JP2006228836A - Translucent conductive film and its manufacturing method, and optical filter using translucent conductive film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a permeable electromagnetic shielding film, and a conductive film which allows a low-cost mass production of an electromagnetic shielding film which has a high EMI shielding property and a high transparency. <P>SOLUTION: A silver halide photosensitive material is exposed to light and developed to form a metal silver. After the metal silver is treated with an activating liquid, a plating treatment or physical development treatment is conducted on the metal silver to obtain the conductive film. Since the activating liquid removes a halide and/or a sulfide formed on the surface of the developed silver during the development process, the translucent conductive film can be obtained. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a translucent conductive film and a method for producing the same. Translucent conductive films include CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, EL (electroluminescence), FED (field emission display) and other display front surfaces, microwave ovens, electronic equipment, printed wiring boards, etc. It is used as an electromagnetic wave shielding film that shields electromagnetic waves generated from the water and has transparency.
In addition to these image display elements, the translucent conductive film is also used for imaging semiconductor elements and the like.

  In recent years, electromagnetic interference (Electro-Magnetic Interference: EMI) has been rapidly increasing with the increase in the use of various electric facilities and electronic application facilities. EMI has been pointed out to be a cause of malfunction and failure of electronic and electrical equipment, as well as a health hazard to operators of these devices. For this reason, in the electronic and electrical equipment, it is required to suppress the intensity of electromagnetic wave emission within the standard or regulation.

  Although it is necessary to shield the electromagnetic wave as a countermeasure against the EMI, it is obvious that a property that does not allow the metal electromagnetic wave to penetrate may be used. For example, a method of making the casing a metal body or a high conductor, a method of inserting a metal plate between the circuit board and the circuit board, a method of covering the cable with a metal foil, and the like are employed. However, in CRT, PDP, etc., since the operator needs to recognize characters displayed on the screen, transparency in the display is required. For this reason, in any of the above methods, the front surface of the display often becomes opaque, which is inappropriate as an electromagnetic wave shielding method.

Particularly, since PDP generates a large amount of electromagnetic waves as compared with CRT or the like, stronger electromagnetic shielding ability is required. The electromagnetic wave shielding ability can be simply expressed by a surface resistance value. In a translucent electromagnetic wave shielding material for CRT, the surface resistance value is required to be about 300 Ω / sq or less, whereas for PDP. The translucent electromagnetic wave shielding material is required to have a resistance of 2.5Ω / sq or less, and in a plasma plasma for consumer use using a PDP, there is a high need for 1.5Ω / sq or less. An extremely high conductivity of sq or less is required.
Further, the required level for transparency is about 70% or more for CRT and 80% or more for PDP, and higher transparency is desired.

  In order to solve the above-described problems, various materials and methods have been proposed so far that achieve both electromagnetic shielding properties and transparency using a metal mesh having openings as will be described below.

(1) Conductive fiber For example, Patent Document 1 discloses an electromagnetic shielding material made of conductive fiber. However, this shielding material has a drawback that when the display screen is shielded with a thick mesh line width, the screen becomes dark and the characters displayed on the display are difficult to see.

(2) Electroless Plating Processed Mesh A method of printing an electroless plating catalyst as a grid pattern by a printing method and then performing electroless plating has been proposed (for example, Patent Document 2, Patent Document 3 and the like). However, the line width of the catalyst to be printed is as thick as about 60 μm, which is inappropriate as a display application that requires a relatively small line width and a dense pattern.
Further, a method of electroless plating after forming a pattern of an electroless plating catalyst by applying a photoresist containing an electroless plating catalyst and performing exposure and development is proposed (for example, Patent Document 4). . However, the visible light transmittance of the conductive film was 72%, and the transparency was insufficient. Furthermore, since it is necessary to use extremely expensive palladium as an electroless plating catalyst that removes most after exposure, there is also a problem in terms of manufacturing cost.

(3) Etching processing mesh using photolithography method A method of forming a metal thin film mesh on a transparent substrate by etching processing using a photolithography method has been proposed (for example, Patent Document 5, Patent Document 6, Patent Document 7, Patent Document 8, etc.). Since this method can be finely processed, it has an advantage that a mesh having a high aperture ratio (high transmittance) can be produced and strong electromagnetic wave emission can be shielded. However, the manufacturing process is complicated and complicated, and the production cost is high. Further, it is known from the etching method that there is a problem that the intersection of the lattice pattern is thicker than the line width of the straight line portion. In addition, the problem of moire was pointed out and improvement was desired.

(4) A method of forming a conductive metal silver pattern using a silver salt has also been proposed.
Photosensitive materials using silver salts have heretofore been mainly used as materials for recording and transmitting images and videos. For example, color negative film, black and white negative film, movie film, photographic film such as color reversal film, photographic printing paper such as color paper, black and white photographic paper, etc. Furthermore, it can be used that metal silver can be formed according to the exposure pattern Emulsion masks (photomasks) that have been used are widely used. All of these have value in the image itself obtained by exposing and developing a silver salt, and use the image itself.

  Since developed silver obtained from a silver salt is metallic silver, it is considered that the conductivity of metallic silver can be used depending on the production method. Such a proposal has been scattered from old times until recently, and as an example of disclosing a specific method for forming a conductive silver thin film, a metal silver thin film pattern was formed by a silver salt diffusion transfer method in which silver was deposited on a physical development nucleus in the 1960s. This method is disclosed in Patent Document 9. Further, Patent Document 10 discloses that a uniform silver thin film without light transmittance obtained by using the same silver salt diffusion transfer method has a microwave attenuation function. Further, Non-Patent Document 1 and Patent Document 11 describe a method of forming a conductive pattern by simply exposing and developing using an instant black-and-white slide film using this principle as it is. Further, Patent Document 12 describes a method of forming a conductive silver film that can be used as a display electrode for a plasma display by the principle of silver salt diffusion transfer method. However, the metal film obtained from developed silver has limitations in terms of translucency, and it has been difficult to achieve both translucency and conductivity.

However, the conductive metallic silver film obtained by such a method has insufficient translucency for image display and image forming elements, and electromagnetic waves radiated from the image display surface of a display such as a CRT or PDP. There has been no known method for shielding without disturbing the image display.
In the methods described in the above five documents, physical development nuclei specially prepared in the layer on which the conductive metal pattern is formed are uniformly provided without distinction between exposed and unexposed areas. For this reason, there is a drawback that opaque physical development nuclei remain in the exposed portion where the metallic silver film is not formed, and the light transmittance is impaired. In particular, when the metal pattern material is used as a light-transmitting electromagnetic wave shielding material for a display such as a CRT or a PDP, the above-mentioned drawback is serious.
In addition, it is difficult to obtain high conductivity, and there is a problem that transparency is impaired when a thick silver film is obtained in order to obtain high conductivity. Therefore, even if the above silver salt diffusion transfer method is used as it is, it is possible to obtain a light-transmitting electromagnetic wave shielding material excellent in light transmittance and conductivity suitable for shielding electromagnetic waves from the image display surface of an electronic display device. I could not.
In addition, when using an ordinary commercially available negative film without using the silver salt diffusion transfer method and imparting conductivity through development, physical development and plating processes, both conductivity and transparency (translucency) can be achieved. In that respect, it was insufficient for use as a translucent electromagnetic shielding material for CRT and PDP.

  For this reason, Patent Document 13 discloses a method for producing a light-transmitting electromagnetic wave shielding material using a silver salt photosensitive material as a measure for shielding an electromagnetic wave emitted from an electronic display device. According to this disclosed technique, improvement was made in terms of both conductivity and translucency. However, sufficient translucency cannot be obtained, and there is still a demand for a solution.

JP-A-5-327274 JP 11-170420 A Japanese Patent Laid-Open No. 5-288989 JP-A-11-170421 JP 2003-46293 A Japanese Patent Laid-Open No. 2003-23290 Japanese Patent Laid-Open No. 5-16281 JP-A-10-338848 Japanese Patent Publication No.42-23746 Japanese Patent Publication No.43-12862 International Publication WO 01/51276 JP 2000-149773 A JP 2004-221564 A Analytical Chemistry, 2000, Vol. 72, paragraph 645

  The present invention has been made in view of such circumstances, and an object of the present invention is to solve the above-described conductivity obstruction even when a silver salt photosensitive material is used. An object of the present invention is to provide an electromagnetic wave shielding film having high electromagnetic shielding properties and high transparency at the same time, and a translucent conductive film having high electrical conductivity and high translucency at the same time. In particular, the present invention is to provide a method for producing a high-performance electromagnetic wave shielding film in that high conductivity is exhibited by the metallic silver part and the light transmittance of the light-transmitting part is maintained high.

  From the viewpoint of obtaining high EMI shielding properties and high transparency at the same time, the inventors have no silver deposition or developer stains in the unexposed area by black-and-white development, and produce highly conductive silver in the exposed area, As a result of intensive studies on means for reinforcing developed silver to form patterned shield silver, it was found that a specific intensification treatment after development processing is effective, and the present invention is completed based on this finding. It came to.

That is, the object of the present invention is achieved by the following production method.
(1) A silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is exposed to light and developed to form a metallic silver portion, and then the metallic silver This is a translucent conductive film obtained by treating the part with an activation liquid and then imparting conductivity by plating or physical development, and the activation liquid is formed on the developed silver surface during the development process. A translucent conductive film, characterized in that the halide and / or sulfide to be removed is removed.
(2) The conductive film as described in (1) above, wherein the conductive film is a translucent conductive film for a transparent electrode of an image display element or an image recording semiconductor element.
(3) The conductive film as described in (1) above, wherein the conductive film is an electromagnetic wave shielding film.
(4) The conductive film as described in (3) above, which is a translucent electromagnetic wave shielding film having a surface resistance of 2.5 Ω / sq or less and a transmittance of the light transmissive part of 95% or more.
(5) The conductive film as described in (1) above, wherein the activation liquid contains an alkali metal salt of borohydride (tetrahydroboric acid).
(6) The conductive film as described in (1) above, wherein the activating solution contains silver nitrate.
(7) The conductive film as described in (1) above, wherein the activating liquid contains an inorganic acid having a pKa of 2 or less.
(8) The conductive film as described in (1) above, wherein the activating liquid contains an alkali halide.

(9) The black and white silver halide photographic light-sensitive material having at least one hydrophilic colloid layer including a silver halide emulsion layer on the support is exposed and developed, and subsequently the surface of the developed silver is developed during the development. A method for producing a conductive film, characterized by performing a treatment using an activating solution for removing a formed halide and / or sulfide, and further performing a plating treatment or a physical development treatment.
(10) The method for producing a conductive film as described in (9) above, wherein the exposure applied to the silver halide photographic light-sensitive material is pattern exposure, and the obtained conductive film is an electromagnetic wave shielding film.

(11) The above (9), wherein the silver halide in the silver halide photographic light-sensitive material is a silver halide containing substantially no silver iodide and containing 50 mol% or more of silver chloride. The manufacturing method of the electroconductive film as described in (10).
(12) The above-mentioned (9) to (11), wherein a light-transmitting electromagnetic wave shielding film having a surface resistance of 2.5 Ω / sq or less and a transmittance of the light-transmitting part of 95% or more is obtained. The manufacturing method of the electroconductive film in any one of.
(13) The conductive film according to any one of (9) to (12), wherein the metallic silver portion is formed in an exposed portion, and the light transmitting portion is formed in an unexposed portion. Method.
(14) The method for producing a conductive film according to any one of (9) to (13), wherein the light-transmitting portion does not substantially have a physical development nucleus.
(15) The method for producing a conductive film as described in any one of (9) to (14) above, wherein a silver salt-containing layer having an Ag / binder volume ratio of 1/4 or more is used.
(16) It is characterized in that it comprises a step of pattern exposure of a black and white silver halide photographic light-sensitive material, and subsequently forming a developed silver portion in an exposed portion and a light transmissive portion in an unexposed portion by dissolution physical development. The method for producing an electromagnetic wave shielding film according to any one of the above (9) to (15).

(17) A plasma display panel comprising a conductive metal part and a light transmissive part obtained by the method for producing a light transmissive electromagnetic wave shielding film according to any one of (9) to (16). Translucent electromagnetic shielding film.
(18) An optical filter for a plasma display panel, comprising the translucent electromagnetic wave shielding film according to (3) or (4).
(19) A plasma display panel characterized by using a light-transmitting conductive film and / or a light-transmitting electromagnetic wave shielding film obtained by the manufacturing method according to any one of (9) to (16). Optical filter.
(20) A plasma display panel comprising the optical filter according to (18) or (19).
(21) A plasma television comprising a translucent electromagnetic wave shielding film obtained by the production method according to any one of (9) to (16).

(22) The conductive film as described in (2) above, which is a translucent conductive film for a transparent electrode of an image display element or an image recording semiconductor element.
(23) The conductive film as described in any one of (1) to (8) above, which has an adhesive layer.
(24) The optical filter as described in (18) or (19) above, which has an adhesive layer.
(25) The conductive film according to any one of (1) to (8), which has a peelable protective film.
(26) The conductive film as described in any one of (1) to (8) above, wherein the surface area of the conductive pattern is 20% or more black.
(27) The optical filter as described in (18) or (19) above, wherein 20% or more of the surface area of the conductive pattern is black.
(28) One or more functions selected from infrared shielding properties, hard coat properties, antireflection properties, antiglare properties, antistatic properties, antifouling properties, ultraviolet ray cutting properties, gas barrier properties, and display panel damage prevention properties The conductive film according to any one of (1) to (8), which has a functional transparent layer.
(29) One or more functions selected from infrared shielding properties, hard coat properties, antireflection properties, antiglare properties, antistatic properties, antifouling properties, ultraviolet ray cutting properties, gas barrier properties, and display panel damage prevention properties The optical filter according to (18) or (19), which has a functional transparent layer.
(30) The conductive film according to any one of (1) to (8), which has infrared shielding properties.

The following embodiments are further exemplified as main embodiments of the present invention.
(31) The production of the light-transmitting electromagnetic wave shielding film according to any one of (9) to (16), wherein a sphere equivalent diameter of the silver salt in the silver salt-containing layer is 0.1 to 100 nm. Method.
(32) The method for producing a translucent electromagnetic wave shielding film according to any one of (9) to (16), wherein the exposure is performed by a scanning exposure method using a laser beam.
(33) The method for producing a translucent electromagnetic wave shielding film according to any one of (9) to (16), wherein the exposure is performed through a photomask.
(34) The method for producing a translucent electromagnetic wave shielding film according to any one of (9) to (16), wherein the developer used in the development treatment of the silver salt-containing layer is a lith developer.
(35) The mass of the metallic silver contained in the exposed area after the development treatment is a content of 50% by mass or more based on the mass of silver contained in the exposed area before the exposure. (9) The manufacturing method of the translucent electromagnetic wave shielding film in any one of (16).
(36) The method for producing an electromagnetic wave shielding film according to any one of (9) to (16), wherein the plating treatment is performed by electroless plating.
(37) The method for producing an electromagnetic wave shielding film according to any one of (9) to (16), wherein the plating treatment is performed by electrolytic plating.
(38) The method for producing an electromagnetic wave shielding film according to any one of (9) to (16), wherein the plating treatment is performed by electroless plating and subsequent electrolytic plating.
(39) The method for producing an electromagnetic wave shielding film according to any one of (9) to (16), wherein the electroless plating is electroless copper plating.
(40) The method for producing an electromagnetic wave shielding film according to any one of (9) to (16), wherein a gradation after development processing of the silver salt-containing layer exceeds 4.0 (gamma value).
(41) The method for producing an electromagnetic wave shielding film according to any one of (9) to (16), wherein the surface of the conductive metal portion is further blackened.
(42) The method for producing an electromagnetic wave shielding film according to any one of (9) to (16), wherein the light-transmitting portion has substantially no physical development nucleus.

Furthermore, the object of the present invention is achieved by a translucent electromagnetic wave shielding film and a plasma display panel having the following aspects.
(43) The total mass of silver, copper, and palladium with respect to the total mass of the metal component contained in the conductive part is 80% by mass or more, and any one of (1) to (8) Translucent conductive film.
(44) The translucent conductive film according to (43), wherein the conductive portion is a mesh-shaped translucent electromagnetic wave shielding film.
(45) The translucent conductive film according to (44), which is a translucent electromagnetic wave shielding film having an aperture ratio of the conductive metal portion of 85% or more.
(46) The layer made of conductive metal particles carried on the conductive metal part has a thickness of 0.1 μm or more and less than 5 μm, and a surface resistance value of 2.5Ω / sq or less. (43) The translucent electromagnetic wave shielding film according to any one of (45).
(47) The translucent electromagnetic wave shielding film according to any one of (45) to (46), wherein a line width of the conductive metal portion is 0.1 μm or more and less than 40 μm.
(48) The translucent electromagnetic wave shielding film according to any one of (45) to (47), wherein a line width of the conductive metal portion is 0.1 μm or more and less than 35 μm.
(49) The translucent electromagnetic wave shielding film according to any one of (45) to (48), wherein a line width of the conductive metal portion is 0.1 μm or more and less than 30 μm.
(50) The translucent electromagnetic wave shielding film according to any one of (45) to (49), wherein a line width of the conductive metal portion is 0.1 μm or more and less than 25 μm.
(51) The light-transmitting electromagnetic wave shielding film according to any one of (45) to (50), wherein the light-transmitting portion has a transmittance of 98% or more.
(52) A plasma display panel having the translucent electromagnetic wave shielding film according to any one of (45) to (51).

The translucent conductive film of the present invention obtained by performing plating or physical development after treatment with an activation bath containing at least one of the compounds described in (5) to (8) following development. Is an electromagnetic wave shielding film for preventing electromagnetic interference that has high conductivity and high translucency, and thus has both high EMI shielding properties and high transparency, and for imaging of image element units and image recording elements of display devices. Used as a transparent electrode for semiconductor elements. Moreover, in these production methods of the present invention, since a photographic photosensitive material is used, a translucent conductive film can be mass-produced at low cost.
Further, the activation treatment can be speeded up by the activation bath conditions defined in the present invention.

Below, the translucent electromagnetic wave shielding film of this invention, the manufacturing method of a translucent conductive film, and the translucent electromagnetic wave shielding film are demonstrated in detail.
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.

<< Translucent conductive film (electromagnetic wave shielding film, transparent electrode, etc.) and manufacturing method thereof >>
The translucent conductive film includes an electromagnetic wave shielding film of an image display panel such as a PDP, and a translucent conductive film (transparent electrode film or the like) used for an image display element, an imaging semiconductor element, or the like.
In the method for producing a light-transmitting conductive film of the present invention, a photosensitive material having an emulsion layer containing a photosensitive silver halide salt on a support and preferably a protective layer in this order is exposed and developed. Thus, a metal silver (development silver) part and a light transmission part are formed in the exposed part and the unexposed part, respectively, and at least one of the compounds described in (5) to (8) is further added to the developed silver part. The conductive silver is supported on the developed silver portion by performing an activation treatment with a liquid containing the catalyst to increase the activity against electroless plating on the developed silver, and then performing a physical development and / or a plating treatment. To do.
Hereinafter, the photosensitive material, exposure, development, activation, plating, physical development processing, etc. used for the production of the translucent conductive film of the present invention will be described in order.

[Photosensitive material]
In the present invention, as described later in the section of development processing, there are two types of combinations of the type of photosensitive material and the development method, but a common photosensitive material can be used. Therefore, the following description of the light-sensitive material applies in common to the above two modes.
<Support>
As the support of the photosensitive material used in the production method of the present invention, a plastic film, a plastic plate, a glass plate, or the like can be used.
Examples of the raw material for the plastic film and plastic plate include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene, EVA; polyvinyl chloride, Vinyl resins such as polyvinylidene chloride; polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC) Etc. can be used.
In the present invention, the plastic film is preferably a polyethylene terephthalate film and / or triacetyl cellulose (TAC) from the viewpoint of transparency, heat resistance, ease of handling, and price.

Since the electromagnetic wave shielding material for display 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. However, when used as an application for an electromagnetic wave shielding film for 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.

<Protective layer>
The photosensitive material used may be provided with a protective layer on the emulsion layer described later. In the present invention, the “protective layer” means a layer made of a binder such as gelatin or a high molecular polymer, and is formed in an emulsion layer having photosensitivity in order to exhibit an effect of preventing scratches and improving mechanical properties. The protective layer is preferably not provided for the plating treatment, and even if it is provided, it is preferably thin. The thickness is preferably 0.2 μm or less. The formation method of the coating method of the said protective layer is not specifically limited, A well-known coating method can be selected suitably.
The photosensitive material used in the production method of the present invention may contain a known dye in the emulsion layer for the purpose of dyeing and the like.

<Emulsion layer>
The light-sensitive material used in the production method of the present invention preferably has an emulsion layer (silver salt-containing layer) containing a silver salt as an optical sensor on a support. The emulsion layer in the present invention may contain a dye, a binder, a solvent and the like, if necessary, in addition to the silver salt.
<Dye>
The light-sensitive material may contain a dye at least in the emulsion layer. The dye is contained in the emulsion layer as a filter dye or for various purposes such as prevention of irradiation. The dye may contain a solid disperse dye. Examples of the dye preferably used in the present invention include dyes represented by general formula (FA), general formula (FA1), general formula (FA2), and general formula (FA3) described in JP-A-9-179243. Specifically, compounds F1 to F34 described in the publication are preferable. Further, (II-2) to (II-24) described in JP-A-7-152112, (III-5) to (III-18) described in JP-A-7-152112, and JP-A-7-152112. (IV-2) to (IV-7) described in the publication are also preferably used.

  In addition, as dyes that can be used in the present invention, solid fine particle dispersed dyes to be decolored during development or fixing processing include cyanine dyes, pyrylium dyes, and aminium dyes described in JP-A-3-138640. Can be mentioned. Further, as dyes that do not decolorize during processing, cyanine dyes having a carboxyl group described in JP-A-9-96891, cyanine dyes not containing an acidic group described in JP-A-8-245902, and those described in JP-A-8-333519 Lake type cyanine dyes, cyanine dyes described in JP-A-1-266536, horopora-type cyanine dyes described in JP-A-3-136638, pyrylium dyes described in JP-A-62-299959, JP-A-7-253039 Polymer type cyanine dyes described in JP-A No. 2-282244, solid fine particle dispersions described in JP-A No. 2-282244, light scattering particles described in JP-A No. 63-131135, Yb3 + compounds described in JP-A No. 9-5913 And ITO powder described in JP-A-7-113072. . In addition, dyes represented by general formula (F1) and general formula (F2) described in JP-A-9-179243, specifically, compounds F35 to F112 described in the same publication can also be used.

  Moreover, as said dye, a water-soluble dye can be contained. Such water-soluble dyes include oxonol dyes, benzylidene dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and benzylidene dyes are particularly useful in the present invention. Specific examples of water-soluble dyes that can be used in the present invention include British Patent Nos. 584,609, 1,177,429, JP-A-48-85130, 49-99620, No. 49-114420, No. 52-20822, No. 59-154439, No. 59-208548, US Pat. No. 2,274,782, No. 2,533,472, No. 2 No. 3,956,879, No. 3,148,187, No. 3,177,078, No. 3,247,127, No. 3,540,887, No. 3 , 575,704 specification, 3,653,905 specification, and 3,718,427 specification.

  The content of the dye in the emulsion layer is preferably 0.01 to 10% by mass with respect to the total solid content, from the viewpoint of preventing irradiation and the like, and from the viewpoint of lowering sensitivity due to an increase in the amount added. More preferred is mass%.

<Silver salt>
Examples of the silver salt used in the present invention include inorganic silver salts such as silver halide. In the present invention, it is preferable to use silver halide having excellent characteristics as an optical sensor.

The silver halide preferably used in the present invention will be described.
In the present invention, it is preferable to use silver halide in order to function as an optical sensor, and silver halide photographic film and photographic paper relating to silver halide, printing plate-making film, emulsion mask for photomask, etc. It can also be used in the present invention.

  The halogen element contained in the silver halide may be any of chlorine, bromine, iodine and fluorine, or a combination thereof. For example, silver halide mainly composed of AgCl, AgBr, and AgI is preferably used, and silver halide mainly composed of AgBr or AgCl is preferably used. Silver chlorobromide, silver iodochlorobromide and silver iodobromide are also preferably used. More preferred are silver chlorobromide, silver bromide, silver iodochlorobromide and silver iodobromide, and most preferred are silver chlorobromide and silver iodochlorobromide containing 50 mol% or more of silver chloride. Used.

  Here, “silver halide mainly composed of AgBr (silver bromide)” refers to silver halide in which the molar fraction of bromide ions in the silver halide composition is 50% or more. The silver halide grains mainly composed of AgBr may contain iodide ions and chloride ions in addition to bromide ions.

Silver halide is in the form of solid grains. From the viewpoint of image quality of the patterned metallic silver layer formed after exposure and development, the average grain size of silver halide is 0.1 to 1000 nm in terms of sphere equivalent diameter ( 1 μm) is preferred, 0.1 to 100 nm is more preferred, and 1 to 50 nm is even more preferred.
Incidentally, the sphere equivalent diameter of silver halide grains is the diameter of grains having the same volume and a spherical shape.

The shape of the silver halide grains is not particularly limited, and may be various shapes such as a spherical shape, a cubic shape, a flat plate shape (hexagonal flat plate shape, triangular flat plate shape, tetragonal flat plate shape, etc.), octahedron shape, and tetrahedron shape. There can be a cube and a tetrahedron.
The silver halide grains may be composed of a uniform phase or a different surface layer. Moreover, you may have the localized layer from which a halogen composition differs in a particle | grain inside or surface.

  The silver halide emulsion, which is a coating solution for the emulsion layer used in the present invention, is Chimie etPhysique Photographique (Paul Montel, 1967) by P. Glafkides, Photographic Emulsion Chemistry (The Forcal Press, 1966) by GF Dufin. VLZelikman et al, Making and Coating Photographic Emulsion (published by The ForcalPress, 1964) and the like.

That is, as a method for preparing the silver halide emulsion, either an acidic method, a neutral method, or the like may be used. Also, as a method of reacting a soluble silver salt and a soluble halogen salt, a one-side mixing method, a simultaneous mixing method, Any combination of them may be used.
As a method for forming silver particles, a method of forming particles in the presence of excess silver ions (so-called back mixing method) can also be used. Furthermore, as one type of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is generated, that is, a so-called controlled double jet method can be used.
It is also preferable to form grains using a so-called silver halide solvent such as ammonia, thioether or tetrasubstituted thiourea. A tetrasubstituted thiourea compound is more preferable as such a method, and is described in JP-A-53-82408 and JP-A-55-77737.
Preferred thiourea compounds include tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. The addition amount of the silver halide solvent varies depending on the type of compound used, the target grain size, and the halogen composition, but is preferably 10 ⁻⁵ to 10 ⁻² mol per mol of silver halide.

In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal type and a narrow grain size distribution, and is preferably used in the present invention. it can.
Further, in order to make the grain size uniform, as described in British Patent No. 1,535,016, Japanese Patent Publication No. 48-36890, and Japanese Patent Publication No. 52-16364, silver nitrate or halogenated A method of changing the alkali addition rate according to the particle growth rate, or a method of changing the concentration of the aqueous solution as described in British Patent No. 4,242,445 and JP-A-55-158124 It is preferable to grow silver quickly in a range not exceeding the critical saturation. The silver halide emulsion used for forming the emulsion layer in the present invention is preferably a monodispersed emulsion, and the coefficient of variation represented by {(standard deviation of grain size) / (average grain size)} × 100 is 20% or less, and more. It is preferably 15% or less, and most preferably 10% or less.

  The silver halide emulsion used in the present invention may be a mixture of a plurality of types of silver halide emulsions having different grain sizes.

The silver halide emulsion used in the present invention may contain a metal belonging to Group VIII or Group VIIB. In particular, in order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, an iron compound, an osmium compound, a rhenium compound, or the like. These compounds may be compounds having various ligands. Examples of such ligands include cyanide ions, halogen ions, thiocyanate ions, nitrosyl ions, water, hydroxide ions, and such pseudohalogens. In addition to ammonia, organic molecules such as amines (methylamine, ethylenediamine, etc.), heterocyclic compounds (imidazole, thiazole, 5-methylthiazole, mercaptoimidazole, etc.), urea, thiourea and the like can be mentioned.
For high sensitivity, doping with a metal hexacyanide complex such as K ₄ [Fe (CN) ₆ ], K ₄ [Ru (CN) ₆ ] or K ₃ [Cr (CN) ₆ ] is advantageous. Done.

A water-soluble rhodium compound can be used as the rhodium compound. Examples of the water-soluble rhodium compound include a rhodium halide (III) compound, a hexachlororhodium (III) complex salt, a pentachloroacorodium complex salt, a tetrachlorodiacolodium complex salt, a hexabromorhodium (III) complex salt, and a hexaamine rhodium (III). ) Complex salt, trizalatodium (III) complex salt, K ₃ Rh ₂ Br _{9 and the} like.
These rhodium compounds are used by dissolving in water or a suitable solvent, and are generally used in order to stabilize the rhodium compound solution, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, odorous acid, hydrofluoric acid). Or a method of adding an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add another silver halide grain previously doped with rhodium and dissolve it at the time of silver halide preparation.

Examples of the iridium compound include hexachloroiridium complex salts such as K ₂ IrCl ₆ and K ₃ IrCl ₆ , hexabromoiridium complex salts, hexaammineiridium complex salts, and pentachloronitrosyliridium complex salts.
Examples of the ruthenium compound include hexachlororuthenium, pentachloronitrosylruthenium, K ₄ [Ru (CN) ₆ ] and the like.
Examples of the iron compound include potassium hexacyanoferrate (II) and ferrous thiocyanate.

The ruthenium and osmium are added in the form of water-soluble complex salts described in JP-A-63-2042, JP-A-1-2855941, JP-A-2-20852, JP-A-2-20855, etc. Preferable examples include hexacoordination complexes represented by the following formula.
[ML ₆ ] ^-n
(Here, M represents Ru or Os, and n represents 0, 1, 2, 3 or 4.)
In this case, the counter ion is not important, and for example, ammonium or alkali metal ions are used. Preferable ligands include a halide ligand, a cyanide ligand, a cyan oxide ligand, a nitrosyl ligand, a thionitrosyl ligand, and the like. Although the example of the specific complex used for this invention below is shown, this invention is not limited to this.

[RuCl ₆ ] ⁻³ , [RuCl ₄ (H ₂ O) ₂ ] ⁻¹ , [RuCl ₅ (NO)] ⁻² , [RuBr ₅ (NS)] ⁻² , [Ru (CO) ₃ Cl ₃ ] ^{− 2} , [Ru (CO) Cl ₅ ] ⁻² , [Ru (CO) Br ₅ ] ⁻² , [OsCl ₆ ] ⁻³ , [OsCl ₅ (NO)] ⁻² , [Os (NO) (CN) ₅ ] ^-2, [Os (NS) Br _5] ^-2, [Os (CN) _6] ^-4, _{[Os (O) 2 (CN)} 5 ] ^-4.

The amount of these compounds added is preferably 10 ⁻¹⁰ to 10 ⁻² mol / mol Ag per mol of silver halide, more preferably 10 ⁻⁹ to 10 ⁻³ mol / mol Ag.

In addition, in the present invention, silver halide containing Pd (II) ions and / or Pd metal can also be preferably used. Pd may be uniformly distributed in the silver halide grains, but is preferably contained in the vicinity of the surface layer of the silver halide grains. Here, Pd “contains in the vicinity of the surface layer of the silver halide grains” means that the Pd content is higher than the other layers within 50 nm in the depth direction from the surface of the silver halide grains. means.
Such silver halide grains can be prepared by adding Pd in the course of forming silver halide grains. After adding silver ions and halogen ions to 50% or more of the total addition amount, Pd Is preferably added. It is also preferred that Pd (II) ions be present in the surface layer of the silver halide by a method such as addition at the time of post-ripening.
The Pd-containing silver halide grains increase the speed of physical development and electroless plating, increase the production efficiency of a desired electromagnetic shielding material, and contribute to the reduction of production cost. Pd is well known and used as an electroless plating catalyst. However, in the present invention, Pd can be unevenly distributed on the surface layer of silver halide grains, so that extremely expensive Pd can be saved. is there.

In the present invention, the content of Pd ions and / or Pd metals contained in the silver halide is preferably 10 ^{−4 to} 0.5 mol / mol Ag with respect to the number of moles of silver in the silver halide. More preferably, it is 0.01 to 0.3 mol / mol Ag.
Examples of the Pd compound to be used include PdCl ₄ and Na ₂ PdCl ₄ .

  In the present invention, in order to further improve the sensitivity as an optical sensor, chemical sensitization performed with a photographic emulsion can be performed. As the chemical sensitization method, sulfur sensitization, selenium sensitization, chalcogen sensitization such as tellurium sensitization, noble metal sensitization such as gold sensitization, reduction sensitization and the like can be used. These are used alone or in combination. When the above chemical sensitization methods are used in combination, for example, sulfur sensitization method and gold sensitization method, sulfur sensitization method and selenium sensitization method and gold sensitization method, sulfur sensitization method and tellurium sensitization. A combination of a method and a gold sensitization method is preferable.

The sulfur sensitization is usually performed by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a predetermined time. As the sulfur sensitizer, known compounds can be used. For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. Can be used. Preferred sulfur compounds are thiosulfate and thiourea compounds. The amount of sulfur sensitizer added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, and is 10 ⁻⁷ to 10 ⁻² mol per mol of silver halide. It is preferably 10 ⁻⁵ to 10 ⁻³ mol.

  A known selenium compound can be used as the selenium sensitizer used for the selenium sensitization. That is, the selenium sensitization is usually carried out by adding unstable and / or non-labile selenium compounds and stirring the emulsion at a high temperature of 40 ° C. or higher for a predetermined time. As the unstable selenium compound, compounds described in JP-B-44-15748, JP-A-43-13489, JP-A-4-109240, JP-A-4-324855 and the like can be used. In particular, it is preferable to use compounds represented by general formulas (VIII) and (IX) in JP-A-4-324855.

  The tellurium sensitizer used for the tellurium sensitizer is a compound that generates silver telluride presumed to be a sensitization nucleus on the surface or inside of a silver halide grain. The silver telluride formation rate in the silver halide emulsion can be tested by the method described in JP-A-5-313284. Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211, No. 1,121,496, No. 1,295,462, No. 1,396,696, Canadian Patent No. 800,958, JP-A-4-204640 No. 4-271341, No. 4-3333043, No. 5-303157, Journal of Chemical Society, Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid 1102 (1979), ibid 645 (1979), Journal of Chemical Society Perkin Transaction (J. Chem. Soc. Perkin. Trans.) 1, 2191 (1980), S.C. Compounds described in S. Patai, The Chemistry of Organic Selenium and Tellunium Compounds, Vol 1 (1986), Vol 2 (1987) Can be used. In particular, compounds represented by the general formulas (II), (III) and (IV) in JP-A-5-313284 are preferred.

The amount of selenium sensitizer and tellurium sensitizer that can be used in the present invention varies depending on the silver halide grains used, chemical ripening conditions, and the like, but is generally 10 ⁻⁸ to 10 ⁻² per mole of silver halide. A mole, preferably about 10 ⁻⁷ to 10 ⁻³ mole is used. The conditions for chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

Examples of the noble metal sensitizer include gold, platinum, palladium, iridium and the like, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used for gold sensitization include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, thioglucose gold (I), and thiomannose gold (I). About 10 ⁻⁷ to 10 ⁻² mol per mol of silver halide. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of silver halide grain formation or physical ripening.

  In the present invention, reduction sensitization can be used. As the reduction sensitizer, stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used. A thiosulfonic acid compound may be added to the silver halide emulsion by the method described in European Patent Publication (EP) 293917. The silver halide emulsion used in the preparation of the light-sensitive material used in the present invention may be only one type, or two or more types (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, Combinations of different chemical sensitization conditions and different sensitivities) may be used. In particular, in order to obtain high contrast, as described in JP-A-6-324426, it is preferable to apply an emulsion with higher sensitivity as it is closer to the support.

[exposure]
In the present invention, the silver salt-containing layer provided on the support is exposed. The exposure can be performed using electromagnetic waves. Examples of the electromagnetic wave include light such as visible light and ultraviolet light, and radiation such as X-rays. Furthermore, a light source having a wavelength distribution may be used for exposure, or a light source having a specific wavelength may be used.

  Examples of the light source include scanning exposure using a cathode ray (CRT). The cathode ray tube exposure apparatus is simpler and more compact and less expensive than an apparatus using a laser. Also, the adjustment of the optical axis and color is easy. As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. For example, any one or two or more of a red light emitter, a green light emitter, and a blue light emitter are used. The spectral region is not limited to the above red, green, and blue, and phosphors that emit light in the yellow, orange, purple, or infrared region are also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used. An ultraviolet lamp is also preferable, and g-line of a mercury lamp, i-line of a mercury lamp, etc. are also used.

  In the present invention, exposure can be performed using various laser beams. For example, the exposure in the present invention is a monochromatic light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) that combines a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. A scanning exposure method using high-density light can be preferably used, and a KrF excimer laser, ArF excimer laser, F2 laser, or the like can also be used. In order to make the system compact and inexpensive, the exposure is preferably performed using a semiconductor laser, a semiconductor laser, or a second harmonic generation light source (SHG) that combines a solid-state laser and a nonlinear optical crystal. In order to design an apparatus that is particularly compact, inexpensive, long-life, and highly stable, it is preferable to perform exposure using a semiconductor laser.

Specifically, as a laser light source, a blue semiconductor laser with a wavelength of 430 to 460 nm (announced by Nichia Chemical at the 48th Applied Physics Related Conference in March 2001), a semiconductor laser (oscillation wavelength of about 1060 nm) is used. About 530 nm green laser, wavelength about 685 nm red semiconductor laser (Hitachi type No. HL6738MG), wavelength about 650 nm red semiconductor laser (wavelength converted by LiNbO ₃ SHG crystal with waveguide inversion domain structure) Hitachi type No. HL6501MG) is preferably used.

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

[Development processing]
In the present invention, after the silver salt-containing layer is exposed, development processing is further performed.
The method for forming a translucent conductive film of the present invention includes the following two forms depending on the form of the development treatment.
A mode in which a photosensitive silver halide black and white photosensitive material is chemically developed to form a metallic silver portion on the photosensitive material.
A mode in which a photosensitive silver halide black and white photosensitive material is dissolved and physically developed to form a metallic silver portion on the photosensitive material.
The aspect (1) is an integrated black-and-white development type, and a light-transmitting conductive film such as a light-transmitting electromagnetic wave shielding film or a light-transmitting conductive film is formed on the photosensitive material. The resulting developed silver is chemically developed silver and is highly active in the subsequent plating or physical development process in that it is a filament with a high specific surface.
In the above aspect (2), in the exposed portion, the silver halide grains are dissolved and deposited on developed silver (physical development nuclei), whereby a light-transmitting electromagnetic wave shielding film or a light-transmitting conductive film is formed on the photosensitive material. The translucent conductive film is formed. This is also an integrated black-and-white development type. Since the developing action is precipitation on the physical development nuclei, it can be highly active, but the resulting developed silver has a spherical shape with a small specific surface.
In any embodiment, either development of negative development processing and reversal development processing can be selected.
The term “chemical development” and “dissolved physical development” as used herein have the same meanings as are commonly used in the art. For example, Shinichi Kikuchi, “Photochemistry” (published by Kyoritsu Publishing Co., Ltd., 1955), C . E. K. It is described in “The Theory of Photographic Processes, 4th ed.” Edited by Mees (Mcmillan, 1977).
The dissolved physical developer used in the embodiment (2) is substantially 0.02 to 1.0 mol / liter, preferably 0.05, of the fixing agent component in the fixer in the chemical developer used in the embodiment (1). Except for this point, there is no essential difference in the composition of the processing solution, so the following description will be made along the aspect of chemical development.

The development processing can be performed using a normal development processing technique used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion coating layer, and the like. As long as the developed silver is obtained, the developer may be a black-and-white developer or a color developer (not required to develop color), and is not particularly limited, but is preferably a black-and-white developer, For example, PQ developer, MQ developer, MAA developer (methol / ascorbic acid developer) and the like can be used. For example, CN-16, CR-56, CP45X, FD-3, designated by Fuji Film Co., Ltd. Developers such as papitol, KODAK company-designated C-41, E-6, RA-4, D-72, or developers included in the kit, and D-19, D-85, D-8, etc. It is also possible to use a lith developer or a high-contrast positive developer known by the prescription name. In the above-described physical development or dissolution physical development mode (as described above as mode (2)), thiosulfate (sodium salt, ammonium salt, etc.) or thiocyanate (sodium salt) is used as a silver halide solubilizer in each developer. Salt, ammonium salt, etc.) may be added, and it is preferably added to highly active developers such as D-19, D-85, D-8, and D-72.
In the present invention, by performing the above exposure and development treatment, a metallic silver portion, preferably a patterned metallic silver portion is formed, and a light transmissive portion described later is formed.

  The development processing in the present invention can include a fixing processing performed for the purpose of removing and stabilizing the silver salt in the unexposed portion. For the fixing process in the present invention, a fixing process technique used for a silver salt photographic film, photographic paper, a printing plate-making film, a photomask emulsion mask, or the like can be used.

<Development process>
In the production method of the present invention, any of the developers described above can be used, but a black and white developer is preferred. As the developing agent, a color developing agent or a black and white developing agent is preferable, and an ascorbic acid developing agent or a dihydroxybenzene developing agent can be used particularly preferably. Examples of the ascorbic acid developing agent include ascorbic acid, isoascorbic acid, erythorbic acid and salts thereof (Na salt, etc.), but Na erythorbate is preferred from the viewpoint of cost. Examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, isopropyl hydroquinone, methyl hydroquinone, hydroquinone monosulfonate, and the like, and hydroquinone is particularly preferable. Ascorbic acid developing agents and dihydroxybenzene developing agents may or may not be used in combination with an auxiliary developing agent exhibiting superadditivity. Examples of the auxiliary developing agent exhibiting superadditivity with the ascorbic acid developing agent and dihydroxybenzene developing agent include 1-phenyl-3-pyrazolidones and p-aminophenols.

Specific examples of 1-phenyl-3-pyrazolidone or a derivative thereof used as an auxiliary developing agent include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4. -Methyl-4-hydroxymethyl-3-pyrazolidone and the like.
Examples of the p-aminophenol auxiliary developing agent include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine and the like. Among them, N-methyl-p-aminophenol is preferable.
The dihydroxybenzene-based developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / liter, but in the present invention, it is particularly preferably used at 0.23 mol / liter or more. More preferably, it is the range of 0.23-0.6 mol / liter. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.23-0.6 mol / liter, more preferably 0.23-0. It is preferable to use 5 mol / liter, and the latter in an amount of 0.06 mol / liter or less, more preferably 0.03 mol / liter to 0.003 mol / liter.

  In the present invention, both the development starter (that is, the mother liquor charged as a new solution in the developing tank) and the development replenisher have a pH increase when 0.1 mol of sodium hydroxide is added to 1 liter of the solution. It preferably has a pH buffering capacity of 0.5 or less. As a method for confirming that the development starting solution or development replenisher used has this pH buffering capacity, the pH of the development starting solution or development replenisher to be tested is adjusted to 10.5, and then 1 liter of this solution is hydroxylated. 0.1 mol of sodium is added, the pH value of the liquid at this time is measured, and if the increase in pH value is 0.5 or less, it is determined that it has the pH buffering ability defined above. In the production method of the present invention, it is particularly preferable to use a development starter and a development replenisher whose pH value rises to 0.4 or less when the above test is performed.

  As a method for imparting the above properties to the development initiator and the development replenisher, it is preferable to use a buffer. Examples of the buffer include carbonates, boric acid described in JP-A-62-286259, saccharides (for example, saccharose), oximes (for example, acetoxime), and phenols described in JP-A-60-93433. (For example, 5-sulfosalicylic acid), tertiary phosphate (for example, sodium salt, potassium salt) and the like can be used, and carbonate and boric acid are preferably used. The amount of the buffer (particularly carbonate) used is preferably 0.25 mol / liter or more, and particularly preferably 0.25 to 1.5 mol / liter.

  In the present invention, the pH of the development initiator is preferably 9.0 to 11.0, and particularly preferably 9.5 to 10.7. The pH of the developer replenisher and the pH of the developer in the developer tank during continuous processing are also in this range. As the alkali agent used for pH setting, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used.

  In the method for producing a light-transmitting conductive film or electromagnetic wave shielding film of the present invention, when processing 1 square meter of photosensitive material, the amount of developer replenisher added (replenisher) in the developer is 645 ml or less, preferably 484 to 30 milliliters, especially 484-100 milliliters. The development replenisher may have the same composition as the development starter, but may have a higher concentration than the starter by an amount commensurate with compensating consumption for the components consumed in development. preferable.

  In the developing solution for developing the light-sensitive material in the present invention (hereinafter, both the development starting solution and the developing replenisher may be simply referred to as “developing solution”), commonly used additives (for example, retaining agents) are used. (Constant, chelating agent). Examples of the preservative include sulfites such as sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The sulfite is preferably used in an amount of 0.20 mol / liter or more, more preferably 0.3 mol / liter or more, but if added in a large amount, it may cause silver stains in the developer. The upper limit is desirably 1.2 mol / liter. Particularly preferred is 0.35 to 0.7 mol / liter. Further, as a preservative for a dihydroxybenzene developing agent, a small amount of an ascorbic acid derivative may be used in combination with sulfite. Here, the ascorbic acid derivative is the same as ascorbic acid as the developing agent described above, and includes ascorbic acid and its stereoisomer erythorbic acid and its alkali metal salts (sodium and potassium salts). As the ascorbic acid derivative, sodium erythorbate is preferably used in terms of material cost. The addition amount of the ascorbic acid derivative is preferably in the range of 0.03 to 0.12, and particularly preferably in the range of 0.05 to 0.10, with respect to the dihydroxybenzene-based developing agent. When an ascorbic acid derivative is used as the preservative, it is preferable that the developer does not contain a boron compound.

  Additives that can be used in the developer other than the above include development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and dimethylformamide; diethanolamine, triethanolamine, and the like A development accelerator such as alkanolamine, imidazole or a derivative thereof, a mercapto compound, an indazole compound, a benzotriazole compound, or a benzimidazole compound may be included as an antifoggant or a black pepper inhibitor. Specific examples of the benzimidazole compound include 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5 -Nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenztriazole, sodium 4-[(2-mercapto-1,3,4-thiadiazol-2-yl) thio] butanesulfonate, 5- Examples include amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The content of these benzimidazole compounds is usually from 0.01 to 10 mmol, more preferably from 0.1 to 2 mmol, per liter of developer.

Further, various organic and inorganic chelating agents can be used in combination in the developer. As said inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate, etc. can be used. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used.
Examples of the above organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, acileic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid. Examples thereof include, but are not limited to, acid, itaconic acid, malic acid, citric acid, and tartaric acid.

  Examples of the aminopolycarboxylic acid include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, Triethylenetetramine hexaacetic acid, 1,3-diamino-2-propanol tetraacetic acid, glycol ether diamine tetraacetic acid, other publications of JP-A Nos. 52-25632, 55-67747, 57-102624, and others Examples thereof include compounds described in JP-A-53-40900.

The addition amount of these chelating agents is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol per liter of the developer.

  Furthermore, the compounds described in JP-A No. 61-267759 can be used as a dissolution aid in the developer. Further, the developer may contain a color toning agent, a surfactant, an antifoaming agent, a hardening agent, and the like as necessary. The development processing temperature and time are related to each other and are determined in relation to the total processing time. In general, the development temperature is preferably from about 20 ° C. to about 50 ° C., more preferably from 25 to 45 ° C. The development time is preferably 5 seconds to 2 minutes, more preferably 7 seconds to 1 minute 30 seconds.

  For the purpose of reducing developer transport cost, packaging material cost, space saving, etc., an embodiment in which the developer is concentrated and diluted before use, that is, supplied as a liquid concentrated developer is also preferred. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer. Note that “concentration of developer” here is a common expression in the industry and means “thickening”, and does not mean “concentration” by vacuum evaporation or the like.

  The development processing in the present invention can include a fixing processing performed for the purpose of removing and stabilizing the silver salt in the unexposed portion. For the fixing process in the present invention, a fixing process technique used for color photographs, black-and-white silver salt photographic films, photographic paper, printing plate-making films, X-ray photographic films, photomask emulsion masks, and the like can be used.

Preferred components of the fixing solution used in the fixing step include the following.
That is, fixing agents such as sodium thiosulfate, ammonium thiosulfate, and potassium thiocyanate, and pH of tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyrone, and salts thereof as necessary It is preferable to contain a hardener softener such as a buffering agent and preservative, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid and salts thereof. However, from the viewpoint of environmental protection in recent years, it is preferable that boric acid is not included. Examples of the fixing agent of the fixing solution used in the present invention include sodium thiosulfate and ammonium thiosulfate. Ammonium thiosulfate is preferable from the viewpoint of fixing speed. In view of this, sodium thiosulfate may be used. The amount of these known fixing agents used can be appropriately changed, and is generally about 0.1 to about 2 mol / liter. Most preferably, it is 0.2-1.5 mol / liter. If desired, the fixer may contain a hardener (eg, a water-soluble aluminum compound), a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, ammonia, sulfuric acid). ), Chelating agents, surfactants, wetting agents, fixing accelerators.

Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. A known antifoaming agent may be added to the fixing solution.
Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include thiourea derivatives described in JP-B Nos. 45-35754, 58-122535, and 58-122536; alcohols having a triple bond in the molecule; Examples include thioether compounds described in US Pat. No. 4,126,459; mesoionic compounds described in JP-A-4-229860, and compounds described in JP-A-2-44355 may be used. Examples of the pH buffer include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, and adipic acid, boric acid, phosphate, sulfite, and the like. Inorganic buffers can be used. As the pH buffer, acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffering agent is used for the purpose of preventing an increase in pH of the fixing agent due to bringing in the developer, and is preferably 0.01 to 1.0 mol / liter, more preferably 0.02 to 0.6 mol / liter. Use degree. The pH of the fixing solution is preferably from 4.0 to 6.5, particularly preferably from 4.5 to 6.0. Further, as the dye elution accelerator, compounds described in JP-A No. 64-4739 can also be used.

  Examples of the hardener in the fixing solution of the present invention include water-soluble aluminum salts and chromium salts. A preferred compound as the hardener is a water-soluble aluminum salt, and examples thereof include aluminum chloride, aluminum sulfate, potash and vane. A preferable addition amount of the hardener is 0.01 mol to 0.2 mol / liter, and more preferably 0.03 to 0.08 mol / liter.

The fixing temperature in the fixing step is preferably about 20 ° C. to about 50 ° C., more preferably 25 to 45 ° C. The fixing time is preferably 5 seconds to 1 minute, more preferably 7 seconds to 50 seconds. The replenishing amount of the fixing solution is preferably 600 ml / m ² or less with respect to the processing of the photosensitive material, 500 ml / m ² or less is more preferred. The concentration of the replenisher is set to a concentration commensurate with compensating consumption during processing under a predetermined replenishment amount.

The photosensitive material that has been subjected to development and fixing processing is preferably subjected to water washing treatment or stabilization treatment (also referred to as water washing substitute stabilization treatment). In the above water washing treatment or stabilization treatment, the amount of washing water (or stabilizing solution replenishment amount) is usually 20 liters or less per 1 m ^{2 of the} photosensitive material, and a replenishing amount of 3 liters or less (including 0, ie, water washing). ). For this reason, not only water saving treatment is possible, but piping for installing an automatic processor can be eliminated. As a method for reducing the replenishment amount of flush water, a multi-stage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. When this multi-stage countercurrent system is applied to the production method of the present invention, the photosensitive material after fixing is gradually processed in contact with the normal direction, that is, in the direction of the processing solution not contaminated with the fixing solution. Furthermore, efficient washing with water is performed. Moreover, when performing water washing with a small amount of water, it is more preferable to provide the washing tank of a squeeze roller and a crossover roller as described in Unexamined-Japanese-Patent No. 63-18350, 62-287252, etc. Further, various oxidant additions and filter filtration may be combined in order to reduce the environmental load related to wastewater pollution, which is a problem at the time of washing with a small amount of water. Further, in the above method, a part or all of the overflow liquid from the washing bath or stabilization bath generated by replenishing the washing bath or stabilization bath with water subjected to the fouling means according to the treatment, As described in JP-A-60-235133, it can also be used for a processing solution having fixing ability, which is a previous processing step. In addition, water-soluble surfactants and antifoaming agents are added to prevent unevenness of water bubbles that are likely to occur during washing with a small amount of water and / or to prevent the processing agent component adhering to the squeeze roller from being transferred to the processed film. Also good.

  In the washing treatment or stabilization treatment, a dye adsorbent described in JP-A-63-163456 may be installed in a washing tank in order to prevent contamination with a dye eluted from the photosensitive material. In the stabilization treatment following the water washing treatment, baths containing the compounds described in JP-A-2-2013357, JP-A-2-132435, JP-A-1-102553, and JP-A-46-44446 are disclosed. May be used as the final bath of the light-sensitive material. At this time, ammonium compounds, metal compounds such as Bi, Al, fluorescent brighteners, various chelating agents, film pH regulators, hardeners, bactericides, fungicides, alkanolamines and surfactants are added as necessary. It can also be added. Water used in the water washing process or stabilization process includes tap water, water deionized, halogen, UV germicidal lamps, and water sterilized by various oxidizing agents (such as ozone, hydrogen peroxide, and chlorates). It is preferable to use it. Further, washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. The bath temperature and time at the water washing treatment or the stabilization temperature are preferably 0 to 50 ° C. and 5 seconds to 2 minutes.

  For storage of processing solutions such as developer and fixing solution used in the present invention, it is preferable to store them in a packaging material having low oxygen permeability described in JP-A-61-73147. Moreover, when reducing the replenishment amount, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the treatment tank with the air. The roller-conveying type automatic developing machine is described in US Pat. Nos. 3,025,795 and 3,545,971 and the like, and is simply referred to as a roller-conveying processor in this specification. The roller transport type processor is preferably composed of four steps of development, fixing, washing and drying. In the present invention, other steps (for example, a stopping step) are not excluded, but the four steps are followed. Most preferred. Further, four steps by a stabilization step may be used instead of the water washing step.

  As long as the silver halide photographic material is applied to the present invention, the mass of the metallic silver contained in the exposed portion after development processing is 50% by mass with respect to the mass of silver contained in the exposed portion before exposure. It is preferable that it is the above content rate, and it is further more preferable that it is 80 mass% or more. If the mass of silver contained in the exposed portion is 50% by mass or more based on the mass of silver contained in the exposed portion before exposure, it is preferable because high conductivity can be obtained.

  The gradation after development processing in the present invention is not particularly limited, but is preferably more than 4.0. When the gradation after the development processing exceeds 4.0, the conductivity of the conductive metal portion can be increased while keeping the transparency of the light transmissive portion high. Examples of means for setting the gradation to 4.0 or higher include the aforementioned doping of rhodium ions and iridium ions.

Even if the development processing agent and the fixing processing agent in the present invention are solid, the same result as the liquid agent can be obtained, but from the viewpoint of storage stability and the like, the solid processing agent is preferable. The following describes the solid processing agent.
As the solid preparation in the present invention, known forms (powder, granules, granules, lumps, tablets, compactors, briquettes, plates, rods, pastes, etc.) can be used. These solid agents may be coated with a water-soluble coating agent or film in order to separate components that react with each other upon contact, or components that react with each other may be separated in a plurality of layers. These may be used in combination.

  Known coating materials and granulation aids can be used, but polyvinyl pyrrolidone, polyethylene glycol, polystyrene sulfonic acid, and vinyl compounds are preferred. In addition, JP-A-5-45805, column 2, line 48 to column 3, line 13 can be referred to.

  In the case of a plurality of layers, a component that does not react even when contacted may be sandwiched between components that react with each other, and processed into tablets, briquettes, etc. It may be configured and packaged. These methods are disclosed in, for example, JP-A-61-259921, JP-A-4-16841, JP-A-4-78848, and JP-A-5-93991.

The bulk density of the solid processing agent is preferably 0.5 to 6.0 g / cm ^3, particularly tablets preferably 1.0 to 5.0 g / cm ^3, the granules is 0.5 to 1.5 g / cm ³ preferable.

  Any known method can be used for producing the solid processing agent in the present invention. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, 4-32837, 4-78848, 5-93991, 4-85533, 4-85534, 4-85535, 5-134362, 5-197070, 5-2029898, 5-224361, 6 Nos. 138604, 6-138605, and 8-286329 can be referred to.

  More specifically, rolling granulation method, extrusion granulation method, compression granulation method, pulverization granulation method, stirring granulation method, spray drying method, dissolution coagulation method, briquetting method, roller compacting method, etc. Can be used.

  The solubility of the solid agent in the present invention can be adjusted by changing the surface state (smooth, porous, etc.), partially changing the thickness, or forming a hollow donut shape. Furthermore, it is also possible to take a plurality of shapes in order to give different solubility to a plurality of granulated products or to match the solubility of materials having different solubility. Moreover, the multilayer granulated material from which a composition differs in the surface and an inside may be sufficient.

  The packaging material of the solid agent is preferably a material having low oxygen and moisture permeability, and the packaging material may be a known material such as a bag shape, a cylindrical shape, or a box shape. JP-A-6-242585 to JP-A-6-242588, JP-A-6-247432, JP-A-6-247448, JP-A-6-301189, JP-A-7-5664, JP-A-7-5666. In order to reduce the storage space for the waste packaging material, it is also preferable to use a foldable shape as disclosed in JP-A-7-5669. These packaging materials may have a screw cap, a pull top, an aluminum seal attached to the processing agent outlet, or heat-sealing the packaging material, but other known materials may be used, and there is no particular limitation. do not do. Furthermore, it is preferable to recycle or reuse waste packaging materials for environmental conservation.

  The method for dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, a dissolution having a dissolution part as described in JP-A-9-80718 and a part for stocking the finished liquid. A processing agent is supplied to the circulation system of an automatic processor as described in a method of dissolving in an apparatus and replenishing from a stock section, JP-A-5-119454, JP-A-6-19102, and JP-A-7-261357. There are a method of charging and dissolving / replenishing, a method of charging and dissolving a processing agent according to the processing of the photosensitive material by an automatic developing machine incorporating a dissolution tank, etc., but any other known method can be used. it can. In addition, the processing agent may be input manually, or may be automatically opened and automatically input by a dissolution apparatus or an automatic developing machine having an opening mechanism as described in JP-A-9-138495, The latter is preferable from the viewpoint of the working environment. Specifically, there are a method of breaking through the take-out port, a method of peeling, a method of cutting, a method of cutting out, and methods described in JP-A-6-19102 and JP-A-6-95331.

  The development process is not limited to the above-described development process using a liquid developer. In this case, for example, JP-A-2004-184693, 2004-334077, 2005-010752, JP-A-2004-244080, 2004-085655, etc. The description is applicable.

[Activation processing]
In the present invention, an activation process is performed on the photosensitive material after the development process. The activation process facilitates metal deposition in a plating or physical development process subsequent to the conductive metal portion formed during development.
The activation liquid in the present invention is a liquid having the ability to remove the plating-inhibiting component formed on the surface of the conductive metal part after the development processing.
The plating inhibiting component refers to an oxide, sulfide, or halide formed on the surface of the conductive metal portion. Specific examples include silver sulfide and silver iodide.
The solution having the ability to remove the plating inhibitory component is a solution containing a reducing substance, a metal dissolving agent, a sulfide dissolving agent, and / or a halogen dissolving agent.

Examples of the reducing substance include alkali metal salts of borohydride (tetrahydroboric acid), preferably sodium borohydride and potassium borohydride. The concentration in the activation bath is 0.005 to 10 g / L, preferably 0.01 to 6 g / L, and more preferably 0.015 to 0.8 g / L.
Examples of the metal solubilizer include water-soluble silver salts, preferably silver nitrate. The concentration in the activation bath is 5 to 1000 g / L, preferably 10 to 1000 g / L, and more preferably 30 to 1000 g / L.
The sulfide solubilizer is a strong acid having a pK of 2 or less, and examples thereof include nitric acid, sulfuric acid, and hydrochloric acid. The concentration in the activation bath is 0.5 to 200 g / L, preferably 1 to 180 g / L, and more preferably 3 to 120 g / L.
Examples of the silver halide solvent include alkali halides, preferably sodium chloride, potassium chloride and ammonium chloride. The concentration in the activation bath is 0.5 to 100 g / L, preferably 5 to 80 g / L, and more preferably 10 to 60 g / L.

The activation treatment is characterized by containing at least one compound selected from the above-described reducing substance, metal dissolving agent, sulfide dissolving agent, and / or halogen dissolving agent. The developed silver surface does not have the harmful effect of being hindered by the adsorbing substance, and plating or physical development is effectively performed to form a conductive metal film having excellent conductivity. The reason why the high conductivity of the translucent conductive film such as the electromagnetic wave shielding film or the transparent electrode obtained by the activation bath of the present invention is improved is that the electrodeposition inhibitor on the surface of developed silver is the above (1) to ( It is considered that a clean surface is secured by being removed from the surface by the compound of group 4). In addition, when the surface of developed silver formed by black and white development of the photosensitive material was analyzed by XPS, a binding energy peak due to the bond of Ag-I or Ag-S was observed. When processed, the disappearance, reduction or movement of these peaks is observed, confirming the above-described mechanism of action.
In this respect, the above-described activation bath according to the present invention is supplemented by a conventionally known activation bath, that is, a noble metal compound bath represented by a palladium compound that reinforces a metal nucleus to be plated (see, for example, 2004-269992). A treatment bath having a force action is completely different in composition and action mechanism, but is functionally called an activation bath.
The immersion time of the activation bath of the present invention is 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes.
The temperature of the activation bath of the present invention is 15 ° C to 60 ° C, preferably 25 ° C to 55 ° C.

[Physical development and plating]
In the present invention, for the purpose of imparting conductivity to the metal silver portion formed by the exposure and development processing, physical development and / or plating treatment for supporting the conductive metal particles on the metal silver portion is performed. In the present invention, it is possible to carry the conductive metal particles on the metallic part only by physical development or plating treatment, but it is also possible to carry the conductive metal particles on the metallic silver part by further combining physical development and plating treatment. it can.
“Physical development” in the present invention means that metal particles such as silver ions are reduced with a reducing agent on metal or metal compound nuclei to deposit metal particles. This physical development is used for instant B & W film, instant slide film, printing plate production and the like, and the technology can be used in the present invention.
Further, the physical development may be performed simultaneously with the development processing after exposure or separately after the development processing.

In the present invention, for the plating treatment, electroless plating (chemical reduction plating or displacement plating), electrolytic plating, or both electroless plating and electrolytic plating can be used. For the electroless plating in the present invention, a known electroless plating technique can be used, for example, an electroless plating technique used for a printed wiring board or the like can be used, and the electroless plating is an electroless copper plating. Preferably there is.
Chemical species contained in the electroless copper plating solution include copper sulfate and copper chloride, formalin and glyoxylic acid as the reducing agent, EDTA and triethanolamine as the copper ligand, etc., as well as stabilization of the bath and plating film. Examples of the additive for improving the smoothness include polyethylene glycol, yellow blood salt, and bipyridine. Examples of the electrolytic copper plating bath include a copper sulfate bath and a copper pyrophosphate bath.

  The plating rate during the plating treatment in the present invention can be performed under moderate conditions, and high-speed plating of 5 μm / hr or more is also possible. In the plating treatment, various additives such as a ligand such as EDTA can be used from the viewpoint of improving the stability of the plating solution.

[Oxidation treatment]
In the present invention, the metallic silver portion after the development treatment and the conductive metal portion formed after the physical development and / or plating treatment are preferably subjected to an oxidation treatment. By performing the oxidation treatment, for example, when a metal is slightly deposited on the light transmissive portion, the metal can be removed and the light transmissive portion can be made almost 100% transparent.
Examples of the oxidation treatment include known methods using various oxidizing agents such as Fe (III) ion treatment. The oxidation treatment can be performed after exposure and development processing of the silver salt-containing layer, or after physical development or plating treatment, and may be performed after development processing and after physical development or plating treatment.

  In the present invention, the metallic silver portion after the exposure and development treatment can be further treated with a solution containing Pd. Pd may be a divalent palladium ion or metallic palladium. This treatment can accelerate electroless plating or physical development speed.

[Conductive metal part]
Next, the conductive metal part in the present invention will be described.
In the present invention, the conductive metal portion is formed by supporting the conductive metal particles on the metal silver portion by subjecting the metal silver portion formed by the exposure and development processing described above to physical development or plating treatment.
Metal silver may be formed in an exposed part or in an unexposed part. The silver salt diffusion transfer method (DTR method) using physical development nuclei is to form metallic silver in unexposed areas. In the present invention, it is preferable to form metallic silver in the exposed portion in order to increase transparency.
As the conductive metal particles supported on the metal part, in addition to the above-mentioned silver, copper, aluminum, nickel, iron, gold, cobalt, tin, stainless steel, tungsten, chromium, titanium, palladium, platinum, manganese, zinc, rhodium And particles of metals such as these, or alloys of these in combination. From the viewpoint of conductivity, cost, etc., the conductive metal particles are preferably copper, aluminum or nickel particles. Moreover, when providing magnetic field shielding properties, it is preferable to use paramagnetic metal particles as the conductive metal particles.

  In the conductive metal part, the conductive metal particles contained in the conductive metal part are copper particles from the viewpoint of increasing the contrast and preventing the conductive metal part from being oxidized and discolored over time. It is more preferable that at least the surface thereof is blackened. The blackening treatment can be performed using a method performed in the printed wiring board field. For example, blackening treatment is performed by treating at 95 ° C. for 2 minutes in an aqueous solution of sodium chlorite (31 g / l), sodium hydroxide (15 g / l), and trisodium phosphate (12 g / l). Can do.

The conductive metal part preferably contains 50% by mass or more, and more preferably 60% by mass or more of silver with respect to the total mass of the metal contained in the conductive metal part. When silver is contained in an amount of 50% by mass or more, the time required for physical development and / or plating treatment can be shortened, the productivity can be improved, and the cost can be reduced.
Furthermore, when copper and palladium are used as the conductive metal particles forming the conductive metal part, the total mass of silver, copper and palladium is 80% by mass or more based on the total mass of the metal contained in the conductive metal part. It is preferable that it is 90 mass% or more.

Since the conductive metal portion in the present invention carries conductive metal particles, good conductivity can be obtained. For this reason, the surface resistance value of the translucent electromagnetic wave shielding film (conductive metal portion) of the present invention is preferably 10 ³ Ω / sq or less, more preferably 2.5 Ω / sq or less. More preferably, it is 5 Ω / sq or less, and most preferably 0.1 Ω / sq or less.

When the conductive metal portion of the present invention is used as a light-transmitting electromagnetic wave shielding material, a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid, and the like, It is preferably a geometric figure combining (positive) n-gons such as (positive) hexagons and (positive) octagons, circles, ellipses, stars, etc., and has a mesh shape composed of these geometric figures. Is more preferable. From the viewpoint of EMI shielding properties, the triangular shape is the most effective, but from the viewpoint of visible light transmittance, if the line width is the same, the larger the n number of (positive) n-gons, the higher the aperture ratio and the visible light transmittance. This is advantageous because it becomes larger.
In addition, when it is a use of an electroconductive wiring material, the shape of the said electroconductive metal part is not specifically limited, Arbitrary shapes can be determined suitably according to the objective.

  In the use of the translucent electromagnetic wave shielding material, the conductive metal portion preferably has a line width of 40 μm or less and a line interval of 50 μm or more. The conductive metal portion may have a portion whose line width is wider than 20 μm for the purpose of ground connection or the like. From the viewpoint of making the image inconspicuous, the line width of the conductive metal portion is preferably less than 40 μm, more preferably less than 35 μm, further preferably less than 30 μm, and less than 25 μm. Is most preferred.

  The conductive metal portion in the present invention has an aperture ratio of preferably 85% or more, more preferably 90% or more, and most preferably 95% or more from the viewpoint of visible light transmittance. The aperture ratio is the ratio of the portion without fine lines forming the mesh to the whole. For example, the aperture ratio of a square lattice mesh having a line width of 10 μm and a pitch of 200 μm is 90%.

[Light transmissive part]
The “light transmitting part” in the present invention means a part having transparency other than the conductive metal part in the light transmitting electromagnetic wave shielding film. As described above, the transmittance of the light-transmitting portion is 90% or more, preferably 95, as shown by the minimum transmittance in the wavelength range of 380 to 780 nm excluding the contribution of light absorption and reflection of the support. % Or more, more preferably 97% or more, even more preferably 98% or more, and most preferably 99% or more.

It is preferable that the light transmissive portion substantially has no physical development nucleus from the viewpoint of improving the transparency. Unlike the conventional silver complex diffusion transfer method, the present invention does not require diffusion after dissolving unexposed silver halide and converting it to a soluble silver complex compound. It is preferable that it has substantially no nucleus.
Here, “substantially no physical development nuclei” means that the abundance of physical development nuclei in the light-transmitting portion is in the range of 0 to 5%.

  The light transmissive part in the present invention is formed together with the metal silver part by exposing and developing the silver salt-containing layer. The light transmissive part is preferably subjected to an oxidation treatment after the development treatment, and further after the physical treatment or plating treatment, from the viewpoint of improving the transparency.

[Layer structure of translucent electromagnetic shielding film]
The thickness of the support in the translucent electromagnetic wave shielding film of the present invention is preferably 5 to 200 μm, and more preferably 30 to 150 μm. If it is the range of 5-200 micrometers, the transmittance | permeability of a desired visible light will be obtained and handling will also be easy.

  The thickness of the metallic silver portion provided on the support before physical development and / or plating can be appropriately determined according to the coating thickness of the silver salt-containing layer coating applied on the support. The thickness of the metallic silver part is preferably 30 μm or less, more preferably 20 μm or less, further preferably 0.01 to 9 μm, and most preferably 0.05 to 5 μm. Moreover, it is preferable that a metal silver part is pattern shape. The metallic silver part may be a single layer or a multilayer structure of two or more layers. When the metallic silver portion has a pattern shape and has a multilayer structure of two or more layers, different color sensitivities can be imparted so that it can be exposed to different wavelengths. Thereby, when the exposure wavelength is changed and exposed, a different pattern can be formed in each layer. The translucent electromagnetic wave shielding film including the multilayered patterned metal silver portion formed as described above can be used as a high-density printed wiring board.

The thickness of the conductive metal part is preferable as the use of the electromagnetic shielding material for the display because the viewing angle of the display increases as the thickness decreases. Furthermore, as a use of the conductive wiring material, a thin film is required because of a demand for high density. From such a viewpoint, the thickness of the layer made of the conductive metal carried on the conductive metal part is preferably less than 9 μm, more preferably 0.1 μm or more and less than 5 μm, and more preferably 0.1 μm or more. More preferably, it is less than 3 μm.
In the present invention, a metallic silver portion having a desired thickness is formed by controlling the coating thickness of the silver salt-containing layer, and the thickness of the layer made of conductive metal particles can be freely controlled by physical development and / or plating treatment. Therefore, even a translucent electromagnetic wave shielding film having a thickness of less than 5 μm, preferably less than 3 μm, can be easily formed.

  In the conventional method using etching, it was necessary to remove and discard most of the metal thin film by etching, but in the present invention, a pattern containing only a necessary amount of conductive metal is provided on the support. Therefore, it is sufficient to use only the minimum amount of metal, which is advantageous from the viewpoints of reducing the manufacturing cost and the amount of metal waste.

[Functional films other than electromagnetic shielding]
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 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 a compound or metal that absorbs visible light in a specific wavelength range, anti-smudge layer with a function that easily removes dirt such as fingerprints, and hard to scratch A coating 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 silver salt-containing layer and the support, or may be provided on the same side.
These functional films may be directly bonded to the PDP, or may be bonded to a transparent substrate such as a glass plate or an acrylic resin plate separately from the plasma display panel main body. These functional films are called optical filters (or simply filters).

  In order to suppress reflection of external light and suppress a decrease in contrast, an antireflection layer provided with an antireflection function contains inorganic substances such as metal oxides, fluorides, silicides, borides, carbides, nitrides and sulfides. , Vacuum deposition method, sputtering method, ion plating method, ion beam assist method, etc., a method of laminating a single layer or a multilayer, such as a method of laminating a resin having different refractive index such as acrylic resin, fluorine resin, etc. There is. Moreover, the film which gave the antireflection process can also be affixed on this filter. If necessary, a non-glare layer or an anti-glare layer can be provided. For the non-glare layer or the anti-glare layer, a method of coating fine powders such as silica, melamine, acrylic, etc. into an ink and coating the surface can be used. The ink can be cured by thermal curing or photocuring. Further, a non-glare-treated or anti-glare-treated film can be pasted on the filter. Further, if necessary, a hard coat layer can be provided.

  The near-infrared absorbing layer is a layer containing a near-infrared absorbing dye such as a metal complex compound or a silver sputtered layer. Here, the silver sputter layer can cut light of 1000 nm or more from near infrared rays, far infrared rays to electromagnetic waves by alternately laminating dielectric layers and metal layers on a substrate by sputtering or the like. The dielectric layer is a transparent metal oxide such as indium oxide or zinc oxide, and the metal layer is generally silver or a silver-palladium alloy. Usually, the dielectric layer starts with 3 layers, 5 layers, 7 or 11 layers are stacked.

  A layer having a color tone adjustment function that absorbs visible light in a specific wavelength range is displayed in blue because the PDP has a characteristic that the phosphor that emits blue light emits red light in addition to blue. There is a problem that a portion to be displayed is displayed in a purplish color, and as a countermeasure against this, it is a layer that corrects colored light and contains a dye that absorbs light at around 595 nm.

  Since the translucent electromagnetic shielding film obtained by the production method of the present invention has good electromagnetic shielding properties and transparency, it can be used as a transparent electromagnetic shielding material. Furthermore, it can be used as various conductive wiring materials such as circuit wiring. In particular, the translucent electromagnetic wave shielding film of the present invention is a plasma front such as CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, EL (electroluminescence) display, microwave oven, electronic device, printed wiring board, etc. It can use suitably as a translucent electromagnetic wave shielding film used with a display panel.

[Other components of translucent conductive film]
Regarding the light-transmitting conductive film of the present invention represented by the light-transmitting electromagnetic wave shielding film and the light-transmitting conductive film, additional components other than those described above will be described.
(1) Adhesive layer A light-transmitting electromagnetic wave shielding film or a light-transmitting conductive film (for example, a transparent electrode) is represented by an optical filter, a liquid crystal display panel, a plasma display panel, other image display grat panels, or a CCD. When incorporated in an imaging semiconductor integrated circuit or the like, they are joined via an adhesive layer.

  The refractive index of the adhesive used in the present invention is preferably 1.40 to 1.70. This is because the difference between the transparent base material such as a plastic film used in the present invention and the refractive index of the adhesive is reduced to prevent the visible light transmittance from being lowered. When it is .40 to 1.70, the decrease in visible light transmittance is small and good.

The adhesive used in the present invention is preferably an adhesive that flows by heating or pressurization, and particularly an adhesive that exhibits fluidity by heating at 200 ° C. or lower or pressurization at 1 Kgf / cm ² or higher. Preferably there is. By using such an adhesive, the electromagnetic wave shielding adhesive film according to the present invention in which the conductive layer is embedded in the adhesive layer is allowed to flow and adhere to the display or plastic plate as the adherend. can do. Since it can flow, the electromagnetic wave shielding adhesive film can be easily adhered to an adherend having a curved surface or a complicated shape by lamination or pressure molding, particularly pressure molding. For this purpose, the softening temperature of the adhesive is preferably 200 ° C. or lower. Since the environment in which the electromagnetic wave shielding adhesive film is used is usually less than 80 ° C., the softening temperature of the adhesive layer is preferably 80 ° C. or more, and most preferably 80 to 120 ° C. from the viewpoint of workability. The softening temperature is a temperature at which the viscosity becomes 10 ¹² poises or less, and normally, the flow is recognized within a time of about 1 to 10 seconds at that temperature.

  Typical examples of the adhesive that flows by heating or pressurization as described above include the following thermoplastic resins. For example, natural rubber (refractive index n = 1.52), polyisoprene (n = 1.521), poly-1,2-butadiene (n = 1.50), polyisobutene (n = 1.505 to 1.51), polybutene (n = 1.513), poly- Such as 2-heptyl-1,3-butadiene (n = 1.50), poly-2-tert-butyl-1,3-butadiene (n = 1.506), poly-1,3-butadiene (n = 1.515) ) Polyenes such as ene, polyoxyethylene (n = 1.456), polyoxypropylene (n = 1.450), polyvinyl ethyl ether (n = 1.454), polyvinyl hexyl ether (n = 1.459), polyvinyl butyl ether (n = 1.456) Ethers, polyesters such as polyvinyl acetate (n = 1.467), polyvinyl propionate (n = 1.467), polyurethane (n = 1.5 to 1.6), ethyl cellulose (n = 1.479), polyvinyl chloride (n = 1.54 to 1.55) ), Polyacrylonitrile (n = 1.52), polymethacrylonitrile (n = 1.52), polysulfone (n = 1.633), polysulfide (n = 1.6), phenoxy resin (n = 1.5 to 1.6), polyethyl acrylate (n = 1.469), polybutyl acrylate (n = 1.466), poly-2-ethylhexyl acrylate (n = 1.463) Poly-t-butyl acrylate (n = 1.464), poly-3-ethoxypropyl acrylate (n = 1.465), polyoxycarbonyltetramethylene (n = 1.465), polymethyl acrylate (n = 1.472-1.480), polyisopropyl Methacrylate (n = 1.473), polydodecyl methacrylate (n = 1.474), polytetradecyl methacrylate (n = 1.475), poly-n-propyl methacrylate (n = 1.484), poly-3,3,5-trimethylcyclohexyl methacrylate ( n = 1.484), polyethyl methacrylate (n = 1.485), poly-2-nitro-2-methylpropyl methacrylate (n = 1.487), poly-1,1-diethylpropyl methacrylate (n = 1.489) and poly (meth) acrylic acid esters such as polymethyl methacrylate (n = 1.489) can be used. Two or more kinds of these acrylic polymers may be copolymerized as needed, or two or more kinds may be blended and used.

  Further, copolymer resins other than acrylic resin and other than acrylic include epoxy acrylate (n = 1.48 to 1.60), urethane acrylate (n = 1.5 to 1.6), polyether acrylate (n = 1.48 to 1.49), polyester acrylate (n = 1.48 ~ 1.54) can also be used. In particular, urethane acrylate, epoxy acrylate, and polyether acrylate are excellent from the viewpoint of adhesiveness. Examples of epoxy acrylate include 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, and resorcinol. (Meth) acrylic such as diglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether An acid adduct is mentioned. A polymer having a hydroxyl group in the molecule such as epoxy acrylate is effective for improving the adhesion. These copolymer resins can be used in combination of two or more as required. The softening temperature of the polymer used as these adhesives is preferably 200 ° C. or less, and more preferably 150 ° C. or less from the viewpoint of handleability. Since the environment in which the electromagnetic wave shielding adhesive film is used is usually 80 ° C. or lower, the softening temperature of the adhesive layer is most preferably 80 to 120 ° C. in view of processability. On the other hand, it is preferable to use a polymer having a weight average molecular weight (measured using a standard polystyrene calibration curve by gel permeation chromatography, the same applies hereinafter) of 500 or more. When the molecular weight is 500 or less, the cohesive force of the adhesive composition is too low, and the adhesion to the adherend may be reduced. You may mix | blend additives, such as a diluent, a plasticizer, antioxidant, a filler, a coloring agent, a ultraviolet absorber, and a tackifier, with the adhesive agent used by this invention as needed. The thickness of the adhesive layer is preferably 10 to 80 μm, and more preferably 20 to 50 μm, more than the thickness of the conductive layer.

  The adhesive that covers the geometric figure has a refractive index difference of 0.14 or less with respect to the transparent plastic substrate. When the transparent plastic substrate is laminated with the conductive material via the adhesive layer, the difference in refractive index between the adhesive layer and the adhesive covering the geometric figure is 0.14 or less. This is because if the refractive index of the transparent plastic substrate and the adhesive, or the refractive index of the adhesive and the adhesive layer are different, the visible light transmittance is lowered. If the difference in refractive index is 0.14 or less, the visible light transmittance is reduced. The decrease in light transmittance is small and good. Adhesive materials that satisfy these requirements include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and tetrahydroxyphenylmethane type epoxy resin when the transparent plastic substrate is polyethylene terephthalate (n = 1.575; refractive index). , Novolac epoxy resin, resorcinol type epoxy resin, polyalcohol / polyglycol type epoxy resin, polyolefin type epoxy resin, epoxy resin such as alicyclic and halogenated bisphenol (all have a refractive index of 1.55 to 1.60) it can. Other than epoxy resin, natural rubber (n = 1.52), polyisoprene (n = 1.521), poly1,2-butadiene (n = 1.50), polyisobutene (n = 1.505 to 1.51), polybutene (n = 1.5125), poly- Such as 2-heptyl-1,3-butadiene (n = 1.50), poly-2-tert-butyl-1,3-butadiene (n = 1.506), poly-1,3-butadiene (n = 1.515) ) Polyenes such as ene, polyoxyethylene (n = 1.4563), polyoxypropylene (n = 1.4495), polyvinyl ethyl ether (n = 1.454), polyvinyl hexyl ether (n = 1.4591), polyvinyl butyl ether (n = 1.4563) Ethers, polyesters such as polyvinyl acetate (n = 1.4665), polyvinyl propionate (n = 1.4665), polyurethane (n = 1.5 to 1.6), ethyl cellulose (n = 1.479), polyvinyl chloride (n = 1.5 4-1.55), polyacrylonitrile (n = 1.52), polymethacrylonitrile (n = 1.52), polysulfone (n = 1.633), polysulfide (n = 1.6), phenoxy resin (n = 1.5-1.6), etc. Can do. These express suitable visible light transmittance.

  On the other hand, when the transparent plastic substrate is an acrylic resin, in addition to the above resins, polyethyl acrylate (n = 1.4685), polybutyl acrylate (n = 1.466), poly-2-ethylhexyl acrylate (n = 1.463), poly- t-butyl acrylate (n = 1.4638), poly-3-ethoxypropyl acrylate (n = 1.465), polyoxycarbonyltetramethacrylate (n = 1.465), polymethyl acrylate (n = 1.472-1.480), polyisopropyl methacrylate (n = 1.4728), polydodecyl methacrylate (n = 1.474), polytetradecyl methacrylate (n = 1.4746), poly-n-propyl methacrylate (n = 1.484), poly-3,3,5-trimethylcyclohexyl methacrylate (n = 1.484) ), Polyethyl methacrylate (n = 1.485), poly-2-nitro-2-methylpro Poly (meth) acrylic acid such as pill methacrylate (n = 1.4868), polytetracarbanyl methacrylate (n = 1.4889), poly-1,1-diethylpropyl methacrylate (n = 1.4889), polymethyl methacrylate (n = 1.4893) Esters can be used. Two or more kinds of these acrylic polymers may be copolymerized as necessary, or two or more kinds may be blended and used.

  Furthermore, epoxy acrylate, urethane acrylate, polyether acrylate, polyester acrylate, or the like can also be used as a copolymer resin of an acrylic resin and other than acrylic. In particular, epoxy acrylate and polyether acrylate are excellent from the viewpoint of adhesiveness. As the epoxy acrylate, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, resorcinol diglycidyl ether (Meth) acrylic acid adducts such as adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether Is mentioned. Epoxy acrylate has a hydroxyl group in the molecule and is effective in improving adhesiveness. These copolymer resins can be used in combination of two or more as required. The polymer used as the main component of the adhesive has a weight average molecular weight of 1,000 or more. When the molecular weight is 1,000 or less, the cohesive force of the composition is too low, and the adhesion to the adherend is reduced.

  As the curing agent for the adhesive, amines such as triethylenetetramine, xylenediamine, diaminodiphenylmethane, acid anhydrides such as phthalic anhydride, maleic anhydride, dodecyl succinic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, Diaminodiphenyl sulfone, tris (dimethylaminomethyl) phenol, polyamide resin, dicyandiamide, ethylmethylimidazole and the like can be used. These may be used alone or in combination of two or more. The addition amount of these crosslinking agents is selected in the range of 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight with respect to 100 parts by weight of the polymer. If the amount added is less than 0.1 parts by weight, curing may be insufficient, and if it exceeds 50 parts by weight, excessive crosslinking may occur, which may adversely affect adhesiveness. You may mix | blend additives, such as a diluent, a plasticizer, antioxidant, a filler, and a tackifier, with the resin composition of the adhesive agent used by this invention as needed. Then, the resin composition of this adhesive is applied to cover a part or the whole surface of the base material of the constituent material provided with a geometric figure drawn with a conductive material on the surface of the transparent plastic base material, After the solvent drying and heat curing steps, the adhesive film according to the present invention is obtained. The adhesive film having electromagnetic shielding properties and transparency obtained above can be used by directly attaching to an adhesive film adhesive such as a CRT, PDP, liquid crystal, EL display, an acrylic plate, a glass plate, etc. Affixed to a plate or sheet of a sheet and used as a display. Further, the adhesive film is used in the same manner as described above for a window or a case for looking inside a measuring apparatus, measuring apparatus or manufacturing apparatus that generates electromagnetic waves. Furthermore, it is provided in a window of a building or a window of an automobile that may be affected by an electromagnetic wave interference by a radio tower or a high voltage line. And it is preferable to provide a ground wire in the geometric figure drawn with the electroconductive material.

  The portion of the transparent plastic substrate from which the conductive material has been removed intentionally has unevenness to improve adhesion, or light is scattered on the surface to transfer the back surface of the conductive material. However, the transparency is impaired, but when a resin having a refractive index close to that of the transparent plastic substrate is smoothly applied to the uneven surface, irregular reflection is suppressed to a minimum and transparency is exhibited. Furthermore, the geometrical figure drawn with the conductive material on the transparent plastic substrate is not visually recognized because the line width is very small. Moreover, since the pitch is sufficiently large, it is considered that apparent transparency is expressed. On the other hand, since the pitch of the geometric figure is sufficiently smaller than the wavelength of the electromagnetic wave to be shielded, it is considered that excellent shielding properties are exhibited.

  As shown in Japanese Patent Application Laid-Open No. 2003-188576, the lamination of a transparent base film and a metal foil is performed by using heat such as an ethylene-vinyl acetate copolymer resin or an ionomer resin having high heat-fusibility as the transparent base film. When a fusible resin film is used alone or laminated with another resin film, it can be performed without providing an adhesive layer, but usually a dry laminating method using an adhesive layer. Lamination is performed by such means. Examples of the adhesive constituting the adhesive layer include adhesives such as acrylic resin, polyester resin, polyurethane resin, polyvinyl alcohol resin, vinyl chloride / vinyl acetate copolymer resin, or ethylene-vinyl acetate copolymer resin. In addition to these, thermosetting resins and ionizing radiation curable resins (such as ultraviolet curable resins and electron beam curable resins) can also be used.

  In general, the surface of the display is made of glass, so sticking with an adhesive is a transparent plastic film and a glass plate. If bubbles are formed on the adhesive surface or peeling occurs, the image is distorted. Problems such as the color appearing different from the original display occur. In any case, the problem of bubbles and peeling occurs when the pressure-sensitive adhesive peels from the plastic film or glass plate. This phenomenon may occur on both the plastic film side and the glass plate side, and peeling occurs on the side with weaker adhesion. Therefore, it is necessary that the adhesive force between the pressure-sensitive adhesive, the plastic film and the glass plate is high. Specifically, the adhesive strength between the transparent plastic film and glass plate and the pressure-sensitive adhesive layer is preferably 10 g / cm or more at 80 ° C. More preferably, it is 30 g / cm or more. However, a pressure-sensitive adhesive exceeding 2000 g / cm may not be preferable because the bonding operation becomes difficult. However, if this problem does not occur, it can be used without problems. Furthermore, it is also possible to provide an interleaving paper (separator) so that the portion of the pressure-sensitive adhesive not facing the transparent plastic film does not unnecessarily come into contact with other portions.

  The adhesive is preferably transparent. Specifically, the total light transmittance is preferably 70% or more, more preferably 80% or more, and most preferably 85 to 92%. Furthermore, it is preferable that the degree of purity is low. Specifically, 0 to 3% is preferable, and 0 to 1.5% is more preferable. The pressure-sensitive adhesive used in the present invention is preferably colorless so as not to change the original display color of the display. However, even if the resin itself is colored, if the thickness of the pressure-sensitive adhesive is thin, it can be regarded as substantially colorless. Similarly, when intentionally coloring as described later, it is not within this range.

  Examples of the pressure-sensitive adhesive having the above properties include acrylic resins, α-olefin resins, vinyl acetate resins, acrylic copolymer resins, urethane resins, epoxy resins, vinylidene chloride resins, vinyl chloride resins, Examples thereof include ethylene-vinyl acetate resin, polyamide resin, and polyester resin. Of these, acrylic resins are preferred. Even when the same resin is used, tackiness can be improved by methods such as reducing the amount of crosslinking agent added, adding a tackifier, or changing molecular end groups when synthesizing the pressure-sensitive adhesive by a polymerization method. Is also possible. Even if the same pressure-sensitive adhesive is used, it is possible to improve the adhesion by modifying the surface to which the pressure-sensitive adhesive is bonded, that is, the surface of the transparent plastic film or glass plate. Examples of such surface modification methods include physical methods such as corona discharge treatment and plasma glow treatment, and methods such as forming an underlayer for improving adhesion.

  From the viewpoints of transparency, colorlessness, and handling properties, the thickness of the pressure-sensitive adhesive layer is preferably about 5 to 50 μm. In the case where the pressure-sensitive adhesive layer is formed of an adhesive, the thickness is preferably reduced within the above range. Specifically, it is about 1 to 20 μm. However, when the display color of the display itself is not changed as described above and the transparency is within the above range, the thickness may exceed the above range.

(2) The peelable protective film The protective film does not necessarily have to be provided on both surfaces of the electromagnetic wave shielding sheet 1, and as shown in (a) of JP-A-2003-188576, Only the protective film 20 is provided on the mesh-like metal foil 11 ′, and it may not be provided on the transparent substrate film 14 side. Moreover, as shown to (b) of the said gazette, it has only the protective film 30 in the transparent base film 14 side of the laminated body 10, and does not need to have on metal foil 11 '. In addition, the part which attached | subjected the code | symbol common in the said gazette and shows the same thing.

  Lamination formed by laminating at least a transparent base film 14 in the electromagnetic wave shielding sheet 1 of the present invention and a transparent electromagnetic wave shielding layer made of a mesh-like metal foil 11 ′ in which apertures are closely arranged. Next, the layer structure of the body and the manufacturing process of the laminate will be described with reference to (a) to (f) of the above publication. In addition, about lamination | stacking of the protective film 20 or / and the protective film 30, it demonstrates anew after description of the manufacturing process of a laminated body.

  First, as shown to (a) of the said gazette, the laminated body by which the transparent base film 14 and the metal foil 11 were laminated | stacked through the adhesive bond layer 13 is prepared. As the transparent substrate film 14, a film such as an acrylic resin, a polycarbonate resin, a polypropylene resin, a polyethylene resin, a polystyrene resin, a polyester resin, a cellulose resin, a polysulfone resin, or a polyvinyl chloride resin can be used. Usually, a film of polyester resin such as polyethylene terephthalate resin having excellent mechanical strength and high transparency is preferably used. The thickness of the transparent substrate film 14 is not particularly limited, but is preferably about 50 μm to 200 μm from the viewpoint of mechanical strength and increasing resistance to bending, and the thickness may be increased. When the shielding sheet 1 is used by being laminated on another transparent substrate, the thickness may not necessarily be greater than this range. As needed, it is good to give a corona discharge process to one side or both surfaces of the transparent base film 14, or to provide an easily bonding layer.

  As described later with reference to the above-mentioned publication, the electromagnetic shielding sheet 1 is formed by laminating the above laminate on a substrate via an infrared cut filter layer, etc., and further strengthening the outermost surface. Since sheets having effects such as imparting antireflection properties and imparting antifouling properties are laminated and used, the protective film described above needs to be peeled off during such further lamination. It is desirable that the protective film is laminated on the metal foil side so that it can be peeled off.

  The peel strength when the protective film is laminated on the metal foil is preferably 5 mN / 25 mm width to 5 N / 25 mm width, more preferably 10 mN / 25 mm width to 100 mN / 25 mm width. If it is less than the lower limit, peeling is too easy and the protective film may peel off during handling or inadvertent contact, which is not preferable, and if it exceeds the upper limit, a large force is required for peeling, and at the time of peeling, The mesh-shaped metal foil may peel off from the transparent base film (or from the adhesive layer), which is also not preferable.

  In the electromagnetic wave shielding sheet 1 of the present invention, the lower surface side of a laminate (which may be accompanied by a blackening layer) in which a mesh-like metal foil is laminated on a transparent substrate film 14 via an adhesive layer 13. That is, the protective film to be laminated on the transparent base film side is such that the lower surface of the transparent base film is not damaged by handling or inadvertent contact, and each step of etching by providing a resist layer on the metal foil In order to protect the exposed surface of the transparent substrate film from contamination or erosion, particularly during etching.

  As in the case of the protective film described above, this protective film also needs to be peeled off when the laminated body is further laminated. Therefore, it is desirable that the protective film be laminated on the transparent substrate film side so as to be peelable. As with the protective film, the peel strength is preferably 5 mN / 25 mm width to 5 N / 25 mm width, more preferably 10 mN / 25 mm width to 100 mN / 25 mm width. If it is less than the lower limit, peeling is too easy and the protective film may be peeled off during handling or inadvertent contact. This is not preferable, and if it exceeds the upper limit, a large force is required for peeling.

  The protective film to be laminated on the transparent substrate film side is preferably resistant to etching conditions, for example, is not eroded during etching for several minutes by an etching solution of about 50 ° C., particularly its alkaline component, or dry etching. In this case, it is desirable to withstand a temperature condition of about 100 ° C. In addition, when laminating the photosensitive resin layer, when the laminate is dip coated (dip coating), the coating liquid adheres to the opposite surface of the laminate, so the photosensitive resin is used during the etching process. It is preferable that the adhesive strength of the photosensitive resin is obtained so that it does not peel off and drift in the etching solution, and when using the etching solution, it depends on the etching solution containing iron chloride, copper chloride, etc. It is preferable to have durability that resists contamination, or durability that resists erosion or contamination by a resist removing solution such as an alkaline solution.

  In order to satisfy each of the above points, as a film constituting the protective film, a polyolefin resin such as polyethylene resin, polypropylene resin, polyester resin such as polyethylene terephthalate resin, polycarbonate resin, or resin film such as acrylic resin is used. In addition, from the above viewpoint, at least the surface of the protective film, when applied to the laminate, is subjected to a corona discharge treatment or is laminated with an easy adhesion layer. Is preferred.

  Moreover, as an adhesive which comprises a protective film, an acrylate ester type | system | group, a rubber type, or a silicone type thing can be used.

  The protective film film material and the pressure sensitive adhesive material described above can also be applied as they are to the protective film applied to the metal foil side, so different protective films may be used as the two protective films. Things can be both protective films.

(3) Blackening treatment When the configuration diagram shown in JP-A-2003-188576 is described as an example, the metal foil may have a blackening layer (by a blackening treatment) on the transparent substrate film side, In addition to the antirust effect, it can impart antireflection properties, and the blackened layer can be formed by, for example, Co—Cu alloy plating, and can prevent reflection of the surface of the metal foil 11. Furthermore, a chromate treatment may be applied as a rust-proof treatment, which is immersed in a solution containing chromic acid or dichromate as a main component and dried to form a rust-proof coating. If necessary, it can be performed on one side or both sides of the metal foil, but commercially available chromated copper foil, etc., may be used. In the appropriate process The blackening layer may be formed by forming a photosensitive resin layer, which will be described later, as a resist layer using a composition colored in black, and after etching is completed. It can be formed by leaving the layer without removing it, or by a plating method that gives a black film.

  Further, as an example of the configuration including the blackening layer, the configuration shown in JP-A-11-266095 may be used. In the electromagnetic wave shielding plate, for example, the first blackening layer 3a and the second blackening layer 3a that form a mesh-like conductive pattern P formed by crossing a horizontal line x and a vertical line y. The blackened layer constituting the blackened layer 3b and the like can be formed by appropriately selecting and using it based on the following concept. In the present invention, there are two methods for forming the mesh-like conductive pattern P which is the main purpose, one of which is a metal plating method and the other method is an etching method. . In the present invention, the method of forming the first blackened layer 3a, the second blackened layer 3b, the materials used, and the like are different by adopting any of the above methods. That is, in the present invention, in order to form the conductive pattern P on the first blackened layer 3a, the second blackened layer 3b, and the like by a metal plating method or the like, it is possible to conduct the metal plating. When a blackening layer is necessary, and when blackening is performed in the final process by an etching method or an electrodeposition method, a nonconductive blackening layer can be formed using a nonconductive material or the like. . The conductive blackening layer can generally be formed using a conductive metal compound, for example, a compound such as nickel (Ni), zinc (Zn), copper (Cu), etc. The blackening layer is a paste-like black polymer material, such as black ink, or a black chemical conversion material, for example, a black compound formed by chemical conversion of the metal plating surface, and further electrodeposition. It can be formed using a cationic ionic polymer material such as an electrodeposition coating material. In the present invention, using the blackening layer forming method as described above, an appropriate method according to the manufacturing process in the manufacturing method of the electromagnetic wave shielding plate is selected and adopted to form the blackening layer. Can do.

Next, as a method of providing the blackening layer in the present invention, as shown in JP-A-11-266095, an insulating film that inhibits electrodeposition on the conductive substrate 11 such as a metal plate produced as described above. First, an electrodeposition substrate 14 having a mesh-like resist pattern 12 composed of the following is first immersed in an electrolytic solution such as blackened copper or blackened nickel, and plated by a known electrochemical plating method: Then, a mesh-like second blackened layer 3b made of a blackened copper layer or a blackened nickel layer is formed. In the present invention, the black plating bath can be a black plating bath mainly composed of nickel sulfate, and a commercially available black plating bath can also be used. For example, Shimizu Corporation black plating bath (trade name, Novroi SNC, Sn-Ni alloy system), Nippon Chemical Industry Co., Ltd. black plating bath (trade name, Nikka Black, Sn-Ni alloy system) ), A black plating bath (trade name, Ebony-chrome 85 series, Cr series) manufactured by Metal Chemical Industry Co., Ltd. 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 said black plating bath. Next, in the present invention, as shown in the above publication, the electrodeposition substrate 14 provided with the second blackening layer 3b is immersed in an electrolytic solution of a metal for shielding electromagnetic waves, A mesh-like conductive pattern 4 having a desired thickness is laminated and electrodeposited at a position corresponding to the second blackening layer 3b of the electrodeposition substrate. In the above, as the material constituting the mesh-like conductive pattern 4, the metal as the above-mentioned good conductive substance can be used as the most advantageous material. Therefore, when forming the above-mentioned metal electrodeposition layer, a general-purpose metal electrolyte can be used, so there are many kinds of inexpensive metal electrolytes, and the choice suitable for the purpose is free. There is an advantage that can be done. In general, Cu is frequently used as an inexpensive good conductive metal, and in the present invention, it is useful to use Cu in accordance with the purpose. Of course, other metals are also the same. It can be used for. Next, in the present invention, the mesh-like conductive pattern 4 need not be composed of only a single metal layer. For example, although not shown, the mesh-like conductive pattern 4 made of Cu in the above example is used. Since P is relatively soft and easily scratched, it can be a two-layer metal electrodeposition layer using a general-purpose hard metal such as Ni or Cr as its protective layer. Next, in the present invention, as shown in the following, after forming the mesh-like conductive pattern 4 as described above, for example, the surface of the mesh-like conductive pattern 4 is subjected to chemical conversion treatment. Specifically, for example, if the conductive pattern P is made of copper (Cu), the surface of copper is blackened as copper sulfide (CuS) by treating with hydrogen sulfide (H ₂ S). Then, the surface of the metal electrodeposition layer constituting the mesh-like conductive pattern 4 is blackened to form the first blackened layer 3a. The second blackened layer 3b, A mesh-like conductive pattern P formed by sequentially layering the pattern layer 4 and the first blackening layer 3a in this order is formed. In the present invention, the copper surface blackening treatment agent can be easily produced using a sulfide-based or sulfide-based compound, and there are many types of commercially available products, for example, Product name: Copa Black CuO, CuS, Selenium Copa Black No. 65 (made by Isolate Chemical Laboratories, Inc.), trade name, Ebonol C Special (made by Meltex Co., Ltd.), etc. can be used.

  In the electromagnetic wave shielding plate according to the present invention, the etching resist pattern 35 may be removed or may be left. When the etching resist pattern 35 is further removed, the etching resist pattern 35 is removed. After removing the pattern 35, the surface of the remaining conductive metal layer 33 can be blackened. Thus, the blackening treatment is performed using a known blackening treatment method such as a plating method such as black copper (Cu) or black nickel (Ni) or a chemical blackening treatment method. be able to.

(4) Composite Functional Layer Next, the function of the functional film will be described.
Since the display screen is difficult to see due to the reflection of lighting equipment, etc., the functional film (C) has anti-reflection (AR: anti-reflection) properties to suppress external light reflection, or a mirror image. It is necessary to have a function of anti-glare (AG: anti-glare) property to prevent engraving or anti-glare and anti-glare (ARAG) property having both characteristics. When the visible light reflectance on the display filter surface is low, not only the reflection is prevented but also the contrast and the like can be improved.

  The functional film having antireflection has an antireflection film, and specifically, a fluorine-containing transparent polymer resin having a refractive index of 1.5 or less, preferably 1.4 or less in the visible range, Magnesium fluoride, silicon-based resin, silicon oxide thin film, etc. formed as a single layer with an optical film thickness of 1/4 wavelength, metal oxides, fluorides, silicides, nitrides, sulfides with different refractive indexes However, the present invention is not limited to these, although there are two or more layers of organic compounds such as inorganic compounds such as silicon resins, acrylic resins, and fluorine resins. The visible light reflectance of the surface of the functional film (C) having antireflection properties is 2% or less, preferably 1.3% or less, more preferably 0.8% or less.

  The functional film having anti-glare property has an anti-glare film that is transparent to visible light having a fine uneven surface state of about 0.1 μm to 10 μm. Specifically, acrylic, silicon-based resin, melamine-based resin, urethane-based resin, alkyd-based resin, fluorine-based resin and other thermosetting or photo-curable resins, silica, organosilicon compounds, melamine, acrylic, etc. Inorganic particles or organic compound particles dispersed in an ink are applied and cured on a substrate. The average particle diameter of the particles is 1 to 40 μm. Alternatively, the anti-glare property can be obtained by applying the above-mentioned thermosetting or photo-curing resin to a substrate and pressing and curing a mold having a desired gloss value or surface state, but it is not necessarily limited to these methods. Is not to be done. The haze of the functional film having antiglare properties is 0.5% or more and 20% or less, preferably 1% or more and 10% or less. If the haze is too small, the antiglare property is insufficient, and if the haze is too large, the transmitted image sharpness tends to be low.

  In order to add scratch resistance to the display filter, it is also preferable that the functional film has a hard coat property. Examples of the hard coat film include thermosetting or photocurable resins such as acrylic resins, silicon resins, melamine resins, urethane resins, alkyd resins, and fluorine resins. There is no particular limitation. The thickness of these films is about 1 to 50 μm. As for the surface hardness of the functional film having hard coat properties, the pencil hardness according to JIS (K-5400) is at least H, preferably 2H, more preferably 3H or more. When an antireflection film and / or an antiglare film is formed on the hard coat film, a functional film having scratch resistance / antireflection property and / or antiglare property is preferably obtained.

The display filter is likely to adhere to dust due to electrostatic charging, and may be discharged and receive an electric shock when a human body comes into contact therewith, so an antistatic treatment may be required. Therefore, the functional film may have conductivity in order to impart antistatic ability. The electrical conductivity required in this case may be about 10 ¹¹ Ω / □ or less in terms of surface resistance. Examples of the method for imparting conductivity include a method of adding an antistatic agent to the film and a method of forming a conductive layer. Specific examples of the antistatic agent include trade name Pelestat (manufactured by Sanyo Kasei Co., Ltd.), trade name electro slipper (manufactured by Kao Corporation) and the like. Examples of the conductive layer include known transparent conductive films such as ITO, and conductive films in which conductive ultrafine particles such as ITO ultrafine particles and tin oxide ultrafine particles are dispersed. It is preferable that the hard coat film, the antireflection film, and the antiglare film have a conductive film or contain conductive fine particles.

  When the surface of the functional film (C) has antifouling properties, it is preferable since it can be easily removed when it is prevented from being smudged or smudged with fingerprints. What has antifouling property has non-wetting property with respect to water and / or fats and oils, and examples thereof include fluorine compounds and silicon compounds. Specific examples of the fluorine-based antifouling agent include trade name Optool (manufactured by Daikin), and examples of the silicon compound include trade name Takata Quantum (manufactured by NOF Corporation). When these antifouling layers are used for the antireflection film, an antireflection film having antifouling properties is obtained, which is preferable.

  The functional film preferably has UV-cutting properties for the purpose of preventing deterioration of pigments and polymer films described later. Examples of the functional film having an ultraviolet cutting property include a method of adding an ultraviolet absorbent to the polymer film described later and an ultraviolet absorbing film.

When the display filter is used in a temperature / humidity environment higher than room temperature and humidity, the pigment described later deteriorates due to moisture that has passed through the film, or moisture is present in the adhesive used for bonding or at the bonding interface. It is preferred that the functional film has gas barrier properties because it may be agglomerated and cloudy, or a tackifier in the adhesive material may be phase separated and deposited due to the influence of moisture. In order to prevent such pigment deterioration and fogging, it is important to prevent moisture from entering the pigment-containing layer and the adhesive layer, and the water vapor permeability of the functional film is 10 g / m ² · day or less. , Preferably 5 g / m ² · day or less.

  The polymer film, the conductive mesh layer, the functional film, and a transparent molded product, which will be described later, if necessary, are bonded together via an arbitrary pressure-sensitive adhesive or adhesive transparent to visible light. Specific examples of adhesives or adhesives include acrylic adhesives, silicone adhesives, urethane adhesives, polyvinyl butyral adhesives (PVB), ethylene-vinyl acetate adhesives (EVA), polyvinyl ether, Examples include regular polyester, melamine resin, etc. As long as there is practical adhesive strength, it may be in sheet form or liquid form. The pressure-sensitive adhesive can be suitably used as a pressure-sensitive adhesive. Bonding is performed by laminating each member after applying the sheet-like adhesive material or after applying the adhesive. The liquid material is an adhesive that is cured by being left at room temperature or heated after coating and bonding. Examples of the coating method include a bar coating method, a reverse coating method, a gravure coating method, a die coating method, and a roll coating method, and are selected in consideration of the type of adhesive, viscosity, coating amount, and the like. The thickness of the layer is not particularly limited, but is 0.5 μm to 50 μm, preferably 1 μm to 30 μm. It is preferable that the surface on which the pressure-sensitive adhesive layer is formed and the surface to be bonded are previously improved in wettability by an easy adhesion treatment such as an easy adhesion coat or a corona discharge treatment. In the present invention, the above-mentioned adhesive or adhesive transparent to visible light is referred to as a translucent adhesive.

  In the present invention, when a functional film is bonded onto the conductive mesh layer, a translucent adhesive layer is particularly used. A specific example of the translucent adhesive material used for the translucent adhesive material layer is the same as described above, but it is important that the thickness of the translucent adhesive layer can be sufficiently embedded. If the thickness of the conductive mesh layer is too thin, a gap will be formed due to insufficient embedding, and bubbles will be caught in the recesses, resulting in a display filter with turbidity and insufficient translucency. On the other hand, when the thickness is too large, problems such as an increase in the cost for producing the adhesive material and a deterioration in the handling of the members occur. When the thickness of the conductive mesh layer is d μm, the thickness of the translucent adhesive material is preferably (d−2) to (d + 30) μm.

  The visible light transmittance of the display filter is preferably 30 to 85%. More preferably, it is 35 to 70%. If it is less than 30%, the luminance is too low and the visibility is deteriorated. Further, if the visible light transmittance of the display filter is too high, the display contrast cannot be improved. The visible light transmittance in the present invention is calculated according to JIS (R-3106) from the wavelength dependence of the transmittance in the visible light region.

  In addition, when the functional film is bonded onto the conductive mesh layer through the translucent adhesive layer, air bubbles may be trapped in the recesses and become cloudy and the translucency may be insufficient. For example, when pressure treatment is performed, the gas that has entered between the members at the time of bonding can be defoamed or dissolved in an adhesive material to eliminate turbidity and improve translucency. The pressurizing process may be performed in the state of the above configuration or in the state of the display filter of the present invention.

  Examples of the pressurizing method include a method in which a laminate is sandwiched between flat plates, a method of pressing while pressing between nip rolls, and a method of pressing in a pressure vessel, but are not particularly limited. The method of pressurizing in the pressure vessel is preferable because the entire laminate is uniformly pressurized and there is no unevenness in pressurization, and a plurality of laminates can be processed at a time. An autoclave device can be used as the pressurized container.

  As the pressurizing condition, the higher the pressure is, the more air bubbles can be eliminated, and the processing time can be shortened. About 2 MPa to 2 MPa, preferably 0.4 to 1.3 MPa. The pressurization time varies depending on the pressurization conditions and is not particularly limited. However, if the pressurization time is too long, the processing time is increased and the cost is increased. Therefore, the holding time is preferably 6 hours or less under appropriate pressurization conditions. In particular, in the case of a pressurized container, it is preferable to hold for about 10 minutes to 3 hours after reaching the set pressure.

  Moreover, it may be preferable to heat simultaneously at the time of pressurization. By heating, the fluidity of the translucent pressure-sensitive adhesive material temporarily rises, and it becomes easy to defoam the entrained air bubbles, or the air bubbles easily dissolve in the adhesive material. The heating condition is room temperature or higher and about 80 ° C. or lower depending on the heat resistance of each member constituting the display filter, but is not particularly limited.

  Furthermore, the pressurizing process or the pressurizing and heating process is preferable because it can improve the adhesion after bonding between the members constituting the display filter.

  In the display filter of the present invention, a light-transmitting pressure-sensitive adhesive layer is provided on the other main surface on which the conductive mesh layer of the polymer film is not formed. Specific examples of the translucent adhesive material used for the translucent adhesive material layer are as described above, and are not particularly limited. The thickness is not particularly limited, but is 0.5 μm to 50 μm, preferably 1 μm to 30 μm. It is preferable that the surface on which the light-transmitting pressure-sensitive adhesive layer is formed and the surface to be bonded are previously improved in wettability by an easy adhesion treatment such as an easy adhesion coating or a corona discharge treatment.

  A release film may be formed on the translucent adhesive layer. That is, at least functional film / translucent adhesive layer / conductive mesh layer / polymer film / translucent adhesive layer) / release film. The release film is obtained by coating silicone or the like on the main surface of the polymer film that is in contact with the adhesive material layer. When the display filter of the present invention is bonded to the main surface of a transparent molded product described later, or when bonded to the display surface, for example, the front glass of a plasma display panel, the release film is peeled off to obtain a light-transmitting property. After the adhesive layer is exposed, it is bonded.

  The display filter of the present invention is mainly used for the purpose of blocking electromagnetic waves generated from various displays. A preferable example is a plasma display filter.

  As described above, since the plasma display generates intense near-infrared rays, the display filter of the present invention needs to cut not only electromagnetic waves but also near-infrared rays to a level where there is no practical problem. It is necessary that the transmittance in the wavelength region of 800 to 1000 nm is 25% or less, preferably 15% or less, and more preferably 10% or less. In addition, a display filter used in a plasma display is required to have a transmission color of neutral gray or blue gray. This is because it is necessary to maintain or improve the light emission characteristics and contrast of the plasma display, and a white having a slightly higher color temperature than the standard white may be preferred. Furthermore, it is said that a color plasma display has insufficient color reproducibility, and it is preferable to selectively reduce unnecessary light emission from the phosphor or discharge gas which is the cause. In particular, the emission spectrum of red display shows several emission peaks ranging from about 580 nm to about 700 nm, and the emission intensity on the short wavelength side is relatively strong and the red emission is not good in color purity close to orange. There is a problem. These optical properties can be controlled by using a dye. In other words, a near-infrared absorber is used for near-infrared cut, and a dye that selectively absorbs unnecessary light emission can be used to reduce unnecessary light emission. The color tone can be made suitable by using a dye having appropriate absorption in the visible region.

  As a method of containing a dye, (1) at least one kind of dye, a polymer film or a resin plate kneaded with a transparent resin, (2) at least one kind of dye, resin or resin monomer / organic system A polymer film or resin plate dispersed and dissolved in a solvent concentrate of a solvent and prepared by a casting method. (3) At least one dye is added to a resin binder and an organic solvent to form a paint, a polymer film or Any one or more of those coated on a resin plate and (4) a transparent adhesive material containing at least one pigment can be selected, but the invention is not limited thereto. The term “inclusion” as used in the present invention means that it is contained in a layer such as a base material or a coating film or an adhesive material, and of course, is applied to the surface of the base material or layer.

  The dye is a general dye or pigment having a desired absorption wavelength in the visible region, or a near-infrared absorber, and the type thereof is not particularly limited. For example, anthraquinone, phthalocyanine, methine Azomethine, oxazine, imonium, azo, styryl, coumarin, porphyrin, dibenzofuranone, diketopyrrolopyrrole, rhodamine, xanthene, pyromethene, dithiol, diiminium compounds, etc. In general, organic dyes that are also commercially available are listed. The type / concentration is determined by the absorption wavelength / absorption coefficient of the dye, the transmission characteristics / transmittance required for the display filter, and the type / thickness of the medium or coating film to be dispersed, and is not particularly limited.

  The plasma display panel has a high panel surface temperature, and especially when the environmental temperature is high, the temperature of the filter for the display also rises. Therefore, the dye has heat resistance that does not deteriorate significantly due to decomposition at 80 ° C., for example. Is preferred. In addition to heat resistance, some dyes have poor light resistance. When deterioration of plasma display light emission or external light due to ultraviolet rays / visible rays becomes a problem, by using a member containing an ultraviolet absorber or a member that does not transmit ultraviolet rays, it is possible to reduce deterioration of the dye due to ultraviolet rays, It is important to use a dye that does not significantly deteriorate by visible light. The same applies to humidity and a combined environment in addition to heat and light. When it deteriorates, the transmission characteristics of the display filter change, and the color tone changes or the near-infrared cutting ability decreases. Furthermore, in order to disperse in a medium or a coating film, solubility and dispersibility in an appropriate solvent are also important. In the present invention, two or more kinds of dyes having different absorption wavelengths may be contained in one medium or a coating film, or two or more mediums and coating films containing a dye may be contained.

  In the present invention, the methods (1) to (4) containing the above-described dye are polymer film (A) containing the dye, functional film (C) containing the dye, and translucency containing the dye. Any one or more forms of the pressure-sensitive adhesives (D1) and (D2) and other light-transmitting pressure-sensitive adhesives or adhesives containing a dye used for bonding can be used for the display filter of the present invention.

  In general, dyes are easily deteriorated by ultraviolet rays. Ultraviolet rays that the display filter receives under normal use conditions are included in external light such as sunlight. Therefore, in order to prevent deterioration of the dye due to ultraviolet rays, at least one layer selected from the dye-containing layer itself and the layer on the human side that receives external light from the layer has a layer having an ultraviolet cutting ability. It is preferable that For example, when the polymer film (A) contains a pigment, the light-transmitting pressure-sensitive adhesive layer and / or the functional film contains an ultraviolet absorber or has a functional film having an ultraviolet cutting ability. The pigment can be protected from ultraviolet rays contained in outside light. As the ultraviolet ray cutting ability necessary for protecting the dye, the transmittance in the ultraviolet region shorter than the wavelength of 380 nm is 20% or less, preferably 10% or less, more preferably 5% or less. The functional film having the ability to cut ultraviolet rays may be a coating film containing an ultraviolet absorber or an inorganic film that reflects or absorbs ultraviolet rays. Conventionally known UV absorbers such as benzotriazoles and benzophenones can be used, and their types and concentrations are dispersibility / solubility in the medium to be dispersed or dissolved, absorption wavelength / absorption coefficient, thickness of the medium. It is determined from the above and is not particularly limited. In addition, it is preferable that the layer or film having the ultraviolet ray cutting ability has little absorption in the visible light region and does not significantly reduce the visible light transmittance or exhibit a color such as yellow. In a functional film containing a dye, when a layer containing a dye is formed, the film or functional film on the human side of the layer only needs to have an ultraviolet cutting ability, and the polymer film contains the dye. When it does, what is necessary is just to have the functional film and functional layer which have ultraviolet-ray cutting ability in the person side from a film.

  The dye may also deteriorate due to contact with a metal. When using such a pigment | dye, it is still more preferable to arrange | position so that a pigment | dye may not contact a conductive mesh layer as much as possible. Specifically, the dye-containing layer is preferably a functional film, a polymer film, or a translucent adhesive layer, and particularly preferably a translucent adhesive layer.

  The display filter of the present invention has a polymer film (A), a conductive mesh layer (B), a functional film (C), a translucent adhesive layer (D1), and a translucent adhesive layer (D2). , (C) / (D1) / (B) / (A) / (D2), preferably composed of a conductive mesh layer (B) and a polymer film (A) and a function. The transparent film is bonded with the translucent adhesive layer (D1), and the translucent adhesive layer (D2) is provided on the main surface of the polymer film (A) opposite to the conductive mesh layer (B). It is attached.

  When the display filter of the present invention is mounted on the display, the functional film (C) is mounted on the person side, and the translucent adhesive layer (D2) is mounted on the display side.

  The display filter of the present invention is used by providing it on the front surface of the display as a front filter plate using a transparent molded product (E) described later as a support, and a translucent adhesive layer on the display surface. There is a method of using by bonding via (D2). In the former case, the display filter is relatively easy to install, and the support improves the mechanical strength and is suitable for protecting the display. In the latter case, it is possible to reduce the weight and thickness by eliminating the support, and it is possible to prevent reflection on the display surface, which is preferable.

  Examples of the transparent molded product include a glass plate and a translucent plastic plate. A plastic plate is preferable from the viewpoint of mechanical strength, lightness, and resistance to cracking. However, a glass plate can also be suitably used because of thermal stability with little deformation due to heat. Specific examples of the plastic plate include acrylic resin such as polymethyl methacrylate (PMMA), polycarbonate resin, transparent ABS resin and the like, but are not limited to these resins. In particular, PMMA can be suitably used because of its high transparency in a wide wavelength region and high mechanical strength. The thickness of the plastic plate is not particularly limited as long as sufficient mechanical strength and rigidity to maintain flatness without bending are obtained, but it is usually about 1 mm to 10 mm. The glass is preferably a semi-tempered glass plate or a tempered glass plate subjected to a chemical strengthening process or an air cooling strengthening process in order to add mechanical strength. Considering the weight, the thickness is preferably about 1 to 4 mm, but is not particularly limited. The transparent molded product can be subjected to various known pretreatments necessary before the film is bonded, and may be printed with a colored frame such as black on the portion that becomes the peripheral edge of the display filter.

  In the case of using a transparent molded product, the structure of the display filter is at least functional film (C) / translucent adhesive layer (D1) / conductive mesh layer (B) / polymer film (A) / translucent. Adhesive layer (D2) / transparent molded product (E). Moreover, the functional film (C) is provided through the translucent adhesive material layer on the main surface opposite to the surface to be bonded to the translucent adhesive material layer (D2) of the transparent molded product (E). Also good. In this case, it is not necessary to have the same function and configuration as the functional film (C) provided on the person side. For example, when it has antireflection ability, the back reflection of the display filter having the support is reduced. can do. Similarly, a functional film (C2) such as an antireflection film may be formed on the main surface opposite to the surface to be bonded to the transparent adhesive material layer (D2) of the transparent molded product (E). In this case, the functional film (C2) can be installed on the display with the human side, but as described above, the layer having the ability to cut off ultraviolet rays is provided on the human layer from the dye-containing layer and the dye-containing layer. Is preferred.

  For equipment that requires electromagnetic shielding, it is necessary to provide a metal layer inside the equipment case or use a conductive material in the case to shield the electromagnetic waves, but the display must be transparent like a display. In some cases, a window-like electromagnetic wave shielding filter having a light-transmitting conductive layer, such as the display filter of the present invention, is installed. Here, since the electromagnetic wave induces an electric charge after being absorbed in the conductive layer, if the electric charge is not released by taking the ground, the display filter oscillates again as an antenna and the electromagnetic wave shielding ability is lowered. Therefore, the display filter and the ground portion of the display body must be in electrical contact. Therefore, the above-mentioned translucent pressure-sensitive adhesive layer (D1) and functional film (C) need to be formed on the conductive mesh layer (B) leaving a conductive portion that can be electrically connected from the outside. is there. The shape of the conducting portion is not particularly limited, but it is important that there is no gap for electromagnetic wave leakage between the display filter and the display body. Therefore, it is preferable that the conductive portion is provided continuously at the peripheral edge of the conductive mesh layer (B). That is, it is preferable that the conducting portion is provided in a frame shape except for the central portion which is the display portion of the display.

  The conductive portion may be a mesh pattern layer or an unpatterned layer of metal foil, for example, but the metal foil solid layer may be used for good electrical contact with the ground portion of the display body. It is preferable that the conductive portion is not patterned like a layer.

  For example, when the conductive part is not patterned like, for example, a solid metal foil, and / or when the mechanical strength of the conductive part is sufficiently strong, the conductive part itself can be used as an electrode.

In order to protect the conductive part and / or to make good electrical contact with the ground part when the conductive part is a mesh pattern layer, it may be preferable to form an electrode on the conductive part. The electrode shape is not particularly limited, but is preferably formed so as to cover all the conductive portions.
The material used for the electrode is a single or a combination of two or more of silver, copper, nickel, aluminum, chromium, iron, zinc, carbon, etc. in terms of conductivity, resistance to contact and adhesion to a transparent conductive film. Alternatively, a paste made of a synthetic resin and a mixture of these simple substances or alloys, or a paste made of a mixture of borosilicate glass and these simple substances or alloys can be used. Conventionally known methods can be employed for printing and coating the paste. Moreover, a commercially available conductive tape can also be used conveniently. The conductive tape has conductivity on both sides, and a single-sided adhesive type and a double-sided adhesive type using a carbon-dispersed conductive adhesive can be suitably used. The thickness of the electrode is not particularly limited, but is about several μm to several mm.

  ADVANTAGE OF THE INVENTION According to this invention, the filter for displays excellent in the optical characteristic which can maintain or improve the image quality, without significantly impairing the brightness | luminance of a plasma display can be obtained. In addition, it has excellent electromagnetic shielding ability to block electromagnetic waves that have been pointed out to be harmful to the health generated from plasma displays, and more efficient near-infrared rays near 800 to 1000 nm emitted from plasma displays. Since it cuts well, it is possible to obtain a display filter that does not adversely affect the wavelengths used by the remote control of peripheral electronic devices, transmission optical communication, etc., and can prevent malfunctions thereof. Furthermore, a display filter having excellent weather resistance can be provided at low cost.

  Hereinafter, the present invention will be described in more detail with reference to Examples 1 and 2 of the present invention. In addition, the material, usage-amount, ratio, processing content, processing procedure, etc. which are shown in the following Examples can be changed suitably unless it deviates from the meaning of this invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

1. Preparation of Sample An emulsion containing 7.5 g of gelatin per 60 g of Ag in an aqueous medium and containing silver iodobromide grains (I = 2 mol%) having an average sphere equivalent diameter of 0.05 μm was prepared. At this time, the Ag / gelatin volume ratio was 1/1, and a low molecular weight gelatin having an average molecular weight of 20,000 was used as the gelatin species.
In this emulsion, K ₃ Rh ₂ Br ₉ and K ₂ IrCl ₆ were added so as to have a concentration of 10 ⁻⁷ (mol / mol silver), and silver bromide grains were doped with Rh ions and Ir ions. . After adding Na ₂ PdCl ₄ to this emulsion and further performing gold-sulfur sensitization with chloroauric acid and sodium thiosulfate, together with the gelatin hardener, the coating amount of silver is 7 g / m ^2. It was coated on polyethylene terephthalate (PET). A sample (101) was prepared using PET that had been subjected to hydrophilic treatment before coating.

2. Sample exposure and processing conditions A grid-like photomask (line / space = 195 μm / 5 μm (pitch 200 μm)) capable of giving a developed silver image of line / space = 5 μm / 195 μm to the coating film of the dried sample (101) Then, exposure was performed using parallel light using a high-pressure mercury lamp as a light source through a photomask having a lattice-like space, and the following processing steps and processing liquid were performed. A running process (until the cumulative replenishment amount of the developer reached three times the tank capacity) was performed with the processing steps and processing solutions shown below.

Processing process Temperature Time Black and white development 35 ° C 40 seconds Fixing 35 ° C 40 seconds Rinse 1 * 35 ° C 10 seconds Rinse 2 * 35 ° C 10 seconds Activation Table 1 Rinse 3 * 25 ° C 30 seconds Rinse 4 * 25 ° C 30 Second Plating 25 ° C 900 seconds Rinse 5 * 25 ° C 60 seconds Rinse 6 * 25 ° C 60 seconds Drying 50 ° C 60 seconds
* The water-washing process was a two-tank counter-flow system from rinse 2 to 1, rinse 4 to 3, and rinse 6 to 5.

The composition of each treatment liquid is as follows.
[Black and white developer 1L prescription]
Hydroquinone 20 g
Sodium sulfite 50 g
Potassium carbonate 40 g
Ethylenediamine tetraacetic acid 2 g
Potassium bromide 3 g
Polyethylene glycol 2000 1 g
Potassium hydroxide 4 g
Adjust to pH 10.3

[Fixing solution 1L prescription]
Ammonium thiosulfate solution (75%) 300 ml
Ammonium sulfite monohydrate 25 g
1,3-diaminopropane tetraacetic acid 8 g
Acetic acid 5 g
Ammonia water (27%) 1 g
Adjust to pH 6.2

[Activation A solution 1L prescription]
Sodium borohydride 2 g
Sodium hydroxide 8 g

[Activation B solution 1L prescription]
Silver nitrate 500 g

[Plating solution 1L prescription]
Copper sulfate pentahydrate 15g
18 g of triethanolamine (80%)
Polyethylene glycol 0.1g
Sodium hydroxide 8.5g
Formalin (37%) 5.5g
Yellow blood salt 0.05g
m, α, α'-bipyridine 0.02g
Adjust to pH 12.5

[Rinse solution 1L prescription (Rinse 1-6 are common)]
Deionized water (conductivity 5μS / cm or less) 1000mL
pH 6.5

3. Method for evaluating conductivity The sample obtained above was cut into a size of 35 mm × 45 mm, and the surface resistance was measured. For the surface resistance, a Loresta-GP MCP-T600 / ASP probe manufactured by Mitsubishi Chemical was used.
The results are shown in Table 1 below.

4). Method for evaluating the ability to remove plating-inhibiting components A sample (101) exposed without a photomask was processed in the same manner as described above, and the S _2p (160 to 163 eV) and I _3d (615 to 625 eV) peaks were analyzed by ESCA. did.
5. Results The results are shown in Table 1 below.

In Table 1, “ND” indicates that it was not detected (Non Detected). As shown in Table 1 above, in the processing conditions of the present invention in which the treatment with the activation bath A or B was performed, the surface resistance was 0.09 and 0.08, and the comparative example in which the activation treatment was not performed. The conductivity was remarkably improved with respect to 48.2.
In addition, it was found that the Ag-S and Ag-I bonds of the adsorbate on the developed silver surface disappeared by ESCA measurement performed on the developed silver surface as a reference, confirming that this led to the effect of the invention. It was.

The electromagnetic wave shielding film prepared in the above example was prepared on a biaxially stretched polyethylene terephthalate (hereinafter PET) film (thickness: 100 μm).
Next, the copper surface was blackened by treatment with a copper blackening solution. The blackening treatment solution used was commercially available Copper Black (manufactured by Isolate Chemical Laboratory Co., Ltd.).
A protective film (manufactured by Panac Industry Co., Ltd., product number: HT-25) having a total thickness of 28 μm was bonded to the PET surface side using a laminator roller.
In addition, a protective film (product name: Sanitect Y-26F, manufactured by Sanei Kaken Co., Ltd.) with a total thickness of 65 μm in which an acrylic adhesive layer is laminated on a polyethylene film on the electromagnetic shielding film (metal mesh) side is a laminator roller. And pasted together.

Next, the PET surface was used as a bonding surface, and the resultant was bonded to a glass plate having a thickness of 2.5 mm and an outer dimension of 950 mm × 550 mm via a transparent acrylic adhesive material.

  Next, on the conductive mesh layer on the inner side excluding the outer edge portion 20 mm, from a 100 μm thick PET film, an antireflection layer, and a near-infrared absorber-containing layer via a 25 μm thick acrylic translucent adhesive material An infrared absorption film near the antireflection function (trade name Clearus AR / NIR, manufactured by Sumitomo Osaka Cement Co., Ltd.) was attached. The acrylic light-transmitting pressure-sensitive adhesive layer contained a toning dye (PS-Red-G, PS-Violet-RC manufactured by Mitsui Chemicals) that adjusts the transmission characteristics of the display filter. Further, an antireflection film (trade name Realak 8201 manufactured by Nippon Oil & Fats Co., Ltd.) was bonded to the opposite main surface of the glass plate via an adhesive material to produce a display filter.

  Since the obtained display filter was prepared using an electromagnetic wave shielding film having a protective film, it had very few scratches and defects in the metal mesh. In addition, the metal mesh is black and the display image does not have a metallic color, and has an electromagnetic wave shielding ability and a near infrared ray cutting ability (transmittance of 300 to 800 nm of 15% or less) that has no practical problem. It was excellent in visibility due to the antireflection layer. Further, by adding a pigment, a toning function can be imparted and it can be suitably used as a display filter such as a plasma display.

Claims (30)

  A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is subjected to exposure and development, and then the metal silver portion is processed with an activating solution and then plated. A translucent conductive film obtained by processing or physical development, wherein the activating solution removes halides and / or sulfides formed on the developed silver surface during the development processing Conductive film.   The conductive film according to claim 1, wherein the conductive film is a light-transmitting conductive film for a transparent electrode of an image display element or an image recording semiconductor element.   The conductive film according to claim 1, wherein the conductive film is a translucent electromagnetic wave shielding film.   4. The conductive film according to claim 3, wherein the conductive film is a light-transmitting electromagnetic wave shielding film having a surface resistance of 2.5 Ω / sq or less and a transmittance of the light-transmitting part of 95% or more.   2. The conductive film according to claim 1, wherein the activation liquid contains an alkali metal salt of borohydride (tetrahydroboric acid).   The conductive film according to claim 1, wherein the activation liquid contains silver nitrate.   2. The conductive film according to claim 1, wherein the activation liquid contains an inorganic acid having a pKa of 2 or less.   The conductive film according to claim 1, wherein the activating liquid contains an alkali halide.   A black and white silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is exposed to light and developed, and subsequently formed on the developed silver surface during the development. A method for producing a conductive film, characterized in that after treatment with an activating solution for removing halides and / or sulfides, plating treatment or physical development treatment is further performed.   10. The method for producing a conductive film according to claim 9, wherein the exposure applied to the silver halide photographic light-sensitive material is pattern exposure, and the light-transmitting conductive film obtained is a light-transmitting electromagnetic wave shielding film. .   The silver halide in a silver halide photographic light-sensitive material is a silver halide containing substantially no silver iodide and containing 50 mol% or more of silver chloride. A method for producing a conductive film.   The light-transmitting electromagnetic wave shielding film having a surface resistance of 2.5Ω / sq or less and a transmittance of the light-transmitting portion of 95% or more is obtained. A method for producing a conductive film.   The method for producing a conductive film according to claim 9, wherein the metallic silver portion is formed in an exposed portion, and the light transmitting portion is formed in an unexposed portion.   The method for producing a conductive film according to any one of claims 9 to 13, wherein the light-transmitting portion has substantially no physical development nucleus.   The method for producing a conductive film according to claim 9, wherein a silver salt-containing layer having an Ag / binder volume ratio of ¼ or more is used.   16. The method according to claim 9, further comprising a step of pattern exposure of the black and white silver halide photographic material, and subsequently forming a developed silver portion in the exposed portion and a light transmissive portion in the unexposed portion by dissolution physical development. The manufacturing method of the electroconductive film in any one.   An electromagnetic shielding film for a plasma display panel, comprising a conductive metal portion and a light transmissive portion obtained by the method for producing a light transmissive conductive film according to claim 9.   An optical filter for a plasma display panel, comprising the electromagnetic wave shielding film according to claim 3.   An optical filter for a plasma display panel, wherein the conductive film and / or electromagnetic wave shielding film obtained by the production method according to claim 9 is used. A plasma display panel comprising the optical filter according to claim 18.   A plasma television comprising the electromagnetic wave shielding film obtained by the manufacturing method according to claim 9.   The translucent conductive film according to claim 2, which is a conductive film for a transparent electrode of an image display element or an image recording semiconductor element.   It has an adhesive bond layer, The translucent conductive film in any one of Claims 1-8 characterized by the above-mentioned.   The optical filter according to claim 18, further comprising an adhesive layer.   The conductive film according to claim 1, which has a peelable protective film.   The conductive film according to claim 1, wherein 20% or more of the surface area of the conductive pattern surface is black.   20. The optical filter according to claim 18, wherein 20% or more of the surface area of the conductive pattern is black.   It has a function selected from one or more of infrared shielding properties, hard coat properties, antireflection properties, antiglare properties, antistatic properties, antifouling properties, ultraviolet ray cut properties, gas barrier properties, and display panel damage prevention properties. The conductive film according to claim 1, which has a functional transparent layer.   It has a function selected from one or more of infrared shielding properties, hard coat properties, antireflection properties, antiglare properties, antistatic properties, antifouling properties, ultraviolet ray cutting properties, gas barrier properties, and display panel damage prevention properties. The optical filter according to claim 18, further comprising a functional transparent layer.   The conductive metal film according to claim 1, which has an infrared shielding property.