JP4911459B2 - Conductive film, method for producing the same, electromagnetic shielding film, method for producing the same, and plasma display panel - Google Patents

Description

The present invention relates to a conductive film and a method for manufacturing the same. More specifically, the present invention relates to a method for producing a conductive film that is homogeneous and has both high conductivity and excellent translucency. Moreover, it is related with the transparent electromagnetic wave shielding film and transparent electrode using the obtained electroconductive film. Furthermore, displays such as CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, EL (electroluminescence), and FED (field emission display) equipped with the electromagnetic shielding film and transparent electrodes, microwave ovens, electronic devices, etc. Related.
In addition to these image display elements, the conductive film obtained by the present invention is also used for imaging semiconductor elements and printed wiring boards.

  2. Description of the Related Art In recent years, with the increase in use of various electric facilities and electronic application facilities, electromagnetic interference (Electro-Magnetic Interference: EMI) has increased rapidly. 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, it is requested | required that the intensity | strength of the electromagnetic wave emission of an electronic / electrical apparatus shall be suppressed within a specification or regulation.

  Various methods of shielding electromagnetic waves have been proposed and used for EMI countermeasures, but when applied to CRT, PDP, etc., images and characters displayed on the screen in addition to the electromagnetic wave shielding ability are displayed. Since it is necessary to visually recognize, transparency is also required.

In particular, since PDP generates a larger amount of electromagnetic wave than CRT and the like, stronger electromagnetic wave shielding ability is required, and the surface resistance value required for a light-transmitting electromagnetic wave shielding material for CRT is about 300Ω / sq or less. On the other hand, it is preferably 2.5 Ω / sq or less for a light-transmitting electromagnetic wave shielding material for PDP, and 1.5 Ω / sq or less for a consumer plasma television using PDP. There is a demand for extremely high conductivity of 0.1 Ω / sq or less.
Regarding transparency, a transmittance of about 70% or more is required for CRT, whereas a transmittance of 80% or more is desired for PDP.

  As a material and method that achieves both electromagnetic shielding properties and transparency using a metal mesh with openings to solve the above problems, for example, printing a shielding material made of conductive fiber mesh, electroless plating catalyst A method of printing as a grid pattern by electroless plating and electroless plating on the pattern, a method of patterning electroless plating catalyst-containing photoresist in a mesh shape, electroless plating on it, etching by photolithography Various methods such as a method of forming a metal thin film mesh have been proposed. However, in these methods, the manufacturing process is complicated and complicated, and the production cost is expensive, the line width is uneven at the intersection of the lattice pattern, etc., moire occurs, or one of translucency and conductivity is achieved. There are problems such as lack of both.

As an improvement means, a method of forming a conductive metal silver pattern using a silver salt photosensitive material has been proposed.
Silver salt photosensitive materials have been widely used as photographic films such as color negative films, black and white negative films, movie films, and color reversal films, and photographic printing papers such as color paper and black and white photographic paper. Can be used to obtain patterned metallic silver by a simple process using a photographic method by pattern exposure and development, and this metallic silver can be made conductive depending on the composition of the photosensitive material and the development method. It is. In 1960s, Patent Document 1 discloses a method of forming a conductive metal silver thin film pattern by silver salt diffusion transfer method in which silver is deposited on physical development nuclei. Further, Patent Document 2 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. Non-Patent Document 1 and Patent Document 3 describe a method of applying this principle to an instant black-and-white slide film and simply performing exposure and development to form a conductive pattern. Patent Document 4 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 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. The ability to shield the image without disturbing the image display was also insufficient.
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 improve conductivity. Therefore, even if the above-mentioned silver salt diffusion transfer method and physical development method are used as they are, it is suitable for shielding electromagnetic waves from the image display surface of an electronic display device, and is excellent in light transmittance and conductivity. The material could not be obtained.
In addition, using a commercially available negative film and a negative development process without using a silver salt diffusion transfer method or a physical development method is more disadvantageous in terms of achieving both conductivity and transparency. It was insufficient for use as a translucent electromagnetic shielding material for PDP.

  For this reason, Patent Document 5 proposes a method for producing a light-transmitting electromagnetic wave shielding material in which a silver salt photosensitive material is used to form a pattern by development, and then the developed silver is further subjected to plating or physical development. It came to. Although this method has an improvement effect on the above problem, the developed silver is highly resistant, or the power supply from the power supply roller to the developed photosensitive material is not always smooth, and uneven plating (electrolytic unevenness) occurs. easy. In particular, in the initial process of plating, and in the continuous processing method where plating is performed while continuously carrying the developed film, the uniformity of conductivity and translucency is impaired due to local fluctuations in the metal deposition rate on the developed silver. I understood. There is a need for a means for achieving both transparency and conductivity.

Japanese Patent Publication No.42-23746 Japanese Patent Publication No.43-12862 WO 01/51276 pamphlet 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 form a conductive film for further electrolytic plating on a developed silver pattern obtained by pattern exposure and development of a silver halide photographic material. It is to reduce plating unevenness generated in the electrolytic plating process in the method. In addition, it solves uneven plating and has a highly conductive film, particularly a light-transmitting conductive film having both high conductivity and high light-transmitting properties, and particularly high electromagnetic shielding and high transparency. An object of the present invention is to provide an electromagnetic wave shielding film, and to provide a production method capable of mass production of these films at a low cost and in which the electromagnetic wave shielding ability does not deteriorate even when mass produced. It is another object of the present invention to provide an electromagnetic wave shielding film having high translucency and high conductivity to be installed in a display device such as a PDP.

  As a result of detailed examination of the electrodeposition process on the fine developed silver surface, the present inventors have found that electrodeposition unevenness is prominent in the initial stage of the plating process, and the amount of electrodeposition is reduced as the plating bath becomes more fatigued. It was found that the decrease in translucency increases. Further, it was also found that unevenness of electrodeposition is suppressed when the photosensitive material is pre-bathed with a hardening solution prior to immersion of the developed photosensitive material in a plating solution. Based on these findings, the present invention has been completed by devising a series of processing steps including development, pre-plating bath and electrolytic plating that ensure electrical conductivity and translucency.

The present invention is as follows.
(1)
A conductive film comprising a conductive functional layer including a conductive metal part and a light transmissive part on a support, wherein the swelling ratio of the light transmissive part is 180% or less.
(2)
The conductive film according to (1), wherein a surface resistance of the conductive film is 2.5 Ω / sq or less and / or a transmittance of the light transmissive part is 95% or more.
(3)
The conductive film according to (1) or (2), wherein a dry film thickness of the light transmitting portion is 2.0 μm or less.
(4)
The conductive film according to any one of (1) to (3), wherein the light transmissive portion is substantially made of a water-soluble polymer.
(5)
A method for producing a conductive film having a conductive functional layer including a conductive metal part and a light transmissive part on a support, and reacting a dura solution with the surface of the conductive film having a surface resistance of 1 to 1000 Ω / □ And a hardening process for setting the swelling ratio of the light-transmitting part to 180% or less .
(6)
The conductive film according to (5), wherein the conductive film is a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support. Method.
(7)
The method for producing a conductive film according to (5) or (6), wherein the hardening solution contains a hardening agent, and the hardening agent has a function of hardening gelatin. .
(8)
The conductive film according to (7), wherein the hardener is a compound selected from formaldehyde, pivalylaldehyde, glutaraldehyde, succinaldehyde, potash alum, chromium alum, and aluminum sulfate. Manufacturing method.
(9)
A conductive film obtained by the method for producing a conductive film according to any one of (5) to (8).
(10)
An electromagnetic wave shielding film manufactured by the method for manufacturing a conductive film according to any one of (5) to (8).
(11)
(5) An electromagnetic wave shielding film, wherein the electromagnetic wave shielding film produced by the method for producing a conductive film according to any one of (8) has a surface resistance of 2.5 Ω / sq or less.
(12)
The electromagnetic wave shielding film as described in (11), wherein the surface resistance is 1.5Ω / sq or less.
(13)
A development step in which a silver halide film having a silver halide emulsion layer is exposed and developed on a support , a metallic silver portion is formed in an exposed portion, and a light transmissive portion is formed in an unexposed portion ;
The metallic silver portion and the light-transmitting portion the surface of the formed film, by reacting a hardener solution containing the hardener, the swelling ratio of the light transmitting unit and the hardening step shall be the 180% or less ,
An electrolytic plating treatment step for performing an electrolytic plating treatment on the metal silver portion of the film subjected to the hardening step,
The manufacturing method of the electroconductive film which has this.
In the production method of the present invention, by pre-bathing the film surface with a hardening solution, electrodeposition unevenness in the electrolytic plating process is suppressed, and the surface resistance of the resulting conductive film can be sufficiently reduced. Although the reason why the surface resistance of the conductive film thus obtained can be sufficiently reduced is not clear, the present inventors presume this reason as follows. Since the silver halide emulsion layer has a small amount of hardener in the silver halide emulsion layer, its film quality is weak and scratches are easily generated during the electroplating process, which causes uneven electrodeposition. However, in the present invention, the film quality of the silver salt-containing layer can be strengthened by crosslinking or the like by the hardening process, the generation of scratches can be suppressed even when the electrolytic plating treatment is performed, and uneven electrodeposition in the electrolytic plating treatment can be prevented. it can.
(14)
The method for producing a conductive film as described in (13), wherein the silver halide emulsion layer contains silver halide and a binder.
(15)
The method for producing a conductive film as described in (14), wherein the silver (Ag) and binder (B) content mass ratio in the silver halide emulsion layer is in the range of the following formula (1).
Ag / B = 3-15 (1)
(16)
The method for producing a conductive film according to (14) or (15), wherein a silver salt-containing layer having an Ag / binder volume ratio of 1/4 or more is used.
(17)
The method for producing a conductive film according to any one of (14) to (16), wherein the binder is gelatin.
(18)
The method for producing a conductive film according to any one of (13) to (17), wherein the hardener is a compound having a function of hardening gelatin.
(19)
Any of (13) to (18), wherein the hardener is a compound selected from formaldehyde, pivalylaldehyde, glutaraldehyde, succinaldehyde, potash alum, chromium alum, and aluminum sulfate. A method for producing the conductive film according to claim 1.
(20)
The method for producing a conductive film according to any one of (13) to (19), wherein the hardener is glutaraldehyde or aluminum sulfate.
(21)
The method for producing a conductive film according to any one of (13) to (20), wherein the dura solution contains 0.005 to 1.000 mol / L of a hardening agent.
(22)
The method for producing a conductive film according to any one of (13) to (21), wherein the dura mater solution further contains a compound having a swelling-inhibiting action.
(2 3 )
The method for producing a conductive film according to any one of (13) to (2 2 ), wherein the light-transmitting portion has substantially no physical development nucleus.
(2 4 )
An electromagnetic wave shielding film for a plasma display panel having a conductive metal portion and a light transmissive portion, which is obtained by the production method according to any one of (13) to (2 3 ).
(2 5 )
An optical filter for a plasma display panel, comprising the electromagnetic wave shielding film according to (11) or (12).
(2 6 )
(13) An optical filter for a plasma display panel, comprising an electromagnetic wave shielding film obtained by the production method according to any one of (2 3 ).
(2 7 )
A plasma display panel comprising the optical filter according to (2 5 ) or (2 6 ).
(2 8 )
A plasma television comprising an electromagnetic wave shielding film obtained by the production method according to any one of (13) to (2 3 ).
The present invention relates to the above (1) to (28), but other matters are also described for reference.
( 29 )
A method for producing a conductive film, comprising subjecting a film surface having a surface resistance of 1 to 1000 Ω / □ to a pretreatment with a hardening solution continuously, followed by electrolytic plating.
(3 0)
A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer containing a silver halide emulsion layer on a support is successively subjected to a development treatment and an electroplating treatment to a metallic silver portion formed by the development treatment. A method for producing a conductive film, comprising: carrying out a pretreatment with a hardening solution immediately before subjecting a developed silver halide photosensitive material to an electrolytic plating treatment.
(3 1 )
Method for producing a conductive film according to the above (29) or (3 0), wherein the hardening agent of the hardening solution is a compound having an effect of hardening the gelatin.
(3 2 )
A silver halide photographic material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support is subjected to development treatment to form a metallic silver portion, and the metallic silver portion is treated with a hardening solution. A method for producing an electromagnetic wave shielding film, comprising sequentially performing electrolytic plating treatment.

According to the method for producing a conductive film of the present invention, the photosensitive material is pre-bathed with a hardening solution prior to immersion of the developed photosensitive material in a plating solution. Can be reduced. Therefore, it is possible to form a conductive film having a uniform and high conductivity and a high translucency at the same time, and an electromagnetic wave shielding film having a fine line pattern excellent in EMI shielding properties can be obtained.
The conductive film is used as a transparent electrode for an image element unit of a display device or an imaging semiconductor element of an image recording element, and the electromagnetic wave shielding film is used as a member for preventing electromagnetic interference of the image element unit. In particular, in the manufacturing method of the present invention in which the photosensitive material to be processed is continuously electrolytically plated, the effect of preventing plating unevenness, the fatigue of the plating solution, and the effect of preventing development stains on the translucent part without deteriorating the electromagnetic wave shielding ability. It is significantly improved and the membrane can be mass-produced at low cost.

Hereinafter, the electromagnetic shielding film will be described in detail among the method for producing a conductive film of the present invention and the translucent conductive film, and the conductive film derived from developed silver used for a transparent electrode such as a semiconductor element is also compliant with this. Can be manufactured.
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.

<Features of the present invention>
The manufacturing method of the electroconductive film of this invention has a hardening process which makes a hardening solution react with the surface of a film whose surface resistance is 1-1000 ohm / square. More specifically, an exposed portion and an unexposed portion are exposed by exposing a photosensitive material having an emulsion layer containing a photosensitive silver halide salt on a support, and performing a development process and preferably a fixing process continuously. And a conductive film manufacturing method and apparatus for forming a metallic silver portion and a light transmissive portion, and then subjecting the developed photosensitive material to a pre-bath treatment with a hardening solution followed by an electrolytic plating treatment. It is an invention of application of a membrane. In the present invention, it is preferable to perform a pre-bath treatment (hardening step) with a hardening solution immediately before the developed silver is immersed in the electrolytic plating solution.
The pre-bath treatment with the hardened solution uniformly deposits metal on the developed silver to suppress uneven electrodeposition, and also reduces the adhesion of development stains to the translucent part. The task to accomplish is achieved.
As a reminder, in the above, “continuous” means that the photosensitive material to be processed is continuously conveyed (that is, the process flow is continuous), and is not necessarily developed, plated. It does not indicate that processes such as processing are continuous without interruption. In addition, “immediately before immersion of the developed silver in the electrolytic plating solution” means that after processing with the hardening solution, the process enters the plating solution processing step without interposing other steps. It doesn't mean a long gap. The mesh-like silver produced by simply developing a pattern-exposed silver halide photographic light-sensitive material is thin filamentary silver (or ultrafine, discrete spherical silver) and has very poor electrical conductivity (usually surface resistance) 1 to 1000Ω / □). The present inventor has found that it is effective to deposit metal on the patterned developed silver by electrolytic plating in order to increase the conductivity. However, the metal film thus obtained is deposited. Electrolytic unevenness resulting from the non-uniformity of the conductive film is lacking and the uniformity of the conductive film is lacking. When the electrolysis time is lengthened or the electrolysis conditions are strengthened, an increase in electrical conductivity is recognized, but a photosensitive material stain is also generated and the translucency is impaired. In the present invention, when a means for applying a hardening solution to a photosensitive material before immersing the photosensitive material carrying developed silver in a plating solution is used, nonuniformity of electrodeposition is reduced, and photosensitive material contamination is also reduced. As a result, it is based on the fact that the conductivity is increased while maintaining the translucency and the above-mentioned drawbacks can be solved.
As the form of the pre-curing treatment of the light-sensitive material, a bathing treatment into a hardening solution by a front tub or a coating treatment by a coating apparatus is preferable, but any other means for bringing the hardening solution into contact with the photosensitive material surface should be used Can do. The hardening agent in the hardening solution used in the present invention is preferably a compound having a function of hardening gelatin, and details thereof will be described later. The concentration in the dura mater solution may be any concentration as long as the desired effect is exhibited, but is preferably 0.005 to 1.0 mol / L. The surface tension is preferably lower than that of water, and the effect is further increased when the surface tension is 60 mN / m or less. Further details of the dura solution will be described later.

The electroplating process that follows the development process and preferably the fixing process can use a known electroplating process, which is covered with a binder and usually has insufficient conductivity due to its nonuniform shape and nonuniform thickness. The conductivity of filamentary silver is enhanced, and the pre-treatment with the hardening solution before the penetration of the developed sample into the plating solution has improved both the translucency of the unexposed area and the exposed area. A conductive film can be formed.
Hereinafter, the elements constituting the present invention will be sequentially described in detail.

<Conductive film>
The “transmittance” of the light-transmitting part in the present invention refers to the transmittance indicated by the minimum value of the transmittance in the wavelength region of 380 to 780 nm excluding the contribution of light absorption and reflection of the support. The transmittance of the conductive electromagnetic shielding material) / (the transmittance of the support) × 100 (%). The transmittance of the light transmissive part is preferably 90% or more, more preferably 95% or more, further preferably 97% or more, still more preferably 98% or more, and 99% The above is most preferable.
<Binder>
A binder can be used for the purpose of supporting the conductive film of the present invention. In the present invention, as the binder, both water-insoluble polymers and water-soluble polymers can be used as binders, but it is preferable to use water-soluble polymers.
Examples of the binder include polysaccharides such as gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch, cellulose and derivatives thereof, polyethylene oxide, polysaccharides, polyvinylamine, chitosan, polylysine, polyacrylic acid, poly Examples include alginic acid, polyhyaluronic acid, and carboxycellulose. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group.
The content of the binder is not particularly limited, and can be appropriately determined as long as dispersibility and adhesion can be exhibited. In the present invention, the Ag / binder mass ratio is preferably 3 or more, more preferably 4.5 or more and 12 or less, and most preferably 6 or more and 10 or less. Further, gelatin is the most preferable type of binder.
<Swelling rate>
The conductive film of the present invention is characterized in that the swelling ratio of the light transmitting portion is 180% or less. In the present invention, the swelling rate is defined as follows. That is, the layer thickness (a) at the time of drying and the layer thickness (b) after being immersed in distilled water at 25 ° C. for 1 minute are measured.
Swell rate (%) = 100 × ((b)-(a)) / (a)
And Here, the film thickness of the emulsion layer is measured by observing the cross section of the sample with a scanning electron microscope. The film thickness after swelling is measured by observing the cross section of the sample after freeze-drying the swollen sample with liquid nitrogen using a scanning electron microscope. In the present invention, the swelling ratio of the light transmissive part layer is preferably 150% or less, and more preferably 130% or less. Although there is no lower limit to the swelling rate in the present invention, the swelling rate is preferably 50% or more from the viewpoints of suppressing a decrease in the amount of liquid in the film during plating and suppressing a decrease in plating rate. In the present invention, the swelling rate can be controlled by the type, addition amount, and pH of the hardening agent in the hardening treatment.
In addition, the swelling rate prescribed | regulated by this invention is prescription | regulation with the last form as an electromagnetic wave shielding film. That is, the swelling rate defined in the present invention is a value after the electrolytic plating process. Any value may be used for the swelling ratio of the photosensitive material before processing, which will be described later.

《Conductive film and its manufacturing method》
In the method for producing a conductive film of the present invention, a silver halide film having a silver halide emulsion layer on a support is exposed and developed to form a metallic silver portion, and the metallic silver is formed. A hardening step for reacting a hardening solution containing a hardening agent on the surface of the film, and an electrolytic plating treatment step for carrying out an electrolytic plating treatment on the metal silver portion of the film subjected to the hardening step. It is a manufacturing method of the electroconductive film which has.
In the production method of the present invention, by pre-bathing the film surface with a hardening solution, electrodeposition unevenness in the electrolytic plating process is suppressed, and the surface resistance of the resulting conductive film can be sufficiently reduced. Although the reason why the surface resistance of the conductive film thus obtained can be sufficiently reduced is not clear, the present inventors presume this reason as follows. Since the silver halide emulsion layer has a small amount of hardener in the silver halide emulsion layer, its film quality is weak and scratches are easily generated during the electroplating process, which causes uneven electrodeposition. However, in the present invention, the film quality of the silver salt-containing layer can be strengthened by crosslinking or the like by the hardening process, the generation of scratches can be suppressed even when the electrolytic plating treatment is performed, and uneven electrodeposition in the electrolytic plating treatment can be prevented. it can.
The silver halide emulsion layer preferably contains silver halide and a binder (preferably gelatin). In the conductive film according to the present invention, in order to sufficiently reduce the surface resistance, the content ratio of silver (Ag) and binder (B) in the silver halide emulsion layer is within the range of the following formula (1). Preferably there is.
Ag / B = 3-15 (1)
The silver halide emulsion layer preferably has an Ag / binder volume ratio of 1/4 or more in order to sufficiently reduce the surface resistance.
In the production method of the present invention, in order to obtain a sufficient effect in the hardening treatment, the hardener is preferably a compound having a function of hardening gelatin, such as formaldehyde, pivalylaldehyde, glutaraldehyde, A compound selected from aldehyde, potassium alum, chromium alum, and aluminum sulfate is preferable, and glutaraldehyde or aluminum sulfate is particularly preferable. By using such a compound as a hardener, the crosslinking density of gelatin on the surface of the silver halide emulsion layer can be further improved, and it is particularly effective for hardening the silver halide emulsion layer.
In addition, it is preferable that a hardening solution contains 0.005-1.000 mol / L of a hardening agent, and it is further preferable to contain the compound which has a swelling inhibitory effect.

[Photosensitive material (silver halide film)]
<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 of an electromagnetic wave shielding film for 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>
In the light-sensitive material used in the present invention, a protective layer may be provided 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 included 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 of oxonol dyes described in JP-A No. 2-282244, light scattering particles described in JP-A No. 63-131135, Yb ³⁺ described in JP-A No. 9-5913 Compounds and ITO powders described in JP-A-7-113072 The 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. 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 the surface.

  The silver halide emulsion which is a coating solution for an emulsion layer used in the present invention is described in P.I. By Glafkides, Chimie et Physique Photographic (published by Paul Montel, 1967), G. F. Dufin, Photographic Emission Chemistry (published by The Focal Press, 1966), V. L. It can be prepared using a method described in, for example, Making and Coating Photographic Emulsion (published by The FormalPress, 1964) by Zelikman et al.

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 salts, trioxalatodium (III) complex salts, K ₃ Rh ₂ Br _{9 and the} like.

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.

  Examples of the ruthenium compound and osmium compound include water-soluble complex salts described in JP-A-63-2042, JP-A-1-285941, JP-A-2-20852, JP-A-2-20855, and the like.

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. 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.

  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. Specifically, the compounds described in Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid 1102 (1979), ibid 645 (1979) and the like are used. 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 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 the development processing, either negative development processing or reversal development processing can be selected. Further, chemical development or physical development (in the aspect of the present invention, exactly, dissolution physical development) may be used.
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." Pages 373-377 (Mcmillan, 1977 publication) edited by Mees.
As long as the developed silver is obtained, the chemical 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, As the solution, 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 specified by Fuji Film , Papitol, a developer such as C-41, E-6, RA-4, D-72 specified by KODAK, or a developer included in the kit, and D-19, D-85, D-8 It is also possible to use a lith developer or a high-contrast positive developer known by a prescription name such as In the mode of dissolution physical development, thiosulfate (sodium salt, ammonium salt, etc.) or thiocyanate (sodium salt, ammonium salt, etc.) may be added as a silver halide solubilizer to each developer described above. It is preferably added to a high activity developer such as -19, D-85, D-8, 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.

<Developer composition and development process>
In 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.
The bathing potential of the developer, that is, the oxidation-reduction potential, is a total of the oxidation-reduction properties of the components of the developer, but is mainly determined by the developing agent and pH. A preferred redox potential is baser than 290 mV vs SCE, more preferably baser than −320 mVvs SCE, and more preferably baser than −340 mVvs SCE.
In order to make the oxidation-reduction potential of the developer lower than the preferable 290 mV vs. SCE in the present invention, it is carried out by adjusting the pH according to the type of the selected developing agent using the above-mentioned preferable developing agents. A preferable pH value is 0 to 2, preferably 0.5 to 1.5 higher than the pK value of the developing agent, and is appropriately selected according to the type of the developing agent.

  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 initiator or developer replenisher used (hereinafter, both may be referred to as a developer) has this pH buffering ability, the pH of the development initiator or developer replenisher to be tested is adjusted. Then, 0.1 mol of sodium hydroxide was added to 1 liter of this liquid, and the pH value of the liquid at this time was measured, and if the increase in pH value was 0.5 or less, it was defined as above. Determined to have pH buffering capacity. 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 the photosensitive material, the amount of replenishment of the developer replenisher in the developer (replenishment amount) is 645 ml or less, preferably 30 to 484 milliliters, in particular 100-484 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, or 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 organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, azelaic 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.

[Fixing process]
Subsequent to the development process, a fixing process is preferably performed for the purpose of removing and stabilizing the silver salt in the unexposed portion, but the fixing process may be omitted in the present invention. In particular, when the development process is carried out by dissolution physical development, the unexposed silver halide is generally dissolved and disappeared during the development process. However, when the development is performed with a chemical development type development formula, it is preferable to increase the transparency of the unexposed portion, that is, the translucent portion, by a fixing process.
The fixing process is not necessarily performed following the developing process, and may be performed after an electroplating process described later.
For the fixing process in the present invention, a conventional fixing process technique used for color photographic or black-and-white silver salt photographic film, photographic paper, printing plate-making film, X-ray photographic film, photomask emulsion mask, etc. may be used. it can.

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 if necessary, pH of tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyrone, and salts thereof 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 the pH of the fixing agent due to the introduction of 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 8.0, particularly preferably from 4.5 to 7.5.
In the present invention, it is preferable to add a water-soluble halide in order to make the fixing solution highly active so that rapid fixing is possible. Preferred water-soluble halides are alkali metal bromides and iodides and ammonium bromide and ammonium iodide, and preferred alkali metal salts are sodium and potassium salts. The total amount of water-soluble halide added is 0.035 to 0.5 mol / L, more preferably 0.05 to 0.4 mol / L. It is particularly preferable that the water-soluble halide contains a water-soluble iodide such as potassium iodide, sodium iodide, or ammonium iodide. In this case, the amount of the water-soluble iodide added is 0.005 to 0.005. 0.05 mol / L.
The water-soluble halide has an effect of increasing the metal deposition rate in the plating step subsequent to the fixing step in addition to adjusting pAg high, and the effect of iodine ions is particularly large.

  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 processing temperature and time in the fixing process are related to each other and are determined in relation to the total processing time. It has an activity to complete fixing of silver halide grains in the exposed area. A preferable fixing temperature is 30 ° C. to 60 ° C., and 35 to 55 ° C. is more preferable. The fixing time is preferably 5 seconds to 40 seconds, and more preferably 7 seconds to 30 seconds.
The replenishing amount of the fixing solution is preferably from 1600 ml / m ² or less with respect to the processing of the photosensitive material, more preferably 700 ml / m ² or less. The concentration of the replenisher is set to a concentration commensurate with compensating consumption during processing under a predetermined replenishment amount.

[Washing treatment, stabilization treatment, etc.]
The photosensitive material that has been subjected to development and fixing treatment is washed or stabilized (washing substitute alternative stabilization treatment) subsequently or after the plating treatment described below, or both after development and fixing treatment and after plating treatment. (Also referred to as). 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 when 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.

  In order to store the processing solution such as a developing solution and a fixing solution used in the present invention, it is preferable to store with a packaging material having a 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. As the roller-conveying type automatic developing machine, those described in US Pat. Nos. 3,025,795 and 3,545,971 can be used. 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 agents, the same results as in the liquid agent can be obtained. From the viewpoint of storage stability and the like, a 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, reference can be made to the 48th line to the 13th line in the second column of JP-A-5-45805.

  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 that can be used 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.

[Pretreatment with dura solution]
The manufacturing method of the electroconductive film of this invention has the hardening process which makes the surface of a film react a hardening solution. Further, the treatment with the hardening solution can be performed prior to the electrolytic plating, and the effect of improving the uniformity of the subsequent plating and suppressing the contamination of the photosensitive material can be obtained by performing the hardening solution treatment.
In the present invention, the hardening agent contained in the hardening solution is preferably any compound that increases gelatin film hardening in an aqueous solvent, such as formaldehyde, pivalylaldehyde, glutaraldehyde, sputum aldehyde, potash alum, Chromium alum, mucochloric acid, glyoxal, 1,2-dihydroxypyridines, diglycolaldehyde, hydroxy-s-triazines such as 2,4-dichloro-6-hydroxy-s-triazine, crotonaldehyde, boric acid, bladder Examples thereof include glass, paraformaldehyde, aluminum sulfate and the like, and among them, a compound selected from formaldehyde, pivalylaldehyde, glutaraldehyde, succinaldehyde, potash alum, chromium alum and aluminum sulfate is preferable. More preferably, the hardener is glutaraldehyde or aluminum sulfate.
The concentration of the hardener is preferably 0.005 to 1.0 mol / L, more preferably 0.01 to 1.0 mol / L, and 0.05 to 0.8 mol / L. Most preferred.
The solvent of the dura mater solution is an aqueous solvent mainly composed of water, and is preferably water or an aqueous electrolyte solution.
In addition, it is preferable to add a compound having a swelling inhibiting action to the dura solution. Specifically, NaCl, NaBr, KI, KCl, LiCl, NaClO ₄ , Na ₂ SO ₄ , CH ₃ CO ₂ Na, CH ₃ CO ₂ K, CH ₃ CO ₂ NH ₄ , (NH ₄ ) ₂ SO ₄ Salt, etc. Tetraethylammonium or tetrabutylammonium as cation part of water-soluble salt, quaternary ammonium salt combining halide ion, perchlorate ion, tosylate ion, tetrafluoroborate ion, hexafluorophosphate ion, etc. as anion part, etc. May be added. Particularly preferred as a swelling inhibitor is Na ₂ SO ₄ .
The immersion time in the dura mater solution of the present invention is preferably 2 seconds to 10 minutes, more preferably 5 seconds to 5 minutes.
The temperature of the dura mater solution of the present invention is preferably 15 ° C to 60 ° C, more preferably 25 ° C to 55 ° C.

[Electrolytic plating treatment]
In the present invention, for the purpose of imparting conductivity to the metal silver portion formed by the exposure and development processing, an electroplating process for supporting the conductive metal particles on the metal silver portion is performed.
In the present invention, the electrolytic plating process is performed after the development process or after the fixing process after the development process, or after the development process or after the water washing or rinsing instead of the water washing after the development process. In which stage the electroplating is performed can be appropriately selected. However, the hardening process is preferably performed prior to the plating process.

(Electrolytic plating)
In the present invention, electroplating is preferable to electroless plating in that it can be performed under mild electrolyte conditions (high stability) in which metal deposition does not occur in unexposed areas, and high-speed plating of 5 μm / hr or more is also possible. Is 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.
The metal species used for electrolytic plating are the same as the metal species described in the section of electroless plating, and the preferred metal species are also the same. Copper and silver plating are particularly preferable.

The electrolytic solution can dissolve the metal compound of the metal to be plated at the required concentration, and can ensure a sufficiently low liquid resistance suitable for electrolysis (the total contact resistance with the developed silver as the electrode and the current resistance of the electrolytic solution). As long as any of them can be used. Therefore, although it selects suitably according to the metal compound to be used, since the metal for plating is generally copper, silver, etc., the aqueous solution of inorganic acids, such as a sulfuric acid, hydrochloric acid, nitric acid, is preferable. Further, since silver and copper are easy to form an ammine complex and a hydroxyamino complex, an ammonium hydroxide (ammonia water), an alkanolamine aqueous solution, preferably an ethanolamine, jeethanolamine, or triethanolamine aqueous solution is also preferable.
The concentration of acid, ammonium hydroxide and alkanolamines used in these electrolytes is 0.1 mol / L to 10 mol / L, preferably 0.2 mol / L to 8 mol / L, particularly preferably 0. .25 mol / L to 5 mol / L. Further, the metal compound of the plating metal is 0.05 mol / L to 10 mol / L, preferably 0.07 mol / L to 5 mol / L, particularly preferably 0.1 mol / L to 3 mol / L.
The temperature of the plating solution in the electrolytic plating is preferably 10 ° C to 60 ° C, more preferably 20 ° C to 50 ° C, and particularly preferably 25 ° C to 45 ° C. The charge time can be appropriately adjusted so as to obtain the desired metal coating thickness, but the applied voltage (allowable range) is 10 to 600 seconds, preferably 20 to 450 seconds, particularly preferably 30 to 300 seconds. Adjust the liquid composition and temperature.
As an example of a preferable metal compound and plating solution composition, for example, in the case of copper plating, one containing 30 to 300 g / L of copper sulfate pentahydrate and 30 to 300 g / L of sulfuric acid can be used. In the case of silver plating, a neutral or acidic aqueous solution or ammoniacal alkaline aqueous solution containing 30 to 300 g / L of silver nitrate can be used. In the case of nickel plating, nickel sulfate, nickel hydrochloride, or silver plating containing silver cyanide can be used. Moreover, you may add additives, such as surfactant, a sulfur compound, and a nitrogen compound, to a plating solution.

  Although the typical example of the aspect of the electrolytic plating in this invention is demonstrated by the following, this invention is not limited to this. The plating apparatus for suitably carrying out the plating treatment according to the present invention, like the known apparatus, sends the film sequentially fed from the reel for unwinding (not shown) around which the film is wound, to the electrolytic plating tank, It is preferable that the plated film is sequentially wound on a winding reel (not shown).

  FIG. 1 shows an example of an electrolytic plating tank suitably used for the plating treatment according to the present invention. The electroplating apparatus 10 shown in FIG. 1 is capable of continuously plating a long film 16. The arrow indicates the conveyance direction of the film 16. The electrolytic plating apparatus 10 includes an electrolytic tank 11 that stores a plating solution 15. A pair of anode plates 13 are arranged in parallel in the electrolytic cell 11, and a pair of guide rollers 14 are arranged inside the anode plate 13 so as to be rotatable in parallel with the anode plate 13. The guide roller 14 can move in the vertical direction, thereby adjusting the plating processing time of the film 16.

Above the electrolytic cell 11, a pair of feed rollers (cathodes) 12 a and 12 b for guiding the film 16 to the electrolytic cell 11 and supplying current to the film 16 are rotatably disposed. Further, above the electrolytic cell 11, a liquid draining roller 17 is rotatably disposed below the power supply roller 12b on the outlet side.
The anode plate 13 is connected to a plus terminal of a power supply device (not shown) via an electric wire (not shown), and the power supply rollers 12a and 12b are connected to a minus terminal of the power supply device (not shown). .

The film 16 is set in a state where the film 16 is wound around a supply reel (not shown), and the film 16 is conveyed by a conveying roller (see FIG. Wrap it around (not shown).
A voltage is applied to the anode plate 13 and the power supply rollers 12a and 12b, and the film 16 is conveyed while being in contact with the power supply rollers 12a and 12b. The film 16 is introduced into the electrolytic cell 11 and immersed in the plating solution 15 to form copper plating. When passing between the liquid draining rollers 17, the plating solution 15 adhered to the film 16 is wiped off and collected in the electrolytic cell 11. This is repeated in a plurality of electrolytic plating tanks, finally washed with water, and then wound up on a take-up reel (not shown).
The conveyance speed of the film 16 is set in the range of 1 to 30 m / min. The conveyance speed of the film 16 is preferably in the range of 1 to 10 m / min, more preferably in the range of 2 to 5 m / min.

Although the number of electrolytic plating tanks is not particularly limited, 2 to 10 tanks are preferable, and 3 to 6 tanks are more preferable.
The applied voltage is preferably in the range of 0.5 to 100V, more preferably in the range of 1 to 60V.
The power supply rollers 12a and 12b are preferably in contact with the entire surface of the film (the portion of the contact area that is substantially in electrical contact is 80% or more).

  The thickness of the conductive metal part plated by the above plating treatment is preferable because the viewing angle of the display is increased as the thickness of the electromagnetic shielding material for the display is reduced. 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 plated conductive metal layer is preferably less than 9 μm, more preferably from 0.1 μm to less than 5 μm, and from 0.1 μm to less than 3 μm. Is more preferable.

  FIG. 2 shows an example of the conductive film of the present invention. The conductive film 21 shown in FIG. 2 has a conductive functional layer 22 on a support 23. The conductive functional layer 22 contains a silver halide emulsion layer 28. For example, by performing exposure / development processing or the like on the exposed portion 24, a metallic silver portion can be formed, and in order to further increase the conductivity, the conductive metal portion can be formed by performing electrolytic plating. As an example, there is an aspect in which Cu is electroplated on the electroplating treatment portion 26 and Ni is electroplating on the electroplating treatment portion 27. The unexposed portion 25 becomes a light transmissive portion (for example, one made of gelatin).

[Oxidation treatment]
In the present invention, oxidation treatment is preferably performed on the metal silver portion after the development treatment and the conductive metal portion formed after the plating 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 the exposure and development treatment of the silver salt-containing layer or after the plating treatment, and may be performed after the development treatment and after the 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 the electroless plating rate.

[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 carrying conductive metal particles on the metal silver portion by plating the metal silver portion formed by the exposure and development processes described above.
The metallic silver may be formed in the exposed portion, or may be formed in the unexposed portion by using an auto positive material as the photosensitive material or by using reversal development for the development process. In the present invention, it is preferable to form metallic silver in the exposed portion in order to increase transparency.
Examples of the conductive metal to be carried on the metal part include the above-described silver and copper, aluminum, nickel, iron, gold, cobalt, tin, stainless steel, tungsten, chromium, titanium, palladium, platinum, manganese, zinc, rhodium, and the like. Or particles of alloys of these metals. From the viewpoint of conductivity, cost, etc., the conductive metal is preferably copper, aluminum or nickel particles. Moreover, when providing a magnetic field shielding property, it is preferable to use a paramagnetic metal as a conductive metal.

  From the viewpoint of increasing the contrast in the conductive metal part and preventing the conductive metal part from being oxidized and fading over time, the conductive metal contained in the conductive metal part may be copper. Preferably, 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. If silver is contained in an amount of 50% by mass or more, the time required for the 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 electromagnetic wave shielding film (conductive metal part) of the present invention is preferably 10 ³ Ω / sq or less, more preferably 2.5 Ω / sq or less, and 1.5 Ω / sq. More preferably, it is 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 transmissive part” in the present invention means a part having transparency other than the conductive metal part in the 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.

  The dry film thickness of the light transmissive part is preferably 2.0 μm or less. The light transmissive part is preferably made of a water-soluble polymer.

[Layer structure of electromagnetic shielding film]
The thickness of the support in the 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 the plating treatment 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 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, the thickness of the layer made of conductive metal particles can be freely controlled by forming a metallic silver portion of a desired thickness by controlling the coating thickness of the silver salt-containing layer described above, Even an 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 films]
The electromagnetic wave shielding film of the present invention is separately used in combination with a functional layer having functionality 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 electromagnetic wave shielding film obtained by the production method of the present invention has good electromagnetic wave shielding properties and transparency, it can be used as a transparent electromagnetic wave shielding material. Furthermore, it can be used as various conductive wiring materials such as circuit wiring. Particularly, the electromagnetic wave shielding film of the present invention is used in front of displays such as CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, EL (electroluminescence), microwave oven, electronic equipment, printed wiring board, etc., particularly in plasma display panels. It can be suitably used as an electromagnetic shielding film to be used.

[Other conductive film components]
Regarding the conductive film of the present invention represented by the electromagnetic wave shielding film and the conductive film, additional components other than those described above will be described.
(1) Adhesive layer An electromagnetic wave shielding film or a conductive film (for example, a transparent electrode) is an optical filter, a liquid crystal display panel, a plasma display panel, other image display grat panels, or an imaging semiconductor integrated circuit represented by a CCD. When it is incorporated in the above, it is 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 poise or less (10 ¹³ Pa · s or less). Usually, the flow is recognized within 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, diglycidyl adipate, diglycidyl phthalate, 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 mass 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 mass 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 mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polymer. If the added amount is less than 0.1 parts by mass, curing may be insufficient, and if it exceeds 50 parts by mass, 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 translucent part on the transparent plastic substrate is intentionally uneven to improve adhesion, or light is scattered on its surface to transfer the back shape of the conductive material, so that the transparency However, if a resin having a refractive index close to that of the transparent plastic substrate is smoothly applied to the uneven surface, irregular reflection is minimized 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 JP-A-2003-188576, when the electromagnetic wave shielding film of the present invention and another substrate are bonded together, as a transparent substrate film, an ethylene-vinyl acetate copolymer resin having high heat-fusibility, Alternatively, when a film of a heat-fusible resin such as an ionomer resin is used alone or laminated with another resin film, it can be performed without providing an adhesive layer. Lamination is performed by a dry laminating method using 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.
The electromagnetic wave shielding sheet in the above publication refers to a functional layer described as “electromagnetic wave shielding film” in the present invention.

  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 haze 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) Peelable protective film The optical filter according to the present invention can be provided with a peelable protective film.
The protective film may be provided on one side or both sides of the optical filter.
In general, optical filters are used by laminating sheets with effects such as reinforcing the outermost surface, imparting antireflection properties, imparting antifouling properties, etc. The film needs to be peeled off during such further lamination, and therefore, it is desirable that the protective film is laminated so-called peelable.

  The peel strength when the protective film is laminated on the conductive metal part 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-like conductive metal part may peel off from the transparent base film (or from the adhesive layer), which is also not preferable.

  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.

  Since the above-described protective film material and adhesive material can be applied as they are to the protective film applied to the conductive metal part side, different protective films may be used. The same thing can be used as both protective films.

(3) Blackening treatment The electromagnetic wave shielding film according to the present invention may be subjected to blackening treatment.
The blackening process is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-188576. The blackened layer formed by the blackening treatment can impart antireflection properties in addition to the antirust effect. The blackened layer can be formed by, for example, Co—Cu alloy plating. By providing the blackened layer on the conductive metal portion, reflection of the surface can be prevented. Further, a chromate treatment may be performed thereon as a rust prevention treatment. The chromate treatment is performed by dipping in a solution containing chromic acid or dichromate as a main component and drying to form a rust-preventive coating, which can be performed on one or both sides of the conductive metal portion as necessary. However, a commercially available chromate-treated copper foil or the like may be used.

  Further, as another example of the configuration including the blackening layer, the configuration described in JP-A-11-266095 may be used. That is, the first blackening layer is provided on the conductive metal portion, the electrolytic plating is performed on the first blackening layer, and then the second blackening layer is further provided on the plating. is there. In order to perform electroplating on the first blackened layer, at least the first blackened layer needs to be conductive. In general, the conductive blackening layer can be formed using a conductive metal compound, for example, a compound such as nickel (Ni), zinc (Zn), copper (Cu), or the like. It can be formed using an ionic polymer material such as an electrodeposition coating material.

A method of providing a blackened layer is known (for example, see FIG. 5 of JP-A-11-266095). For example, a transparent support on which a conductive metal part is formed may be dipped in an electrolytic solution containing a blackening material and plated by an electrochemical plating method. In the present invention, the electrolytic solution bath (black plating bath) containing the blackening material may be a black plating bath containing nickel sulfate as a main component, and a commercially available black plating bath. Specifically, for example, a black plating bath manufactured by Shimizu Co., Ltd. (trade name, Novroi SNC, Sn—Ni alloy system), a black plating bath manufactured by Nippon Chemical Industry Co., Ltd. (Trade name, Nikka Black, Sn—Ni alloy system), black plating bath (trade name, Ebony-Chromium 85 series, Cr system) manufactured by Metal Chemical Co., Ltd., etc. can be used. Moreover, in this invention, various black plating baths, such as Zn type | system | group, Cu type | system | group, others, can be used as said black plating bath. Next, after conducting the conductive plating to form a conductive mesh pattern, a second blackening layer is formed thereon. For example, when the electroplating metal is Cu, a hydrogen sulfide (H ₂ S) solution treatment is performed to blacken the Cu surface as copper sulfide (CuS), thereby forming a second blackened layer. In the present invention, as the blackening treatment agent for the second blackening layer, it can be easily produced using a sulfide-based compound, and there are also various types of treatment agents on the market, 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.

-Composite functional layer Next, the function of a functional film is demonstrated.
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 refractive index of 1.5 or less, preferably 1.4 or less in the visible region, such as a fluorine-based transparent polymer resin or 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 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 (antistatic 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. The display filter of the present invention having one or more forms of an adhesive material (D1), a translucent adhesive material (D2), a light-transmitting adhesive material or an adhesive containing a dye used for bonding. Can be used for

  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.

  In the display filter of the present invention, the polymer film (A), the conductive mesh layer (B), the functional film (C), the translucent adhesive material (D1) and the translucent adhesive material (D2) are ( C) / (D1) / (B) / (A) / (D2), preferably composed of a conductive mesh layer (B) and a polymer film (A) and a functional film Are bonded with a translucent adhesive (D1), and a translucent adhesive (D2) is attached to the main surface of the polymer film (A) opposite to the conductive mesh layer (B). .

  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 (D2) is mounted on the display side.

  As a method of using the display filter of the present invention by providing it on the front surface of the display, a method of using it as a front filter plate using a transparent molded product (E) described later as a support, a translucent adhesive ( There is a method of pasting and using 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 mass, 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.

  The structure of the display filter in the case of using a transparent molded article is at least a functional film (C) / translucent adhesive material (D1) / conductive mesh layer (B) / polymer film (A) / translucent adhesive. It is material (D2) / transparent molding (E). Moreover, even if a functional film (C) is provided through the translucent adhesive material layer in the main surface opposite to the surface bonded with the translucent adhesive material (D2) of a transparent molding (E). 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 (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 adhesive material (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. . 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 a solid metal foil and / or when the conductive part has a sufficiently strong mechanical strength, 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 it also efficiently emits near infrared rays around 800 to 1000 nm emitted from plasma displays. Therefore, 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, and the like 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 more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Example 1
<Creation of support>
Undercoat layer first and second layers having the following composition were applied to both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm).

<Undercoat layer 1st layer>
Core-shell type vinylidene chloride copolymer (1) 15 g
2,4-dichloro-6-hydroxy-s-triazine 0.25 g
Polystyrene fine particles (average particle size 3μ) 0.05g
Compound (Cpd-20) 0.20g
Colloidal silica (Snowtex ZL: particle size 70-100 μm, manufactured by Nissan Chemical Co., Ltd.)
0.12g
100g with water
Further, 10% by mass of KOH was added, and the coating solution adjusted to pH = 6 was applied at a drying temperature of 180 ° C. for 2 minutes so that the dry film thickness was 0.9 μm.

<2nd undercoat layer>
1g of gelatin
Methylcellulose 0.05g
Compound (Cpd-21) 0.02g
C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g
Proxel 3.5 × 10 ^-3 g
Acetic acid 0.2g
100g with water
This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm.

1. Preparation of silver halide photographic material sample <Preparation of sample>
(Preparation of emulsion A)
・ 1 liquid water 750ml
20g gelatin
Sodium chloride 1.6g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
・ Two liquids 300ml
150 g silver nitrate
・ 3 liquid water 300ml
Sodium chloride 38g
Potassium bromide 32g
Hexachloroiridium (III) potassium (0.005% KCl 20% aqueous solution) 5ml
Ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) 7ml
Potassium hexachloroiridium (III) (0.005% KCl 20% aqueous solution) and ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) used in the three liquids were dissolved in KCl 20% aqueous solution and NaCl 20% aqueous solution, respectively. And heated for 120 minutes.

To 1 liquid maintained at 38 ° C. and pH 4.5, 90% of the 2 and 3 liquids were simultaneously added over 20 minutes with stirring to form 0.15 μm core particles. Subsequently, the following 4th and 5th liquids were added over 8 minutes, and the remaining 10% of the 2nd and 3rd liquids were further added over 2 minutes to grow particles to 0.18 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete grain formation.
・ 4 liquid water 100ml
Silver nitrate 50g
・ 5 liquid 100ml
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 5mg

Then, it washed with water by the flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of anionic precipitation agent-1 shown below was added, and the pH was lowered using sulfuric acid until the silver halide was precipitated. Next, about 3 liters of the supernatant was removed (first water wash). Further, 3 liters of distilled water was added, and sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second water wash). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing / desalting process. 8 g of gelatin was added to the emulsion after washing and desalting, adjusted to pH 5.6 and pAg 7.5, 10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, 15 mg of sodium thiosulfate and 10 mg of chloroauric acid were added. Chemical sensitization was performed to obtain an optimum sensitivity at 0 ° C., and 100 mg of 1,3,3a, 7-tetraazaindene as a stabilizer and 100 mg of proxel (trade name, manufactured by ICI Co., Ltd.) as a preservative were added. It was. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain diameter of 0.18 μm and a coefficient of variation of 9% was obtained. (Finally, the emulsion had pH = 5.7, pAg = 7.5, conductivity = 60 μS / m, density = 1.28 × 10 ³ kg / m ³ , and viscosity = 60 mPa · s.)

<Emulsion layer>
Emulsion A was subjected to spectral sensitization by adding sensitizing dye (SD-1) 5.7 × 10 ⁻⁴ mol / mol Ag. Further, KBr 3.4 × 10 ⁻⁴ mol / mol Ag and compound (Cpd-3) 8.0 × 10 ⁻⁴ mol / mol Ag were added and mixed well.
Then, 1,3,3a, 7-tetraazaindene 1.2 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻⁴ mol / mol Ag, surfactant (Sa -1), (Sa-2) and (Sa-3) were added so that the coating amounts were 60 mg / m ² , 40 mg / m ² and 2 mg / m ² , respectively, and the pH of the coating solution was adjusted using citric acid. Adjusted to 5.6. The thus emulsion layer coating liquid prepared by coated so on Ag7.6g / m ^2, gelatin 1.1 g / m ² the support.

<UL layer>
Gelatin 0.23 g / m ²
Compound (Cpd-7) 40mg / m ²
Compound (Cpd-14) 10mg / m ²
Preservative (Proxel) 1.5mg / m ²
In addition, the coating liquid of each layer added the thickener represented by the following structure (Z), and adjusted the viscosity.

Moreover, the sample used by this invention formed the back layer and antistatic layer of the following composition.
<Back layer>
Gelatin 3.3 g / m ²
Compound (Cpd-15) 40mg / m ²
Compound (Cpd-16) 20mg / m ²
Compound (Cpd-17) 90mg / m ²
Compound (Cpd-18) 40mg / m ²
Compound (Cpd-19) 26mg / m ²
1,3-divinylsulfonyl-2-propanol 60 mg / m ²
Polymethyl methacrylate fine particles (average particle size 6.5 μm) 30 mg / m ²
Liquid paraffin 78mg / m ²
Compound (Cpd-7) 120mg / m ²
Calcium nitrate 20mg / m ²
Preservative (Proxel) 12mg / m ²

<Antistatic layer>
Gelatin 0.1 g / m ²
Sodium dodecylbenzenesulfonate 20mg / m ²
SnO ₂ / Sb (9/1 mass ratio, average particle diameter 0.25 μ) 200 mg / m ²
Preservative (Proxel) 0.3mg / m ²

<Application method>
First, two layers of the UL layer and the emulsion layer from the side closer to the support as the emulsion surface side were coated on the support with the above-mentioned subbing layer in the order of a simultaneous multi-layer by a slide bead coater method while maintaining at 35 ° C. It was passed through a set zone (5 ° C.). Here, Cpd-7, which is a hardener, was added to the UL layer immediately before coating, and was added to the emulsion layer by diffusing from the UL layer. Then, on the side opposite to the emulsion surface, the antistatic layer and the back layer were coated in the order of the antistatic layer and the back layer simultaneously with the addition of the hardener solution by the curtain coater method, and the cold air set zone (5 ° C) Was passed. When passing through each set zone, the coating solution showed a sufficient setting property. Subsequently, both sides were simultaneously dried in the drying zone. In this way, Sample (1-1) was prepared.
In the obtained sample (1-1), the coated silver amount was 7.6 g / m ² , the Ag / gelatin mass ratio of the emulsion layer was 6.9, the swelling ratio was 209%, and the product of the Ag / gelatin mass ratio and the swelling ratio was 13.2. The photosensitive material having an emulsion layer as the uppermost layer. Here, the swelling ratio of the emulsion layer was determined as follows. That is, the thickness (a) of the emulsion layer at the time of drying is obtained by observing a section of the sample at the time of drying with a scanning electron microscope, immersed in distilled water at 25 ° C. for 1 minute, and then freeze-dried with liquid nitrogen Was observed with a scanning electron microscope to determine the film thickness (b) of the emulsion layer during swelling, and the swelling ratio was calculated by the following equation.
Swell rate (%) = 100 × ((b) − (a)) / (a)

  The surface resistance of the obtained sample 1-1 was 30Ω / □ as a result of measurement using a Loresta-GP MCP-T600 / ASP probe manufactured by Mitsubishi Chemical.

2. Sample Exposure and Processing Conditions A lattice-like photomask (line / space = 290 μm / 10 μm (line / space = 290 μm / 10 μm)) that can give a developed silver image of line / space = 10 μm / 290 μm to the emulsion layer coating film of the dried sample (1-1) Exposure was performed using parallel light using a high-pressure mercury lamp as a light source through a photomask having a pitch of 300 μm and a space in the form of a lattice to obtain an exposed silver halide film.
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.
Black and white development processing (temperature 30 ° C., time 40 seconds), fixing processing (temperature 30 ° C., time 40 seconds), and hardening processing (temperature 30 ° C., time 40 seconds) are sequentially performed on the exposed silver halide film. It was.
Furthermore, the electroplating process was divided into 15 times for the silver halide film that had been subjected to the hardening process. Finally, a rust prevention treatment was performed to obtain a conductive film.

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 4000 0.5 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
Ethylenedimine ・ tetraacetic acid 0.5 g
Potassium iodide 2 g
Adjust to pH 5.8

[Hardening treatment (hardening treatment before plating) 1L formulation]
Additives (described in Table 1) 50 g
Adjust to pH 5.1 1 L by adding pure water

  In the present invention, the additive was hardened using glutaraldehyde. In addition, as a comparative example, a sample in which no additive was added without adding glutaraldehyde and a sample in which sulfuric acid was used without containing glutaraldehyde were used.

[Electroplating solution 1-14 1L prescription]
Copper sulfate pentahydrate 200 g
60 g of sulfuric acid
Cu-Brite 20 mL
(Made by Sugawara Eugelite)
Add pure water 1 L

[Prescription of electroplating solution 15 1L]
Nickel sulfate hexahydrate 100 g
Ammonium sulfate 15 g
Zinc sulfate heptahydrate 25 g
Sodium thiocyanate 15 g
Adjust to pH 4.5

[Anti-rust solution 1L prescription]
Sulcup AT-21 20 mL
(Made by Uemura Kogyo Co., Ltd.)

[Measurement of swelling rate]
The swelling rate of the obtained conductive film was determined as follows. That is, the thickness (a) of the light-transmitting part layer at the time of drying is obtained by observing a section of the light-transmitting part at the time of drying with a scanning electron microscope, and the liquid is immersed in distilled water at 25 ° C. for 1 minute. The thickness (b) of the light-transmitting part layer at the time of swelling was determined by observing a section of the sample freeze-dried with nitrogen with a scanning electron microscope, and the swelling ratio was calculated by the following equation.
Swell rate (%) = 100 × ((b) − (a)) / (a)

(Evaluation method of vertical stripes by plating)
The sample after the running treatment was visually evaluated according to the following four steps.
Xx ... There are too many vertical stripes and it is not acceptable at all.
× ... Many vertical warts are not acceptable.
Δ: Vertical distortion is acceptable but barely acceptable.
○ ... Vertical streaks cannot be confirmed by visual inspection and is acceptable.
The results are shown in Table 1.

(Plating quality evaluation method)
The sample after the running treatment was randomly observed with a light microscope (× 500) for 100 fields of view, and evaluated according to the following five levels.
5 ... All 100 fields of view have uniform plating and are acceptable.
4 ... Non-uniform plating is observed in less than 5 out of 100 views, but barely acceptable.
3 ... Non-uniform plating is observed in 5 to 10 views out of 100 views and is unacceptable.
2 ... Non-uniform plating is observed in 11 to 50 views out of 100 views and is unacceptable.
1 ... Non-uniform plating is observed in 51 or more views out of 100 views, which is unacceptable.
The results are shown in Table 1.

(Plating progress evaluation method)
Prior to the treatment of electrolytic plating 1, 3, 5, 7, 9, 11, 13, and 15, the photosensitive materials of Example 1 and Comparative Examples 1 and 2 were sampled. The sampled photosensitive materials of Example 1 and Comparative Examples 1 and 2 were cut into 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.

Table 2 shows the measurement results of the surface resistance of the photosensitive materials of Example 1 and Comparative Examples 1 and 2.

  As can be seen from the results shown in Table 2, it was confirmed that in the photosensitive material of Example 1, the surface resistance after electrolytic plating was sufficiently reduced as compared with those of Comparative Examples 1 and 2.

  As shown in Table 1, in Example 1 in which glutaraldehyde was added as a hardening agent, it was found that uneven stripes were suppressed and plating uniformity was improved.

(Example 2)
It implemented similarly to Example 1 except having changed the plating pretreatment of the said Example 1 into the following prescription. As a result, like Example 1, it was a favorable result.

[1L pre-plating hardening solution]
Acetic acid 50% 15 mL
Sodium sulfate 130 g
Anhydrous sodium acetate 12 g
Aluminum sulfate 5 g
Sulfuric acid 0.5 g
Adjust to pH 4.0 1 L by adding pure water

Example 3
Sample (3-1) to (3-4) were obtained by adjusting the amount of hardener (Cpd-7) added and the amount of gelatin applied to sample (1-1) of Example 1. Using these samples, the same evaluation as in Example 1 was performed except that the conditions of the dura treatment were changed. The obtained results are shown in Table 3.
The dry film thickness of the obtained light-transmitting part was obtained by observing a section of the light-transmitting part at the time of drying with a scanning electron microscope to obtain the film thickness (a) of the light-transmitting part layer at the time of drying.

It is a schematic diagram which shows an example of the electroplating tank suitably used for this invention. It is a schematic diagram which shows an example of the electroconductive film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Electroplating apparatus 11 Electrolysis tank 12a, 12b Feed roller 13 Anode plate 14 Guide roller 16 Film 17 Liquid roller 21 Conductive film 22 Conductive functional layer 23 Support body 24 Exposure part (metal silver part)
25 Unexposed portion 26 Electrolytic plating treatment portion 27 Electrolytic plating treatment portion 28 Silver halide emulsion layer

Claims (28)

  A conductive film comprising a conductive functional layer including a conductive metal portion and a light transmissive portion on a support, wherein the light transmissive portion has a swelling ratio of 180% or less.   2. The conductive film according to claim 1, wherein a surface resistance of the conductive film is 2.5 Ω / sq or less and / or a transmittance of the light transmissive portion is 95% or more.   The conductive film according to claim 1, wherein a dry film thickness of the light transmissive portion is 2.0 μm or less.   The conductive film according to claim 1, wherein the light transmissive portion is substantially made of a water-soluble polymer. A method for producing a conductive film having a conductive functional layer including a conductive metal part and a light transmissive part on a support, and reacting a dura solution with the surface of the conductive film having a surface resistance of 1 to 1000 Ω / □ And a hardening process for setting the swelling ratio of the light-transmitting part to 180% or less . 6. The conductive film production according to claim 5, wherein the conductive film is a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer including a silver halide emulsion layer on a support. Method.   7. The method for producing a conductive film according to claim 5, wherein the hardening solution contains a hardening agent, and the hardening agent has a function of hardening gelatin.   8. The conductive film according to claim 7, wherein the hardener is a compound selected from formaldehyde, pivalylaldehyde, glutaraldehyde, succinaldehyde, potash alum, chromium alum, and aluminum sulfate. Manufacturing method.   A conductive film obtained by the method for manufacturing a conductive film according to claim 5.   An electromagnetic shielding film manufactured by the method for manufacturing a conductive film according to claim 5.   An electromagnetic wave shielding film having a surface resistance of 2.5 Ω / sq or less of the electromagnetic wave shielding film produced by the method for producing a conductive film according to claim 5.   The electromagnetic wave shielding film according to claim 11, wherein the surface resistance is 1.5Ω / sq or less. A development step in which a silver halide film having a silver halide emulsion layer is exposed and developed on a support , a metallic silver portion is formed in an exposed portion, and a light transmissive portion is formed in an unexposed portion ;
The metallic silver portion and the light-transmitting portion the surface of the formed film, by reacting a hardener solution containing the hardener, the swelling ratio of the light transmitting unit and the hardening step shall be the 180% or less ,
An electrolytic plating treatment step for performing an electrolytic plating treatment on the metal silver portion of the film subjected to the hardening step,
The manufacturing method of the electroconductive film which has this.   The method for producing a conductive film according to claim 13, wherein the silver halide emulsion layer contains silver halide and a binder. The method for producing a conductive film according to claim 14, wherein the mass ratio of silver (Ag) and binder (B) in the silver halide emulsion layer is in the range of the following formula (1).
Ag / B = 3-15 (1)   The method for producing a conductive film according to claim 14 or 15, wherein a silver salt-containing layer having an Ag / binder volume ratio of 1/4 or more is used.   The method for producing a conductive film according to claim 14, wherein the binder is gelatin.   The method for producing a conductive film according to claim 13, wherein the hardener is a compound having a function of hardening gelatin.   19. The hardener is a compound selected from formaldehyde, pivalylaldehyde, glutaraldehyde, succinaldehyde, potash alum, chromium alum, and aluminum sulfate. The manufacturing method of the electroconductive film of description.   The method for producing a conductive film according to claim 13, wherein the hardener is glutaraldehyde or aluminum sulfate. The said dura solution contains 0.005-1.000 mol / L of a hardening agent.
The manufacturing method of the electroconductive film in any one of 0.   The method for producing a conductive film according to any one of claims 13 to 21, wherein the dura mater solution further contains a compound having a swelling-inhibiting action. Method for producing a conductive film according to any one of claims 13 to 2 2, wherein the light transmitting portion has substantially no physical development nuclei. Characterized in that it is obtained by the method according to any one of claims 13 to 2 3, conductive metal portion and a plasma display panel electromagnetic wave shielding film having optical transparency unit.   An optical filter for a plasma display panel, comprising the electromagnetic wave shielding film according to claim 11. An optical filter for plasma display panel characterized by having an electromagnetic wave shielding film obtained by the production method according to any one of claims 13 to 2 3. A plasma display panel comprising the optical filter according to claim 2 5, or 2 6. Plasma televisions, characterized in that it comprises an electromagnetic wave shielding film obtained by the production method according to any one of claims 13 to 2 3.

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