JP4694282B2 - Apparatus and method for producing film with plating film - Google Patents

Description

  The present invention relates to an apparatus and a method for producing a film with a plating film by forming a plating film on the film while conveying the film, and more particularly to an apparatus and a method for producing a film with a plating film suitable for a resin film. In particular, it shields electromagnetic waves generated from the front of displays such as CRT (cathode ray tube), PDP (plasma display panel), liquid crystal, EL (electroluminescence), FED (field emission display), microwave oven, electronic equipment, etc. and is transparent The present invention relates to a manufacturing apparatus and a manufacturing method suitable for manufacturing an electromagnetic shielding material having properties.

  This production apparatus and production method are suitable for producing these conductive films. After pattern exposure of a photographic photosensitive silver salt film, development processing is performed to form a pattern of developed silver fine particles on the surface, and then electroplating is performed. Manufacture of laminated film of electroplated film to form a film, after depositing metal on the film, then deposit metal deposited film / metal plated film to form plated film, electroless plating on film, It is suitable for the production of laminated films of electroless plating / electroplating coatings that form plating coatings. In addition to the electromagnetic shielding materials described above, these devices can reduce the size, weight, and cost of electronic devices and parts. Adhesive-less two-layer flexible printed wiring board, flexible printing suitable for TAB, COF, PGA, etc. in semiconductor packaging It is also suitable for the preparation of the wiring board.

  As described in Patent Document 1, a method of continuously forming a plating film while conveying a film is such that the conductive surface of a film or a metal film is brought into contact with a cathode roll, or the film conductive surface is placed through a liquid film. A method is known in which a plating bath in which an anode is introduced is placed in contact with a cathode roll and before or after that, and a plating film is formed in the plating bath. If a plating film is continuously formed on a film by such a method, it is possible to easily form a plating film having a desired thickness on the film by repeatedly passing a unit in which a cathode and an anode are arranged. It is.

  The conductive metal part of the translucent conductive film formed by patterning the conductive metal part and the visible light transmissive part on a transparent support often used in PDP (plasma display panel) is a silver halide photographic photosensitive. In the case of developed silver formed by developing a material, and the mesh pattern is formed from a fine mesh wire of 1 μm to 40 μm, it has a conductivity of about 10Ω / □ to 500Ω / □, and in principle Can be continuous metal (for example, Cu) plating by electroplating.

  However, since the electrical conductivity is insufficient at about 10Ω / □ to 500Ω / □, the distance from the plating solution surface to the cathode roll is about 3 to 20 cm, which is shorter than that of a normal plating apparatus, and comes out of the plating solution surface. The plating solution remains on the film conductive surface, and the film conductive surface and the cathode roll surface come into contact with each other through the liquid film. As a result, it has been found that a part of the developed silver dissolves in the liquid film and causes silver contamination and film peeling of the cathode roll.

  In recent years, in order to solve the above-described problems, as described in Patent Document 2, a spherical body that is freely rotatable from the back of the film is pressed against the film to facilitate contact between the film conductive surface and the cathode roll to supply power. A method has been proposed. However, in this method, although the contact is promoted, the liquid between the film conductive surface and the cathode roll is not completely removed, so that a part of the developed silver dissolves in the liquid film and the silver stain on the cathode roller or the film The problem that causes peeling cannot be solved.

  From the above situation, translucent conductivity formed by patterning a conductive metal portion and a visible light transmissive portion on a transparent support using developed silver obtained by developing a silver halide photographic light-sensitive material. In the case of plating a conductive film, it is difficult to apply electroplating suddenly. Therefore, after applying electroless copper plating first so that the surface resistance of the film becomes about 2Ω / □, Copper plating was performed by the method described in Document 2.

  However, in such a method using electroless copper plating, the process becomes longer and the cost of chemicals is increased, leading to an increase in product cost.

Patent Documents 3 and 4 describe a translucent electromagnetic wave shielding film and a manufacturing method thereof. These documents describe the layer configuration of the translucent electromagnetic wave shielding film and the physical properties of the layer, etc., but describe the configuration related to the apparatus specifically for the plating process and the processing method using the specific apparatus. It has not been.
Japanese Patent Laid-Open No. 7-22473 JP 2004-263215 A JP 2004-221564 A JP 2004-221565 A

  As a result of intensive studies to solve the above problems, the present inventors have found that the conductive metal portion and the visible portion of the silver halide photographic light-sensitive material are visible on the transparent support using developed silver obtained by developing the silver halide photographic light-sensitive material. With a plating coating that prevents the development of silver stains on the cathode roll when a light-transmitting conductive film formed by patterning the light-transmitting portion is plated. Reached film production equipment and method.

  That is, an object of the present invention is to pattern a conductive metal portion and a visible light transmissive portion on a transparent support using a film having a conductive surface, particularly developed silver obtained by developing a silver halide photographic light-sensitive material. Even if it is a translucent conductive film to be formed, it is to obtain a film with a plating film that can prevent a part of developed silver from being dissolved in a liquid film and causing silver contamination of a cathode roll.

In order to solve the above-described problem, the apparatus for producing a film with a plating film according to claim 1 is configured to bring a film conductive surface into contact with a cathode roll while conveying a film having a conductive surface, and in a plating bath. An apparatus for manufacturing a film with a plating film that obtains a desired plating thickness by repeating the formation of a plating film on the film conductive surface a plurality of times, wherein the film from the plating solution surface of the plating bath is the next cathode roll Until the contact with the film, a water removing means for removing the liquid or moisture of the layer to be plated on the conductive surface of the film is provided, and the moisture removing means is at least an air knife or heated air or dehumidified air to the layer to be plated. It is characterized by having a device for spraying . The number of times is preferably 10 or more and 30 or less.

According to the first aspect of the present invention, there is provided a moisture removing means for removing the liquid or moisture of the layer to be plated before the film coming out of the plating treatment liquid surface of the plating bath contacts the next cathode roll. Therefore, the liquid of the layer to be plated or the moisture in the inside is removed, and even if silver is going to dissolve, there is no solvent. For this reason, silver elution does not occur, and the occurrence of silver contamination on the cathode roll can be prevented.
Further, since the moisture removing means is equipped with at least an air knife or a device for spraying heated air or dehumidified air to the plated layer, the film coming out from the plating solution surface of the plating bath contacts the next cathode roll. In the meantime, it is possible to effectively remove the liquid or internal moisture of the layer to be plated.

According to a second aspect of the present invention, in the apparatus for producing a film with a plating film according to the first aspect, the film that has come out from the plating solution surface of the plating bath is in contact with the next cathode roll. is characterized in that a said moisture removing means for removing a liquid or moisture on the plated layer of the film conductive surface on washing the both surfaces.

  According to the second aspect of the present invention, even if both surfaces of the film that have come out from the plating solution surface of the plating bath are washed, the liquid of the layer to be plated or the moisture inside is removed by the moisture removing means. For this reason, silver elution does not occur, and the occurrence of silver contamination on the cathode roll can be prevented.

Invention of Claim 3 is a manufacturing apparatus of the film with a plating film of Claim 1 or Claim 2, The said moisture removal means is further equipped with the heat roller made to contact the back surface of the said film, or the said An infrared heating device for heating the layer to be plated is provided, or a device for spraying heated steam on the back surface of the film is provided .

According to invention of Claim 3, the said moisture removal means is further provided with the heat roller which contacts the back surface of the said film, or the infrared heating apparatus which heats the said to-be-plated layer, or the said film Since it is equipped with a device that sprays heated steam on the back side, the liquid in the layer to be plated or the moisture inside is effectively used until the film coming out of the plating treatment liquid surface of the plating bath contacts the next cathode roll. It is possible to remove.

The invention according to claim 4 uses the film-coated film production apparatus according to any one of claims 1 to 3, and transports a film having a conductive surface to the film conductive surface as a cathode. A method for producing a film with a plating film, which is obtained by repeatedly contacting a roll and forming a plating film on a film conductive surface in a plating bath a plurality of times to obtain a desired plating thickness , the plating treatment liquid surface of the plating bath The liquid or moisture of the layer to be plated on the conductive surface of the film is removed by using the moisture removing means until the film that comes off comes into contact with the next cathode roll .

According to the invention described in claim 4, the liquid of the layer to be plated or the moisture inside is removed until the film coming out from the plating treatment liquid surface of the plating bath comes into contact with the next cathode roll. Even if silver is going to dissolve, there is no solvent, silver elution does not occur, and the occurrence of silver contamination on the cathode roll can be prevented.

Invention of Claim 5 WHEREIN: In the manufacturing method of the film with a plating film of Claim 4 , the moisture content rate of the said to-be-plated layer just before contacting the said cathode roll shall be 7 g / m < ² > or less. It is a feature.

According to the invention described in claim 5, since the moisture content of the layer to be plated immediately before the cathode roll contacts is as small as 7 g / m ² or less, it is possible to prevent silver from dissolving.

Invention of Claim 6 is a manufacturing method of the film with a plating film of Claim 4 or Claim 5, The said film with a plating film has a conductive metal part and a visible light transmissive part on a transparent support body. It is characterized by being a translucent conductive film formed by patterning.

A seventh aspect of the present invention is the method for producing a film with a plating film according to the sixth aspect, wherein the conductive metal portion is formed from a fine mesh wire of 1 μm to 40 μm, and the mesh pattern is continuous for 3 m or more. It is characterized by being a translucent conductive film.

The invention according to claim 8 is the developed silver obtained by developing the silver halide photographic light-sensitive material in the conductive metal part in the method for producing a film with a plating film according to claim 6 or 7. It is characterized by that.

The invention of claim 9 is a method of manufacturing a plated film according to any one of claims 4-8, is characterized in that said plating coating is copper.

The invention of claim 10 is a method of manufacturing a plated film according to any one of claims 6-8, wherein the transparent support is characterized by comprising a polyimide resin or polyester resin.

  According to the apparatus and method for producing a film with a plating film according to the present invention, the liquid of the layer to be plated or the internal moisture until the film coming out of the plating solution surface of the plating bath contacts the next cathode roll. Since silver is removed, silver dissolution does not occur, and silver contamination of the cathode roll can be prevented.

  BEST MODE FOR CARRYING OUT THE INVENTION The best embodiment of the apparatus and method for producing a film with a plating film according to the present invention will be described based on the drawings.

  FIG. 1 is a schematic longitudinal sectional view showing an electroplating apparatus 10 for carrying out an apparatus and method for producing a film with a plating film according to the present invention, and in particular, an example showing the characteristics of the production apparatus and method of the present invention. As shown in FIG.

  FIG. 1 is an overall schematic longitudinal sectional view of a continuous electroplating apparatus 10 for unwinding, plating and winding a long film from a roll state. The main steps are to remove the unrolled portion 301 for unwinding the roll-shaped film, the pretreatment portion 302 for subjecting the conductive surface of the film to acid treatment, degreasing treatment, water washing, etc., the electroplating portion 303, the plating solution, or washing away, It consists of a rust preventive treatment, a wash-out treatment, a post-treatment portion 304 for performing drying, and a winding portion 305 for winding on a roll film. In addition, when the electroconductive surface which is an electroplating to-be-processed part is clean, a pre-processing may be abbreviate | omitted and a post-processing process may be abbreviate | omitted as needed. Further, if necessary, an electroplating portion 303 ′ may be provided between the electroplating portion 303 and the post-processing portion 304, and for example, 303 may be an electrolytic copper plating portion and 303 ′ may be an electric Ni plating portion.

  In FIG. 1, the film 4 unwound from the roll film 306 is adjusted in tension through the accumulator 307 and the balance roll unit 308, and then the speed is substantially constant by the speed control unit 309. After passing through the acid, degreasing unit 310, and the water washing unit 312, a plating bath containing the plating solution 7 in the plating tank 6 is entered.

  Next, an example showing the characteristics of the present invention by enlarging a part of the plating bath of FIG. 1 is shown in FIG.

  As shown in FIG. 2 (A), the film 4 moves to the right while the conductive surface 5 is in contact with the cathode roll 1 </ b> A, and is conveyed to the plating tank 6. In this step, after the conductive surface 5 of the film 4 is brought into contact with the cathode roll 1A, the plating bath in the plating tank 6 is brought into contact with the cathode roll 1B via the submerged roll 101A. Cases 102A and 102B filled with copper balls are used as anodes, cathodes are used as cathode rolls 1A and 1B, and power is supplied from a DC power source 3A to form a layered plating film on the film 4. In the plating bath, shielding plates 106A to 106C are provided for the respective anodes.

In this embodiment, cases 102A and 102B laminated and filled with copper balls are used as anodes, and a DC power source 3A supplies power from the cathode roll 1 to the cases 102A and 102B, which are copper anodes, with a current of 1A. A plating film is formed on the film 4 so as to have a current density of ^{2 to} 10 A / dm ² . The current density here is a value obtained by dividing the current supplied from the DC power source by the area of the portion of the unit film immersed in the plating bath in the unit portion indicated by the one-dot chain line in FIG. Hereinafter, the cathode roll 1B and the cathode roll 1C are used as cathodes, the cases 102C and 102D serve as anodes, power is supplied from the DC power source 3B, and a plating film is formed on the film. Thereafter, the plating film is formed by repeating this process.

  The conductive surface 5 of the film 4 in contact with the cathode roll 1A exits the plating solution 7 and then contacts the cathode roll 1B, but the conductive surface 5 between the liquid surface of the plating solution 7 and the cathode roll 1B. An air knife device 20A as a moisture removing means of the present invention is disposed at a position facing the. The air knife device 20 </ b> A is for removing the plating solution or moisture inside the plating layer on the conductive surface 5. Further, the conductive surface 5 of the film 4 in contact with the cathode roll 1B exits the plating solution 7 and then contacts the cathode roll 1C. However, the conductive surface 5 is electrically conductive between the liquid surface of the plating solution 7 and the cathode roll 1C. An air knife device 20B for removing the plating solution of the layer to be plated on the surface 5 or moisture inside is disposed. In the following, although not shown, an air knife device is similarly provided at a position facing the inside of the film 4 after leaving the plating solution 7, and the plating solution or the inside of the layer to be plated on the film conductive surface The moisture is removed.

As shown in FIG. 2B, the air knife device 20 includes a slit 22 in a convex portion 21 </ b> A formed on the housing 21, and air is supplied by the air supply device 23, and the air knife is supplied from the slit 22. Is blown out. After the conductive surface 5 of the film 4 exits the plating solution 7 and is contacted with the cathode roll 1B, air is blown by the air knife device 20A, so that the plating solution attached to the layer to be plated on the conductive surface 5; Or the water | moisture content in the gelatin layer formed in the film 4 surface is removed. At that time, the moisture content of the plated layer on the conductive surface 5 immediately before the cathode roll 1B comes into contact is 7 g / m ² or less. Here, the moisture content (g / m ² ) is obtained from the mass of water / unit area. In this way, by removing the plating solution of the layer to be plated on the conductive surface 5 or the moisture inside the conductive surface 5 with an air knife, even if the developed silver is about to dissolve, there is no solvent, and elution of the developed silver can be prevented. For this reason, generation | occurrence | production of the silver stain of a cathode roll can be prevented.

In this embodiment, as air knife devices 20A and 20B, Super Air Knife Mod. Model 110036 is used. The effective width of the air knife is 910 mm, the pressure is 2.8 kg / cm ² , the flow rate is 36 mm / sec, and the air consumption is 144 L / min.

As shown in FIG. 2A, one unit is a unit indicated by a one-dot chain line, and this is repeated. The current condition is such that the current density is 0.2 to 10 A / dm ^{2 with} respect to the film, and a plating film is formed on the film 300. Then, by repeating this, a plating film is sequentially formed, and a plating film having a thickness of 1 to 30 μm is formed on the conductive surface of the film in total.

  In order to maintain the uniformity of plating, fresh air 331A to 331D is introduced from air inlets (air stirring nozzles) 330A to 330D, and the liquid in the plating tank 6 is sufficiently stirred. This is effective to aim at the plating film portion, and is performed in order to increase the concentration of plating film metal ions in the vicinity of the extreme surface of the formed plating film. Although not shown, the plating solution 7 is always circulated by removing dirt through a filter.

  Next, as shown in FIG. 1, through a roll 325 capable of detecting film tension, a water washing part 314 for removing the plating solution, and a rust prevention treatment part 316 containing a rust prevention treatment liquid 317 for protecting the plating film, After the water washing unit 318 for removing excess rust prevention treatment liquid, the drying process unit 320 having a drying furnace for removing moisture, the speed adjusting unit 321, the balance roll unit 322, and the tension is adjusted, A roll film 324 is formed through the accumulator 323. Thus, a film with a plating film is obtained.

  The substantial film transport tension is preferably 10 N / m or more and 320 N / m or less. When the tension was actually less than 10 N / m, the film began to meander and the control of the conveyance path was not successful. On the other hand, when it exceeds 320 / m, the plating film metal on which the film is formed has an internal distortion, which causes problems such as curling of the product.

  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. In the speed control in FIG. 1, the cathode roll is the drive roll, and the basic speed is set by the speed control unit 309, and the draw ratio can be set between the cathode rolls 1A and 1B. Thus, the drawing ratio is set to gradually increase, and the final speed is controlled by the speed control unit 321. With such a configuration, the maximum transport tension of the film on the cathode roll on the plating tank is highest at 325 parts of the tension detection roll, and it is more preferable to control based on this value.

  The enlarged view of the cathode roll part of the 2nd-6th embodiment which shows the characteristic of this invention in FIGS. 3-8 is shown. The schematic process is the same as in FIG. 1 except that the means for removing moisture from the layer to be plated on the conductive surface 5 of the film 4 is different. In addition, the same code | symbol is attached | subjected to the same member as FIG. 2, and the overlapping description is abbreviate | omitted. 3 to 8, only the vicinity of the cathode roll 1B is illustrated in an enlarged manner, and the vicinity of the other cathode rolls is not shown.

  In FIG. 3, a blade wiper device 30 is provided in place of the air knife devices 20A and 20B shown in FIG. The blade wiper device 30 includes a blade 34 that comes into contact with the conductive surface 5 on the inner side of the film 4 that leaves the plating solution 7 and is conveyed in the direction of the arrow. The blade 34 is disposed such that the tip is directed toward the downstream side in the transport direction of the film 4, and the other end is fixedly supported by the support body 32. On the back side of the film 4 facing the blade 34, a facing member 36 for stabilizing the contact between the conductive surface 5 and the blade 34 is disposed. In this embodiment, the blade effective width of the blade wiper device 30 is 900 mm, and the blade 34 is made of urethane rubber. In FIG. 3, when the blade 34 abuts on the conductive surface 5 of the film 4, the plating solution or the moisture inside the plating layer on the conductive surface 5 is removed. For this reason, even if the developed silver is dissolved, the solvent is not present, so that the developed silver can be prevented from being eluted and the silver contamination of the cathode roll can be prevented.

  In FIG. 4, instead of the air knife devices 20 </ b> A and B shown in FIG. 2, a water absorption roller 40 that comes into contact with the conductive surface 5 is disposed inside the film 4 that leaves the plating solution 7 and is conveyed in the direction of the arrow. Yes. This water absorption roller 40 is provided with an elastic member 40B having water absorption around a core material 40A made of metal, and can rotate in the same direction as the conveyance direction (arrow direction) at the contact portion with the film 4. It is supported by. A counter roll 42 for stabilizing the contact between the conductive surface 5 and the water absorbing roller 40 is disposed on the back side of the film 4 facing the water absorbing roller 40. In the present embodiment, a ruby cell water-absorbing urethane elastomer manufactured by Toyo Polymer Co., Ltd. is used as the water-absorbing roller 40, the roll diameter is 30 mm, the effective width (surface length) is 900 mm, the hardness is 60 degrees, and the porosity is 75. %. Here, the hardness is a value measured by ASKER C type manufactured by Kobunshi Keiki Co., Ltd. In FIG. 4, when the water absorbing roller 40 is brought into contact with the conductive surface 5 of the film 4, the plating solution of the layer to be plated on the conductive surface 5 or the moisture inside is absorbed and removed. For this reason, even if the developed silver is dissolved, the solvent is not present, so that the developed silver can be prevented from being eluted and the silver contamination of the cathode roll can be prevented.

  In FIG. 5 (A), instead of the air knife devices 20A and B shown in FIG. 2, a heating air device 50 for blowing warming air to the inside of the film 4 that leaves the plating solution 7 and is conveyed in the direction of the arrow. It is arranged. As shown in FIG. 5B, the warming air device 50 has a plurality of air outlets 54 arranged in the longitudinal direction of the casing 52. A heater (not shown) is provided inside the housing 52, and heated air is blown out from the outlet 54 by the fan 56. In FIG. 5A, the heated air is blown onto the conductive surface 5 of the film 4 by the heated air device 50, thereby removing the plating solution of the layer to be plated on the conductive surface 5 or the internal moisture. For this reason, even if the developed silver is dissolved, the solvent is not present, so that the developed silver can be prevented from being eluted and the silver contamination of the cathode roll can be prevented.

  In FIG. 6, in addition to the heated air device 50 shown in FIG. 5, a heat roller 60 is disposed on the opposite side across the film 4 so as to contact the back surface of the film 4. This heat roller 60 has a halogen lamp 64 disposed inside a hollow cylindrical member 62. In the present embodiment, Nissei Electric Co., Ltd. silicone rubber is used as the hollow cylindrical member 62, the roll diameter is 30 mm, the effective width (surface length) is 900 mm, and the rubber thickness is 3 mm. As the halogen lamp 64, a halogen heater lamp manufactured by USHIO INC., With a thermocouple is used. In FIG. 6, while heating air is sprayed by the heating air apparatus 50 to the conductive surface 5 of the film 4, and the back surface of the film 4 is heated by the heat roller 60, the plating solution for the layer to be plated on the conductive surface 5 Alternatively, it is possible to more reliably remove moisture inside.

  In FIG. 6, the heat roller 60 is disposed on the back side of the film 4, but the heat roller 60 may be disposed so as to contact the conductive surface 5 of the film 4. At that time, only the heat roller 60 may be disposed or used in combination with the heated air device 50.

  In FIG. 7A, in addition to the heating air device 50 shown in FIG. 5 on the inner side of the film 4 leaving the plating solution 7 and conveyed in the direction of the arrow, an infrared heating device is provided upstream in the conveyance direction of the film 4. 70 is disposed. In this infrared heating device 70, as shown in FIG. 7B, a lamp 74 is attached to the inside of a concave reflecting plate 72A formed on a support member 72. In this embodiment, a near infrared heating device UHU-30PW manufactured by Ushio Electric is used, the rated voltage is 200 V, the power consumption is 2000 W, the light emission length is 290 mm, and the reflector 72A has an aluminum mirror specification. In FIG. 7A, after the conductive surface 5 of the film 4 is heated by the infrared heating device 70, the heated air is blown by the heated air device 50, so that the plating solution of the layer to be plated on the conductive surface 5 or It is possible to more reliably remove the internal moisture.

  In FIG. 7, the infrared heating device 70 and the heating air device 50 are used together, but only the infrared heating device 70 may be disposed at a position facing the conductive surface 5 of the film 4.

  In FIG. 8, in addition to the heated air device 50 disposed inside the film 4 that is transported in the direction of the arrow after leaving the plating solution 7, the wet side of the back side of the film 4 is upstream of the transport direction of the film 4. An air device 80 is provided. The wet air device 80 sprays heated steam on the back side of the film 4. In the present embodiment, Toshiba JQ-25 is used as the wet air device 80, the maximum pressure is 50 bar, and the heating temperature is 155 ° C. In FIG. 8, steam is blown onto the back surface of the film 4 by the wet air device 80, so that the heated air is blown onto the conductive surface 5 of the film 4 by the heated air device 50 after the film 4 is heated. For this reason, it is possible to more reliably remove the plating solution or the moisture inside the plating layer on the conductive surface 5.

  In addition, although the plating apparatus 10 shown in FIG. 1 repeatedly performs the electric power feeding and plating bath of the conductive surface 5 of the film 4 by the cathode roll 1, it is not limited to this structure. For example, even in a plating apparatus that repeatedly performs the steps of feeding the film conductive surface and plating bath, rinsing the layer to be plated, feeding the film conductive surface and plating bath, and rinsing the layer to be plated, In the meantime, the water removing means of the present invention can be used. As a result, the water in the gelatin layer on the film surface is removed after washing with water, so that the developed silver is not eluted and silver contamination of the cathode roll can be prevented.

  FIG. 9 shows an example in which the electroplating section 303 in FIG. 1 is changed, a water washing tank 116 is provided after the plating tank 6, and water is removed when the film 4 comes out of the water washing tank 116. FIG. 9 shows an example of a method in which plating, water washing, drying, plating, water washing, and drying are repeated. The film 4 exiting the plating tank 6 is wound and transported on the two upper transport rolls 117, and is further transported by being wound on an underwater roll 118 disposed in the washing tank 116. At the position where the film 4 comes out of the water surface of the water rinsing tank 116, a moisture removing device 90 is disposed that dries the heated air against the surface of the film 4 to be plated. In this example, since the film 4 is washed with water and then dried by the moisture removing device 90, the plating solution of the layer to be plated of the film 4 or the moisture inside can be more reliably removed.

  In the example of FIG. 9, an example in which heated air is applied to the surface to be plated and dried is shown. However, as a drying means, the air knife device shown in FIG. 2B and the blade wiper shown in FIG. 3 are used. The apparatus, the apparatus in which the water absorption roller shown in FIG. 4 was arrange | positioned may be sufficient. Further, in addition to the heated air device shown in FIG. 6, a device in which the heat roller is in contact with the back surface of the film on the opposite side of the film may be used. Further, as shown in FIG. 7 (A), in addition to the heating air device shown in FIG. 5, in addition to the heating air device shown in FIG. A device provided with a heating device may be used. As a washing means, a means such as a shower may be used instead of the washing tank 116.

  Next, the detail of a film with a plating film is demonstrated.

  As a film material of the film with a plating film, a polyimide resin or a polyester resin is 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. These copolymers and those containing other organic polymers may also be used. Known additives such as lubricants and plasticizers may be added to these plastics.

  Among the plastics, an unstretched film obtained by melt-extruding a polymer containing 85 mol% or more of a repeating unit as shown in Chemical Formula 1 below 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）部に銅めっきを施す本件記載の電気めっき装置及び方法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 apparatus and method 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 image-receiving sheet. 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 of the photosensitive material used in the production method of the present invention, a plastic film, a plastic plate, a glass plate, or the like can be used. Examples of the raw material for the plastic film and plastic plate include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene, EVA; polyvinyl chloride, Vinyl resins such as polyvinylidene chloride; polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC) Etc. can be used.

  In the present invention, the plastic film is preferably a polyethylene terephthalate film 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 for an electromagnetic wave shielding film for a display, it is preferable to use tempered glass having a tempered layer on the surface. There is a high possibility that tempered glass can prevent breakage compared to glass that has not been tempered. Furthermore, the tempered glass obtained by the air cooling method is preferable from the viewpoint of safety because even if it is broken, the crushed pieces are small and the end face is not sharp.
[Protective layer]
The 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 light-sensitive material used in the production method of the present invention has an emulsion layer (silver salt-containing layer) containing a silver salt as an optical sensor on a support. The emulsion layer in the present invention may contain a dye, a binder, a solvent and the like, if necessary, in addition to the silver salt.

<Dye>
The light-sensitive material 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>
Examples of the silver salt used in the present invention include inorganic silver salts such as silver halide and organic silver salts such as silver acetate. In the present invention, it is preferable to use silver halide having excellent characteristics as an optical sensor.

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

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

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

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

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

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

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

  The silver halide emulsion that is the 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 increase the sensitivity, doping of a hexacyanide metal 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. Preferable ligands include a halide ligand, a cyanide ligand, a cyan oxide ligand, a nitrosyl ligand, a thionitrosyl ligand, and the like. Although the example of the specific complex used for this invention below is shown, this invention is not limited to this.
[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. In addition, in the capstan method, a DMD described in Japanese Patent Application Laid-Open No. 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 production 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 of 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 is added, and the pH value of the liquid at this time is measured. If the increase in pH value is 0.5 or less, it is determined that the liquid has the properties defined above. In the production method of the present invention, it is particularly preferable to use a development starter and a development replenisher whose pH value rises to 0.4 or less when the above test is performed.

  As a method for imparting the above properties to the development initiator and the development replenisher, 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 production method of the present invention, when processing 1 square meter of the photosensitive 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, and more preferably 0.3 mol / liter or more. However, since an excessive amount of the sulfite causes silver stain in the developer, 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, acylate, 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 the pH of the fixing agent due to the introduction of the developer, and is preferably 0.01 to 1.0 mol / liter, more preferably 0.02 to 0.6 mol / liter. Use degree. The pH of the fixing solution is preferably from 4.0 to 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. Further, in the above method, a part or all of the overflow liquid from the washing bath or stabilization bath generated by replenishing the washing bath or stabilization bath with water subjected to the fouling means according to the treatment, As described in JP-A-60-235133, it can also be used for a processing solution having fixing ability, which is a previous processing step. In addition, water-soluble surfactants and antifoaming agents are added to prevent unevenness of water bubbles that are likely to occur during washing with a small amount of water and / or to prevent the processing agent component adhering to the squeeze roller from being transferred to the processed film. Also good.

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

  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, physical development and / or plating treatment for supporting the conductive metal particles on the metal silver portion is performed. In the present invention, the conductive metal particles can be supported on the metallic silver portion by only one of physical development and plating. However, the combination of physical development and plating is used to convert the conductive metal particles to metallic silver. It can also be carried on the part. A metal silver portion subjected to physical development and / or plating is referred to as a “conductive metal portion”.

  “Physical development” in the present invention means that metal particles such as silver ions are reduced with a reducing agent on metal or metal compound nuclei to deposit metal particles. This physical phenomenon is used for instant B & W film, instant slide film, printing plate manufacturing, and the like, and the technology can be used in the present invention.

  Further, the physical development may be performed simultaneously with the development processing after exposure or separately after the development processing.

Each characteristic value in the examples was measured according to the following method.
(1) Film 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) Transport tension A load cell type sensor was attached to 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.
Example 1
Formation of plating film Rolled developed silver mesh patterned film 2000m obtained by the method described in the above embodiment is divided into five 400m rolls, and a 650mm x 400m roll conductive film. Five sticky films were prepared, and one of them was passed through a plating apparatus shown below to form a plating film.

  As the electroplating apparatus, the apparatus shown in FIGS. 1 and 2 was used, and copper was used for the anode to form a copper plating film having a thickness of 5 μm. In FIG. 2, a plating circuit and a plating apparatus having 16 units in the chain line are configured.

  As the cathode roll, a SUS316 circular tube having a diameter of 210 mm, a length of 800 mm, and a thickness of 10 mm was used to feed power. 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. An apparatus having a film path length of 4 m was used when the film was passed from the cathode roll 1A to the cathode roll 1B through the submerged roll 101A. The path length is from the top to the top of the cathode roll. Therefore, the total path length of the plating part is 64 m.

  The film pretreatment conditions, plating conditions, and rust prevention treatment conditions were as shown in Table 1. The copper plating was set so that the current density gradually increased as the number of cathode roll passes repeated.

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, the draw ratio was set step by step to the cathode roll motor drive settings of the cathode rolls 1A to 1Q, and the speed was gradually increased to gradually increase the tension.

  As a result, there was no silver deposition on the surface of the cathode roll, the conveyance state was very stable, and a roll film having a good winding shape was obtained.

Then, when the plated copper surface was observed by inspection, a film with copper excellent in surface quality with few abnormal protrusions and dents on the plated surface was obtained.
(Example 2)
As in Example 1, an example is shown in which a silver halide photographic light-sensitive material is exposed to a mesh pattern and subjected to black-and-white development, and the electroplating method and apparatus described herein are applied.
(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 plating apparatus, the apparatus of any one of FIG. 1 and FIGS. 3 to 8 was used, and copper was used for the anode, and a copper plating film was formed to 5 μm. In addition, the plating circuit and plating apparatus which set the unit (refer FIG. 2) in a dashed-dotted line to 16 units were comprised.

  As the cathode roll, a SUS316 circular tube having a diameter of 210 mm, a length of 800 mm, and a thickness of 10 mm was used to feed power. 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. An apparatus having a film path length of 4 m when the film was passed from the cathode roll 1A to the cathode roll 1B was used. The path length is from the top to the top of the cathode roll. Therefore, the total path length of the plating part is 64 m.

  The film pretreatment conditions, plating conditions, and rust prevention treatment conditions were as shown in Table 1. The copper plating was set so that the current density gradually increased as the number of cathode roll passes repeated.

  The film tension was set by a method in which the tension was appropriately cut by the S-wrap speed control unit 309 shown in FIG. 1 and then the roll rotation speed was sequentially drawn. The tension was automatically detected by a load cell at 325 parts of a cathode roll (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, the draw ratio was set stepwise to the cathode roll motor drive settings of the cathode rolls 1A to 1Q, the speed was increased sequentially, and the tension was gradually increased.

  As a result, there was no silver deposition on the surface of the cathode roll, the conveyance state was very stable, and a roll film having a good winding shape was obtained.

  Then, when the plated copper surface was observed by inspection, a film with copper excellent in surface quality with few abnormal protrusions and dents on the plated surface was obtained.

It is a schematic longitudinal cross-sectional view which shows an example of the whole plating apparatus in this invention. It is the expansion schematic longitudinal cross-sectional view of the cathode roll part of the plating apparatus which concerns on 1st embodiment in this invention, and the perspective view of an air knife apparatus. It is an expansion schematic longitudinal cross-sectional view of the cathode roll part of the plating apparatus which concerns on the 2nd embodiment in this invention. It is an expansion schematic longitudinal cross-sectional view of the cathode roll part of the plating apparatus which concerns on the 3rd embodiment in this invention. It is the expansion schematic longitudinal cross-sectional view of the cathode roll part of the plating apparatus which concerns on the 4th embodiment in this invention, and the perspective view of a heating air apparatus. It is an expansion schematic longitudinal cross-sectional view of the cathode roll part of the plating apparatus which concerns on the 5th embodiment in this invention. It is an expansion schematic longitudinal cross-sectional view of the cathode roll part of the plating apparatus which concerns on the 6th embodiment in this invention, and a perspective view of an infrared heating apparatus. It is an expansion schematic longitudinal cross-sectional view of the cathode roll part of the plating apparatus which concerns on the 7th embodiment in this invention. It is a figure which shows a part of plating apparatus concerning the aspect which rinses with water after plating in this invention, and dries with a heating air.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Cathode roll 1A, 1B, 1C Cathode roll 2 Anode 3A, 3B DC power supply 4 Film 5 Conductive surface of film 6 Plating tank 7 Plating solution 10 Plating apparatus (Production apparatus of film with plating film)
20A, 20B Air knife device (moisture removal means)
30 Blade wiper device (moisture removal means)
34 Blade 40 Water absorption roller (moisture removing means)
50 Heating air device (moisture removal means)
54 Air outlet 60 Heat roller (moisture removal means)
62 Hollow cylindrical member 64 Halogen lamp 70 Infrared heating device (water removal means)
74 Lamp 80 Wet air device (moisture removal means)
101A, 101B Film transport rolls in liquid 102A, 102B, 102C, 102D, 102E Anode metal 106A, 106B, 106C Shield plate 301 Unwinding section 302 Pretreatment section 303 Electroplating section 304 Posttreatment section 305 Winding section 306 Plating Previous roll film 307 Accumulator 308 Balance roll unit 309 Speed control unit 310 Acid, degreasing treatment unit 311 Acid, degreasing treatment solution 312 Washing solution 313 Washing solution 314 Washing solution 315 Washing solution 316 Rust prevention treatment unit 317 Rust prevention solution 318 Washing with water 319 Washing liquid 320 Drying process unit 321 Speed adjustment unit 322 Balance roll unit 323 Accumulator 324 Rolled film 325 with plating film Tension detection rolls 330A, 330B, 330C, 330D Air stirring nozzles 331A, 331B, 331C, 33 D

Claims (10)

While carrying a film having a conductive surface, a film with a plating film that obtains a desired plating thickness by repeatedly contacting the film conductive surface with a cathode roll and forming a plating film on the film conductive surface in a plating bath multiple times Manufacturing equipment,
A moisture removing means for removing the liquid or moisture of the layer to be plated on the conductive surface of the film until the film coming out of the plating solution surface of the plating bath comes into contact with the next cathode roll;
The apparatus for producing a film with a plating film, wherein the moisture removing means comprises at least an air knife or a device for spraying heated air or dehumidified air onto the layer to be plated.   The water removing means for removing the liquid or moisture of the layer to be plated on the conductive surface of the film after washing both surfaces of the film until the film coming out of the plating treatment liquid surface of the plating bath contacts the next cathode roll The apparatus for producing a film with a plating film according to claim 1, wherein: The moisture removing means further comprises:
A heat roller for contacting the back surface of the film;
Or an infrared heating device for heating the plated layer,
Or the apparatus which sprays the heated steam on the back surface of the said film is provided, The manufacturing apparatus of the film with a plating film of Claim 1 or Claim 2 characterized by the above-mentioned. Using the apparatus for producing a film with a plating film according to any one of claims 1 to 3, while conveying a film having a conductive surface, the film conductive surface is brought into contact with a cathode roll, and a plating bath is used. It is a method for producing a film with a plating film to obtain a desired plating thickness by repeatedly forming a plating film on the film conductive surface,
The liquid or moisture of the layer to be plated on the film conductive surface is removed using the moisture removing means until the film coming out from the plating treatment liquid surface of the plating bath contacts the next cathode roll. The manufacturing method of the film with a plating film to do. The method for producing a film with a plating film according to claim 4, wherein a moisture content of the layer to be plated immediately before contacting the cathode roll is 7 g / m ² or less.   6. The light-transmitting conductive film formed by patterning a conductive metal portion and a visible light transmitting portion on a transparent support, the film with a plating film. Manufacturing method of the film with a plating film.   7. The plating film according to claim 6, wherein the conductive metal part is a light-transmitting conductive film formed of a fine mesh wire having a thickness of 1 μm to 40 μm, and the mesh pattern is continuous for 3 m or more. A method for producing a film.   The method for producing a film with a plating film according to claim 6 or 7, wherein the conductive metal part is developed silver obtained by developing a silver halide photographic light-sensitive material.   The said plating film is copper, The manufacturing method of the film with a plating film of any one of Claims 4-8 characterized by the above-mentioned. Method for producing a plated film according to any one of claims 6-8, wherein the transparent support is characterized by comprising a polyimide resin or polyester resin.

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