JP2007039738A - Electrolytic plating method and apparatus therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming a plated film on a photo sensitive material of a silver halide, while inhibiting irregularity or a flaw from forming in the plated film. <P>SOLUTION: The electrolytic plating apparatus for forming the plated film on an electroconductive face of a film (F) has a plurality of electrolytic plating tanks 50 for electrolytically plating the film (F) while passing it therein. The respective electrolytic plating tanks 50 contain a plating liquid 7 of which the concentration becomes gradually lower toward a downstream side from an upstream side in a transportation direction. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electrolytic plating process in which a silver halide photosensitive material having a metallic silver part formed is conveyed in an electrolytic plating process layer filled with a plating solution, and a plating film is formed on the metallic silver part by electrolytic plating. The present invention relates to a method and an apparatus.

  As a method of forming a plating film by electrolytic plating treatment on the metallic silver portion formed on the silver halide photosensitive material, an electrolytic plating treatment tank in which an anode is introduced is disposed before or after the cathode roll in contact with the metallic silver portion. A method of forming a plating film on a metallic silver part by energizing the metallic silver part while conveying a silver halide photosensitive material between a cathode roll and an anode is known (for example, Patent Documents 1 and 2). reference). In this method, a plating film having a desired thickness is formed on a metallic silver portion by repeatedly arranging a unit in which a cathode and an anode are arranged, and repeatedly forming a plating film on the metallic silver portion. Can be formed.

Here, when the electrical resistance of the metal silver part of the silver halide photosensitive material is high resistance (for example, 10 Ω / cm ² or more, generally 1 Ω / cm ² or less), the metal silver part has a necessary amount. In order to pass an electric current, a high voltage must be applied to the metallic silver part, and in order not to cause burning in the metallic silver part, it is essential to supply a high concentration plating solution to the metallic silver part.

However, when the metal silver part is energized in a high-concentration plating solution, decomposition of oxidized water in the metal silver part becomes active and the metal silver part becomes hot. Therefore, if energization of the metallic silver part in a high concentration plating solution is continued for a long time, binders such as gelatin of the silver halide photosensitive material become brittle. There was a problem that the silver photosensitive material was damaged.
JP 2004-18949 A JP 2004-221564 A

  The present invention has been made in consideration of the above facts, and suppresses uneven plating and scratches generated in the silver halide photosensitive material.

  The electrolytic plating method according to claim 1, wherein the silver halide photosensitive material on which the metallic silver portion is formed is electrolytically plated on the metallic silver portion while being conveyed in an electrolytic plating treatment tank filled with a plating treatment solution. An electroplating method for forming a plating film by using a plurality of the electroplating baths arranged in the conveying direction of the silver halide photosensitive material, and the concentration of the plating solution filled in each electroplating bath Is gradually reduced from the upstream side to the downstream side in the transport direction.

  In the electroplating processing method according to claim 1, a plurality of electroplating baths filled with a plating solution are arranged in the conveying direction of the silver halide photosensitive material, and the silver halides are contained in the plurality of electroplating baths. While conveying the photosensitive material, a plating film is formed by electrolytic plating on the metallic silver portion formed on the silver halide photosensitive material.

  Here, the concentration of the plating solution filled in each electrolytic plating tank gradually decreases from the upstream side to the downstream side in the transport direction. For this reason, on the upstream side in the transport direction where the electrical resistance of the metallic silver part is high, by supplying a high-concentration plating solution to the metallic silver part, the metallic silver part is prevented from being burned, and a plating film is formed and the electrical resistance is increased. On the downstream side in the transport direction when the metal is lowered, by supplying a plating solution of low concentration to the metal silver part, while preventing the metal silver part from burning, it suppresses decomposition of oxidized water in the metal silver part, and the metal silver part Suppresses heat generation.

  As a result, brittleness of the binder such as gelatin of the silver halide photosensitive material can be suppressed, so that uneven plating is less likely to occur and the silver halide photosensitive material is hardly damaged.

  The electrolytic plating treatment method according to claim 2 is the electrolytic plating treatment method according to claim 1, wherein the plating treatment liquid overflowing from the electrolytic plating treatment tank on the upstream side in the transport direction is the electrolysis on the downstream side in the transport direction. It is characterized by using a cascade system supplied to the plating tank.

  In the electrolytic plating method according to claim 2, the supply of the plating treatment liquid to each electrolytic plating treatment tank is performed by a cascade system, and the plating treatment liquid overflowing from the electrolytic plating treatment tank on the upstream side in the conveying direction Sequentially supplied to the electrolytic plating bath on the downstream side in the transport direction.

  Here, the plating solution whose concentration has been reduced in the electrolytic plating treatment tank on the upstream side in the conveyance direction is supplied to the electrolytic plating treatment tank on the downstream side in the conveyance direction, so that each electrolytic plating treatment tank Since the concentration of the plating solution filled in the plate gradually decreases from the upstream side to the downstream side in the conveying direction, the heat generation of the metallic silver portion is suppressed while preventing the burning of the metallic silver portion as in the case of claim 1. it can.

  In addition, by using the waste liquid from the electroplating tank on the upstream side in the transport direction in the electroplating tank on the downstream side in the transport direction, the usage and discharge amount of the plating liquid can be reduced without hindering the formation of the plating film. As a result, the cost of the plating solution itself and the cost required for waste solution treatment can be reduced.

  The electrolytic plating method according to claim 3 is the electrolytic plating method according to claim 1 or 2, wherein the plating tank and the rinsing tank are alternately arranged in the transport direction, and the rinsing tank is halogenated. The silver halide light-sensitive material is washed with water.

  4. The electrolytic plating treatment method according to claim 3, wherein the electrolytic plating treatment tank and the water washing tank are alternately arranged in the conveying direction of the silver halide photosensitive material, and the silver halide photosensitive material is disposed on the upstream side in the conveying direction. The silver halide light-sensitive material is washed with water while being transported from the electroplating bath to the downstream side in the transport direction.

  As a result, the silver halide photosensitive material to which the plating solution of high concentration is attached is not transported as it is to the electrolytic plating bath on the downstream side in the transport direction, so that the silver halide photosensitive material in each electrolytic plating bath is removed. The concentration of the plating treatment liquid near the surface of the material can be reduced to a desired concentration. Therefore, the heat generation of the metallic silver part can be suppressed.

  The electrolytic plating treatment method according to claim 4 is the electrolytic plating treatment method according to claim 3, wherein water overflowed from the washing tank on the downstream side in the conveyance direction is supplied to the washing tank on the upstream side in the conveyance direction. It is characterized by using the cascade method.

  In the electrolytic plating method according to claim 4, water supply to each washing tank is performed by a cascade system, and water overflowed from the washing tank on the downstream side in the conveying direction is supplied to the washing tank on the upstream side in the conveying direction. The

  Here, in the water washing tank on the most downstream side in the transport direction, the plating solution must be completely washed out from the silver halide photosensitive material. In the tank, there is no problem even if some of the plating solution remains in the silver halide photosensitive material, so the requirement for water cleanliness is low.

  For this reason, the amount of water used and the amount of waste water can be reduced without impeding the formation of the plating film by supplying water to each washing tank in a cascade manner from the downstream side in the transport direction to the upstream side. Accordingly, it is possible to reduce the cost of water itself and the cost required for wastewater treatment mixed with a plating solution.

  The electrolytic plating apparatus according to claim 5, wherein the silver halide photosensitive material on which the metallic silver portion is formed is electrolytically plated on the metallic silver portion while being conveyed in an electrolytic plating treatment tank filled with a plating treatment solution. An electrolytic plating apparatus for forming a plating film by using a plurality of electrolytic plating tanks arranged in the conveying direction of the silver halide photosensitive material, and adjusting the concentration of the plating solution filled in each electrolytic plating tank. It is characterized by being gradually lowered from the upstream side to the downstream side in the transport direction.

  In the electroplating processing apparatus according to claim 5, as in the electroplating processing method according to claim 1, since weakening of binders such as gelatin of the silver halide photosensitive material can be suppressed, uneven plating is less likely to occur, Further, the silver halide photosensitive material is hardly damaged.

  The electrolytic plating apparatus according to claim 6 is the electrolytic plating apparatus according to claim 5, wherein the plating solution overflowed from the electrolytic plating tank on the upstream side in the transport direction is the electrolytic plating on the downstream side in the transport direction. It is characterized by using a cascade system supplied to the treatment tank.

  In the electrolytic plating apparatus of claim 6, as in the electrolytic plating method of claim 2, the concentration of the plating solution filled in each electrolytic plating tank is applied from the upstream side to the downstream side in the transport direction. Thus, it is possible to reduce the heat generation of the metal silver part while preventing the metal silver part from burning. In addition, by using the waste liquid from the electroplating tank on the upstream side in the transport direction in the electroplating tank on the downstream side in the transport direction, the usage and discharge amount of the plating liquid can be reduced without hindering the formation of the plating film. it can.

  The electroplating apparatus according to claim 7 is the electroplating apparatus according to claim 5 or 6, wherein the plating tank and the water washing tank are alternately arranged in the transport direction, and the water washing tank is halogenated. The silver halide light-sensitive material is washed with water.

  In the electroplating processing apparatus according to claim 7, as in the electroplating processing method according to claim 3, the silver halide photosensitive material to which a high-concentration plating processing solution is attached is disposed in the electroplating processing tank on the downstream side in the transport direction. Therefore, the concentration of the plating solution near the surface of the silver halide photosensitive material in each electrolytic plating tank can be reduced to a desired concentration. Therefore, the heat generation of the metallic silver part can be suppressed.

  The electrolytic plating apparatus according to claim 8 is the electrolytic plating apparatus according to claim 7, wherein water overflowed from the washing tank on the downstream side in the conveying direction is supplied to the washing tank on the upstream side in the conveying direction. It is characterized by using the cascade method.

  In the electroplating processing apparatus according to claim 8, as in the electroplating processing method according to claim 4, the plating film is formed by supplying water to each washing tank in a cascade manner from the downstream side to the upstream side in the transport direction. The amount of water used and the amount of wastewater can be reduced without any hindrance.

  According to the present invention, plating unevenness and scratches generated in the silver halide photosensitive material can be suppressed. Moreover, the usage-amount and discharge | emission amount of a plating process liquid, the usage-amount of water, and the amount of wastewater can be suppressed, without causing trouble in formation of a plating film.

  Embodiments of the method and apparatus according to the present invention will be described with reference to the drawings.

  As shown in FIG. 1, the electrolytic plating apparatus 100 is a continuous plating apparatus that unwinds, plating, and winds a long film having a mesh-like metallic silver portion formed on one surface. . The main steps are an unwinding portion 301 for unwinding a roll-shaped film, a pretreatment portion 302 for performing acid treatment, degreasing treatment, washing with water, etc. on the conductive surface of the film F (surface on which the metal silver portion is formed), a plurality of electrolytic platings A treatment tank 50, a plating treatment section 303 having a plurality of washing tubs 52 for washing the plating solution, a rust prevention treatment, a treatment for washing away the rust prevention treatment solution, a post-treatment portion 304 for further drying and the like, and winding the film F in a roll shape A winding unit 305 is provided. In addition, when the electroconductive surface of the film F which is an electrolytic plating to-be-processed part is clean, a pre-processing may be abbreviate | omitted and a post-processing process may be abbreviate | omitted as needed.

  In FIG. 1, the film F unwound from the roll-shaped film 306 is adjusted in tension through an accumulator 307 and a balance roll unit 308, and then the speed is controlled to be substantially constant by a speed control unit 309, and acid and degreasing After entering the part 310 and the water washing part 312, it enters the plating part 303.

  As shown in FIG. 2, in the plating unit 303, the electrolytic plating tank 50 and the rinsing tank 52 are alternately arranged in the transport direction. The electroplating bath 50 is filled with a plating solution 7, and the cathode roll 1 is disposed on the upstream side in the transport direction of the electroplating bath 50 and above the surface of the plating solution 7. Further, a transport roll 101A is disposed in the lower part of the electrolytic plating tank 50, and a transport roll 101B is disposed on the downstream side of the electrolytic plating tank 50 in the transport direction and above the surface of the plating solution 7. Yes. Further, a transport roll 101 </ b> C is disposed in the lower part of the washing tank 52. The film F wound around the cathode roll 1 and the transport rolls 101A, 101B, and 101C that are repeatedly arranged in this order is transported in a substantially U shape.

  A case 102 filled with copper balls is immersed in the plating solution 7 in the electrolytic plating bath 50. The case 102 is disposed facing the conductive surface of the film F in the plating solution 7 and is electrically connected to the anode of the DC power source 3. A cathode roll 1 is connected to the cathode of the DC power supply 3.

  That is, the film F transported to the electrolytic plating bath 50 is transported in the plating solution 7 with the conductive surface facing the case 102 </ b> A after bringing the conductive surface into contact with the cathode roll 1. At this time, with the cathode roll 1 as a cathode and the case 102 as an anode, power is supplied from the DC power source 3 to the conductive surface of the film F, and a plating film is formed on the metal silver portion of the film F.

The current condition in the electrolytic plating process is set so that the current density of the film F is 0.2 to 10 A / dm ² .

  In order to maintain the uniformity of plating, fresh air 331 is introduced from an air inlet (air stirring nozzle) 330, and the plating solution 7 in the electrolytic plating tank 50 is sufficiently stirred. This is performed for the purpose of increasing the concentration of the plating film metal ions in the vicinity of the surface of the part of the film F where the plating film is formed (the part near the case 102). For this reason, it is effective to aim fresh air 331 at a portion where the plating film is formed and eject it. Although not shown, the plating solution 7 is always circulated through the filter, and the dirt is removed by the filter.

  And the film F in which the plating film was formed on the metallic silver part once leaves the electrolytic plating treatment tank 50 and then enters the water washing tank 52 on the downstream side in the transport direction. The washing tank 52 is filled with water 53, and the plating solution 7 on the film F is washed out.

  The film F that has been washed with the plating solution 7 repeatedly passes through the electrolytic plating treatment tank 50 and the washing tank 52 on the downstream side in the transport direction. As a result, the plating film is formed on the conductive surface of the film F so that a total thickness of 1 to 30 μm is formed on the metal silver portion of the film F.

  By the way, each electrolytic plating tank 50 is provided with a drain port 50A. A liquid supply pipe (not shown) extends from the drain port 50A to the upper part of the electroplating tank 50 on the downstream side in the transport direction. The height of the drain port 50 gradually decreases from the upstream side to the downstream side in the transport direction.

  In the plating processing unit 303, as indicated by a dotted line in the figure, the plating processing solution 7 is continuously supplied to the electrolytic plating processing tank 50 on the most upstream side in the transport direction, and is filled up to the height of the drain port 50A. Is discharged from the drainage port 50A and flows into the electrolytic plating tank 50 on the downstream side in the transport direction through the liquid feeding pipe.

  That is, in the plating unit 303, the plating solution 7 is supplied to each electrolytic plating tank 50 by a cascade method, and the plating solution 7 overflowed from the electrolytic plating tank 50 on the upstream side in the transport direction is supplied. It is sequentially supplied to the electrolytic plating tank 50 on the downstream side in the transport direction.

  In other words, the plating treatment liquid 7 in which the concentration of the plating film metal ions is reduced in the electrolytic plating treatment tank 50 on the upstream side in the conveyance direction is supplied to the electrolytic plating treatment tank 50 on the downstream side in the conveyance direction. . For this reason, the density | concentration of the plating film metal ion of the plating process liquid 7 with which each electrolytic plating tank 50 was filled falls gradually from the conveyance direction upstream to the downstream.

  Here, on the upstream side in the transport direction, the electric resistance of the conductive surface of the film F is high due to the thin film thickness of the plating film, and it is necessary to apply a high voltage to the conductive surface of the film F. As the process proceeds, the thickness of the plating film gradually increases, whereby the electrical resistance of the conductive surface of the film F gradually decreases, and the voltage applied to the conductive surface of the film F can be reduced.

  For this reason, it is necessary to supply a high concentration plating solution 7 to the conductive surface of the film F in order to prevent the conductive surface of the film F from burning on the upstream side in the transport direction. The concentration of the plating treatment liquid 7 supplied to the conductive surface of F can be lowered.

  In addition, when energization is performed on the conductive surface of the film F in the high-concentration plating solution 7, oxidation water decomposition on the conductive surface of the film F becomes active, and the conductive surface of the film F becomes hot. For this reason, if the conductive surface of the film F is energized in the plating solution 7 having a high concentration continuously for a long time, the binder such as gelatin of the film F becomes brittle. The silver halide photosensitive material is easily damaged.

  Therefore, in the present invention, in the electrolytic plating tank 50 on the upstream side in the transport direction, a high concentration plating solution 7 is supplied to the conductive surface of the film F, so that the metallic silver portion is prevented from being burned, and the downstream side in the transport direction. In the electrolytic plating bath 50, by supplying a low concentration plating solution 7 to the conductive surface of the film F, decomposition of oxidized water on the conductive surface of the film F is suppressed, and heat generation on the conductive surface of the film F is suppressed. is doing.

  Further, in the present invention, the electrolytic plating tank 50 and the washing tank 52 are alternately arranged in the transport direction of the film F, and the film F is electroplated downstream from the electrolytic plating tank 50 upstream in the transport direction. While being transported to the tank 50, the film F is washed with water.

  As a result, the film F to which the high-concentration plating solution 7 is adhered is not transported as it is to the electroplating bath 50 on the downstream side in the transport direction, so that the conductivity of the film F in each electroplating bath 50 is eliminated. The concentration of the plating solution 7 near the surface of the surface can be reduced to a desired concentration. Therefore, the heat generation of the film F can be further suppressed.

  In addition, by using the waste liquid from the electroplating bath 50 upstream in the transport direction in the electroplating bath 50 downstream in the transport direction, the usage amount and discharge of the plating solution 7 can be achieved without hindering the formation of the plating film. Since the amount can be reduced, the cost of the plating treatment liquid 7 itself and the cost required for the waste liquid treatment can be reduced.

  Each flushing tank 52 is also provided with a drain port 52A. A liquid feed pipe (not shown) extends from the drain port 52A to the upper part of the washing tank 52 on the upstream side in the transport direction. The height of the drain port 52 gradually decreases from the downstream side in the transport direction to the upstream side.

  In the plating processing unit 303, as indicated by a chain line in the figure, the water 53 continues to be supplied to the washing tank 52 on the most downstream side in the transport direction, and the water 53 filled up to the height of the drainage port 52A is discharged to the drainage port 52A. And flows into the washing tank 52 on the upstream side in the transport direction through the liquid feeding pipe.

  That is, in the plating processing unit 303, the water 53 is supplied to each washing tank 52 by a cascade system, and the water 53 overflowed from the washing tank 52 on the downstream side in the transport direction is flushed on the upstream side in the transport direction. Will be supplied sequentially.

  Here, in the washing tank 52 on the most downstream side in the transport direction, the plating solution 7 must be completely washed out from the film F, so that the requirement for the cleanliness of water becomes high, but the washing tank on the upstream side in the transport direction. In 52, since a problem does not arise even if some of the plating solution 7 remains on the film F, the requirement for the cleanliness of water is low.

  For this reason, the amount of water 53 used and the amount of waste water can be reduced without impeding the formation of the plating film by supplying water to each washing tank 52 in a cascade manner from the downstream side in the transport direction to the upstream side. Therefore, the cost of the water 53 itself and the cost required for the wastewater treatment mixed with the plating treatment liquid 7 can be reduced.

  Next, as shown in FIG. 1, the film F on which the plating film is formed includes a roll 325 that detects the tension of the film F, a rust prevention treatment unit 316 that contains a rust prevention treatment liquid 317 that protects the plating film, and an excessive amount. It passes through the accumulator 323 after the tension is adjusted through the water washing part 318 for removing the rust preventive treatment liquid, the drying process part 320 having a drying furnace for removing moisture, the speed adjusting part 321 and the balance roll part 322. Finally, the film F is wound up into a roll shape to form a roll film 324. Thus, a film F with a plating film is obtained.

  Here, it is preferable that the conveyance tension of the substantial film F is 10 N / m or more and 320 N / m or less. When the tension was actually less than 10 N / m, the film F started to meander and the control of the conveyance path was not successful. On the other hand, when it exceeds 320 N / m, there is a problem that the product is curled due to the internal strain of the plated metal formed on the film F.

  In the conveyance tension control, it is preferable to perform a feedback control in which the conveyance tension is detected using the tension detection roll 325 and the speed is adjusted by the speed adjustment unit 321 so that the tension value becomes constant.

  As the protrusion material of the cathode roll 1, since a battery phenomenon (oxidation-reduction phenomenon) is not preferable, a resin material or a ceramic material is suitable. Among the resins, for example, PVC or nylon is suitable.

  Moreover, as a film material of such a film with a plating film, a polyimide resin and a polyester resin are preferably used.

  Specific examples of the material of the base plastic film used in the present invention include polyethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene-α, β-bis (2-chlorophenoxyethane-4,4′-dicarboxyl. Polyester), polyetheretherketone, aromatic polyamide, polyarylate, polyimide, polyamideimide, polyetherimide, polyparazic acid, polyoxadiazole, and halogen group or methyl group-substituted products thereof. Moreover, you may contain these copolymers and another organic polymer. Known additives such as lubricants and plasticizers may be added to these plastics.

  Among the above plastics, an unstretched film obtained by melt-extruding a polymer containing 85 mol% or more of a repeating unit as shown in the following chemical formula 1 is particularly preferably a film in which mechanical properties are improved by stretching and orientation in a biaxial direction. used.

また、下記化２に示すような繰り返し単位を５０モル％以上含むポリマーからなり、湿式あるいは乾式製膜したフィルム、あるいは該フィルムを二軸延伸および／または熱処理せしめたフィルムも好ましく使用される。

Further, a film made of a polymer containing 50 mol% or more of repeating units as shown in the following Chemical Formula 2 and wet or dry film formation, or a film obtained by biaxial stretching and / or heat treatment of the film is also preferably used.

ＰＤＰ（プラズマディスプレイパネル）に使用される透光性導電性膜の場合、基材であるプラスチックフィルムの厚さは５０〜１５０μｍ程度のものが多用され、とくに７５〜１００μｍの厚さのものが好適に用いられる。
（透光性導電性金属膜の形成方法）
ハロゲン化銀写真感光材料にメッシュパターンを露光し、黒白現像処理して透光性導電性金属膜を作成し、その金属銀（現像銀）部に銅メッキを施す本件記載の電解メッキ方法及び装置を応用した例を示す。

In the case of a translucent conductive film used for PDP (plasma display panel), the thickness of the plastic film as the base material is frequently about 50 to 150 μm, and particularly preferably about 75 to 100 μm. Used for.
(Method for forming translucent conductive metal film)
The electroplating method and apparatus according to the present invention, wherein a silver halide photographic light-sensitive material is exposed to a mesh pattern, black-and-white developed to form a light-transmitting conductive metal film, and copper plating is applied to the metal silver (development silver) portion. The example which applied is shown.

The method for forming a translucent conductive metal film in the present invention includes the following three forms depending on the photosensitive material and the form of development processing.
(1) A mode in which a photosensitive silver halide black-and-white photosensitive material not containing physical development nuclei is chemically developed to form a metallic silver portion on the photosensitive material.
(2) An embodiment in which a photosensitive silver halide black-and-white photosensitive material containing physical development nuclei in a silver halide emulsion layer is dissolved and physically developed to form a metallic silver portion on the photosensitive material.
(3) A photosensitive silver halide black-and-white photosensitive material containing no physical development nuclei and an image receiving sheet having a non-photosensitive layer containing physical development nuclei are overlapped and developed by diffusion transfer, and the metallic silver portion is non-photosensitive. Form formed on top.

  The aspect (1) is an integrated black-and-white development type, and a light-transmitting conductive metal film such as a light-transmitting electromagnetic wave shielding film or a light-transmitting conductive film is formed on the photosensitive material. The resulting developed silver is chemically developed silver and is highly active in the subsequent plating or physical development process in that it is a filament with a high specific surface.

  In the above aspect (2), the light-sensitive electromagnetic shielding film or the light-transmitting conductive film is formed on the photosensitive material by dissolving silver halide grains closely related to each physical development and depositing on the development nucleus in the exposed portion. A translucent conductive metal film such as is formed. This is also an integrated black-and-white development type. Although the developing action is precipitation on physical development nuclei, it is highly active, but developed silver has a spherical shape with a small specific surface.

  In the above aspect (3), the silver halide grains are dissolved and diffused in the unexposed area and deposited on the development nuclei on the image receiving sheet, whereby a light transmitting electromagnetic wave shielding film or a light transmitting conductive film is formed on the image receiving sheet. A translucent conductive metal film such as a film is formed. This is a so-called separate type in which the image receiving sheet is peeled off from the photosensitive material.

  In any embodiment, either negative development processing or reversal development processing can be selected (in the case of the diffusion transfer system, negative development processing is possible by using an auto-positive type photosensitive material as the photosensitive material). .

The chemical development, dissolution physical development, and diffusion transfer development referred to here have the same meanings as commonly used in the industry, and are general textbooks of photographic chemistry such as Shinichi Kikuchi, “Photochemistry” (published by Kyoritsu Shuppansha). ), C.I. E. K. It is described in “The Theory of Photographic Prosess, 4th ed.” Edited by Mees.
<Photosensitive material>
[Support]
As the support for 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 from the viewpoint of transparency, heat resistance, ease of handling and cost.

  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. The thickness is preferably 75 μm to 100 μm.

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]
The light-sensitive material used is preferably provided with a protective layer on the emulsion layer described below. 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 effects of preventing scratches and improving mechanical properties. The thickness of the protective layer is 0.02 to 20 μm, preferably 0.1 to 10 μm, more preferably 0.3 to 3 μm, and the protective layer is not essential. 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 light-sensitive material used in the production method of the present invention may contain a known dye in the emulsion layer to add an emulsion for dyeing.
[Emulsion layer]
The photosensitive material used in the electrolytic plating method of the present invention has an emulsion layer (silver salt-containing layer) containing a silver salt as a photosensor 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 contains a dye at least in the emulsion layer. The dye is contained in the emulsion layer as a filter dye or for various purposes such as prevention of irradiation. The dye may contain a solid disperse dye. Examples of the dye preferably used in the present invention include dyes represented by general formula (FA), general formula (FA1), general formula (FA2), and general formula (FA3) described in JP-A-9-179243. Specifically, compounds F1 to F34 described in the publication are preferable. Further, (II-2) to (II-24) described in JP-A-7-152112, (III-5) to (III-18) described in JP-A-7-152112, and JP-A-7-152112. (IV-2) to (IV-7) described in the publication are also preferably used.

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

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

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

<Silver salt>
As the silver salt used in the present invention, silver halide having excellent characteristics as an optical sensor is used.

  The silver halide used in the present invention will be described.

  In the present invention, silver halide is used to function as an optical sensor, and the technology used in silver salt photographic film, photographic paper, film for printing plate making, emulsion mask for photomask, etc. relating to silver halide is used in the present invention. Can also be used.

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

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

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

  Incidentally, the sphere equivalent diameter of silver halide grains is the diameter of grains having the same volume and a spherical shape.

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

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

  That is, as a method for preparing the silver halide emulsion, either an acidic method, a neutral method, or the like may be used. Also, as a method of reacting a soluble silver salt and a soluble halogen salt, a one-side mixing method, a simultaneous mixing method, Any combination of them may be used.

  As a method for forming silver particles, a method of forming particles in the presence of excess silver ions (so-called back mixing method) can also be used. Furthermore, as one type of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is generated, that is, a so-called controlled double jet method can be used.

It is also preferable to form grains using a so-called silver halide solvent such as ammonia, thioether or tetrasubstituted thiourea. A tetrasubstituted thiourea compound is more preferable as such a method, and is described in JP-A-53-82408 and JP-A-55-77737. Preferred thiourea compounds include tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. The addition amount of the silver halide solvent varies depending on the type of compound used, the target grain size, and the halogen composition, but is preferably 10 ⁻⁵ to 10 ⁻² mol per mol of silver halide.

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

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

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

A water-soluble rhodium compound can be used as the rhodium compound. Examples of the water-soluble rhodium compound include a rhodium halide (III) compound, a hexachlororhodium (III) complex salt, a pentachloroacorodium complex salt, a tetrachlorodiacolodium complex salt, a hexabromorhodium (III) complex salt, and a hexaamine rhodium (III). ) Complex salt, trizalatodium (III) complex salt, K ₃ Rh ₂ Br _{9 and the} like.

  These rhodium compounds are used by dissolving in water or a suitable solvent, and are generally used in order to stabilize the rhodium compound solution, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, odorous acid, hydrofluoric acid). Or a method of adding an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add another silver halide grain previously doped with rhodium and dissolve it at the time of silver halide preparation.

Examples of the iridium compound include hexachloroiridium complex salts such as K ₂ IrCl ₆ and K ₃ IrCl ₆ , hexabromoiridium complex salts, hexaammineiridium complex salts, and pentachloronitrosyliridium complex salts.

Examples of the ruthenium compound include hexachlororuthenium, pentachloronitrosylruthenium, K ₄ [Ru (CN) ₆ ] and the like.

  Examples of the iron compound include potassium hexacyanoferrate (II) and ferrous thiocyanate.

  The above rhenium, ruthenium and osmium are added in the form of water-soluble complex salts described in JP-A-63-2042, JP-A-1-2855941, JP-A-2-20852, JP-A-2-20855 and the like. Particularly preferred is a hexacoordination complex represented by the following formula.

[ML ₆ ] ^-n (where M represents Ru, Re, or Os, and n represents 0, 1, 2, 3, or 4)
In this case, the counter ion is not important, and for example, ammonium or alkali metal ions are used. Preferred ligands include halide ligands, cyanide ligands, cyanide oxide ligands, nitrosyl ligands, thionitrosyl ligands, and the like. Although the example of the specific complex used for this invention below is shown, this invention is not limited to this.
[ReCl ₆ ] ⁻³ , [ReBr ₆ ] ⁻³ , [ReCl ₅ (NO)] ⁻² , [Re (NS) Br ₅ ] ⁻² , [Re (NO) (CN) ₅ ] ⁻² , [Re (O) ₂ (CN) ₄ ] ⁻³ , [RuCl ₆ ] ⁻³ , [RuCl ₄ (H ₂ O) ₂ ] ⁻¹ , [RuCl ₅ (NO)] ⁻² , [RuBr ₅ (NS)] ^{− 2,} [Ru (CO) ₃ Cl _3] ^-2 [Ru (CO) Cl _5] ^-2, [Ru (CO) Br _5] ^-2, [OsCl _6] ^-3, [OsCl ₅ (NO)] ^-2, [Os (NO) (CN) _5] ^-2, [Os (NS) Br _5] ^-2, [Os (CN) _6] ^-4, _{[Os (O) 2 (CN)} 5 ] ^-4 .

Preferably the added amount of these compounds is per mol of silver halide 10 ^-10 to 1 ^0-2 mol / mol Ag, 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 costs. 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 used include PdCl ₄ and Na ₂ PdCl ₄ .

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

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

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

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

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 mole per mole 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.

<Binder>
In the emulsion layer, a binder can be used for the purpose of uniformly dispersing silver salt grains and assisting the adhesion between the emulsion layer and the support. 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, polyacrylic acid, and the like. 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 contained in the emulsion layer is not particularly limited, and can be appropriately determined as long as dispersibility and adhesion can be exhibited.

<Solvent>
The solvent used for forming the emulsion layer is not particularly limited. For example, water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, sulfoxides such as dimethyl sulfoxide, etc. , Esters such as ethyl acetate, ethers, etc.), ionic liquids, and mixed solvents thereof. The content of the solvent used in the emulsion layer of the present invention is in the range of 30 to 90% by mass and in the range of 50 to 80% by mass with respect to the total mass of silver salt, binder and the like contained in the emulsion layer. Preferably there is.
<Each process>
[exposure]
In the present invention, the photosensitive material coated with the silver salt-containing layer or the photopolymer for photolithography 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.

  As the light source, various light emitters that emit light in the visible spectrum 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 is preferably 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, exposure is more 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 most preferable to perform exposure using a semiconductor laser.

Preferably 100 .mu.J / cm ² or less as the exposure energy, more preferably 50μJ / cm ² or less, and most preferably 40μJ / cm ² or less 4μJ / cm ² or more.

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 of exposing the silver salt-containing layer in a pattern is preferably scanning exposure using a laser beam. In particular, a capstan type laser scanning exposure apparatus described in Japanese Patent Application Laid-Open No. 2000-39677 is preferable. Further, in the capstan method, a DMD described in Japanese Patent Application Laid-Open No. 2004-1224 is optically used instead of beam scanning by rotating a polygon mirror. It is also preferable to use it for a beam scanning system.
[Development processing]
In the present invention, after the emulsion layer is exposed, further development processing is performed. The development processing can be performed by a normal development processing technique used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion mask, and the like. The developer is not particularly limited, but PQ developer, MQ developer, MAA developer and the like can also be used. Commercially available products include, for example, CN-16, CR-56, CP45X, FD manufactured by Fuji Film Co., Ltd. -3, Papitol, a developer such as C-41, E-6, RA-4, D-19, D-72 manufactured by KODAK, or a developer included in the kit can be used. A lith developer can also be used.

  As the lith developer, KODAK D85 or the like can be used. In the present invention, by performing the above exposure and development processing, a metal silver portion, preferably a patterned metal silver portion, is formed in the exposed portion, and a light transmissive portion described later is formed in the unexposed portion.

  In the present invention, a dihydroxybenzene developing agent can be used as the developer. Examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, isopropyl hydroquinone, methyl hydroquinone, hydroquinone monosulfonate, and the like, and hydroquinone is particularly preferable. Examples of the auxiliary developing agent exhibiting superadditivity with the dihydroxybenzene developing agent include 1-phenyl-3-pyrazolidones and p-aminophenols. As the developer used in the method of the present invention, a combination of a dihydroxybenzene developer and 1-phenyl-3-pyrazolidones; or a combination of a dihydroxybenzene developer and p-aminophenols is preferably used.

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

  In the present invention, both the development initiator and the development replenisher have a property that “the pH increase when 0.1 mol of sodium hydroxide is added to 1 liter of the solution is 0.5 or less”. preferable. As a method for confirming that the development starting solution or development replenisher used has this property, the pH of the development starting solution or development replenisher to be tested is adjusted to 10.5, and then sodium hydroxide is added to 1 liter of this solution. 0.1 mol was added, and the pH value of the liquid at this time was measured. In the present invention, it is particularly preferable to use a development starting solution 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, a method using a buffer is preferably used. 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 present invention, when processing 1 square meter of the light-sensitive material, the content of the developer replenisher in the developer is 323 ml or less, preferably 323 to 30 ml, particularly 225 to 50 ml. The development replenisher may have the same composition as the development starter, or it may have a higher concentration than the starter with respect to the components consumed in the development.

  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. However, if added too much, it causes silver stains in the developer, so the upper limit is It is desirable to be 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 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.

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

  Further, various organic and inorganic chelating agents can be used in combination in the developer. As said inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate, etc. can be used. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used.

  Examples of the above organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, acileic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid. Examples thereof include, but are not limited to, acid, itaconic acid, malic acid, citric acid, and tartaric acid.

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

  Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid and Research Disclosure Vol. 181 described in US Pat. Nos. 3,214,454 and 3,794,591, and West German Patent Publication No. 2227639, Item Disclosure. 18170 (May 1979 issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid and the like. In addition, Research Disclosure No. 18170, JP-A-57-208554, No.54. -61125, 55-29883 gazette and 56-97347 gazette etc. can be mentioned.

  Examples of the organic phosphonocarboxylic acid include JP-A Nos. 52-102726, 53-42730, 54-121127, 55-4024, 55-4025, 55-126241, and 55-65955. Nos. 55-65956, and the above-mentioned compounds disclosed in Research Disclosure No. 18170. These chelating agents may be used in the form of alkali metal salts or ammonium salts.

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.

  Further, the compounds described in JP-A-56-24347, JP-B-56-46585, JP-B-62-2849, and JP-A-4-362294 can be used as a silver stain preventing agent in the developer. it can. Moreover, the compound of Unexamined-Japanese-Patent No. 61-267759 can be used as a solubilizing agent. 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.

  From the viewpoint of developer transport cost, packaging material cost, space saving, and the like, it is also preferred that the developer be concentrated and diluted before use. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

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

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

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

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

The fixing temperature in the fixing step is preferably about 20 ° C. to about 50 ° C., more preferably 25 to 45 ° C. The fixing time is preferably 5 seconds to 1 minute, more preferably 7 seconds to 50 seconds. The replenishing amount of the fixing solution is preferably 600 ml / m ² or less with respect to the processing of the photosensitive material, more preferably 500 ml / m ² or less, 300 ml / m ² or less is particularly preferred.

The light-sensitive material that has been subjected to development and fixing processing is preferably subjected to water washing treatment or stabilization treatment. In the water washing treatment or stabilization treatment, the washing water amount is usually 20 liters or less per 1 m ^{2 of the} light-sensitive material, and can be replenished in 3 liters or less (including 0, ie, rinsing with water). For this reason, not only water-saving treatment is possible, but piping for self-installing machines 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. In addition, various oxidizer additions and filter filtration may be combined to reduce the pollution load that becomes a problem when washing with a small amount of water. Furthermore, in the above method, a part or all of the overflow liquid from the washing bath or stabilization bath produced 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.

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

  In each of the above steps, a component obtained by removing water from the composition of the developing solution or the fixing solution may be supplied as a solid, dissolved in a predetermined amount of water and used as a developing solution or a fixing solution. Such a form of treating agent is called a solid treating agent. As the solid processing agent, powder, tablet, granule, powder, lump or paste is used. A preferred form of the treatment agent is a form described in JP-A-61-259921 or a tablet. For example, JP-A-51-61837, JP-A-54-155038, JP-A-52-88025, British Patent No. 1,213,808, etc. Can be manufactured. Furthermore, the granule treating agent can be produced by a general method described in, for example, JP-A-2-109042, JP-A-2-109043, JP-A-3-39735 and JP-A-3-393939. Further, powder processing agents are generally described in, for example, JP-A-54-133332, British Patents 725,892 and 729,862, and German Patent 3,733,861. Can be manufactured in a conventional manner.

The bulk density of the solid processing agent, and in view of its solubility, is preferably a 0.5 to 6.0 g / cm ^3, in particular of 1.0 to 5.0 g / cm ³ are preferred.

  In preparing the solid processing agent, at least two kinds of mutually reactive particulate materials among the materials constituting the processing agent are replaced with at least one intervening separation layer made of a material inert to the reactive material. Alternatively, a method may be employed in which reactive substances are placed in layers so as to be separated into layers, a bag that can be vacuum-packed is used as a packaging material, and the bag is evacuated and sealed. Here, “inert” means that the substances do not react under normal conditions in the package when they are in physical contact with each other or that there is no significant reaction. The inert material may be inactive in the intended use of the two reactive materials, apart from being inert to the two mutually reactive materials. Furthermore, an inert substance is a substance that is used simultaneously with two reactive substances. For example, since hydroquinone and sodium hydroxide react in direct contact with each other in the developer, they can be stored in the package for a long time by using sodium sulfite or the like as a separation layer between hydroquinone and sodium hydroxide in vacuum packaging. In addition, hydroquinone or the like is briquetted to reduce the contact area with sodium hydroxide, so that the storage stability is improved and the mixture can be used. Bags made from an inert plastic film, a laminate of plastic material and metal foil are used as packaging materials for these vacuum packaging materials.

  The mass of the metallic silver contained in the exposed portion after the development treatment is preferably a content of 50% by mass or more, and 80% by mass or more with respect to the mass of silver contained in the exposed portion before exposure. More preferably. 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.
[Physical development and plating]
In the present invention, for the purpose of imparting conductivity to the metal silver portion formed by the exposure and development processing, an electrolytic plating process is performed for supporting the conductive metal particles on the metal silver portion. In the present invention, the conductive metal particles can be supported on the metallic silver portion only by the electrolytic plating treatment, but the conductive metal particles can be supported on the metallic silver portion by combining physical development and electrolytic plating treatment. You can also. In addition, what electroplated the metal silver part is called a "conductive metal part."

Each characteristic value in the examples was measured according to the following method.
(1) Thickness of plating film A part of the plating film was cut and a cross section was obtained by measuring the level difference using a laser microscope manufactured by Keyence Corporation.
(2) Conductivity The sample obtained above was cut into 35 × 45 mm, and the surface resistance was measured. For the measurement of the surface resistance, a Lorester GP MCP-T600 / ASP probe manufactured by Mitsubishi Chemical was used. The results are shown in Table 1 below.
(3) Transport tension A load cell type sensor was mounted on both sides of the transport cathode roll and measured. As the sensor, a “C2G1-25K” type manufactured by Minebea Co., Ltd. was used. The measurement range is a specification capable of measuring 0 to 250N. The value obtained by calibrating by strictly converting the tension value from the roll weight and the holding angle of the film conveyance was taken as the tension value.
(First embodiment)
The roll-form developed silver mesh-patterned film 2000m obtained by the above-described method is divided into five 400-m rolls, and five 650 mm × 400-m rolls with conductive films are prepared. The book was passed through an electrolytic plating apparatus 100 shown below to form a plating film.

As shown in FIG. 1, as an electrolytic plating apparatus, an apparatus in which three electrolytic plating tanks 50 and washing tanks 52 were alternately arranged was used, and a copper plating film was formed to 5 μm using copper as an anode. Note that the metal silver portion of the mesh pattern has a line thickness of 10 μm and a line interval of 300 μm. The electric resistance of the film F used in this example is 35 Ω / cm ² .

  As the cathode roll 1, a SUS316 circular tube having a diameter of 210 mm, a length of 800 mm, and a thickness of 10 mm was used. The height of the protrusion on the cathode roll was 0.5 mm, the width was 1 mm, the interval was 20 mm, and the material was PVC.

  The film pretreatment conditions, plating conditions, and antirust treatment conditions were as shown in Table 1. Note that the copper plating was set such that the current density gradually increased as the number of passes of the cathode roll 1 and the transport rolls 101A to 101C increased.

また、本実施例で用いられるフィルムＦの支持体及び乳剤層の組成、及び、メッキ処理液の組成は、表２に示すとおりである。

Further, the composition of the support and emulsion layer of the film F used in this example and the composition of the plating treatment solution are as shown in Table 2.

フィルム張力設定は、図１に示すようにＳ字ラップの速度制御部３０９によって適度に張力をカットし、その後、順次ロールの回転速度をドローにかける方式で張力を設定した。張力は陰極ロール３２５（張力検出ロール）部でロードセルによって自動で圧力検出を行い、張力が１６０Ｎ／ｍになるように速度制御部３２１の駆動モータの速度でフィードバック制御した。

As shown in FIG. 1, the film tension was set by a method in which the tension was appropriately cut by an S-shaped wrap speed control unit 309 and then the rotation speed of the roll was sequentially drawn. The tension was automatically detected by the load cell at the cathode roll 325 (tension detection roll) section, and feedback control was performed at the speed of the drive motor of the speed control section 321 so that the tension was 160 N / m.

  The conveyance speed was 4 m / min, and the draw ratio was set stepwise in the motor drive setting of each cathode roll 1 to increase the speed sequentially and gradually increase the tension.

  As a result, the transported state was very stable, and a roll film having a good winding shape was obtained.

Further, in this embodiment, the concentration of the plating treatment liquid in each electrolytic plating treatment tank 50 is set to 50 g / L, 45 g / L, and 40 g / L in order from the upstream side in the transport direction, so that the plating treatment liquid is used. The supply flow rate (replenishment amount) of No. 7 is 45 ml / m ² , and the supply flow rate of water 53 is 500 ml / m ² .

As a result, the error in the film thickness of the plating film becomes ± 0.3 μm with respect to the designed value of 5 μm, and it can be seen that the plating unevenness is remarkably small as compared to the (comparative example) described later. Further, the surface resistance of the conductive surface of the film F was 0.2 Ω / cm ² , which was much lower than that of (Comparative Example). Further, no scratch was found on the produced film F with a plating film.
(Comparative example)
As in Example 1, an example is shown in which a silver halide photographic light-sensitive material is exposed to a mesh pattern, black-and-white developed, and a plating film is formed by electrolytic plating.
(1) Production of film with conductive surface A film with a conductive surface exactly the same as in Example 1 was produced.
(2) Formation of plating film One of the roll-like films with a conductive film obtained by dividing the roll-like film obtained in (1) above into five parts is plated through the following plating apparatus. A film was formed.

  As the electrolytic plating apparatus 200, an apparatus including the plating processing unit 202 shown in FIG. 3 was used, and copper was used for the anode to form a copper plating film having a thickness of 5 μm.

The plating unit 202 is provided with one electrolytic plating treatment tank 204, and the concentration in the electrolytic plating treatment tank 204 is copper as in the first electrolytic plating treatment tank 50 of the first embodiment. A plating treatment solution 7 having a concentration of 50 g / L is filled. The plating solution 7 is supplied to the electrolytic plating bath 204 at a replenishment amount of 45 ml / m ² and discharged from the electroplating bath 204 at the same flow rate as in the first embodiment. A plurality of cathode rolls 1 are disposed along the transport direction above the surface of the plating treatment liquid 7, and in the plating treatment liquid 7, a plurality of anodes 102 and a plurality of transport rolls 101 </ b> A are disposed along the transport direction. The plating film is formed by electrolytic plating on the conductive surface of the film F that is disposed and transported in the electrolytic plating tank 50. Further, a washing unit 314 filled with water 315 is provided on the downstream side in the transport direction of the plating unit 204, and the plating solution on the film F on which the plating film is formed is washed with water.

  The cathode roll 1 was supplied with power using a SUS316 circular tube having a diameter of 210 mm, a length of 800 mm, and a thickness of 10 mm. The height of the protrusion on the cathode roll 1 was 0.5 mm, the width was 1 mm, the interval was 20 mm, and the material was PVC.

  The pretreatment conditions, plating conditions, and rust prevention treatment conditions for the film F were the conditions shown in Table 1. Note that the copper plating was set such that the current density gradually increased as the number of passes of the cathode roll 1 and the transport rolls 101A to 101C increased.

  The tension of the film F was set by a method in which the tension was appropriately cut by the S-wrap speed control unit 309 shown in FIG. The tension was automatically detected by a load cell at 325 parts of the tension detection roll, and feedback control was performed at the speed of the drive motor of the speed adjusting unit 321 so that the tension was 160 N / m.

  The conveyance speed was 4 m / min, and the draw ratio was set stepwise in the motor drive setting of each cathode roll 1 to increase the speed sequentially and gradually increase the tension.

As a result, the thickness error of the plating film is ± 2 μm with respect to the design value of 5 μm, and it can be seen that the plating unevenness is much larger than that of Example 1. Further, the surface resistance of the conductive surface of the film F was 0.9Ω / cm ^2, which was higher than that in Example 1 in each step. Further, scratches were generated on the produced film F with a plating film.

It is a schematic longitudinal cross-sectional view which shows the whole electroplating processing apparatus in the Example of this invention. It is the figure which expanded a part of apparatus of FIG. 1, and is a schematic block diagram which shows an example of the electric power feeding method. It is a schematic longitudinal cross-sectional view which shows the whole electroplating processing apparatus in a comparative example.

Explanation of symbols

7 Plating solution 50 Electrolytic plating tank 52 Flushing tank 53 Water 100 Electrolytic plating apparatus F Film (silver halide photosensitive material)

Claims (8)

An electroplating method for forming a plated film by electroplating on the metallic silver portion while transporting the silver halide photosensitive material having the metallic silver portion formed in an electroplating bath filled with a plating solution. And
A plurality of the electroplating baths are arranged in the silver halide photosensitive material transport direction, and the concentration of the plating solution filled in each electroplating bath is gradually decreased from the upstream side to the downstream side in the transport direction. An electrolytic plating method characterized by having been made.   2. The electrolytic plating process according to claim 1, wherein a plating method is used in which a plating solution overflowing from the electrolytic plating bath on the upstream side in the transport direction is supplied to the electrolytic plating bath on the downstream side in the transport direction. Method.   3. The electrolytic plating method according to claim 1, wherein the plating tank and the washing tank are alternately arranged in the conveying direction, and the silver halide photosensitive material is washed with water in the washing tank.   The electrolytic plating method according to claim 3, wherein a cascade system is used in which water overflowed from the washing tank on the downstream side in the conveying direction is supplied to the washing tank on the upstream side in the conveying direction. An electroplating apparatus for forming a plating film by electroplating on the metal silver part while conveying a silver halide photosensitive material having a metal silver part in an electroplating tank filled with a plating solution. And
A plurality of electrolytic plating tanks are arranged in the silver halide photosensitive material transport direction, and the concentration of the plating solution filled in each electrolytic plating tank is gradually decreased from the upstream side to the downstream side in the transport direction. An electrolytic plating apparatus characterized by that.   6. The electroplating process according to claim 5, wherein a plating method is used in which a plating solution overflowing from the electroplating bath on the upstream side in the transport direction is supplied to the electroplating bath on the downstream side in the transport direction. apparatus.   7. The electroplating apparatus according to claim 5, wherein the plating tank and the washing tank are alternately arranged in the conveying direction, and the silver halide photosensitive material is washed with water in the washing tank.   The electroplating apparatus according to claim 7, wherein a cascade system is used in which water overflowed from the washing tank on the downstream side in the conveying direction is supplied to the washing tank on the upstream side in the conveying direction.

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