JP5337342B2 - Translucent electromagnetic shielding film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a translucent electromagnetic-wave shielding film for a touch panel of a liquid-crystal display device which has high conductivity and is excellent in surface physical strength. <P>SOLUTION: The translucent electromagnetic-wave shielding film for a touch panel of a liquid-crystal display device keeps a thin-line pattern, made of a conductive metal including developed silver carried a support. The film is a translucent electromagnetic-wave shielding film for a touch panel, particularly, whose thin-line pattern has a scratching strength which exceeds HB. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a translucent electromagnetic wave shielding film for a touch panel.

Various materials that transmit light and have conductivity are known, and various materials are also used in the industry. As so-called transparent conductive films, those using inorganic metal oxides such as tin oxide (SnO ₂ ), ITO (tin-doped indium oxide), ATO (antimony-doped tin oxide) and the like are well known. A transparent conductive polymer is also well known as one of transparent conductive films.
Patent Document 1 discloses a touch panel having an electromagnetic wave shielding film made of a transparent conductive film, but the conductivity is 30Ω / □ level. In recent years, the display and the touch panel laminated thereon have been increased in size, and the generation of electromagnetic waves from the display panel has increased. Accordingly, there is an increasing demand for electromagnetic shielding materials. In particular, there are increasing demands on the conductivity, durability, strength, and the like of electromagnetic shielding materials used for liquid crystal display devices mounted on aircraft and attached touch panels.

On the other hand, there is also known a material capable of transmitting light by forming a conductive metal material into a thin line shape and providing an opening that transmits light. For example, if a mesh-like metal layer is formed on a transparent substrate and the opening without metal is widened to transmit light and the metal mesh has a very fine shape, the mesh is visually observed. It becomes a translucent conductive substrate in which it is difficult to recognize the presence of the shape. As an example of such a material, a copper mesh for use in electromagnetic wave shielding for plasma display panels disclosed in Patent Document 2 is known. In particular, a material obtained by etching a copper foil is frequently used, but such a material is high in terms of conductivity, but has a problem of low scratch strength and has been desired to be improved.
JP 2006-92031 A JP 2003-46293 A

The patent document described in the previous section (background art section) discloses a technique that meets each purpose, but also has a problem that requires the above-described improvement.
The present invention has been made in view of such circumstances, and the object of the present invention is as follows.
1stly, providing the translucent electromagnetic wave shielding film for touchscreens of a liquid crystal display device which has high electroconductivity.
Second, to provide a translucent electromagnetic wave shielding film for a touch panel of a liquid crystal display device having high scratch strength.
3rdly, providing the translucent electromagnetic wave shielding film of the touchscreen for liquid crystal display devices with few disconnections.
4thly, providing the touchscreen and liquid crystal display device which comprise the above-mentioned electromagnetic wave shielding film.

The object of the present invention is achieved by the following items [1] to [ 5 ].
[1]. A support having thereon fine line patterns made of a conductive metal containing developing silver, between the support and the fine line pattern, crosslinked with an epoxy compound or a carbodiimide compound, and is more formed acrylic resins Easy adhesion layer is laminated ,
The fine line pattern further contains gelatin;
A translucent electromagnetic wave shielding film for a touch panel of a liquid crystal display device, wherein the support is a plastic film made of polyethylene terephthalate (PET) as a raw material .
[ 2 ]. The translucent electromagnetic wave shielding film as described in [ 1 ] above, wherein the width of the fine line of the fine line pattern is 1 μm or more and 30 μm or less.
[ 3 ]. The translucent electromagnetic wave shielding film as described in [1] or [2] above, wherein the metal thickness of the fine line pattern is from 0.2 μm to 30 μm.
[ 4 ]. The light-transmitting electromagnetic wave shielding film according to any one of [1] to [ 3 ], wherein the conductive metal of the fine line pattern has a blackened layer.
[ 5 ]. The translucent electromagnetic wave shielding film according to any one of [1] to [ 4 ], wherein the liquid crystal display device is an aircraft-mounted liquid crystal display device .
The present invention relates to the items [1] to [ 5 ] above, but other matters are also described for reference.
1. A translucent electromagnetic wave shielding film for a touch panel of a liquid crystal display device, comprising a thin line pattern made of a conductive metal containing developed silver on a support.
2. 2. The translucent electromagnetic shielding film for a touch panel of the liquid crystal display device according to the above 1, wherein the fine line pattern has a scratch strength of HB or more.
3. 3. The translucent electromagnetic wave shielding film for a touch panel of the liquid crystal display device according to the above 1 or 2, wherein the rate of change in surface resistance after scratching the fine line pattern surface with an HB pencil is within 2 times.
4). 4. The translucent electromagnetic wave shielding film for a touch panel of a liquid crystal display device according to any one of the above 1 to 3, wherein the fine line pattern is disconnected at 5 or less per 1 m ² .
5. The translucent electromagnetic wave shielding film for a touch panel of a liquid crystal display device according to any one of the above 1 to 4, wherein the fine line pattern is disconnected at 2 or less per 1 m ² .
6). 6. The translucent electromagnetic wave shielding film as described in any one of 1 to 5 above, wherein the width of the fine line of the fine line pattern is 1 μm or more and 30 μm or less.
7). 7. The translucent electromagnetic wave shielding film as described in any one of 1 to 6 above, wherein the fine wire pattern has a metal thickness of 0.2 μm or more and 30 μm or less.
8). 8. The translucent electromagnetic wave shielding film as described in any one of 1 to 7 above, wherein the conductive metal of the fine line pattern has a blackened layer.
9. 9. The translucent electromagnetic wave shielding film as described in any one of 1 to 8 above, wherein the liquid crystal display device is an aircraft-mounted liquid crystal display device.

  ADVANTAGE OF THE INVENTION According to this invention, the translucent electromagnetic wave shielding film for touchscreens for liquid crystal display devices which has high electroconductivity can be provided. Moreover, the translucent electromagnetic wave shielding film for touchscreens for liquid crystal display devices which has high scratch strength can be provided. Moreover, the translucent electromagnetic wave shielding film for touchscreens for liquid crystal display devices with few disconnections can be provided. Furthermore, the touch panel and liquid crystal display device which comprise the above-mentioned electromagnetic wave shielding film can be provided.

  The present invention is described in further detail below. In the present specification, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.

(1) Support As the support for the photosensitive material used in the present invention, a plastic film, a plastic plate, a glass plate, or the like can be used.
Examples of raw materials for the plastic film and plastic plate include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polyolefins such as polyethylene (PE) and polypropylene (PP); polyvinyl chloride, polyvinylidene chloride and the like. Vinyl resin: polystyrene, EVA, others, polyetheretherketone (PEEK), polysulfone (PSF), polyethersulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetylcellulose (TAC) Etc. can be used.
The support used in the present invention is preferably a polyethylene terephthalate film or triacetyl cellulose (TAC) among the plastic films from the viewpoints of transparency, heat resistance, ease of handling and price.

Since an electromagnetic wave shielding material for a display device such as a display or a touch panel requires transparency, it is desirable that the support has high transparency. In this case, the total visible light transmittance of the plastic film or plastic plate is preferably 70 to 100%, more preferably 85 to 100%, and particularly preferably 90 to 100%. Moreover, in this invention, what was colored to such an extent that the objective of this invention is not disturbed can also be used as the said plastic film and a plastic board.
The plastic film and plastic plate in the present invention can be used as a single layer, but can also be used as a multilayer film in which two or more layers are combined.

  When a glass plate is used as the support in the present invention, the type thereof is not particularly limited, but when used for an electromagnetic shielding film for a display device such as a display, it is preferable to use tempered glass having a tempered layer on the surface. There is a high possibility that tempered glass can prevent breakage compared to glass that has not been tempered. Furthermore, the tempered glass obtained by the air cooling method is preferable from the viewpoint of safety because even if it is broken, the crushed pieces are small and the end face is not sharp.

(2) Fine wire pattern (metal fine wire pattern) made of developed silver and a conductive metal containing developed silver.
The developed silver used in the present invention refers to metallic silver obtained by chemically developing silver halide grains by silver salt photography. The developed silver is obtained by chemical development and is an aggregate of filamentous metallic silver or an aggregate of metallic silver in which filamentous metallic silver is bonded and fused together.
As a method for obtaining developed silver, generally well-known principles and methods of silver salt photography can be used. For example, a method described in Japanese Patent Application Laid-Open No. 2004-221564 can be used.
Further, since the developed silver can be made sufficiently conductive to be used as a cathode for electrolytic plating, the developed silver can be electrolytically plated. Further, the developed silver can be used as an electroless plating catalyst, and it is also preferable to apply electroless plating to the developed silver. Therefore, the metal constituting the fine line pattern made of the conductive metal in the present invention may be made of only silver, and in addition to developed silver, various metals such as copper, nickel, zinc, tin, cobalt, gold, platinum, palladium, etc. It may be made of any metal. In particular, copper is low in conductivity and inexpensive, and can be preferably used in the present invention together with silver.
The thickness of the fine line pattern can be appropriately changed depending on the use, but in order to obtain high conductivity, it is preferable to have a thickness of 0.2 μm or more. Since the pattern can be recognized when visually observed and there is a problem in the use of the electrode material of the display device, the thickness is more preferably 0.5 μm or more and 30 μm or less, and further preferably 1 μm or more and 20 μm or less. Even more preferably, it is 1 μm or more and 10 μm or less. Most preferably, they are 1 micrometer or more and 7 micrometers or less.
The line width of the fine line pattern can also be appropriately changed depending on the application. However, obtaining a thick line pattern is a problem for a material that transmits light. In the present invention, the line width is 1 μm or more and 30 μm or less. The fine line pattern is preferably. More preferably, they are 2 micrometers or more and 20 micrometers or less, More preferably, they are 4 micrometers or more and 18 micrometers or less.
As the translucent conductive base material, the ratio of the area of the fine metal wire pattern to the area of the planar translucent conductive base material, that is, the large aperture ratio is preferable for transmitting light. The aperture ratio is preferably 50% or more, more preferably 70% or more, still more preferably 80% or more, and most preferably 90% or more.
As the shape of the fine metal line pattern, various patterns can be selected according to the purpose. As an electromagnetic wave shielding material for display, a lattice-like fine metal wire pattern can be suitably used.

[Blackening layer]
The fine metal wire pattern of the present invention may be subjected to blackening treatment.
The blackening process is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-188576. The blackened layer formed even by the blackening treatment can impart antireflection properties in addition to the antirust effect. The blackened layer is formed by, for example, Co—Cu alloy plating, and can prevent reflection of the surface of the metal foil. Further, a chromate treatment may be performed thereon as a rust prevention treatment. The chromate treatment is performed by immersing in a solution containing chromic acid or dichromate as a main component and drying to form a rust preventive film. Alternatively, a plating method for providing a black film may be used.

  In general, the blackening treatment can be performed by electrolytic plating using a conductive metal compound, for example, a compound such as nickel (Ni), zinc (Zn), copper (Cu), or the like. It can be formed using a cationic ionic polymer material such as an electrodeposition coating material.

  In the present invention, the electrolytic solution bath (black plating bath) used for the blackening treatment can be a black plating bath mainly composed of nickel sulfate, and a commercially available black plating bath is similarly used. Specifically, for example, Shimizu Co., Ltd. black plating bath (trade name, Novroi SNC, Sn—Ni alloy system), Nippon Kagaku Sangyo Co., Ltd. black plating bath (trade name) , Nikka Black, Sn-Ni alloy system), black plating bath (trade name, Ebony-Chromium 85 series-85 series, Cr series) manufactured by Metal Chemical Co., Ltd., etc. can be used. Moreover, in this invention, various black plating baths, such as Zn type | system | group, Cu type | system | group, others, can be used as a black plating bath different from the above. Further, as a metal blackening treatment agent, it can be easily produced using a sulfide-based compound, and there are many kinds of treatment agents in commercial products. For example, trade names such as Copa-Black CuO, CuS, Selenium-based Copa Black No. 65 (made by Isolate Chemical Laboratories, Inc.), trade name, Ebonol C Special (made by Meltex Co., Ltd.), etc. can be used.

(3) Transparent conductive layer In the present invention, in addition to the fine metal wire pattern, a transparent conductive layer may be included. The transparent conductive layer is composed of conductive metal oxide particles or a conductive polymer, and includes a binder. You may have.
As the conductive metal oxide, tin oxide, tin oxide doped with antimony, indium and tin oxide (ITO), zinc oxide, tin oxide doped with fluorine, zinc oxide doped with gallium, etc. are used. It is done.
As the conductive polymer, polythiophenes, polypyrroles, polyanilines, and the like are used.
As a method for forming the transparent conductive layer, various physical methods such as sputtering, generally well-known coating methods such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, Various coating methods such as an extrusion coating method can be used.
When the support to be applied is a plastic film such as polyester, the easy-adhesion layer can be applied before sequential biaxial stretching of the plastic film, before simultaneous biaxial stretching, after uniaxial stretching and before re-stretching, or biaxial stretching. It can be done at any later time. The surface of the plastic support is preferably subjected to surface treatment such as ultraviolet irradiation treatment, corona discharge treatment, glow discharge treatment and the like in advance.

  As the binder used for the transparent conductive layer, acrylic resin, polyester resin, urethane resin, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin and the like can be used.

(4) Easy adhesion layer In this invention, it is preferable that the easy adhesion layer is laminated | stacked between the support body, the metal fine wire pattern, and / or the transparent conductive layer. The easy adhesion layer has a function of imparting / improving adhesion between the support and the fine metal wire and adhesion between the support and the transparent conductive layer.
The easily adhesive layer in the present invention has a swelling ratio of 100% or less. Here, the swelling ratio (%) is [(film thickness after 10 minutes of wetting with 25 ° C. water) − (film thickness when dried] )] / (Dry film thickness) × 100 The swelling rate of 0% means that the film does not swell at all even when wetted with water. The swelling rate of 100% means that the film is wetted with water. This means that the film thickness is doubled.

  As the material for forming the easy adhesion layer in the present invention, acrylic resin, vinyl resin, polyester resin, urethane resin, styrene butadiene rubber, gelatin and the like are used.

  Examples of the acrylic resin include acrylic acid esters such as acrylic acid and alkyl acrylate, methacrylic acid esters such as acrylamide, acrylonitrile, methacrylic acid, and alkyl methacrylate, and a single monomer of methacrylamide and methacrylonitrile. Examples thereof include a copolymer or a copolymer obtained by polymerization of two or more of these monomers. Among these, homopolymers of monomers of acrylic acid esters such as alkyl acrylates and methacrylic acid esters such as alkyl methacrylates, or copolymers obtained by polymerization of two or more of these monomers preferable. For example, mention may be made of homopolymers of monomers of acrylic acid esters and methacrylic acid esters having an alkyl group having 1 to 6 carbon atoms, or copolymers obtained by polymerization of two or more of these monomers. it can. The acrylic resin has the above composition as a main component and, for example, partially uses a monomer having any group of a methylol group, a hydroxyl group, a carboxyl group, and an amino group so that a crosslinking reaction with a carbodiimide compound is possible. The resulting polymer is preferred.

  Examples of the vinyl resin include polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl methyl ether, polyolefin, ethylene / butadiene copolymer, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, vinyl chloride / ( A meth) acrylic acid ester copolymer and an ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / (meth) acrylic acid ester copolymer) can be mentioned. Among these, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl formal, polyolefin, ethylene / butadiene copolymer and ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / acrylic acid ester copolymer) are used. preferable. The vinyl resin can be crosslinked with a carbodiimide compound so that, for example, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl methyl ether, and polyvinyl acetate leave a vinyl alcohol unit in the polymer. Thus, a polymer having a hydroxyl group can be obtained, and the other polymer can be a crosslinkable polymer by partially using a monomer having any of a methylol group, a hydroxyl group, a carboxyl group and an amino group. .

  Examples of the polyurethane resin include: (a) polyhydroxy compounds (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane), aliphatic polyester polyols obtained by reaction of polyhydroxy compounds and polybasic acids, polyether polyols (Eg, poly (oxypropylene ether) polyol, poly (oxyethylene-propylene ether) polyol), polycarbonate polyol, and polyethylene terephthalate polyol, or a mixture thereof and (b) polyurethane derived from polyisocyanate Can be mentioned. In the polyurethane resin, for example, the hydroxyl group remaining unreacted after the reaction between polyol and polyisocyanate can be used as a functional group capable of crosslinking reaction with a carbodiimide compound.

  As the polyester resin, generally used is a polymer obtained by reacting a polyhydroxy compound (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane) with a polybasic acid. In the above-mentioned polyester resin, for example, the hydroxyl group and carboxyl group remaining unreacted after the reaction between the polyol and the polybasic acid can be used as a functional group capable of crosslinking reaction with the carbodiimide compound. Of course, a third component having a functional group such as a hydroxyl group may be added.

  Among the above polymers, acrylic resins and polyurethane resins are preferable, and acrylic resins are particularly preferable.

The easy-adhesion layer of the present invention is preferably crosslinked with a crosslinking agent. Examples of the crosslinking agent include epoxy compounds and carbodiimide compounds.
Examples of the epoxy compound include 1,4-bis (2 ′, 3′-epoxypropyloxy) butane, 1,3,5-triglycidyl isocyanurate, 1,3-diglycidyl-5- (γ-acetoxy-β-oxy Propyl) isosinurate, sorbitol polyglycidyl ethers, polyglycerol polyglycidyl ethers, pentaerythritol polyglycidyl ethers, diglycerol polyglycidyl ether, 1,3,5-triglycidyl (2-hydroxyethyl) isocyanurate, glycerol poly Epoxy compounds such as glycerol ethers and trimethylolpropane polyglycidyl ethers are preferable, and specific examples of commercially available products include Denacol EX-521 and EX-614B (manufactured by Nagase Chemical Industries). Although it is not intended to be limited thereto.
In addition, it can be used in combination with other crosslinkable compounds within the range of addition amount that does not affect the photosensitivity. For example, CEKMees and THJames “The Theory of the Photographic Processes” 3rd edition (1966), USA Patent Nos. 3316095, 3232264, 3288775, 2732303, 2732303, 3635718, 3323276, 2732316, 2586168, 3103437, 3017280, 2983611, 2725294, Examples thereof include curing agents described in the specifications of Nos. 2,725,295, 3,100,704, 3,091,537, 3,213,313, 3,543,292 and 3,125,449 and British Patents 994869, 1,167,207.

  As a typical example, a melamine compound containing at least one of two or more (preferably three or more) methylol groups and an alkoxymethyl group or a condensation polymer thereof, a melamine resin or a melamine urea resin, Mucochloric acid, mucobromic acid, mucofenoxycycloic acid, mucophenoxypromic acid, formaldehyde, glyoxal, monomethylglioxal, 2,3-dihydroxy-1,4-dioxane, 2,3-dihydroxy-5-methyl-1,4 Aldehyde compounds such as dioxane succinaldehyde, 2,5-dimethoxytetrahydrofuran and glutaraldehyde and derivatives thereof; divinylsulfone-N, N′-ethylenebis (vinylsulfonylacetamide), 1,3-bis (vinylsulfonyl) -2 − Lopanol, methylene bismaleimide, 5-acetyl-1,3-diaacryloyl-hexahydro-s-triazine, 1,3,5-triacryloyl-hesahydro-s-triazine and 1,3,5-trivinylsulfonyl-hexahydro- active vinyl compounds such as s-triazine; 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4-dichloro-6- (4-sulfoanilino) -s-triazine sodium salt, 2,4- Active halogen compounds such as dichloro-6- (2-sulfoethylamino) -s-triazine and N, N′-bis (2-chloroethylcarbamyl) piperazine; bis (2,3-epoxypropyl) methylpropylammonium P-toluenesulfonate, 2,4,6-triethylene-s-triazine, Ethyleneimine compounds such as 1,6-hexamethylene-N, N′-bisethyleneurea and bis-β-ethyleneiminoethylthioether; 1,2-di (methanesulfoneoxy) ethane, 1,4-di (methanesulfone) Oxy) butane and methanesulfonic acid ester compounds such as 1,5-di (methanesulfoneoxy) pentane; carbodiimide compounds such as dicyclohexylcarbodiimide and 1-dicyclohexyl-3- (3-trimethylaminopropyl) carbodiimide hydrochloride; Isoxazole compounds such as 5-dimethylisoxazole; inorganic compounds such as chromium alum and chromium acetate; N-carboethoxy-2-isopropoxy-1,2-dihydroquinoline and N- (1-morpholinocarboxy)- 4-methylpyridinium chloride, etc. Dehydrated condensation type peptide reagents; active ester compounds such as N, N′-adipoyldioxydisuccinimide and N, N′-terephthaloyldioxydisuccinimide: toluene-2,4-diisocyanate and 1,6- Examples thereof include, but are not limited to, isocyanates such as hexamethylene diisocyanate; and epichlorohydrin compounds such as polyamide-polyamine-epichlorohydrin reactant.

As the carbodiimide compound used in the present invention, a compound having a plurality of carbodiimide structures in the molecule is preferably used.
Polycarbodiimide is usually synthesized by a condensation reaction of organic diisocyanate. Here, the organic group of the organic diisocyanate used for the synthesis of the compound having a plurality of carbodiimide structures in the molecule is not particularly limited, and either aromatic or aliphatic, or a mixed system thereof can be used. An aliphatic system is particularly preferred from the viewpoint of reactivity.
As the synthetic raw material, organic isocyanate, organic diisocyanate, organic triisocyanate and the like are used.
As examples of organic isocyanates, aromatic isocyanates, aliphatic isocyanates, and mixtures thereof can be used.
Specifically, 4,4′-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane Diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-phenylene diisocyanate, etc. are used. As organic monoisocyanates, isophorone isocyanate, phenyl isocyanate are used. Cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate and the like are used.
Moreover, the carbodiimide type compound that can be used in the present invention is also available as a commercial product such as Carbodilite V-02-L2 (trade name: manufactured by Nisshinbo Co., Ltd.).
The carbodiimide compound is preferably added in an amount of 1 to 200% by weight, more preferably 5 to 100% by weight, based on the binder.

  In addition, it is preferable that binder resin which forms an easily bonding layer has any group of a methylol group, a hydroxyl group, a carboxyl group, and an amino group so that a crosslinking reaction with a crosslinking agent is possible. A hydroxyl group and a carboxyl group are preferred, and a carboxyl group is particularly preferred. The content of hydroxyl group or carboxyl group in the polymer is preferably 0.0001 to 1 equivalent / 1 kg, particularly preferably 0.001 to 1 equivalent / 1 kg.

  The layer thickness of the easy adhesion layer in the present invention is preferably in the range of 0.01 to 1 μm, and more preferably in the range of 0.01 to 0.2 μm. If the coating agent is less than 0.01 μm, it is difficult to uniformly apply the coating agent, so that uneven coating tends to occur on the product.

  In the easy-adhesion layer in the present invention, additives such as a matting agent, a surfactant and a slipping agent can be used in combination as necessary. Examples of the matting agent include particles of oxides such as silicon oxide, aluminum oxide, and magnesium oxide having a particle diameter of 0.001 to 10 μm, and particles of a polymer or a copolymer such as polymethyl methacrylate and polystyrene. Can do. Examples of the surfactant include known anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants. Examples of slip agents include natural waxes such as carnauba wax, phosphate esters of higher alcohols having 8 to 22 carbon atoms or amino salts thereof; palmitic acid, stearic acid, behenic acid and esters thereof; and silicone compounds. Can do.

(Scratch strength)
In the present invention, the fine line pattern made of a conductive metal containing developed silver preferably has a scratch strength of HB or more. Here, when the scratch strength is HB or higher, a fine line pattern surface is scratched with a pencil having a hardness of HB or higher in accordance with JIS K5400. Say that it is below the point.
(Thin wire pattern break)
In the present invention, the fine line pattern made of a conductive metal containing developed silver preferably has 5 or less, more preferably 2 or less, breaks in the fine line pattern portion per 1 m 2. Although this disconnection occurs through the manufacturing process, the disconnection is less likely to occur as the aforementioned scratch strength is higher. This disconnection is undesirable because it causes a reduction in electromagnetic wave shielding ability, and can be a serious problem especially in an aircraft-mounted liquid crystal display device.
In this invention, it is preferable that the change rate of the surface resistivity after scratching the said fine wire pattern surface with an HB pencil is less than 2 times. The scratch resistance is scratched in two directions orthogonal to each other, and the surface resistivity is measured by bringing the probe into contact with the intersection.

[Other functional layers]
In the present invention, a functional layer having functionality may be separately provided as necessary. This functional layer can have various specifications for each application. For example, as an electromagnetic shielding material for displays, an antireflection layer provided with an antireflection function with an adjusted refractive index and film thickness, a non-glare layer or an antiglare layer (both have a glare prevention function), and absorbs near infrared rays. Near-infrared absorbing layer made of compound or metal, layer with a color tone adjustment function that absorbs visible light in a specific wavelength range, antifouling layer with a function that easily removes dirt such as fingerprints, hard coat with little scratches A layer, a layer having an impact absorbing function, a layer having a function of preventing glass scattering when glass is broken, and the like can be provided. These functional layers may be provided on the opposite side of the metal silver part or the conductive metal part and the support, or may be provided on the same side.

  The features of the present invention will be described more specifically with reference to the following examples. 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.

[Example 1]
<Support>
A polyethylene terephthalate resin having an intrinsic viscosity of 0.66 polycondensed using antimony trioxide as a main catalyst was dried to a moisture content of 50 ppm (mg / L) or less and melted in an extruder set at a heater temperature of 280 to 300 ° C.
The molten PET resin is discharged from a die part onto a chill roll electrostatically applied to obtain an amorphous base. The obtained amorphous base was stretched 3.3 times in the base traveling direction, and then stretched 3.8 times in the width direction to produce a support having a thickness of 96 μm in the form of a roll.
As will be described later, after laminating an easy-adhesion layer on this support, an emulsion containing silver halide grains is applied to produce a photographic light-sensitive material to obtain a fine line pattern containing developed silver used in the present invention.

<Easily adhesive layer>
On the support, a coating solution having the following composition was sequentially applied and dried under the following coating conditions to form an easy adhesion layer.

<Easily adhesive layer 1>
After the biaxially stretched polyethylene terephthalate support was transported at a transport speed of 105 m / min, the surface of the general support was subjected to corona discharge treatment, and the following coating solution was applied in an amount of 7.1 mL / m. ² was applied by the bar coating method. Subsequently, it was dried at 180 ° C. for 1 minute in an air floating drying zone.

(First layer coating solution)
Distilled water 781.7 parts by mass Polyacrylic resin (Nippon Pure Chemicals, solid content 30%) 30.9 parts by mass Carbodiimide compound (Carbodilite V-02-L2: Nisshinbo, solid content 40%)
6.4 parts by mass surfactant (manufactured by Sanyo Chemical Industries, solids 44.6%) 2.1 parts by mass

While maintaining the conveying speed of 105 m / min, a surface layer coating solution having the following composition was subsequently applied at a coating amount of 5.05 mL / m ² by the bar coating method. Subsequently, the easy-adhesion layer 1 having a two-layer structure was obtained by drying at 160 ° C. for 1 minute in an air floating drying zone.

(Second layer coating solution)
Distilled water 941.0 parts by mass Polyacrylic resin (Nippon Pure Chemicals, solid content 30%) 57.3 parts by mass epoxy compound (Denacol EX-521: Nagase Chemical Industries, solid content 100%)
1.2 parts by mass surfactant (manufactured by Sanyo Chemical Industries, solids 44.6%) 0.5 parts by mass

<Preparation of emulsion A containing silver halide grains and preparation of photographic material>
While stirring the following 1 solution, an amount corresponding to 90% of each of the 2 and 3 solutions was added simultaneously over 20 minutes to form 0.15 μm silver halide core particles. Subsequently, the following 4th and 5th liquids were added over 8 minutes, and the remaining 10% of the 2nd and 3rd liquids were further added over 2 minutes to grow particles to 0.18 μm. Further, 0.15 g of potassium iodide (in the form of a 0.1% aqueous solution) was added and ripened for 5 minutes to prepare silver halide grains.

・ 1 liquid:
750 ml of water
20g gelatin
Sodium chloride 1.6g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
・ Two liquids 300ml
150 g silver nitrate
・ 3 liquid water 300ml
Sodium chloride 38g
Potassium bromide 32g
Hexachloroiridium (III) potassium (0.005% KCl 20% aqueous solution) 5ml
Ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) 7ml
Potassium hexachloroiridium (III) (0.005% KCl 20% aqueous solution) and ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) used in the three solutions were prepared by dissolving the powder in KCl 20% aqueous solution and NaCl 20% aqueous solution, respectively. did.
・ 4 liquid water 100ml
Silver nitrate 50g
・ 5 liquid 100ml
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 5mg

  Then, after desalting and washing with water according to a conventional method, 8 g of low molecular weight gelatin having a molecular weight of 20,000 was added to adjust to pH 5.6, pAg 7.5, 10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, Sodium sulfate 15mg and chloroauric acid 10mg were added, and chemical sensitization was performed to obtain the optimum sensitivity at 55 ° C. 1,3,3a, 7-tetraazaindene 100mg as a stabilizer and Proxel as a preservative (trade name) 100 mg) from ICI. Finally, a silver iodochlorobromide cubic grain emulsion having an average grain size of 0.18 μm and containing 70 mol% of silver chloride and 0.08 mol% of silver iodide was obtained.

Perform spectral sensitization to the emulsion A, 1,3,3a, 7- tetrazaindene, hydroquinone, citric acid, a surfactant is added, Ag7.6g / m ^2, made of gelatin 1.1 g / m ² Thus, the sample of the photosensitive material used for this invention was produced by apply | coating to the above-mentioned support body which laminated | stacked the easily bonding layer.

(Exposure and development of silver halide photographic materials)
An electromagnetic wave shielding film (sample No. 3) having a copper fine wire pattern in which the halo pitch of each dried sample was 15 μm / 300 μm was obtained.
The surface resistivity was measured in accordance with JIS 7194 using a Mitsubishi Chemical Corporation low resistivity meter Lorester GP / ASP probe.

(Evaluation of scratch strength)
With reference to JIS K5400, a scratch test of the mesh surface was performed with an HB pencil.
Scratching was performed in two directions orthogonal to each other.
Level A: Mesh breakage is 2 or less per 10 fine lines scratched.
Level B: Mesh breakage is 3 to 5 places per 10 fine lines scratched.
Level C: There are 6 or more broken meshes per 10 fine scratches.
The evaluation results are shown in Table 1.

From the results in Table 1, it was found that the sample of the present invention had high scratch strength, and the mesh disconnection hardly occurred even when scratched with a pencil.
The sample of the present invention was found to have a low surface resistivity, excellent scratch strength, and little change in surface resistivity after the scratch test. For this reason, it can use suitably as an electromagnetic wave shield film for touch panels.

Claims (5)

A support having thereon fine line patterns made of a conductive metal containing developing silver, between the support and the fine line pattern, crosslinked with an epoxy compound or a carbodiimide compound, and is more formed acrylic resins Easy adhesion layer is laminated ,
The fine line pattern further contains gelatin;
A translucent electromagnetic wave shielding film for a touch panel of a liquid crystal display device, wherein the support is a plastic film made of polyethylene terephthalate (PET) as a raw material . The translucent electromagnetic wave shielding film according to claim 1 , wherein a width of the fine line of the fine line pattern is 1 μm or more and 30 μm or less. 3. The translucent electromagnetic wave shielding film according to claim 1, wherein a metal thickness of the fine line pattern is 0.2 μm or more and 30 μm or less. Translucent electromagnetic shielding film according to any one of claims 1 to 3, conductive metal of the fine line pattern, characterized by having a black layer. Translucent electromagnetic shielding film according to any one of claims 1 to 4, wherein the liquid crystal display device is a liquid crystal display device of the aircraft.