US20100078330A1 - Apparatus and method for manufacturing plated film - Google Patents

Apparatus and method for manufacturing plated film Download PDF

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Publication number
US20100078330A1
US20100078330A1 US11/993,709 US99370906A US2010078330A1 US 20100078330 A1 US20100078330 A1 US 20100078330A1 US 99370906 A US99370906 A US 99370906A US 2010078330 A1 US2010078330 A1 US 2010078330A1
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Prior art keywords
film
conductive surface
plated layer
plating
plated
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US11/993,709
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English (en)
Inventor
Tomoyoshi Hyodo
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Fujifilm Corp
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Fujifilm Corp
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Publication of US20100078330A1 publication Critical patent/US20100078330A1/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/02—Tanks; Installations therefor
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C25D7/0628—In vertical cells
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
    • C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating

Definitions

  • the present invention relates to an apparatus and a method for manufacturing a plated film by forming a plated layer on a film while conveying the film, and more particularly, to an apparatus and a method for manufacturing a plated film suitably used for forming a plated layer on a resin film.
  • the present invention relates to a manufacturing apparatus and a manufacturing method suitable for manufacturing an electromagnetic shielding material, which shields electromagnetic waves emitted from the front surface of a display such as a cathode ray tube (CRT) display, a plasma display panel (PDP), a liquid crystal display, an electroluminescence (EL) display, or a field emission display (FED), a microwave oven, an electronic apparatus, or the like and which has a transparency.
  • a display such as a cathode ray tube (CRT) display, a plasma display panel (PDP), a liquid crystal display, an electroluminescence (EL) display, or a field emission display (FED), a microwave oven, an electronic apparatus, or the like
  • a method for continuously forming a plated layer on a film while conveying the film there is known a method for forming a plated layer using a plating solution in a plating bath by bringing a conductive surface of a film or a metal film that has passed through the plating bath into contact with a cathode roller or bringing the conductive surface into contact with the cathode roller with a liquid film disposed therebetween in a plating machine having the cathode roller and a plating bath upstream and downstream of the cathode roller, as described in Japanese Patent Application Laid-Open (JP-A) No. 7-22473.
  • JP-A Japanese Patent Application Laid-Open
  • a light-transmitting conductive film which is formed on a transparent support member by patterning a conductive metal portion and a visible-ray transmitting portion and which is often used as a PDP (plasma display panel)
  • the conductive metal portion is formed of a developed silver obtained by developing a silver halide photosensitive material and mesh lines whose a mesh pattern has a size of 1 ⁇ m to 40 ⁇ m are formed
  • the conductive metal portion has conductivity of 10 ⁇ / ⁇ to 500 ⁇ / ⁇ and can be continuously plated with metal (for example Cu) by electroplating in principle.
  • the conductivity of 10 ⁇ / ⁇ to 500 ⁇ / ⁇ of the light-transmitting conductive film is not sufficient, it is necessary to set the distance between a plating solution surface and the cathode roller in the plating machine to 3 to 20 cm, which is shorter than that in a conventional plating machine. Accordingly, the plating solution remains on the conductive surface of the film going out of the plating solution surface, and thus the conductive surface comes in contact with the cathode roller surface with a liquid film therebetween. As a result, it has been found out that a part of the developed silver is dissolved in the liquid film to cause silver contamination of the cathode roller or film peeling.
  • a transparent electromagnetic shielding film and a manufacturing method thereof are disclosed in JP-A Nos. 2004-221564 and 2004-221565.
  • layer structures and physical properties of the transparent electromagnetic shielding film are described, but a processing method using a specific apparatus is not described.
  • the inventors conducted intensive study to solve the above-mentioned problems. As a result, the inventors contrived an apparatus and a method for manufacturing a plated film, in which a part of the developed silver is not dissolved in a liquid film and silver contamination of the cathode roller can be prevented, in plating the light-transmitting conductive film which is formed on the transparent support member out of the developed silver obtained by developing the silver halide photosensitive material and which is patterned in the conductive metal portion and the visible-ray transmitting portion.
  • An object of the present invention is to provide an apparatus and a method for manufacturing a plated film, in which a part of the developed silver is not dissolved in a liquid film and silver contamination of the cathode roller can be thus prevented, in plating a film having a conductive surface, particularly, a light-transmitting conductive film which is formed on the transparent support member out of the developed silver obtained by developing the silver halide photosensitive material and which is patterned in the conductive metal portion and the visible-ray transmitting portion.
  • an apparatus for manufacturing a plated film in which a plated layer is formed on a conductive surface of a film while the film having the conductive surface is conveyed in a predetermined direction
  • the apparatus comprising: a plating bath which contains a plating solution for forming the plated layer on the film and inside of which an anode is provided; a plurality of cathode rollers which is disposed above the plating bath and around which the film that has passed through the plating bath is wrapped so as to bring the conductive surface into contact with the cathode rollers; and a moisture removing device for removing the plating solution or moisture on the conductive surface before the film that has passed through the plating bath comes in contact with the subsequent cathode roller.
  • a plated film having a desired thickness of plated layer is manufactured.
  • the number of repetitions is preferably 10 to 30.
  • the moisture removing device for removing liquid or moisture on the plated layer by the time the film going out of the plating solution of the plating bath comes in contact with the subsequent cathode roller is provided, the liquid on the plated layer or the moisture therein is removed, and thus, no solvent for dissolving silver is present. Accordingly, elution of silver does not occur, whereby silver contamination of the cathode roller can be prevented.
  • An apparatus for manufacturing a plated film according to a second aspect is the apparatus according to the first aspect, wherein the moisture removing device cleans both surfaces of the film and then removes the liquid or the moisture on the conductive surface by the time the film that has passed through the plating solution in the plating bath comes in contact with the subsequent cathode roller.
  • An apparatus for manufacturing a plated film according to a third aspect of the present invention is the apparatus according to the first or the second aspect, wherein the moisture removing device removes the plating solution or the moisture on the conductive surface so that a moisture content of the plated layer right before the film comes in contact with the cathode rollers is 7 g/m 2 or less.
  • the moisture content of the plated layer right before coming in contact with the cathode roller is set small to a content of 7 g/m 2 or less, it is possible to prevent silver from being dissolved.
  • An apparatus for manufacturing a plated film according to a fourth aspect of the present invention is the apparatus according to any one of the first to third aspects, wherein the moisture removing device is selected from an air knife device, a squeeze blade, or a water-absorbing roller.
  • the moisture removing device is an air knife device, a squeeze blade, and/or a water-absorbing roller, it is possible to effectively remove the liquid on the plated layer or the moisture therein, by the time the film going out of the plating solution in the plating bath comes in contact with the subsequent cathode roller.
  • An apparatus for manufacturing a plated film according to a fifth aspect of the present invention is the apparatus according to any one of the first to fourth aspects, wherein the moisture removing device is at least one device selected from: a device for jetting heated air or dehumidified air to the plated layer; a device for bringing a heating roller into contact with the back surface of the film and then jetting heated air or dehumidified air to the plated layer; a device for heating the plated layer with infrared rays and jetting heated air or dehumidified air to the plated layer; and a device for jetting heated steam to the back surface of the film and jetting heated air or dehumidified air to the plated layer.
  • An apparatus for manufacturing a plated film according to a sixth aspect of the present invention is the apparatus according to any one of the first to fifth aspects, wherein the plated film is a light-transmitting conductive film which is formed by patterning a conductive metal portion and a visible-ray transmitting portion on a transparent support member.
  • An apparatus for manufacturing a plated film according to a seventh aspect of the present invention is the apparatus according to the sixth aspect, wherein the light-transmitting conductive film has the patterned conductive metal portion that is formed of mesh-shaped lines having a size of 1 ⁇ m to 40 ⁇ m, and the pattern is a 3 m or more continuous mesh pattern.
  • An apparatus for manufacturing a plated film according to an eighth aspect of the present invention is the apparatus according to the sixth or seventh aspect, wherein the conductive metal portion is formed of developed silver obtained by developing a silver halide photosensitive material.
  • An apparatus for manufacturing a plated film according to a ninth aspect of the present invention is the apparatus according to any one of the first to eighth aspects, wherein the plated layer is a copper layer.
  • An apparatus for manufacturing a plated film according to a tenth aspect of the present invention is the apparatus according to any one of the sixth to ninth aspects, wherein the transparent support member is formed of one of polyimide resin or polyester resin.
  • an eleventh aspect of the present invention is the apparatus of any one of the first to the tenth aspect, wherein plated layer formation is repeated in a plurality of times so as to form a plated layer having a predetermined thickness on the conductive surface of the film.
  • FIG. 1 is a sectional view schematically illustrating an example of a plating machine according to the present invention.
  • FIG. 2A is an enlarged longitudinal section schematically illustrating a cathode roller part of a plating machine according to a first embodiment of the present invention and FIG. 2B is a perspective view of an air knife device.
  • FIG. 3 is an enlarged longitudinal section schematically illustrating a cathode roller part of a plating machine according to a second embodiment of the present invention.
  • FIG. 4 is an enlarged longitudinal section schematically illustrating a cathode roller part of a plating machine according to a third embodiment of the present invention.
  • FIG. 5A is an enlarged longitudinal section schematically illustrating a cathode roller part of a plating machine according to a fourth embodiment of the present invention and FIG. 5B is a perspective view of a heated air supplying device.
  • FIG. 6 is an enlarged longitudinal section schematically illustrating a cathode roller part of a plating machine according to a fifth embodiment of the present invention.
  • FIG. 7A is an enlarged longitudinal section schematically illustrating a cathode roller part of a plating machine according to a sixth embodiment of the present invention and FIG. 7B is a perspective view of an infrared heating device.
  • FIG. 8 is an enlarged longitudinal section schematically illustrating a cathode roller part of a plating machine according to a seventh embodiment of the present invention.
  • FIG. 9 is a diagram illustrating a part of the plating machine according to an example in which a plating process is performed, a washing process is performed, and then a heated-wind drying process is performed.
  • FIG. 1 An entire configuration of a continuous electroplating machine 10 wherein a film strip is unwound from a roll, the unwound film trip is plated, and the plated film is re-wound is schematically shown in FIG. 1 . As shown in FIG. 1 .
  • the machine includes an unwinding unit 301 for unwinding a film roll into a strip of a film, a pre-processing unit 302 for performing an acid-treating process, degreasing, and washing of a conductive surface of the film, an electroplating unit 303 , a post-processing unit 304 for performing removal or washing of a plating solution, a rust preventing process, a washing process, and a drying process, and a winding unit 305 for winding the film into a roll.
  • an unwinding unit 301 for unwinding a film roll into a strip of a film
  • a pre-processing unit 302 for performing an acid-treating process, degreasing, and washing of a conductive surface of the film
  • an electroplating unit 303 for performing an acid-treating process, degreasing, and washing of a conductive surface of the film
  • an electroplating unit 303 for performing removal or washing of a plating solution, a rust preventing
  • An electroplating unit 303 ′ can be disposed between the electroplating unit 303 and the post-processing unit 304 if necessary, and, for example, the unit 303 may be used as a copper electroplating unit, and the unit 303 ′ may be used as a nickel electroplating unit.
  • the film 4 unwound from a film roll 306 passes through an accumulator 307 , the tension of the film is controlled to a predetermined tension at a balance roller portion 308 , and the speed of the film is controlled at a substantially constant speed at a speed control portion 309 , and then the film enters a plating solution 7 in a plating bath 6 through an acid-treating and degreasing portion 310 and a washing portion 312 .
  • the film 4 moves to the right while bringing a conductive surface 5 thereof into contact with a cathode roller 1 A and is conveyed to the plating bath 6 .
  • the conductive surface 5 of the film 4 is brought into contact with the cathode roller 1 A, and then is brought into contact with a cathode roller 1 B through an in-solution roller 101 A in the plating solution of the plating bath 6 .
  • cases 102 A and 102 B filled with copper balls are used as an anode and the cathode rollers 1 A and 1 B are employed as a cathode.
  • a plated layer is formed on the film 4 .
  • Shield plates 106 A to 106 C are formed for each anode in the plating solution.
  • the cases 102 A and 102 B in which copper balls are stacked and filled are used as the anodes, and current of 1 A is supplied to the cases 102 A and 102 B as the copper anodes from the cathode rollers 1 by the DC source 3 A so that the current density of the film 4 is 0.2 to 10 A/dm 2 , thereby forming the plated layer on the film 4 .
  • the current density is a value obtained by dividing the current supplied from the DC source 3 A by an area of the portion, which is immersed in the plating solution, of the film conveyed in the unit indicated by a long dashed short dashed line in FIG. 2A .
  • the conductive surface 5 of the film 4 contacting the cathode roller 1 A comes in contact with the cathode roller 1 B after going out of the plating solution 7 .
  • An air knife device 20 A as the moisture removing device according to the present invention is disposed at a position facing the conductive surface 5 between the liquid surface of the plating solution 7 and the cathode roller 1 B.
  • the air knife device 20 A serves to remove the plating solution on the plated layer formed on the conductive surface 5 or the moisture therein.
  • the conductive surface 5 of the film 4 contacting the cathode roller 1 B comes in contact with the cathode roller 1 C after going out of the plating solution 7 .
  • An air knife device 20 B for removing the plating solution on the plated layer formed on the conductive surface 5 or the moisture therein is disposed between the liquid surface of the plating solution 7 and the cathode roller 1 C.
  • an air knife device is disposed at a position facing the inside surface of the film 4 going out of the plating solution 7 so as to remove the plating solution on the plated layer formed on the conductive surface of the film or the moisture therein.
  • the air knife device 20 has a slit 22 in a convex portion 21 A formed in a case body 21 , air is supplied from an air supply 23 , and an air knife is jetted from the slit 22 . Since air is jetted by the air knife device 20 A before the conductive surface 5 of the film 4 going out of the plating solution 7 comes in contact with the cathode roller 1 B, the plating solution attached to the plated layer formed on the conductive surface 5 or the moisture in a gelatin layer formed on the surface of the film 4 is removed. At this time, the moisture content of the plated layer formed on the conductive surface 5 right before contacting the cathode roller 1 B is 7 g/m 2 or less.
  • the moisture content (g/m 2 ) can be calculated by mass of water per unit area.
  • solvent for dissolving the developed silver is not present, thereby preventing elution of the developed silver. Accordingly, it is possible to prevent silver contamination of the cathode rollers.
  • a Super Air Knife Mod. 110036 (trade name) made by BLOVAC CO., LTD. is used as the air knife devices 20 A and 20 B.
  • the effective width of the air knife is 910 mm, the pressure thereof is 2.8 kg/cm 2 , the flow rate is 36 mm/sec, and the air consumption is 144 L/min.
  • one unit is indicated by the long dashed short dashed line and is repeated.
  • a plated layer is formed on a film 300 .
  • plated layers are sequentially formed by means of repetition of the process, thereby forming a plated layer with a total thickness of 1 to 30 ⁇ on the conductive surface of the film.
  • fresh air 331 A to 331 D is introduced into the plating bath 6 from air inlets (air agitating nozzles) 330 A to 330 D, and the solution in the plating bath is agitated sufficiently.
  • This process is preferably performed on the plated layer portion so as to increase the concentration of metal ions in the plated layer close to the polar surface of the formed plated layer.
  • the plating solution 7 is always circulated with contamination removed by a filter.
  • the film sequentially passes through a roller 325 for detecting film tension, a washing portion 314 for removing the plating solution, a rust-preventing processor 316 that is filled with a rust-preventing agent 317 protecting the plated layer, a washing portion 318 for removing the extra rust-preventing agent, a drying processor 320 having a drying furnace for removing moisture, and a speed controller 321 , then, the tension of the film is adjusted at a balance roller 322 , and then the film passes through an accumulator 323 and finally is rolled into a film roll 324 .
  • a plated film is obtained.
  • the practical film conveyance tension is preferably 10 N/m to 320 N/m.
  • the tension is substantially less than 10 N/m, the film wobbles, thereby making it difficult to control the conveyance path.
  • the tension is more than 320 N/m, metal of the plated layer formed on the film is internally deformed, thereby generating a curl in a product.
  • Conveyance tension control is performed by a feedback control method wherein a conveyance tension is detected by the tension detecting roller 325 and the speed of the film is increased or decreased by the speed controller 321 in accordance with the detected tension so as to keep the tension constant.
  • speed control is performed as described below: the cathode rollers 1 are driving rollers, and a basic rotating speed thereof is set by the speed controller 309 .
  • a draw ratio can be set between the cathode rollers 1 A and 1 B, the draw ratio is set so as to increase slowly, and the final speed is controlled by the speed controller 321 .
  • the conveyance tension of the film on the cathode rollers 1 above the plating bath is the highest at the tension detecting roller 325 , the conveyance tension can be preferably controlled on the basis of the value of the tension measured at the tension detecting roller 325 .
  • FIGS. 3 to 8 Enlarged views of cathode rollers according to second to sixth embodiments of the present invention are shown in FIGS. 3 to 8 .
  • the schematic processes are similar to those of FIG. 1 , but the moisture removing device for the plated layer formed on the conductive surface 5 of the film 4 are different from each other.
  • the same elements as those in FIG. 2 are referenced by the same reference numerals, and repeated description thereof is omitted.
  • FIGS. 3 to 8 only the cathode roller 1 B and the vicinities thereof are enlarged, and the other cathode rollers and vicinities thereof are not shown.
  • a blade wiper device 30 is disposed instead of the air knife devices 20 A and 20 B shown in FIG. 2 .
  • the blade wiper device 30 includes a blade 34 contacting the conductive surface 5 inside the film 4 going out of the plating solution 7 and being conveyed in the direction of the arrow.
  • the blade 34 is disposed so that one end thereof is directed downstream with respect to the conveyance direction and the other end is fixed and supported by a support 32 .
  • a counter member 36 for stabilizing the contact between the conductive surface 5 and the blade 34 is disposed so as to face the back side of the film 4 facing the blade 34 .
  • the effective blade width of the blade wiper device 30 is about 900 mm and the blade 34 is formed of a urethane rubber.
  • the blade 34 since the blade 34 comes in contact with the conductive surface 5 of the film 4 , the plating solution on the plated layer formed on the conductive surface 5 or the moisture therein is removed. Accordingly, no solvent for dissolving the developed silver is present, and it is thus possible to prevent elution of the developed silver, whereby silver contamination of the cathode roller can be prevented.
  • a water-absorbing roller 40 contacting the conductive surface 5 is disposed so as to face the inside surface of the film 4 going out of the plating solution 7 and being conveyed in the direction of the arrow.
  • the absorbing roller 40 comprises an elastic member 40 B having an absorbing property that is disposed around a core 40 A made of metal.
  • the absorbing roller 40 is supported rotatably in the same direction (direction of the arrow) as the conveyance direction at the contact portion with the film 4 .
  • a counter roller 42 for stabilizing the contact between the conductive surface 5 and the absorbing roller 40 is disposed so as to contact with the back side of the film which is opposite to the side facing the absorbing roller 40 .
  • Ruby Cell absorbing urethane elastomer made by TOYOPOLYMER Corporation is used in the absorbing roller 40 .
  • the diameter of the roller is 30 mm
  • the effective width (plane length) is 90 mm
  • the hardness is 60 degrees
  • the pore ratio is 75%.
  • the hardness is measured by the use of an AKSER C made by KOUBUNSHI KEIKI CO., LTD. As shown in FIG.
  • a heated air supplying device 50 for jetting heated air is disposed so as to face the back side of the film 4 going out of the plating solution 7 and being conveyed in the direction of the arrow.
  • the heated air supplying device 50 has a plurality of jet holes 54 arranged in the longitudinal direction of a case body 52 , as shown in FIG. 5B .
  • a heater not shown is formed inside the case body 52 , and the heated air is jetted from the jet holes 54 by a fan 56 . As shown in FIG.
  • the heated air is jetted to the conductive surface 5 of the film 4 by the heated air supplying device 50 , the plating solution on the plated layer formed on the conductive surface 5 or the moisture therein is removed. Accordingly, no solvent for dissolving the developed silver is present, and it is thus possible to prevent elution of the developed silver, whereby silver contamination of the cathode roller can be prevented.
  • a heating roller 60 is disposed at the opposite side with respect to the film 4 so as to contact with the back surface of the film 4 .
  • a halogen lamp 64 is disposed inside a hollow cylindrical member 62 .
  • silicon rubber made by NISSEI ELECTRIC CO., LTD. is used as the hollow cylindrical member 62 , wherein the roller diameter is 30 mm, the effective width (surface length) is 900 mm, and the rubber thickness is 3 mm.
  • a halogen heater lamp including a thermoelectric couple made by USHIO DENKI INC. is used for the halogen lamp 64 .
  • the heating roller 60 is disposed so as to face the back side surface of the film 4 in the example shown in FIG. 6 , the heating roller 60 may be disposed to contact with the conductive surface 5 of the film 4 .
  • the heating roller 60 may be disposed alone or in combination with the heated air supplying device 50 .
  • an infrared heating device 70 is disposed upstream with respect to the conveyance direction of the film 4 so as to face the inside surface of the film 4 that is going out of the plating solution 7 and conveyed in the direction of the arrow.
  • the infrared heating device 70 has a lamp 74 attached to the inside of a concave reflective plate 72 A formed in a support member 72 .
  • a near infrared heating device UHU-30PW made by USHIO DENKI INC.
  • the reflective plate 72 A is formed in an aluminum mirror specification.
  • the conductive surface 5 of the film 4 is heated by the infrared heating device 70 and then the heated air is jetted thereto by the heated air supplying device 50 , it is possible to surely remove the plating solution on the plated layer formed on the conductive surface 5 or the moisture therein.
  • the infrared heating device 70 and the heated air supplying device 50 are used in combination, the infrared heating device 70 may be disposed alone so as to face the conductive surface 5 of the film 4 .
  • a wet air supplying device 80 is disposed upstream with respect to the conveyance direction of the film 4 on the back side of the film 4 , in addition to the heated air supplying device 50 disposed so as to face the back side surface of the film 4 that is going out of the plating solution 7 and conveyed in the direction of the arrow.
  • the wet air supplying device 80 jets heated steam to the back surface of the film 4 .
  • JQ-25 made by TOSHIBA CORPORATION is used as the wet air supplying device 80 , wherein the maximum pressure is 50 bar and the heating temperature is 15° C.
  • the plating machine 10 shown in FIG. 1 repeatedly performs the current supply and the plating bathing to the conductive surface 5 of the film 4 using the cathode roller 1 , but the present invention is not limited to this configuration.
  • the moisture removing device according to the present invention can be used between the washing portion and the cathode roller. Accordingly, since the moisture in a gelatin layer on the film after the washing is removed, the elution of the developed silver does not occur, whereby silver contamination of the cathode roller is prevented.
  • the electroplating unit 303 of the plating machine shown in FIG. 1 is modified to dispose a washing bath 116 next to the plating bath 6 , thereby removing the moisture when the film 4 goes out of the washing bath 116 .
  • the plating machine shown in FIG. 9 is an example of a type for repeatedly performing plating, washing, drying, plating, washing, and drying processes.
  • the film 4 going out of the plating bath 6 is conveyed by two conveyance rollers 117 above the plating bath and is further conveyed by the in-liquid roller 118 disposed in the washing bath 116 .
  • a moisture removing device 90 for jetting the heated air to the plating surface of the film 4 to dry the plating surface is disposed at a position where the film 4 goes out of the liquid surface.
  • the film 4 is washed with water and then is dried by the moisture removing device 90 , it is possible to more surely remove the plating solution on the plated layer on the film 4 or the moisture therein.
  • the drying means may be the air knife device shown in FIG. 2B , the blade wiper device shown in FIG. 3 , or the absorbing roller shown in FIG. 4 .
  • the heating roller may be disposed so as to contact with the back surface of the film.
  • the infrared heating device may be disposed upstream with respect to the conveyance direction of the film so as to face the inside surface of the film that is going out of the plating solution and conveyed in the direction of the arrow.
  • a device such as a shower may be used as the washing means instead of the washing bath 116 .
  • Polyimide resin or polyester resin can be preferably used as a material for the plated film.
  • the material for a plastic film as a substrate used in the present invention can include polyester such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene- ⁇ , ⁇ -bis(2-chlorophenoxyethane-4,4′-dicarboxylate), polyether ether ketone, aromatic polyamide, polyacrylate, polyimide, poly(amide imide), poly(ether imide), polyparaginic acid, polyoxadiazole, and a substitution product thereof substituted by a halogen group or a methyl group.
  • the examples may include copolymers thereof and other organic polymers.
  • Known additives such as a lubricant and a plasticizer may be added to the polymers.
  • a film obtained by biaxially stretching an unstretched film that is made by extruding a polymer containing a repeating unit having a structure shown by the following formulae in an amount of 85 mol % or more is particularly preferably used.
  • a film which is formed by a wet or dry deposition process from a polymer containing a repeating unit having a structure shown by the following formulae in an amount of 50 mol % or more, or a film obtained by stretching biaxially and/or heat treating the film made by depositing the above polymers is preferably used.
  • a film having a substrate thickness of 50 to 150 ⁇ m, and more preferably having a substrate thickness of 75 to 100 ⁇ m is preferably used.
  • the method for forming a transparent conductive metal film according to the present invention can be separated into the following three processes in accordance with photosensitive materials and processes for development employed therein:
  • the process (1) is an integrated white and black type development process and a transparent conductive metal film such as a transparent electromagnetic shielding film or a light-transmitting conductive film is formed on the photosensitive material.
  • Developed silver formed in the process is chemically developed sliver, and thus, is highly active in the subsequent process of plating or physical developing since the developed silver is in a filament shape having a high specific surface area.
  • the silver halide particles around the physical development are dissolved in the exposed portion and deposited on the development seeds, and thus, a transparent conductive metal film such as a transparent electromagnetic shielding film or a light-transmitting conductive film is formed on the photosensitive material.
  • a transparent conductive metal film such as a transparent electromagnetic shielding film or a light-transmitting conductive film is formed on the photosensitive material.
  • This process is also an integrated black-and-white development process.
  • Developed silver is active because it is an extraction onto the physical development seeds, but the developed silver has a spherical shape having a low specific surface area.
  • the silver halide particles are dissolved in the non-exposed portion, are then diffused and deposited on the physical development seeds on the image receiving sheet. Accordingly, a transparent conductive metal film such as a transparent electromagnetic shielding film or a light-transmitting conductive film is formed on the image receiving sheet. Accordingly, the process (3) is a so-called separated process, wherein the image receiving sheet is separated from the photosensitive material before use.
  • one of a negative development process and an inverted development process can be adopted (in a diffused conveyance process, a negative development process can be performed by using an auto-positive type photosensitive material as a photosensitive material).
  • a plastic film, a plastic plate, and a glass plate can be used as the support body of the photosensitive material used in the manufacturing method according to the present invention.
  • the material for the plastic film and the plastic plate can include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene, and EVA, vinyl resin such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acryl resin, and triacetyl cellulose (TAC).
  • PET polyethylene terephthalate
  • PP polypropylene
  • EVA vinyl resin
  • vinyl resin such as polyvinyl chloride and polyvinylidene chloride
  • PEEK polyether ether ketone
  • PSF polysulfone
  • the plastic film is preferably a polyethylene terephthalate film.
  • the transparency of the support body is preferably high.
  • the total visible-ray transmittance of the plastic film or the plastic plate is preferably in the range of 70 to 100%, more preferably in the range of 85 to 100%, and most preferably in the range of 90 to 100%.
  • the plastic film and the plastic plate may be colored to an extent which does not hinder the object of the present invention.
  • the plastic film and the plastic plate according to the present invention may be used as a single layer, but may be used as a multi-layered film in which two or more layers are combined.
  • the thickness of the plastic film or the plastic plate is preferably in the range of 75 ⁇ m to 100 ⁇ m.
  • types of the glass plate are not particularly limited.
  • reinforced glass on a surface of which a reinforcing layer is formed is preferably used. Reinforced glass is less prone to break in comparison with a non-reinforced glass. Reinforced glass produced by an air-cooling process is preferably used in view of safety, since the reinforced glass would break into smaller pieces having dull edges when broken.
  • a protective layer is preferably formed on an emulsion layer that is to be described later.
  • the “protective layer” means a layer including a binder such as gelatin or a polymer, and is formed on the photosensitive emulsion layer so as to prevent the surface of the emulsion layer from being scratched or to improve mechanical characteristics of the emulsion layer.
  • the thickness of the protective layer is in the range of 0.02 to 20 ⁇ m, preferably in the range of 0.1 to 10 ⁇ m, and more preferably in the range of 0.3 to 3 ⁇ m.
  • the protective layer is not essential.
  • the method for depositing the protective layer is not particularly limited, and a known deposition method may be properly selected.
  • the photosensitive material used in the manufacturing method according to the present invention may contain known dyes by adding coloring emulsion in the emulsion layer.
  • the photosensitive material used in the manufacturing method according to the present invention has an emulsion layer (silver halide-containing layer) containing silver salt as an optical sensor on the support body.
  • the emulsion layer according to the present invention can contain dye, binder, and solvent as needed, in addition to silver salt.
  • a dye is contained at least in the emulsion layer of the photosensitive material.
  • the dye is contained in the emulsion layer as a filter dye or for the purpose of prevention of irradiation and the like.
  • a solid dispersion dye can be contained as the dye.
  • the dyes suitably used in the present invention can include dyes shown by Formulae FA, FA1, FA2, and FA3 in JP-A No. 9-179243, and specifically, Compounds F1 to F34 described in the same publication are preferably used.
  • Dyes II-2 to II-24 described in JP-A No. 7-152112, Dyes III-5 to III-18 described in JP-A No. 7-152112, and Dyes IV-2 to IV-7 described in JP-A No. 7-152112 can be also preferably used.
  • examples of solid particle dispersed dye to be decolorized at the time of development or fixation can include a cyanine dye, a pyrylium dye, and an aminium dye described in JP-A No. 3-138640.
  • Dyes not to be decolorized at the time of processing can include a cyanine dye having a carboxyl group described in JP-A No. 9-96891, a cyanine dye not containing an acid group described in JP-A No. 8-245902, a lake cyanine dye described in JP-A No. 8-333519, a cyanine dye described in JP-A No. 1-266536, a hollow-polar cyanine dye described in JP-A No.
  • the dye can include an aqueous dye.
  • the aqueous dye can include an oxonol dye, a benzylidene dye, a merocyanine dye, a cyanine dye, and an azo dye.
  • the oxonol dye, the hemi-oxonol dye, and the benzylidene dye are preferably used in the present invention.
  • Specific examples of the aqueous dye used in the present invention can include dyes described in U.K. Patent Nos. 584,609 and 1,177,429, JP-A Nos. 48-85130, 49-99620, 49-114420, 52-20822, 59-154439, and 59-208548, and U.S. Pat. Nos. 2,274,782, 2,533,472, 2,956,879, 3,148,187, 3,177,078, 3,247,127, 3,540,887, 3,575,704, 3,653,905, and 3,718,427.
  • the dye content of the emulsion layer is preferably in the range of 0.01 to 10 wt % with respect to the total solid content and more preferably in the range of 0.1 to 5 wt %, in view of prevention of irradiation and decrease in sensitivity due to increase in amount of the added dye.
  • Examples of the silver salt used in the present invention can include inorganic silver salt such as silver halide and organic silver salt such as silver acetate. Silver halide having an excellent characteristic as an optical sensor can be preferably used in the present invention.
  • the silver halide preferably used in the present invention is described below.
  • silver halide is preferably used to serve as an optical sensor.
  • the techniques used for a silver salt photographic film or a printing sheet using the silver halide, a printing film, an emulsion mask for a photo mask, and the like can be used in the present invention.
  • a halogen element contained in the silver halide may be any one of chlorine, bromine, iodine, and fluorine, or may be a combination thereof.
  • silver halide containing AgCl, AgBr, or AgI as a major component is preferably used, and silver halide containing AgBr or AgCl as a major component is more preferably used.
  • Silver chloride bromide, silver iodide chloride bromide, silver iodide bromide are also preferably used, and silver chloride bromide, silver bromide, silver chloride iodide bromide, and silver iodide bromide are more preferable.
  • the most preferable are a silver chloride bromide and a silver iodide chloride bromide containing 50 mol % or more of silver chloride.
  • silver halide containing AgBr (silver bromide) as a major component” means silver halide in which the mole content of bromide ions in the composition of the silver halide is 50% or more.
  • the silver halide particles containing AgBr as a major component may contain iodide ions and chloride ions, in addition to bromide ions.
  • the silver halide is in a solid particle state.
  • the average particle size of the silver halide is preferably in the range of 0.1 to 1000 nm (1 ⁇ m) in a sphere equivalent diameter in view of image quality of a patterned metal silver layer formed after the exposure and development processes, more preferably in the range of 0.1 to 100 nm, and most preferably in the range of 1 to 50 nm.
  • the sphere equivalent diameter of a silver halide particle means a diameter of the spherical particle having the same volume as that of the silver halide particle.
  • the shape of the silver halide particles is not particularly limited, and may be different shapes such as sphere, cube, plate (for example, hexagonal plate, triangular plate, and quadrangular plate), octahedron, and 14-hedron.
  • the cube and 14-hedron are preferable.
  • the inside and surface of the silver halide particles can have the same or different phases.
  • the silver halide particles can have a localized layer having a different halogen composition inside or on the surfaces.
  • the silver halide emulsion which is a coating solution for an emulsion layer used in the present invention can be prepared by the use of methods described in “Chimie et Physique Photographique” (published by Paul Montel in 1967) written by P. Glafkides, “Photographic Emulsion Chemistry” (published by the Forcal Press in 1966) written by G. F. Dufin, “Making and Coating Photographic Emulsion” (published by the Forcal Press in 1964) written by V. L. Zeilikman et al.
  • the silver halide emulsion can be prepared by any of acidic and neutral processes. Further, a soluble silver salt can be reacted with a soluble halogen salt by a partial mixing process, a whole mixing process, and a combination thereof to prepare a silver halide.
  • a process for forming silver particles in which silver halide particles are formed under excessive silver ions may be used to form the silver particles.
  • reverse mixing process a process in which pAg in a liquid phase in which the silver halide is formed is kept at a constant value, which is a so-called “controlled double jet process”, can be used.
  • particles are formed by the use of so-called silver halide solvent such as ammonia, thioether, or 4-substituted thiourea.
  • silver halide solvent such as ammonia, thioether, or 4-substituted thiourea.
  • 4-substituted urea compounds are more preferable, which are described in JP-A Nos. 53-82408 and 55-77737.
  • the thiourea compound can include tetramethyl thiourea and 1,3-dimethyl-2-imidazolidinethione.
  • the amount of silver halide solvent added depends on compounds to be used, intended particle sizes, and halogen compositions of the compound to be used, but is preferably in the range of 10 ⁇ 5 to 10 ⁇ 2 mol per 1 mol of silver halide.
  • silver halide particles are preferably grown as rapidly as possible within a critical saturation concentration of silver ions by using a process in which a rate of addition of silver nitrate and alkali halide in accordance with the growth speed of particles as described in U.K. Patent No. 1,535,016 and JP-A Nos. 48-36890 and 52-16364, or by using a process in which concentration of silver ions or halide ions in an aqueous solution is changed as described in U.K. Patent No.
  • the silver halide emulsion used to form the emulsion layer in the present invention is preferably a mono-dispersed emulsion.
  • a variation coefficient expressed by (standard deviation of particle sizes)/(average particle size) ⁇ 100 is preferably 20% or less, more preferably 15% or less, and most preferably 10% or less.
  • the silver halide emulsion used in the present invention may include plural kinds of silver halide emulsion having different particles sizes mixed with each other.
  • the silver halide emulsion used in the present invention may contain metals belonging to Groups VIII and VIIB. Specifically, in order to accomplish high contrast and low photographic fog, the silver halide emulsion may contain a rhodium compound, iridium compound, ruthenium compound, iron compound, osmium compound, rhenium compound, or the like. These compounds can have a variety of ligands.
  • the ligands can include organic molecules such as amines (methylamine, ethylenediamine, and the like), heterocyclic compounds (imidazole, thiazole, 5-methylthiazole, mercaptoimidazole, and the like), urea, and thiourea, in addition to cyanide ions, halogen ions, thiocyanate ions, nitrosyl ions, water, hydrate ions, pseudo-halogen, and ammonia.
  • 6-cyanide metal complex such as K 4 (Fe(CN) 6 or K 4 (Ru(CN) 6 is preferably performed.
  • An aqueous rhodium compound can be used as the rhodium compound.
  • the aqueous rhodium compound can include a rhodium(III) halide compound, a hexachloro rhodium(III) complex, a pentachloro aquo rhodium complex, a tetrachloro diaquo rhodium complex, a hexabromo rhodium(III) complex, a hexamine rhodium(III) complex, a trizarat rhodium(III) complex, and K 3 Rh 2 Br 9 .
  • the rhodium compounds are dissolved in water or proper solvent for use, but a method which is often performed to stabilize the solution of the rhodium compounds, that is, a method for adding a hydrogen halide solution (such as chloric acid, bromic acid, or fluorine acid) or alkali halide (such as KCl, NaCl, KBr, or NaBr) can be used.
  • a hydrogen halide solution such as chloric acid, bromic acid, or fluorine acid
  • alkali halide such as KCl, NaCl, KBr, or NaBr
  • additional silver halide particles doped with rhodium in advance at the time of preparing silver halide may be added and dissolved.
  • Examples of the iridium compound can include a hexachloro iridium complex such as K 2 IrCl 6 or K 3 IrCl 6 , a hexabromo iridium complex, a hexamine iridium complex, and a pentachloro nitrosyl iridium complex.
  • a hexachloro iridium complex such as K 2 IrCl 6 or K 3 IrCl 6
  • a hexabromo iridium complex such as K 2 IrCl 6 or K 3 IrCl 6
  • a hexabromo iridium complex such as K 2 IrCl 6 or K 3 IrCl 6
  • a hexabromo iridium complex such as K 2 IrCl 6 or K 3 IrCl 6
  • a hexabromo iridium complex such as K 2 IrCl 6 or K 3 IrCl 6
  • Examples of the ruthenium compound can include hexachloro ruthenium, pentachloro nitrosyl ruthenium, and K 4 (Ru(CN) 6 .
  • iron compound can include hexacyano potassium ferrate(II) and iron thiocyanate.
  • Rhenium, ruthenium, and osmium compounds are added in the form of aqueous complexes described in JP-A Nos. 63-2042, 1-285941, 2-20852, and 2-20855, and six-coordinated complex expressed by the following formula is preferable.
  • ligands can include a halide ligand, a cyanide ligand, a cyanate ligand, a nitrosyl ligand, and a thionitrosyl ligand.
  • Specific examples of complexes used in the present invention are described as follows, but the present invention is not limited to the specific examples:
  • the amount of the compounds added is preferably in the range of 10 ⁇ 10 to 10 ⁇ 2 mol/mol Ag and more preferably in the range of 10 ⁇ 9 to 10 ⁇ 3 mol/mol Ag.
  • silver halide containing Pd(II) ion and/or Pd metal can be preferably used.
  • Pd may be distributed uniformly in the silver halide particles, but is preferably contained in the vicinity of the surfaces of the silver halide particles.
  • “Pd is contained in the vicinity of the surfaces of the silver halide particles” means that the content of palladium in a region within a depth of 50 nm from the surfaces of the silver halide particles is higher than that in the other regions.
  • the silver halide particles can be formed by adding Pd in the course of forming the silver halogen particles.
  • silver ions and halogen ions are added in an amount of 50% or more of the total amount of ions to be added and then Pd is added thereto.
  • Pd(II) ions may be caused to be present in the surface of the silver halide particles by adding Pd(II) ions at the time of after-ripening.
  • the silver halide particles containing Pd increase the reaction speed of physical development or electroless plating and thus improve the productivity of a desired electromagnetic shielding material, thereby contributing to decrease in production cost.
  • Pd is well known and widely used as an electroless plating catalyst.
  • Pd can be unevenly distributed in the surface of the silver halide particles, it is possible to conserve Pd which is very high in cost.
  • the content of Pd ions and/or Pd metal contained in the silver halide is preferably in the range of 10 ⁇ 4 to 0.5 mol/mol Ag with respect to the molar amount of silver in the silver halide, and more preferably in the range of 0.01 to 0.3 mol/mol Ag.
  • Examples of the Pd compound can include PdCl 4 or Na 2 PdCl 4 .
  • a chemical sensitization used for a photo emulsion may be performed.
  • the chemical sensitization process can include a chalcogen sensitization process such as a sulfur sensitization process, a selenium sensitization process, or a tellurium sensitization process, a noble metal sensitization process such as a gold sensitization process, and a reduction sensitization process. These methods may be used independently or in combination.
  • combinations such as a combination of the sulfur sensitization process and the gold sensitization process, a combination of the sulfur sensitization process, the selenium sensitization process, and the gold sensitization process, and a combination of the sulfur sensitization process, the tellurium sensitization process, and the gold sensitization process are preferably used.
  • the sulfur sensitization process is performed by adding a sulfur sensitizer and agitating the emulsion at a temperature of 40° C. or more for a predetermined time.
  • a sulfur sensitizer can be used as the sulfur sensitizer and examples thereof can include a variety of sulfur compounds such as thiosulfate, thiourea, thiazole, and laudanine, in addition to the sulfur compound contained in gelatin.
  • Preferable examples of the sulfur compound can include thiosulfate and thiourea compounds.
  • the amount of sulfur sensitizer to be added is different depending upon a variety of conditions such as pH and temperature at the time of chemical ripening, and particle sizes, and is preferably in the range of 10 ⁇ 7 to 10 ⁇ 2 mol per 1 mole of the silver halide, and more preferably is in the range of 10 ⁇ 5 to 10 ⁇ 3 mol.
  • selenium compounds can be used as the selenium sensitizer used in the selenium sensitization. That is, the selenium sensitization process is generally performed by adding unstable and/or non-unstable selenium compounds and agitating the emulsion at a temperature of 40° C. or more for a predetermined time.
  • the unstable selenium compound can include compounds described in JP-B Nos. 44-15748 and 43-13489 and JP-A Nos. 4-109240 and 4-324855. It is particularly preferable to use the compounds shown by Formulae VIII and IX in JP-A No. 4-324855.
  • the tellurium sensitizer used in the tellurium sensitization process is a compound for generating silver telluride estimated to be a sensitization seed on the surfaces or the insides of the silver halide particles.
  • the speed of generating silver telluride in the silver halide emulsion can be tested by the method described in JP-A No. 5-313284.
  • examples of the tellurium sensitizer can include compounds described in U.S. Pat. Nos. 1,623,499, 3,320,069, and 3,772,031, U.K. Patent Nos. 235,211, 1,121,496, 1,295,462, and 1,396,696, Canadian Patent No. 800,958, JP-A Nos.
  • the amounts of the selenium sensitizer and the tellurium sensitizer used in the present invention are different depending upon the silver halide particles to be used and chemical ripening conditions, and are generally in the range of 10 ⁇ 8 to 10 ⁇ 2 mol per 1 mol of silver halide, and preferably in the range of 10 ⁇ 7 to 10 ⁇ 3 mol.
  • the chemical sensitization conditions in the present invention are not particularly limited, but pH is in the range of 5 to 8, pAg is in the range of 6 to 11 and more preferably is in the range of 7 to 10, and the temperature is in the range of 40° C. to 95° C. and preferably in the range of 45° C. to 85° C.
  • the noble metal sensitizer can include gold, platinum, palladium, and iridium. Among them, the gold sensitization is preferable. Specific examples of the gold sensitizer used in the gold sensitization can include gold chloride, potassium chloroaurate, potassium aureothiocyanate, gold sulfide, gold thioglucose (I), and gold thiomannose (I), and can be used in an amount of 10 ⁇ 7 to 10 ⁇ 2 mol per 1 mol of silver halide.
  • the silver halide emulsion used in the present invention can coexist with cadmium salt, sulfite, lead salt, thallium salt, or the like in the course of formation of the silver halide particles or the physical ripening.
  • the reduction sensitization can be performed.
  • the reduction sensitizer can include tin salt, amine, formamidine sulfinic acid, and a silane compound.
  • a thiosulfonic acid compound may be added to the silver halide emulsion.
  • only one kind of silver halide emulsion or a combination of two or more kinds of silver halide emulsion (for example, emulsions having different average particle sizes, having different halogen compositions, having different crystal habits, having different chemical sensitization conditions, or having different sensitivities) can be used for manufacturing the photosensitive material.
  • the closer to the support body the more preferable it is to apply an emulsion having high sensitivity to form the emulsion layer.
  • a binder can be used in the emulsion layer for the purpose of uniformly dispersing silver salt particles and enhancing adhesion between the emulsion layer and the support body.
  • a non-aqueous polymer or an aqueous polymer can be used as the binder, but it is preferable to use the aqueous polymer as the binder.
  • binder examples include gelatin, polyvinyl alcohol (PVA), polyvinyl pyrolidone (PVP), polysaccharide such as starch, cellulose and derivatives thereof, polyethylene oxide, polysaccharide, polyvinyl amine, chitosan, polylysine, poly acrylic acid, poly alginic acid, poly hyaluronic acid, and carboxycellulose.
  • PVA polyvinyl alcohol
  • PVP polyvinyl pyrolidone
  • polysaccharide such as starch
  • cellulose and derivatives thereof polyethylene oxide
  • polysaccharide polyvinyl amine
  • chitosan polylysine
  • poly acrylic acid poly alginic acid
  • poly hyaluronic acid poly hyaluronic acid
  • carboxycellulose examples of the binder can include gelatin, polyvinyl alcohol (PVA), polyvinyl pyrolidone (PVP), polysaccharide such as starch, cellulose and derivatives thereof, polyethylene oxide,
  • the content of the binder contained in the emulsion layer is not particularly limited, and can be properly determined within the range in which a dispersion property and an adhesion property can be exhibited.
  • the solvent used for forming the emulsion layer is not particularly limited, and examples thereof can include water, organic solvent (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, sulfoxides such as dimethyl sulfoxide, esters such as ethyl acetate, esters, and the like), an ionic solution, and a mixture solvent thereof.
  • the content of the solvent used in the emulsion layer according to the present invention is in the range of 30 to 90 wt % with respect to the total mass of the silver salt and the binder contained in the emulsion layer, and preferably in the range of 50 to 80 wt %.
  • the layer containing silver salt formed on the support body or the photosensitive material coated with photo polymer for photolithography is subjected to an exposure process.
  • the exposure process can be performed by the use of an electromagnetic wave.
  • the electromagnetic wave can include light such as a visible ray or a UV ray and a radioactive ray such as an X ray.
  • a light source having a wavelength distribution or a light source having a specific wavelength may be used for the exposure process.
  • a variety of luminescent substances emitting light in the visible spectrum region are used as the light source if necessary.
  • a red luminescent substance, a green luminescent substance, a blue luminescent substance, or a mixture thereof can be used.
  • the spectrum region of the light the luminescent emits is not limited to red, green, and blue, a luminescent substance emitting light in a region of yellow, orange, violet, or infrared may be used.
  • a cathode ray tube in which a mixture of luminescent substances is used and which emits white light is often used.
  • a UV lamp is also preferable, and a g ray or an i ray emitted by a mercury lamp may be also used.
  • the exposure process can be preferably performed using a variety of laser beams.
  • a gas laser, a light emitting diode, a semiconductor laser, and scan exposing means employing single-color high-density light of a second harmonic generator (SHG) in which the semiconductor laser or a solid layer using the semiconductor laser as an excitation light source and a non-linear optical crystal are combined can be preferably used for the exposure process according to the present invention.
  • a KrF excimer laser, an ArF excimer laser, and an F 2 laser may be also used.
  • the exposure process is performed using the semiconductor laser or the second harmonic generator (SHG) in which the semiconductor laser or the solid laser and the non-linear optical crystal are combined.
  • SHG second harmonic generator
  • the exposure process is performed using the semiconductor laser.
  • the energy for exposure is preferably 100 ⁇ J/cm 2 or less, more preferably 50 ⁇ J/cm 2 or less, and most preferably in the range of 4 ⁇ J/cm 2 to 40 ⁇ J/cm 2 .
  • the laser source can include a blue semiconductor laser with a wavelength of 430 to 460 nm (announced by NICHIA CORPORATION at the 48 th Associated Lecture relating to Applied Physics in March of 2001), a green laser with a wavelength of about 530 nm obtained by converting the wavelength of a semiconductor laser (having an oscillation wavelength of about 1060 nm) using SHG crystals of LiNbO 3 having an inverted domain structure of a waveguide shape, and a red semiconductor laser with a wavelength of about 685 nm (Hitachi Type No. HL6738MG), a red semiconductor laser with a wavelength of about 650 nm (Hitachi Type No. HL6501MG).
  • a blue semiconductor laser with a wavelength of 430 to 460 nm announced by NICHIA CORPORATION at the 48 th Associated Lecture relating to Applied Physics in March of 2001
  • a green laser with a wavelength of about 530 nm obtained by converting the wavelength
  • a scan exposure method is preferably used to expose the layer containing silver salt in a pattern.
  • a laser scan exposure machine of a capstan type described in JP-A No. 2000-39677 is preferably used.
  • a DMD described in JP-A No. 2004-1224 is also preferably used for a light scanning system, in place of the beam scanning by rotation of a polygon mirror.
  • the emulsion layer is subjected to the exposure process and then is further subjected to the development process.
  • Conventional development techniques used for a silver salt photographic film or printing sheet, a printing film, an emulsion mask for a photo mask, and the like can be employed in the development process.
  • the developer used in the development process is not particularly limited, and a PQ developer, an MQ developer, and an MAA developer can be used as the developer.
  • CN-16, CR-56, CP45X, FD-3, and PAPITOL made by FUJI PHOTO FILM CO., LTD.
  • developers such as C-41, E-6, RA-4, D-19, and D-72 made by KODAK CO., or developers contained in the kits thereof can be used.
  • a lithography developer may be used.
  • D85 made by KODAK CO. can be used as the lithography developer.
  • a metal silver portion, and preferably a patterned metal silver portion is formed in the exposed portion, and a light transmitting portion to be described below is formed in the non-exposed portion.
  • a dihydroxybenzene developing agent can be used as the developer.
  • the dihydroxybenzene developing agent can include hydroquinone, chlorohydroquinone, isopropyl hydroquinone, methyl hydroquinone, and hydroquinone monosulfonate. Among them, hydroquinone is preferable.
  • the dihydroxybenzene developing agent and an assistant developing agent exhibiting a super-additive property can include 1-phenyl-3-pyrazolidones or p-aminophenols.
  • a combination of the dihydroxybenzene developing agent and the 1-phenyl-3-pyrazolidones or a combination of the dihydroxybenzene developing agent and p-aminophenols can be preferably used.
  • the developing agent combined with 1-phenyl-3-pyrazolidone or the derivatives thereof used as the assistant developing agent can include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone.
  • the p-aminophenol assistant developing agent can include N-methyl-p-aminophenol, p-aminophenol, N-( ⁇ -hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl) glycin, but among these, N-methyl-p-aminophenol is preferable.
  • the dihydroxybenzene developing agent is preferably used in the range of 0.05 to 0.8 mol/liter, but in the present invention, it is preferably used in an amount of 0.23 mol/liter or more and more preferably in the range of 0.23 to 0.6 mol/liter.
  • the former is used in the range of 0.23 to 0.6 mol/liter, and more preferable that the former is used in the range of 0.23 to 0.5 mol/liter and the latter is used in 0.06 mol/liter or less, and still more preferable that the latter is used in the range of 0.03 to 0.003 mol/liter.
  • both of a development initiating solution and a development replenishing solution preferably have a property such that “an increase in pH when 0.1 mol of sodium hydroxide is added to 1 liter of the solution is 0.5 or less.”
  • pH of the development initiating solution and the development replenishing solution is set to 10.5, 0.1 mol of sodium hydroxide is added to 1 liter of the solution, and the value of pH at this time is measured.
  • increment in pH is 0.5 or less, it is determined that the solutions have the above-defined property.
  • it is preferable that a development initiating solution and a development replenishing solution in which the increase in pH at the time of performing the above-mentioned test is 0.4 or less is used.
  • the above-mentioned property is preferably given to the development initiating solution and the development replenishing solution by the use of a method using a buffer agent.
  • the buffer agent can include carbonate, boric acid described in JP-A No. 62-186259, saccharide (for example, sucrose) described in JP-A No. 60-93433, oxime (for example, acetoxime), phenol (for example, 5-sulfosalicylate), and triphosphate (for example, sodium salt and potassium salt), and among them, carbonate and boric acid are preferably used.
  • the amount of buffer agent (specifically, carbonate) to be used is preferably 0.25 mol/liter or greater and more preferably in the range of 0.25 to 1.5 mol/liter.
  • the pH of the development initiating solution is preferably in the range of 9.0 to 11.0, and more preferably in the range of 9.5 to 10.7.
  • the pH of the development replenishing solution and the pH of a developer in a development tank at the time of performing a subsequent process are in these ranges.
  • the alkali agent used for adjusting the pH may be a common aqueous inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate).
  • the content of the development replenishing solution in the developer is 323 milliliters or less, more preferably 323 to 30 milliliters, and particularly 225 to 50 milliliters.
  • the development replenishing solution may have the same composition as that of the development initiating solution or may have a component consumed by the development having a concentration higher than that of the development initiating solution.
  • the developer used for developing the photosensitive material in the present invention may include common additives (for example, preservative or chelate).
  • preservative can include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, sodium metabisulfite, and formaldehyde sodium bisulfite.
  • concentration of sulfite is preferably 0.2 mol/liter or more and more preferably 0.3 mol/liter or more.
  • the upper limit thereof is preferably 1.2 mol/liter.
  • the amount thereof is more preferably in the range of 0.35 to 0.7 mol/liter.
  • a small amount of a derivative of ascorbic acid may be used in addition to sulfite salt.
  • the derivative of ascorbic acid include ascorbic acid, erythorbin acid which is stereoisomer, and alkali metal salt (sodium or potassium salt).
  • sodium erythorbin acid is preferable in view of material cost.
  • the amount of the derivative of ascorbic acid to be added is preferably in the range of 0.03 to 0.12 and more preferably in the range of 0.05 to 0.10 in mole ratio in the dihydroxybenzene developer.
  • the developer does not contain a boron compound.
  • Additives which can be used in the developing material may include a development inhibitor such as sodium bromide or potassium bromide; an organic solvent such as ethylene glycol, diethylene glycol, triethylene glycol, or dimethylformamide; alkanolamine such as diethanolamine or triethanolamine, a development accelerant such as imidazole and a derivative thereof, a mercapto compound, an indazole compound, a benzotriazole compound, or s benzoimidazole compound as a fog preventing agent or a black pepper preventing agent.
  • a development inhibitor such as sodium bromide or potassium bromide
  • an organic solvent such as ethylene glycol, diethylene glycol, triethylene glycol, or dimethylformamide
  • alkanolamine such as diethanolamine or triethanolamine
  • a development accelerant such as imidazole and a derivative thereof, a mercapto compound, an indazole compound, a benzotriazole compound, or s benzoimidazole compound as a fog
  • benzoimidazole compound can include 5-nitroindazole, 5-p-nitrobenzoilaminoindazole, 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-thiadiazole-2-il)thio]butanesulfonic acid, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-melcaptobenzotriazole.
  • the content of the benzoimidazole compound is 0.01 to 10 mmol and more preferably 0.1 to 2 mmol per 1 liter of the developer.
  • organic or inorganic chelate agents may be added to the developer.
  • the inorganic chelate agent can include sodium tetrapolyphosphate or sodium hexametaphosphate.
  • examples of the organic chelate can include organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid, and phosphonocarboxylic acid.
  • organic carboxylic acid can include acrylic acid, oxalic acid, malonic acid, succinic acid, glutalic acid, pimelic acid, succinic acid, aselaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid, itaconic acid, malic acid, citric acid, and tartaric acid, but are not limited thereto.
  • aminopolycarboxylic acid can include iminodiacetic acid, nitrotriacetic acid, nitrotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycolethertetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethyltriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycoletherdiaminetetraacetic acid, and compounds described in JP-A Nos. 52-25632, 55-67747, and 57-102624, and JP-B No. 53-40900.
  • Examples of the organic phosphonic acid can include hydroxyalkylidene-diphosphonic acid disclosed in U.S. Pat. Nos. 3,214,454 and 3,794,591 and German Patent No. 2227639 and compounds disclosed in Research Disclosure, volume 181 , Item No. 18170 (May, 1979).
  • Examples of the aminophosphonic acid can include aminotris(methylphosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid, and also compounds disclosed in Research Disclosure, Item No. 18170, and JP-A Nos. 57-208554, 54-61125, 55-29883, and 56-97347.
  • organic phosphonocarboxylic acid can include compounds disclosed in JP-A Nos. 52-102726, 53-42730, 54-121127, 55-4024, 55-4025, 55-126241, 55-65955, and 55-65956 and Research Disclosure, Item No. 18170.
  • the chelate agent may be alkali metal salt or ammonium salt.
  • the amount of the chelate agent to be added is preferably 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 ⁇ 1 mol, and more preferably 1 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 2 mol, per 1 liter of the developer.
  • Examples of a silver contamination preventing agent in the developer can include compounds disclosed in JP-A No. 56-24347, JP-B Nos. 56-46585, and 62-2849, and JP-A No. 4-362942.
  • the developer may include a dye agent, a surface active agent, an antifoam agent, and a hardener.
  • the developing temperature and time are related to each other and the developing temperature is determined by a relationship with the total processing time and is preferably in the range of about 20° C. to 50° C. and more preferably 25° C. to 45° C.
  • the developing time is preferably 5 sec to 2 min and more preferably 7 sec to 90 sec.
  • the developer may be concentrated and then, diluted at the time of use. In order to concentrate the developer, it is effective to convert a salt component contained in the developer into a corresponding potassium salt.
  • the developing process of the present invention may include a fixing process for removing silver salt from a non-exposure portion to perform stabilization.
  • a technology for a fixing process used for a silver salt photographic film, photographic paper, a printing film, or a emulsion mask for photomask can be employed.
  • the fixing solution preferably includes sodium thiosulfate, ammonium thiosulfate, if necessary, tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanic acid, tiron, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, nitrilotriacetic acid, or salts thereof.
  • boric acid is not included.
  • the fixing agent of the fixing solution used in the present invention may be sodium thiosulfate or ammonium thiosulfate. Although ammonium thiosulfate is preferable in view of the fixing speed, sodium thiosulfate may be used in view of recent environmental protection consideration.
  • the amount of the fixing agent may be appropriately changed and is preferably in the range of about 0.1 to 2 mol/liter and more preferably 0.2 to 1.5 mol/liter.
  • the fixing solution may include a hardener (for example, an aqueous aluminum compound), a preservative (for example, sulfite or bisulfite), a pH buffer agent (for example, acetic acid), a pH adjuster (for example, ammonia or sulfuric acid), a chelate agent, a surface active agent, a wetting agent, and a fixation accelerant as desired.
  • a hardener for example, an aqueous aluminum compound
  • a preservative for example, sulfite or bisulfite
  • a pH buffer agent for example, acetic acid
  • a pH adjuster for example, ammonia or sulfuric acid
  • a chelate agent for example, a surface active agent, a wetting agent, and a fixation accelerant as desired.
  • the surface active agent may be, for example, an anion surface active agent such as a sulfur oxide or a sulfone compound, a polyethylene-based surface active agent, or an ampholytic surface active agent disclosed in JP-A No. 57-6740.
  • An antifoam agent may be added to the fixing solution.
  • the wetting agent can include an alkanolamine or an alkylene glycol.
  • the fixation accelerant can include a thiourea derivative disclosed in JP-A Nos. 45-35754, 58-122535, and 58-122536, an alcohol having a triple bond in a molecule, a thioether compound disclosed in U.S. Pat. No.
  • the pH buffer agent can include organic acid such as acetic acid, malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, and adipic acid or an inorganic buffer agent such as boric acid, phosphate, or sulfite.
  • the pH buffer agent is used for preventing the pH of the fixing solution from increasing due to the introduction of the developer, and the amount thereof is preferably in the range of 0.01 to 1.0 mol/liter and more preferably in the range of 0.02 to 0.6 mol/liter.
  • the pH of the fixing solution is preferably in the range of 4.0 to 6.5 and more preferably in the range of 4.5 to 6.0.
  • the dye elution accelerant can include compounds disclosed in JP-A No. 64-4739.
  • Examples of a hardener of the fixing solution of the present invention can include aqueous aluminum salt and chromium salt.
  • the hardener is preferably an aqueous aluminum salt such as aluminum chloride, aluminum sulfate, or potassium alum.
  • the amount of the hardener to be added is preferably in the range of 0.01 to 0.2 mol/liter and more preferably in the range of 0.03 to 0.08 mol/liter.
  • the fixing temperature of the fixing process is preferably in the range of about 20° C. to about 50° C. and more preferably 25 to 45° C.
  • the fixing time is preferably in the range of 5 sec to 1 min and more preferably 7 sec to 50 sec.
  • the amount of the fixing solution to be replenished is preferably 600 ml/m 2 or less, more preferably 500 ml/m 2 or less, and most preferably 300 ml/m 2 or less.
  • the photosensitive material which is subjected to the developing and fixing processes is preferably subjected to a cleaning process or a stabilizing process.
  • the amount of cleaning water is generally 20 liters per 1 m 2 or less, and the cleaning process may be performed with the replenishment amount of 3 liters or less (including 0, that is, a cleaning process using stored water).
  • a multi-step counter flow method for example, two steps or three steps has been conventionally known.
  • the photosensitive material after fixing gradually moves in a regular direction, that is, in a direction of a treatment solution which is not contaminated by the fixing solution, and thus, a cleaning process having good efficiency is performed.
  • a cleaning bath having a squeeze roller or a crossover roller which is disclosed in JP-A Nos. 63-18350 and 62-287252, is more preferably used.
  • addition of oxidizers and/or filtration may be incorporated into the process.
  • a portion or all of overflow solution from a cleaning bath or a stabilizing bath generated by replenishing water containing fungicidal means in the cleaning bath or the stabilizing bath may be used in a treating solution having fixing performance of a previous process as disclosed in JP-A No. 60-235133.
  • an aqueous surface active agent or an antifoam agent may be added.
  • a dye absorbing agent disclosed in JP-A No. 63-163456 may be provided in the cleaning bath in order to prevent contamination due to dye eluted from the photosensitive material.
  • a bath containing compounds disclosed in JP-A Nos. 2-201357, 2-132435, 1-102553, and 46-44446 may be used as a final bath for the photosensitive material.
  • an ammonium compound, a metal compound such as a Bi or Al compound, a fluorescent bleaching, various chelate agents, an adjuster of pH of a film, a hardener, a germicidal agent, a fungicide, alkanolamine or a surface active agent may be added.
  • Water used for the cleaning process or the stabilizing process is preferably deionized water or water sterilized with halogen or ultraviolet rays or various oxidizing agents (ozone, hydrogen peroxide, or chlorate).
  • tap washing water containing compounds disclosed in JP-A Nos. 4-39652 and 5-241309 may be used.
  • the bath temperature and time are preferably 0 to 50° C. and 5 sec to 2 min, respectively.
  • the treatment solution such as the developer or the fixing solution used in the present invention is preferably stored by a packing material having low oxygen permeability disclosed in JP-A No. 61-073147.
  • a contact area between the treatment bath and air is preferably decreased to prevent evaporation of the solution or air oxidization.
  • the roller carrying type automatic developing machine is disclosed in U.S. Pat. Nos. 3,025,779 and 3,545,971 and is referred to as a roller carrying type processor in the specification.
  • the roller carrying type processor preferably includes four processors performing development, fixation, cleaning and drying processes. In the present invention, the other processes (for example, a stopping process) are not excluded, but most preferably, all these four processes are performed in the present invention.
  • the four processes can include a stabilizing process instead of the cleaning process.
  • a component obtained by removing water from the composition of the developer or the fixing solution may be supplied in a solid state and dissolved with a predetermined amount of water to be used as the developer or the fixing solution.
  • a treating agent is called a solid treatment agent.
  • the solid treating agent may be provided as a powder, a tablet, a granule, a lump, or a paste.
  • the treating agent is more preferably provided in a form disclosed in JP-A No. 61-259921 or in a tablet. Examples of a method for manufacturing the tablet can include general methods disclosed in JP-A Nos. 51-61837, 54-155038, and 52-88025 and U.K. Patent No. 1,213,808.
  • the granular treating agent may be manufactured by general methods disclosed in JP-A Nos. 2-109042, 2-109043, 3-39735 and 3-39739.
  • the powdered treating agent may be manufactured by general methods disclosed in JP-A No. 54-133332, U.K. Patent Nos. 725,892 and 729,862 and German Patent No. 3,733,861.
  • the volume density of the solid treating agent is preferably in the range of 0.5 to 6.0 g/cm 3 and more preferably 1.0 to 5.0 g/cm 3 in view of solubility.
  • a method for disposing reactive materials in a layered form such that at least two kinds of granular materials of the treating agent, which react with each other, are separated from each other by at least one interposed layer using a material which is inert to a reactive material, using a bag which can be vacuum packed as a packing material, and evacuating and sealing the bag may be used.
  • inert described herein means that a reaction is hardly generated under a general state in the package when the materials are physically brought into contact with each other.
  • the inert material is not active in the use of the two reactive materials, aside from that the inert material is inert to the two reactive materials.
  • the inert material is simultaneously used with the two reactive materials.
  • hydroquinone and sodium hydroxide react with each other when brought into contact in a developer, however by arranging sodium sulfite between hydroquinone and sodium hydroxide as a separation layer in a vacuum package, long-term storage of the vacuum package is possible.
  • hydroquinone or the like may be solidified to reduce a contact area with sodium hydroxide so as to improve storage stability and enable combined use thereof.
  • the packing material of the vacuum packing material may be a bag made of an inert plastic film, a laminate of a plastic material and a metal foil.
  • the content ratio of the mass of the metal silver contained in the exposure portion after the developing process to the mass of silver contained in the exposure portion before exposure is preferably 50 mass % or more and more preferably 80 mass % or more.
  • the content ratio of the mass of the metal silver contained in the exposure portion after the developing process to the mass of silver contained in the exposure portion before exposure is 50 mass % or more, it is possible to preferably obtain high conductivity.
  • the gradation after the developing process in the present invention is not particularly limited, but is preferably more than 4.0.
  • the gradation after the developing process is more than 4.0, it is possible to increase conductivity of a conductive metal portion while maintaining high transparency of a light transmission portion.
  • the above-described doping of rhodium ions or iridium ions may be used.
  • the conductive metal particles can be immersed in the metal silver portion by either one of the physical development and the plating process. However, the conductive metal particles may be immersed in the metal silver portion by combining the physical development and the plating process.
  • the metal silver portion which is subjected to the physical development and/or the plating process is referred to as the “conductive metal portion.”
  • the physical development in the present invention refers to reduction of metal ions such as silver ions into metal particles and deposition of the metal particles onto nuclei of a metal or a metal compound. This physical development is used in an instant B&W film, an instant slide film or a printing plate, and the same technique can be applied to the present invention.
  • the physical development may be performed simultaneously with the developing process after exposure or separately performed after the developing process.
  • the thickness of the plated layer was measured by cutting a part of the plated layer and then measuring a step difference of the cut section with a laser microscope made by KEYENCE CORPORATION.
  • the conveyance tension was measured by attaching a load-cell sensor to both sides of the cathode roller.
  • a “C2G1-25K” made by MINEBEA CO., LTD. was used as the sensor.
  • the range of measurement is 0 to 250 N.
  • a value obtained by precisely calculating and correcting the tension from the weight of the roller and the embracing angle of the film onto the cathode roller was used as the tension value.
  • a copper plated layer was formed with a thickness of 5 ⁇ m.
  • a plating circuit and a plating machine were constructed to have 16 units, each corresponding to the portion was encircled by the long dashed short dashed line in FIG. 2 .
  • a cylindrical tube of SUS316 with a diameter of 210 mm, a length of 800 mm, and a thickness of 10 mm was used as the cathode roller, and current was supplied thereto.
  • Protrusions on the cathode roller having a height of 0.5 mm, and a width of 1 mm were disposed at intervals of 20 mm, and were made of PVC.
  • a machine in which the pass distance of the film is 4 m when the film is passed through the in-liquid roller 101 A to the cathode roller 1 B from the cathode roller 1 A was used.
  • the pass distance means a distance from the vertex of one cathode roller to the vertex of an adjacent cathode roller. Accordingly, the total pass distance of the plating unit was in.
  • Pre-processing conditions, plating conditions, and rust-preventing conditions were as described in Table 1.
  • current density was set so that among two adjacent cathode rollers, higher current density was applied to the cathode roller located downstream with respect to the conveyance direction of the film.
  • the film tension was properly reduced at the speed controller 309 where the film is wrapped around in an S-shape as shown in FIG. 1 , and then the film was sequentially drawn by sequentially increasing the rotational speed of the rollers.
  • the tension was controlled by a drive motor speed of the speed controller 321 in a strength of 160 N/m on the basis of the pressure detected automatically by a load cell in the cathode roller 325 (tension detecting roller).
  • the conveyance speed was 4 m/min and the rotation of the motors driving the cathode rollers 1 A to 1 Q was set so that the cathode rollers 1 located downstream rotated at a higher rotation, and the film was drawn so that the tension of the film gradually increased.
  • the plated surface of the resultant copper-plated film was observed, and no irregular protrusions and no depressions were found, and thus, it was found that the copper-plated film has an excellent surface quality.
  • Example 2 In the same manner as described in Example 1, a silver halide photosensitive material was exposed in a mesh pattern, developed in black and white, and then, subjected to the same electro-plating process as that of Example 1 by using the same equipment.
  • a film with a conductive surface that was completely the same as that of the Example 1 was prepared.
  • a copper plated layer with a thickness of 5 ⁇ m was formed.
  • the plating machine and the plating circuit thereof had 16 units, each corresponding to the portion encircled by the long dashed short dashed line in FIG. 2 .
  • a cylindrical tube of SUS316 with a diameter of 210 mm, a length of 800 mm, and a thickness of 10 mm was used as the cathode roller, and current was supplied thereto.
  • Protrusions on the cathode roller having a height of 0.5 mm, and a width of 1 mm were disposed at intervals of 20 mm and were made of PVC.
  • a machine that the pass distance of the film is 4 in when the film is passed from the cathode roller 1 A to the cathode roller 1 B was used.
  • the pass distance means a distance from the vertex of one cathode roller to the vertex of an adjacent cathode roller. Accordingly, the total pass distance of the plating unit was 64 m.
  • the pre-processing conditions, the plating conditions, and the rust-preventing conditions were as described in Table 1.
  • current density was set so that among two adjacent cathode rollers, higher current density was applied to the cathode roller located downstream with respect to the conveyance direction of the film.
  • the film tension was properly reduced at the speed controller 309 where the film is wrapped around in an S-shape as shown in FIG. 1 , and then the film was sequentially drawn by sequentially increasing the rotational speed of the rollers.
  • the tension was controlled by a drive motor speed of the speed controller 321 in a strength of 160 N/m on the basis of the pressure detected automatically by a load cell in the cathode roller 325 (tension detecting roller).
  • the conveyance speed was 4 m/min and the rotation of the motors driving the cathode rollers 1 A to 1 Q was set so that the cathode rollers 1 located downstream rotated at a higher rotation and the film was drawn so that the tension of the film gradually increased.
  • the plated surface of the resultant copper-plated film was observed, and no irregular protrusions and no depressions were found, and thus, it was found that the copper-plated film had an excellent surface quality.
  • the apparatus and method according to the present invention are suitable for manufacturing laminated films such as a laminated film of electroplated layers in which the electroplated layer is formed after photosensitive silver salt film is exposed in pattern and developed, a pattern is formed on the surface of the film out of developed silver particles, and then the electroplated layer is formed, a laminated film of a metal deposited layer and a metal plated layer in which metal is deposited on a film and then a plated layer is formed thereon, and a laminated film of an electroless plated layer and an electroplated layer in which a film is electroless plated and then the electroplated layer is formed thereon.
  • the laminated films manufactured by the use of the apparatus and method according to the present invention are suitably used for manufacturing a substrate for a two-layered flexible printed circuit board without any adhesive and a flexible printed circuit board used for TAB, COF, and PGA in semiconductor packaging, in addition to an electromagnetic shielding material.

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* Cited by examiner, † Cited by third party
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US11519093B2 (en) 2018-04-27 2022-12-06 Modumetal, Inc. Apparatuses, systems, and methods for producing a plurality of articles with nanolaminated coatings using rotation
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Families Citing this family (9)

* Cited by examiner, † Cited by third party
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US9725817B2 (en) * 2011-12-30 2017-08-08 Ashworth Bros., Inc. System and method for electropolishing or electroplating conveyor belts
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JP2016178041A (ja) * 2015-03-20 2016-10-06 昭和電線ケーブルシステム株式会社 超電導線材の製造方法及び超電導線材の製造装置
KR102620936B1 (ko) * 2023-08-14 2024-01-08 주식회사 우성이엔지 2차전지 동도금 초박판 필름소재 롤투롤 반송 시스템

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3264143A (en) * 1962-07-16 1966-08-02 Selas Corp Of America Heat treating strip material
US4282073A (en) * 1979-08-22 1981-08-04 Thomas Steel Strip Corporation Electro-co-deposition of corrosion resistant nickel/zinc alloys onto steel substrates
US4755271A (en) * 1986-07-28 1988-07-05 Siemens Aktiengesellschaft Electroplating apparatus for plate-shaped workpieces, particularly printed circuit boards
US4978431A (en) * 1989-08-07 1990-12-18 Eltech Systems Corporation Continuous electroplating of conductive foams
US5737846A (en) * 1996-11-22 1998-04-14 Mitsubishi Semiconductor America, Inc. Lead frame dryer
US6471848B1 (en) * 1998-02-17 2002-10-29 Canon Kabushiki Kaisha Electrodeposition method of forming an oxide film
US20040229028A1 (en) * 2002-12-27 2004-11-18 Fuji Photo Film Co., Ltd. Method for producing light-transmitting electromagnetic wave-shielding film, light-transmitting electromagnetic wave-shielding film and plasma display panel using the shielding film
US20050150773A1 (en) * 2003-12-08 2005-07-14 Canon Kabushiki Kaisha Method for forming deposition film and method for producing photovoltaic device

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03188296A (ja) * 1989-12-18 1991-08-16 Kawasaki Steel Corp めっき設備
JPH05140797A (ja) * 1991-11-18 1993-06-08 Sumitomo Metal Ind Ltd 連続電気めつき鋼帯の製造方法
JPH06346279A (ja) * 1993-06-03 1994-12-20 Kawasaki Steel Corp めっき密着性に優れた両面めっき鋼板の製造方法
JPH08127896A (ja) * 1994-10-28 1996-05-21 Nippon Steel Corp 金属ストリップの連続電気めっき装置
JPH08333698A (ja) * 1995-06-07 1996-12-17 Nippon Steel Corp 高速処理ラインにおける鋼板の液切り装置
JP4641719B2 (ja) * 2002-12-27 2011-03-02 富士フイルム株式会社 透光性電磁波シールド膜の製造方法及び透光性電磁波シールド膜
JP4279606B2 (ja) * 2003-06-11 2009-06-17 東洋鋼鈑株式会社 フィルムめっき材料の製造方法及び製造装置

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3264143A (en) * 1962-07-16 1966-08-02 Selas Corp Of America Heat treating strip material
US4282073A (en) * 1979-08-22 1981-08-04 Thomas Steel Strip Corporation Electro-co-deposition of corrosion resistant nickel/zinc alloys onto steel substrates
US4755271A (en) * 1986-07-28 1988-07-05 Siemens Aktiengesellschaft Electroplating apparatus for plate-shaped workpieces, particularly printed circuit boards
US4978431A (en) * 1989-08-07 1990-12-18 Eltech Systems Corporation Continuous electroplating of conductive foams
US5737846A (en) * 1996-11-22 1998-04-14 Mitsubishi Semiconductor America, Inc. Lead frame dryer
US6471848B1 (en) * 1998-02-17 2002-10-29 Canon Kabushiki Kaisha Electrodeposition method of forming an oxide film
US20040229028A1 (en) * 2002-12-27 2004-11-18 Fuji Photo Film Co., Ltd. Method for producing light-transmitting electromagnetic wave-shielding film, light-transmitting electromagnetic wave-shielding film and plasma display panel using the shielding film
US20050150773A1 (en) * 2003-12-08 2005-07-14 Canon Kabushiki Kaisha Method for forming deposition film and method for producing photovoltaic device

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11242613B2 (en) 2009-06-08 2022-02-08 Modumetal, Inc. Electrodeposited, nanolaminate coatings and claddings for corrosion protection
CN104271814A (zh) * 2012-05-10 2015-01-07 印可得株式会社 连续电镀装置
US20160002813A1 (en) * 2013-03-15 2016-01-07 Modumetal, Inc. Method and Apparatus for Continuously Applying Nanolaminate Metal Coatings
US11851781B2 (en) 2013-03-15 2023-12-26 Modumetal, Inc. Method and apparatus for continuously applying nanolaminate metal coatings
US11118280B2 (en) 2013-03-15 2021-09-14 Modumetal, Inc. Nanolaminate coatings
US11168408B2 (en) 2013-03-15 2021-11-09 Modumetal, Inc. Nickel-chromium nanolaminate coating having high hardness
US11692281B2 (en) 2014-09-18 2023-07-04 Modumetal, Inc. Method and apparatus for continuously applying nanolaminate metal coatings
US11560629B2 (en) 2014-09-18 2023-01-24 Modumetal, Inc. Methods of preparing articles by electrodeposition and additive manufacturing processes
US20170136503A1 (en) * 2015-11-13 2017-05-18 Sumitomo Chemical Company, Limited Film producing method and film washing device
US20190005859A1 (en) * 2015-12-21 2019-01-03 Siemens Aktiengesellschaft Representation of specific information on an apparatus
US10453364B2 (en) * 2015-12-21 2019-10-22 Siemens Aktiengesellschaft Representation of specific information on an apparatus
CN108431884A (zh) * 2015-12-21 2018-08-21 西门子股份公司 关于设备的特定信息的显示
US11365488B2 (en) 2016-09-08 2022-06-21 Modumetal, Inc. Processes for providing laminated coatings on workpieces, and articles made therefrom
US11286575B2 (en) 2017-04-21 2022-03-29 Modumetal, Inc. Tubular articles with electrodeposited coatings, and systems and methods for producing the same
US20220020591A1 (en) * 2018-01-25 2022-01-20 Semsysco Gmbh Method and device for plating a recess in a substrate
US11908698B2 (en) * 2018-01-25 2024-02-20 Semsysco Gmbh Method and device for plating a recess in a substrate
US11519093B2 (en) 2018-04-27 2022-12-06 Modumetal, Inc. Apparatuses, systems, and methods for producing a plurality of articles with nanolaminated coatings using rotation
CN109531893A (zh) * 2018-10-11 2019-03-29 徐州华邦塑业有限公司 一种eva胶膜除湿装置
WO2022134491A1 (zh) * 2020-12-24 2022-06-30 重庆金美新材料科技有限公司 一种防止电镀设备挤液组件镀液结晶的装置及方法
CN114214711A (zh) * 2021-11-22 2022-03-22 重庆金美新材料科技有限公司 一种多功能复合薄膜生产加工系统和生产加工方法
CN114717623A (zh) * 2022-02-07 2022-07-08 昆山鑫美源电子科技有限公司 一种导电薄膜生产设备和生产方法

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