, but it is preferable to use one that does not alter the antireflection film and does not damage the antireflection film during peeling. From such a viewpoint, an acrylic or silicone adhesive is preferably used. Further, the adhesive strength is preferably 0.008-0.6NZ25mm.

 Example

[0097] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Absent. In the examples, “part” or “%” is used as a force to indicate “part by mass” or “% by mass” unless otherwise specified.

 [0098] Example 1

 (Preparation of EMP-1)

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

 [0099] (Aim)

 Potassium bromide 104g

 Potassium iodide 3. Og

 1300ml with water

 (B1 solution)

 Silver nitrate 150g

 1360ml with water

 (C1 liquid)

 Potassium bromide 310g

To Kisakuro port iridium (IV) potassium 4 X 10- ⁸ Monore

To Kisashiano iron (II) potassium 2 X 10- ⁵ moles

 Potassium iodide 10g

 4000ml with water

 (D1 solution)

 Silver nitrate 480g

 4200ml with water

After the soaking process, desalting was performed using a 5% aqueous solution of Demol N made by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.04 m and particle size distribution. A silver halide emulsion EMP-1 having a coefficient of variation of 0.13 was obtained. [0100] (Preparation of EMP-2 to EMP-3)

 In the preparation of EMP-1, the average particle size was set to 0, except that (A1 solution) and (B1 solution) were added and (C1 solution) and (D1 solution) were added at a temperature of 40 ° C. 07 ^ m, Halogenous silver emulsion EMP-2 with a coefficient of variation of 0.14, and an average particle size of 0.12 m, a coefficient of variation of the particle size distribution of 0.13. Of silver halide emulsion EMP-3 was obtained.

 [0101] (Preparation of EM— 1)

 EMP-1 is chemically sensitized with 2. Omg of sodium thiosulfate per mol of silver halide at 40 ° C for 80 minutes, and after completion of chemical sensitization, 4-hydroxy-6-methyl-1, 3, 3a, 7-tetrazaindene (TAI) was added in an amount of 500 mg per mole of silver halide to obtain a silver halide silver emulsion EM-1.

 [0102] (Preparation of EM-2 to EM-3)

 For the preparation of EM-1, the silver halide emulsion was changed from EMP-1 to EMP-2 and EMP-3, and the amount of sodium thiosulfate and TAI added was adjusted to the total surface of the silver halide grains. Similarly, except for adjusting in proportion to the product, Halogenous silver emulsions EM-2 and EM-3 were obtained, respectively.

 [0103] (Production of photosensitive materials 101 to 117)

 On a 180 μm-thick polyethylene terephthalate film support with an undercoat layer, the silver halide emulsions EM-1 to EM-3 prepared as described above were prepared as shown in Table 1. Coating was performed so that the amount of gelatin was the same, and then drying was performed to produce photosensitive materials 101 to 117. In the preparation of each light-sensitive material, a hardener (H-1: tetrakis (bulusulfol-methyl) methane) was added at a ratio of 50 mg per lg of gelatin. As a coating aid, a surfactant (SU-2: di (2-ethylhexyl sulfosuccinate) • sodium) was added to adjust the surface tension. In Table 1, the amount of silver is shown as a value obtained by converting the amount of the halogeno silver emulsion used to equimolar silver.

[0104] [Table 1] Silver halide

 Cefno δ

 Photosensitive material Silver amount ζ grain size Remarks

 Type (9 / η)

 101 EM- 1 0.03 0.007 0.75 Comparative example

 102 EM- 1 0.07 0.015 1.8 The present invention

 103 EM— 1 0.2 0.043 5.0 The present invention

 104 EM— 1 0.5 0.108 13 The present invention

 105 EM- 1 0.7 0.152 18 The present invention

 106 EM- 1 0.9 0.195 23 The present invention

 107 EM- 1 1.2 0.260 30 Comparative example

 108 EM- 1 0.5 0.070 13 The present invention

 109 EM- 1 0.5 0.100 13 The present invention

 no EM- 1 0.5 0,150 13 The present invention

 111 EM— 1 0.5 0.18 3 The present invention

 112 EM-2 0.03 0.10 0.43 Comparative example

 113 EM— 2 0.5 0.10 7,1 Present invention

 ! H EM- 2 1, 2 0.10 17 Comparative example

 115 EM— 3 0.03 0.10 0.25 Comparative example

 Π6 EM-3 0.5 0.10 4.2 The present invention

 Π7 EM— 3 1.2 0.10 10 Comparative example

[0105] (Preparation of transparent electromagnetic wave shielding films S101 to S117)

 After the photosensitive materials 101 to 117 manufactured as described above are exposed using an ultraviolet lamp through a grid-like photomask having a line width of 10 / ζπι and a distance between lines of 240 m. After developing for 60 seconds at 25 ° C using the following developer (DEV-1), fix for 120 seconds at 25 ° C using the following fixer (FIX-1). , And then washed with water. Furthermore, using the following physical developer (PD-1), physical development was performed at 25 ° C for 300 seconds, followed by washing with water. Then, after immersing in a Pd catalyst solution (CAT-1) at 25 ° C for 30 seconds, it is washed with water and further treated with electroless copper plating at 45 ° C using a plating solution (PL-1). Second, transparent electromagnetic wave shielding films S101 to S117 were produced.

[0106] (DEV—1: Developer)

 500ml of pure water

 Metol 2g

 Anhydrous sodium sulfite 80g

Hydroquinone 4g Borax 4g Sodium thiosulfate 10g Potassium bromide 0.5g Add water to make 1 liter

 (FIX-1: Fixer)

 Pure water 750ml Sodium thiosulfate 250g Anhydrous sodium sulfite 15g Glacial acetic acid 15ml Potassium bromide 15g Add water to bring the total volume to 1 liter

 (PD-1: Physical developer)

 Pure water 800ml Quenic acid 5g Hydroquinone 7g Silver nitrate 3g Add water to make 1 liter.

 (CAT-l: Pd catalyst solution)

 Add 20 mg of palladium sulfate to make a total volume of 1 liter.

[0107] (PL-1: Plating solution)

 Copper sulfate 0.04 Monoform formaldehyde (37%) 0.08 mol Sodium hydroxide 0.10 mol 卜 Diethanola 0.05 mol Polyethylene glycol lOOppm Add water to bring the total volume to 1 liter.

[0108] (Evaluation of transparent electromagnetic wave shielding films S101 to S117) For each of the transparent electromagnetic wave shielding films S101 to S117 having a conductive metal mesh portion obtained in this way, the surface specific resistance value and the transmittance were respectively measured with a resistivity meter (mouth rester GP (MCP— T610 type): Measured using Dia Instruments Ltd. and a spectrophotometer (Hitachi spectrophotometer U-3210: manufactured by Hitachi, Ltd.). For transparent electromagnetic wave shielding films S101 to S117, left in a constant temperature and humidity chamber at 60 ° C 90% RH for 24 hours, left in a constant temperature and humidity chamber at 80 ° C 20% RH, and further 10 A forced deterioration test with 15 cycles of standing in a constant temperature and humidity chamber at 50 ° C at 50 ° C is conducted for 15 cycles, and the transmittance after forced deterioration is compared to the transmittance before forced deterioration. The ratio was calculated. In addition, the state of the film after storage was visually observed, and “generation of cracks after storage” was evaluated according to the following criteria, and used as a measure of film vulnerability.

 [0109] ○: Even when the film is rolled, no cracks are observed.

 Δ: No cracks are observed when placed on a flat surface, but cracks are observed when the film is rolled.

 X: Generation of cracks in the film is observed when placed on a flat surface.

 [0110] Regarding whether or not film peeling occurred from the edge portion of the film during cutting of each sample, 10 films of each level were observed, and the number of film peeling portions was counted. The results are shown in Table 2.

[0111] [Table 2]

Electromagnetic wave transmittance table!] Specific resistance ΪΛ Evaluation after forced degradation test

 '

 Barrier film (%) (Ω / Π) Permeability change film

 S 101 81 8.5 95 〇 0 Comparative example

S 102 81 0.45 95 ○ 0 Present invention

S 103 81 0.35 93 o 0 The present invention

S S 04 81 0.25 90 o 0 The present invention

S 105 81 0. 15 86 〇 0 Present invention

S 106 80 0. 12 83 ○ 1 Present invention

S 107 77 0.09 73 X 8 Comparative example

S 108 81 0.35 92 Δ 0 The present invention

S 109 81 0.4 90 Δ 0 The present invention

S 1 10 80 0.5 87 O 0 The present invention

S 1 1 1 80 0.55 82 ○ 0 Present invention

S 1 1 2 81 1 1 90 o 0 Comparative example

S 1 1 3 81 0.85 89 Δ 0 The present invention

S 1 14 77 0.6 88 X 0 Comparative example

S 1 1 5 81 15 91 O 0 Comparative example

S 1 16 81 0.9 90 Δ 0 The present invention

S 1 17 77 0 .65 89 X 0 Comparative example

[0112] From the results of Table 2, the transparent electromagnetic wave shielding films S102 to S106, SI 08 to S111, S113 and S116 satisfying the requirements of the present invention have high transmittance and low surface resistivity, and after forced degradation test It is obvious that the effect of the present invention can be obtained that the degree of deterioration of the film brittleness is small when the transmittance change of the film is small. In particular, the value obtained by dividing the coating silver amount (gZm ² ) by the particle size (μm) is in the range of 6 to 25 [this transparent electromagnetic wave shielding Finolem S104 to S106, S108 to S111, and S113 are the same photosensitive halogen compounds. Compared with other transparent electromagnetic wave shielding films using a silver halide emulsion, the coating of the edge partial force at the time of cutting has almost no peeling and a low surface specific resistance, indicating that this is a preferred embodiment of the present invention.

[0113] Example 2

 Table 3 shows the immersion time in the Pd catalyst solution (CAT-1) and the immersion solution (PL-1) in the transparent electromagnetic wave shielding films S101, S105, and S107 produced in Example 1. Transparent electromagnetic wave shielding films S201 to S209 were produced in the same manner except for changing to.

[0114] In the production of the transparent electromagnetic wave shielding films S201 to S209, the amount of developed silver after the development of silver halide was completed at the stage when (DEV-1), (FIX-1) and water washing were completed. Quantitatively by X-ray fluorescence analysis, and after the processing of (PD-1), (CAT-1) and (PL-1) is completed, X-ray fluorescence analysis is performed again, and the amount of physical developed silver and copper The amount of adhesion was quantified. Using the amount of metal thus determined, the ratio of the amount of metal imparted by physical development or metal plating to the amount of developed silver obtained by exposing and developing the photosensitive material was determined as a mass ratio.

 [0115] The transparent electromagnetic wave shielding films S201 to S209 thus produced were evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0116] [Table 3]

[0117] From the results in Table 3, the amount of metal imparted by physical development and metal plating is less than 10 times in terms of mass with respect to developed silver obtained by exposing and developing the photosensitive material. The transparent electromagnetic wave shielding film S201 has high transmittance and low! / Surface specific resistance, but is 10 times or more in terms of mass, compared with other transparent electromagnetic wave shielding films according to the present invention. As a result, the surface resistivity was slightly high. In addition, the transparent electromagnetic wave shielding film S205 in which the amount of metal applied by physical development and metal plating is 100 times greater than the developed silver obtained by exposing and developing the photosensitive material in terms of mass is: Although high transmittance, low V, and surface specific resistance were obtained, it was less than 100 times in terms of mass, resulting in slightly lower transmittance than other transparent electromagnetic wave shielding films according to the present invention. . The amount of the metal that satisfies the requirements of the present invention and is imparted by physical development and metal plating is used for the photosensitive material. The transparent electromagnetic wave shielding films S105 and S202 to S204, which are 10 times to 100 times in terms of mass with respect to developed silver obtained by exposure and development processing, have particularly high transmittance and low surface resistivity. It can be seen that this is a preferred embodiment of the present invention.

 In addition, the electromagnetic wave shielding films S208 and S209 produced using the photosensitive material 107 that does not satisfy the constituent requirements of the present invention, like S107, were found to have cracks in the coating after the forced deterioration test and were inferior in brittleness.

[0118] Example 3

 In the production of the transparent electromagnetic wave shielding films S 106 and S 110 prepared in Example 1, the following acid solution (OX-1) was used for 45 seconds at 45 ° C for 120 seconds between physical development and Pd catalyst treatment. Transparent electromagnetic wave shielding films S301 and S302 were prepared in the same manner except that the acid-soaking treatment was performed. In addition, S106, S107, S301 and S302 were prepared. After finishing the treatment with the plating solution (P L-1), use the following black solution (BP-1) at 80 ° C for 120 seconds. Transparent electromagnetic wave shielding films S303 to S306 were produced in the same manner except that the blackening treatment was performed. Evaluation similar to Example 1 was implemented with respect to the transparent electromagnetic wave shielding films S301-S306 obtained in this way. In addition, the transparent electromagnetic wave shielding film with the conductive pattern side down was placed on black paper and the opposite surface force film was observed to confirm whether metallic gloss reflection was observed. The results are shown in Table 4.

[0119] (OX-1: oxidation solution)

 Ferricyan 匕 potassium 0.lg

 Add water to bring the total volume to 1 liter.

[0120] (BP—1: Black 匕 treatment solution)

 Sodium chlorite aqueous solution (76%) 40g

 Sodium hydroxide 5g

 Add water to bring the total volume to 1 liter.

[0121] [Table 4] After the observation of the strong relative permeability,

 (Nor Sawam 1Ω0X 1BP rate-variable permeability permeable fl membrane weakening

_) And

 〇 〇

 Light

From the results in Table 4, it can be seen that the transparent electromagnetic wave shielding films S301, S302, S305 and S306 subjected to the oxidation treatment can obtain particularly high transmittance and are preferable embodiments of the present invention. In addition, the transparent electromagnetic wave shielding films 303 to S306 treated with black glazing are not only capable of achieving both high transmittance and low surface resistivity, but also the metal reflection gloss of the conductive pattern is inconspicuous. Sometimes the visibility is low and high quality It can be seen that the transparent electromagnetic wave shielding film is particularly preferable.

[0123] Example 4

 Preparation of photosensitive silver halide emulsions EM-1G and EM-1R

In the preparation of the light-sensitive halogenated silver emulsion EM-1 prepared in Example 1, sensitizing dye SD-1 or SD-2 was added to each mole of silver halide 1 mol after completion of chemical sensitization and before adding TAI. except for using添Ka卩so that per 3 X 10- ⁴ mole in the same manner, green-sensitive silver halide emulsion EM-1G, and the red-sensitive Harogeni匕銀emulsion EM-1R manufactured.

[0124] [Chemical 1]

[0125] Production of photosensitive material 401

 Coating was performed in the same manner as in the preparation of the photosensitive material 105 prepared in Example 1, except that the photosensitive halogenated silver halide emulsion was changed from EM-1 to EM-1G. After drying, the photosensitive material is coated on the back side of the photosensitive material using the same coating solution except that the photosensitive halogen silver emulsion is changed to EM-1G for EM-1G. Double-sided photosensitive material 401 having

 [0126] In the photosensitive material 401 produced in this manner, green and red laser beams were subjected to separate no-turn exposure on the front and back surfaces with different line widths and line intervals, followed by development, physical development, and plating. A transparent electromagnetic wave shielding film S401 in which different conductive patterns were formed on the front and back surfaces was prepared.

[0127] In this way, using the spectrally sensitized halogen silver halide emulsion, the front and back surfaces of the support were each different. By forming a layer containing a photosensitive silver halide emulsion having a color sensitivity, an electromagnetic wave shielding layer having different properties can be obtained by preparing different electromagnetic wave shielding patterns on the front and back surfaces. A plurality of films can be provided on a sheet of film, which is a preferable aspect of the present invention.

 [0128] Example 5

In the preparation of the photosensitive material 105 prepared in Example 1, 1 part by mass of the UV absorber (UV-1) was mixed with 20 parts by mass of polyvinyl acetal (Esreck BM-S: Sekisui Chemical Co., Ltd.) and ethyl acetate Z Photosensitive material was the same except that a polyethylene terephthalate support coated with UV — 1 at 0.2 g / m ² after being dissolved in a methyl ethyl ketone mixed solvent (mixing ratio 2: 1) was used. 501 was produced, and transparent electromagnetic wave shielding film S501 was produced using the same method as transparent electromagnetic wave shielding film S105.

[0129] [Chemical 2]

UV-1

[0130] The same evaluation as in Example 1 was performed on the transparent electromagnetic wave shielding film S501 thus obtained. In addition, using a Xe fade meter, light was irradiated for 24 hours at 71 X in an environment of 24 ° C 60% RH, and the ratio of the transmittance after forced deterioration to the transmittance before forced deterioration was obtained. Similar to Example 1, “generation of cracks after storage” was evaluated and used as a measure of durability.

 [0131] The results are shown in Table 5.

[0132] [Table 5]

[0133] From the results shown in Table 5, the transparent electromagnetic wave shielding film S501 having at least one ultraviolet absorbing layer has improved durability of the coating film against light irradiation, and is a particularly preferred embodiment of the present invention. I know that there is.

 [0134] Example 6

 Preparation of antireflection film (AR— 1)

Preparation of antireflection film No. 14 described in Example 1 of JP-A-2005-338550 In this case, the support was changed from a cellulose ester film to a polyethylene terephthalate film (thickness 180 m), and the backcoat layer was <A-1> described in Example 1 of JP-A-10-039448, Using the <A-2> solution, a layer with a dry film thickness of 0.8 m is provided using the <A-1> solution on the side close to the support, and the dry film using the A-2> solution is provided on the outermost layer. An antireflection film AR-1 was prepared in the same manner except that a 0.1 m thick layer was applied.

[0135] Preparation of transparent electromagnetic wave shielding films S601 to S603

 After the protective film as shown in Table 6 was attached to the antireflection processed surface side of the antireflection film AR-1 produced in this way, the same procedure as in the production of the transparent electromagnetic wave shielding film S105 of Example 1 was made on the back side. The transparent electromagnetic wave shielding films S601 to S603 were produced.

 [0136] Preparation of transparent electromagnetic wave shielding film S604

 A transparent electromagnetic wave shielding film S640 was prepared by providing an antireflection layer on the back surface of the transparent electromagnetic wave shielding film S105 produced in Example 1 by the same method as in the production of the above-described antireflection film (AR-1).

 [0137] The transparent electromagnetic wave shielding films S601 to S604 thus obtained were evaluated in the same manner as in Example 1. Further, the state of the antireflection layer after completion of the transparent electromagnetic wave shielding film was visually observed. The results are shown in Table 6.

[0138] [Table 6]

,

 Electromagnetic wave protect m

 Prevention of odds! Heat resistance, strong surface specific resistance; moisture degradation test surface ¾

 Anti-reflective state anti-blocking rufumflumyi permeability production forward permeation () film brittleness rate change% slightly over 09S L

 Z09S

 Invention & £ 09 S

 Invention 09S f

 Irregular warp unevenness

O ○ ○ o

m

 o o O

 oo

#i

 CM

 _i

 1 1

Protective film (PF-l): Sumilon EC-700

 Protective film (PF-2): Hitachi Chemical Co., Ltd. L 5030

From the results in Table 6, the transparent electromagnetic wave shielding films S601 to S604 according to the present invention all show high transmittance and low surface resistivity, and the transmittance change after the forced deterioration test is small. Although the effect of the present invention is small, the conductive pattern is particularly important. A transparent electromagnetic wave having an antireflection layer on the opposite side of the film support with respect to the layer having a turn, and after forming the antireflection layer, bonding the protective film, and then forming the conductive pattern layer The shielding films S602 and S603 are a preferable embodiment of the present invention that can provide a transparent electromagnetic wave shielding film having a good antireflection layer without causing occurrence of uneven reflection in the antireflection layer and occurrence of an antireflection function. I understand.

Claims

The scope of the claims

[1] In a transparent electromagnetic wave shielding film produced by subjecting a photosensitive material having a layer having at least a photosensitive halogen silver and a binder force on a support to a development treatment after exposure, the photosensitive halogen silver in the photosensitive material is produced. A transparent electromagnetic wave shielding film, wherein the silver content is 0.05 g / m ² or more and less than 1 gZm ^{2 in} terms of silver, and the amount of the binder is lOmgZm ² or more and 0.2 gZm ² or less.

[2] The transparent electromagnetic wave shielding film is subjected to physical development or metal plating after exposure and development treatment, and the amount of metal imparted by physical development or metal plating is obtained by exposing and developing the photosensitive material. 2. The transparent electromagnetic wave shielding film according to claim 1, which is 10 to 100 times in terms of mass relative to the developed silver amount.

[3] To the transparent electromagnetic wave shielding film! The value obtained by dividing the silver halide content (gZm ² ) by the average grain size (μm) of the silver halide is 6 or more and 25 or less. 2. The transparent electromagnetic wave shielding film according to item 2.

[4] The transparent electromagnetic wave shielding film according to any one of claims 1 to 3, wherein the transparent electromagnetic wave shielding film is subjected to an oxidation treatment after exposure and development.

 [5] The transparent electromagnetic wave shielding film according to any one of claims 1 to 4, wherein the transparent electromagnetic wave shielding film is blackened after exposure and development processing. .

 [6] The force according to any one of claims 1 to 5, wherein the transparent electromagnetic wave shielding film is spectrally sensitized with photosensitive silver halide grains. Transparent electromagnetic wave shielding film.

 [7] The transparent electromagnetic wave according to any one of [1] to [6], wherein the transparent electromagnetic wave shielding film has at least one ultraviolet absorbing layer. Barrier film.

[8] The transparent electromagnetic wave shielding film according to any one of claims 1 to 7, wherein the transparent electromagnetic wave shielding film has different conductive patterns on both surfaces sandwiching the support of the film. Any of 2. The transparent electromagnetic wave shielding film according to item 1.

[9] The transparent electromagnetic wave shielding film has an antireflection layer on the opposite side of the layer having the conductive pattern with respect to the layer having the conductive pattern, and after forming the antireflection layer, the protective film is bonded together. The transparent electromagnetic wave shielding film according to any one of claims 1 to 7, wherein a conductive pattern layer is formed thereafter.

[10] A method for producing a transparent electromagnetic wave shielding film according to any one of claims 1 to 9, wherein the intensifying treatment is applied to the developed silver obtained by exposure and development. A method for producing a transparent electromagnetic wave shielding film characterized by being applied.