APPARATUS AND METHOD FOR MANUFACTURING PLATED FILM
A conductive surface 5 of a film 4 is plated with copper by allowing the film 4 to pass through a plating solution 7 in a plating bath 6 while conveying the film in a direction indicated by the arrow. Air knife devices 20A and 20B are disposed between the plating solution 7 and a next cathode roller 1B so as to face a conductive surface 5 of the film 4. The air knife devices 20A and 20B remove liquid and moisture on the conductive surface 5 by jetting heated air to the conductive surface 5 drawn out of the plating solution 7. Accordingly, even when the conductive surface 5 comes in contact with the next cathode roller 1B, developed silver is not dissolved, thereby preventing the silver contamination of the cathode rollers 1B and 1C.
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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. Specifically, 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.
As 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. By continuously forming the plated layer on the film by passing the film repeatedly through a unit in which a cathode and an anode are disposed, it is possible to form a desired thickness of plated layer such as a thick plated layer on the film.
In 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), when 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 μm to 40 μm are formed, the conductive metal portion has conductivity of 10Ω/□ to 500Ω/□ and can be continuously plated with metal (for example Cu) by electroplating in principle.
However, since the conductivity of 10Ω/□ to 500Ω/□ 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.
Recently, in order to solve the above-mentioned problem, as described in JP-A No. 2004-263215, there has been suggested a method of supplying electricity while rotatably pressing a sphere-shaped body on the back surface of the film to urge contact between the conductive surface of the film and the cathode roller. However, in the method, although the contact between the conductive surface and the cathode roller is urged, liquid between the conductive surface and the cathode roller is not removed completely, and thus, it is not possible to solve the problem that a part of the developed silver is dissolved in the liquid film to cause the silver contamination of the cathode roller or the film peeling.
In this situation, when plating the light-transmitting conductive film which is formed by patterning a conductive portion and a visible-ray transmitting portion using a developed silver obtained by developing a silver halide photosensitive material, it is difficult to directly perform the electroplating. Accordingly, firstly, electroless copper plating is performed on the film so that the surface resistance of the film is about 2Ω/□, and then the film is plated with copper by the use of the method described in JP-A No. 7-22473 or the method described in JP-A No. 2004-263215.
However, in the method in which electroless copper plating is employed, the process is lengthened, and the cost of chemicals is increased, whereby the cost of the product is increased.
A transparent electromagnetic shielding film and a manufacturing method thereof are disclosed in JP-A Nos. 2004-221564 and 2004-221565. In these patent documents, 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.
According to a first aspect of the present invention, there is provided 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.
In the plated film manufacturing apparatus, by repeating plural times a process of forming a plated layer formed on the conductive surface of a film having a conductive surface in the plating solution with the conductive surface contacting with the cathode roller while conveying the film having the conductive surface, a plated film having a desired thickness of plated layer is manufactured. The number of repetitions is preferably 10 to 30.
In addition, since 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.
By the above-mentioned apparatus, even when both surfaces of the film going out of the plating solution in the plating bath are cleaned, the liquid or the moisture on the plated layer is removed by the moisture removing device. Accordingly, the elution of silver does not occur, and thus it is possible to prevent silver contamination of the 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/m2 or less.
By the above-mentioned apparatus, since 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/m2 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.
By the above-mentioned apparatus, since 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.
By the above-mentioned apparatus, by jetting heated air or dehumidified air to the plated layer, 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, heating the plated layer with infrared rays and jetting heated air or dehumidified air to the plated layer, or jetting heated steam to the back surface of the film and jetting heated air or dehumidified air to the plated layer, 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 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 μm to 40 μm, 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.
According to 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.
According to a twelfth aspect of the present invention, there is provided a method for manufacturing a plated film in which a desired thickness of a plated layer is obtained by repeating in plural times a process of bringing the conductive surface into contact with a cathode roller and forming the plated layer on a conductive surface of a film in a plating solution while conveying the film having the conductive surface, wherein liquid or moisture on the plated layer formed on the conductive surface is removed before the film that has passed through the plating solution in a plating bath comes in contact with the subsequent cathode roller.
In the method according to the eleventh aspect, since the liquid or moisture on the plated layer is removed by the time the film going out of the plating solution in the plating bath comes in contact with the subsequent cathode roller, no solvent for dissolving sliver is present and elution of silver does not occur, whereby silver contamination of the cathode roller is prevented.
ADVANTAGESIn the apparatus and method for manufacturing a plated film according to the present invention, since the liquid on the plated layer or the moisture therein is removed by the time the film going out of the plating solution in the plating bath comes in contact with the subsequent cathode roller, dissolution of silver does not occur, and it is thus possible to prevent silver contamination of the cathode rollers.
A best mode of an apparatus and a method for manufacturing a plated film according to the present invention will be described with reference to the drawings.
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
In
As shown in
In the present embodiment, the cases 102A and 102B in which copper balls are stacked and filled are used as the anodes, and current of 1 A is supplied to the cases 102A and 102B as the copper anodes from the cathode rollers 1 by the DC source 3A so that the current density of the film 4 is 0.2 to 10 A/dm2, thereby forming the plated layer on the film 4. Here, the current density is a value obtained by dividing the current supplied from the DC source 3A 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
The conductive surface 5 of the film 4 contacting the cathode roller 1A comes in contact with the cathode roller 1B after going out of the plating solution 7. An air knife device 20A 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 1B. The air knife device 20A serves to remove the plating solution on the plated layer formed on the conductive surface 5 or the moisture therein. In addition, the conductive surface 5 of the film 4 contacting the cathode roller 1B comes in contact with the cathode roller 1C after going out of the plating solution 7. An air knife device 20B 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 1C. Although not shown, similarly, 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.
As shown in
In the present embodiment, a Super Air Knife Mod. 110036 (trade name) made by BLOVAC CO., LTD. is used as the air knife devices 20A and 20B. The effective width of the air knife is 910 mm, the pressure thereof is 2.8 kg/cm2, the flow rate is 36 mm/sec, and the air consumption is 144 L/min.
As shown in
In order to maintain uniformity of the plated layer, fresh air 331A to 331D is introduced into the plating bath 6 from air inlets (air agitating nozzles) 330A to 330D, 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. Although not shown, the plating solution 7 is always circulated with contamination removed by a filter.
Subsequently, as shown in
The practical film conveyance tension is preferably 10 N/m to 320 N/m. When the tension is substantially less than 10 N/m, the film wobbles, thereby making it difficult to control the conveyance path. When 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. In the machine shown in
Enlarged views of cathode rollers according to second to sixth embodiments of the present invention are shown in
As shown in
As shown in
As shown in
In a fifth embodiment shown in
Although the heating roller 60 is disposed so as to face the back side surface of the film 4 in the example shown in
In a sixth embodiment, as shown in
In the example shown in
In a seventh embodiment, as shown in
The plating machine 10 shown in
In
Although the drying process is performed by jetting the heated air to the plating surface in the example shown in
Next, the plated film is described in detail.
Polyimide resin or polyester resin can be preferably used as a material for the plated film.
Specific examples of 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-α,β-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.
Among films made from the above materials, 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.
(where X denotes one of H, CH3, F, or Cl groups)
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.
(wherein X denotes one of H, CH3, F, or Cl groups, and m and n denote integers of 0 to 3)
As a light-transmitting conductive film used for a PDP, a film having a substrate thickness of 50 to 150 μm, and more preferably having a substrate thickness of 75 to 100 μm is preferably used.
(Method for Forming Transparent Conductive Metal Film)An example of a method according to the present invention, wherein a transparent conductive metal film is formed by exposing a silver halide photosensitive material in a mesh pattern and developing the film in black and white, and the metal silver (developed silver) portion is plated with copper, is described below.
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:
(1) a process of chemically developing a silver halide black-and-white type photosensitive material not containing physical development seeds and forming a metal silver portion thereon;
(2) a process of physically developing a silver halide black-and-white type photosensitive material containing physical development seeds in a silver halide emulsion layer and forming a metal silver portion thereon; and
(3) a process of covering a silver halide black-and-white type photosensitive material not containing physical development seeds with an image receiving sheet having a non-photosensitive layer containing physical development seeds so as to diffuse the silver halide in the photosensitive material to the image receiving sheet and developing the diffused photosensitive material to form a metal silver portion thereon.
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.
In the process (2), 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. 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.
In the process (3), 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.
In any of the processes (1) to (3), 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).
The chemical development, the dissolved physical development, and the diffused conveyance development described above have the same meaning as generally used in the art. General meaning of the terms are described in general text books for photographic chemistry such as “Photographic Chemistry” (published by Kyoritsu Shuppan) written by Shinichi Kikuchi, and “The Theory of Photographic Process, 4th ed.” edited by C. E. K. Mees.
<Photosensitive Material>(Support Body)
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. Examples of 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).
In the present invention, in view of transparency, heat resistance, convenience of handling, and cost, the plastic film is preferably a polyethylene terephthalate film.
Since transparency is required in an electromagnetic shielding material for a display, the transparency of the support body is preferably high. In this case, 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%. In the present invention, 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 μm to 100 μm.
When a glass plate is used as the support body in the present invention, types of the glass plate are not particularly limited. However, when it is used as an electromagnetic shield for a display, 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.
[Protective Layer]In the photosensitive material, a protective layer is preferably formed on an emulsion layer that is to be described later. In the present invention, 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 μm, preferably in the range of 0.1 to 10 μm, and more preferably in the range of 0.3 to 3 μm. 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.
(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.
<Dye>
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. Examples of 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.
Among the dyes used in the present invention, 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. 3-136038, a pyrylium dye described in JP-A No. 62-299959, a polymer-type cyanine dye described in JP-A No. 7-253639, a solid particle dispersion substance of an oxonol dye described in JP-A No. 2-282244, light scattering particles described in JP-A No. 63-131135, a Yb3+ compound described in JP-A No. 9-5913, and ITO powders described in JP-A No. 7-113072. Dyes shown by Formulae F1 and F2 described in JP-A No. 9-179243, and specifically, compounds F35 to F112 described in the same publication can be used.
The dye can include an aqueous dye. Examples of the aqueous dye can include an oxonol dye, a benzylidene dye, a merocyanine dye, a cyanine dye, and an azo dye. Among them, 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.
<Silver Salt>
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.
In the present invention, 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. For example, 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.
Here, “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 μm) 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 (so-called reverse mixing process) may be used to form the silver particles. As an example of the whole 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.
It is also preferable that particles are formed by the use of so-called silver halide solvent such as ammonia, thioether, or 4-substituted thiourea. In this method, 4-substituted urea compounds are more preferable, which are described in JP-A Nos. 53-82408 and 55-77737. Preferable examples of 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.
By the controlled double jet process using the silver halide solvent, it is easy to form the silver halide emulsion having a regular crystal shape and a narrow distribution of particle sizes, and thus it can be preferably used in the present invention. In order to make the particle sizes uniform, 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. 4,242,445 and JP-A No. 55-158124. 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. Examples of 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. For increase in sensitivity, the doping of 6-cyanide metal complex such as K4(Fe(CN)6 or K4(Ru(CN)6 is preferably performed.
An aqueous rhodium compound can be used as the rhodium compound. Examples of 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 K3Rh2Br9.
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. Instead of using aqueous rhodium, 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 K2IrCl6 or K3IrCl6, a hexabromo iridium complex, a hexamine iridium complex, and a pentachloro nitrosyl iridium complex.
Examples of the ruthenium compound can include hexachloro ruthenium, pentachloro nitrosyl ruthenium, and K4(Ru(CN)6.
Examples of the 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.
[ML6]−n (wherein M denotes Ru, Re, or Os and n denotes 0, 1, 2, 3, or 4)
In this case, counter ions are not important and ammonium or alkali metal ions are used. Preferable examples of the 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:
[ReCl6]−3, [ReBr6]−3, [ReCl5(NO)]−2, [Re(NS)Br5]−2, [Re(NO)(CN)5]−2, [Re(O)2(CN)4]−3, [RuCl6]−3, [RuCl4(H2O)2]−1, [RuCl5(NO)]−2, [RuBr5(NS)]−2, [Ru(CO)3Cl3]−2, [Ru(CO)Cl5]−2, [Ru(CO)Br5]−2, [OsCl6]−3, [OsCl5(NO)]−2, [Os(NO)(CN)5]−2, [Os(NS)Br5]−2, [Os(CN)6]−4, and [Os(O)2(CN)5]−4.
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.
In the present invention, 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. Here, “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. At this time, it is preferable that 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. However, in the present invention, since 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.
In the present invention, 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 PdCl4 or Na2PdCl4.
In the present invention, in order to enhance the sensitivity of the optical sensor, a chemical sensitization used for a photo emulsion may be performed. Examples of 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. When the chemical sensitization processes are used 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. Known compounds 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.
Known 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. Examples of 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. Specifically, 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. 4-204640, 4-271341, 4-333043, and 5-303157, J. Chem. Soc. Chem. Commun. 635 (1980), ibid 1102 (1979) and ibid 645 (1979), J. Chem. Soc. Perkin. Trans. 1, 2191 (1980), and “The Chemistry of Organic Selenium and Tellurium Compounds” edited by S. Patai, Vol. 1 (1986) and Vol. 2 (1987). The compounds expressed by Formulas II, III, and IV in JP-A No. 5-313284 are particularly preferable.
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.
Examples of 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.
In the present invention, the reduction sensitization can be performed. Examples of the reduction sensitizer can include tin salt, amine, formamidine sulfinic acid, and a silane compound. As described in EP Laid-Open No. 293917, a thiosulfonic acid compound may be added to the silver halide emulsion. In the present invention, 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. In order to obtain high contrast, as described in JP-A 6-324426, the closer to the support body, the more preferable it is to apply an emulsion having high sensitivity to form the emulsion layer.
<Binder>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. In the present invention, either of 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.
Examples of the binder can 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. These binders have a neutral property, a cationic property, or an anionic property, depending upon ionic properties of functional groups thereof.
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.
<Solvent>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 %.
<Processes> [Exposure]In the present invention, 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. Examples of 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. For example, a red luminescent substance, a green luminescent substance, a blue luminescent substance, or a mixture thereof can be used. However 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.
In the present invention, the exposure process can be preferably performed using a variety of laser beams. For example, 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 F2 laser may be also used. In order to make a system compact and cheap, it is more preferable that 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. Particularly, in order to design a device which is compact, cheap, long in lifetime, and high in safety, it is most preferable that the exposure process is performed using the semiconductor laser.
The energy for exposure is preferably 100 μJ/cm2 or less, more preferably 50 μJ/cm2 or less, and most preferably in the range of 4 μJ/cm2 to 40 μJ/cm2.
Specific examples of the laser source can include a blue semiconductor laser with a wavelength of 430 to 460 nm (announced by NICHIA CORPORATION at the 48th 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 LiNbO3 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 scan exposure method is preferably used to expose the layer containing silver salt in a pattern. Specifically, a laser scan exposure machine of a capstan type described in JP-A No. 2000-39677 is preferably used. In the capstan type, 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.
[Development]In the present invention, 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. As marketed products, 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. In addition, a lithography developer may be used.
D85 made by KODAK CO. can be used as the lithography developer. In the present invention, by performing the exposure process and the development process, 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.
In the present invention, a dihydroxybenzene developing agent can be used as the developer. Examples of 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. As the developer used in the manufacturing method according to the present invention, 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.
Specific examples of 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. Examples of the p-aminophenol assistant developing agent can include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl) glycin, but among these, N-methyl-p-aminophenol is preferable. In general, 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. When dihydroxybenzene and 1-phenyl-3-pyrazolidones or p-aminophenols are combined, it is preferable that 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.
In the present invention, 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.” In order to check whether the development initiating solution and the development replenishing solution having the property, 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. When increment in pH is 0.5 or less, it is determined that the solutions have the above-defined property. In the manufacturing method according to the present invention, 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. Examples of 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.
In the present invention, 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).
In the manufacturing method of the present invention, when 1 square meter of the photosensitive material is treated, 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 (hereinafter, the development initiating solution and the development replenishing solution are sometimes referred to collectively as “developer”) used for developing the photosensitive material in the present invention may include common additives (for example, preservative or chelate). Examples of the preservative can include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, sodium metabisulfite, and formaldehyde sodium bisulfite. The concentration of sulfite is preferably 0.2 mol/liter or more and more preferably 0.3 mol/liter or more. However, when the amount of the sulfite to be added is too large, the silver in the developer is contaminated, and thus, 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. As the preservative of a dihydroxybenzene developer, a small amount of a derivative of ascorbic acid may be used in addition to sulfite salt. Example of the derivative of ascorbic acid include ascorbic acid, erythorbin acid which is stereoisomer, and alkali metal salt (sodium or potassium salt). As the derivative of ascorbic acid, 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. When the derivative of ascorbic acid is used as the preservative, it is preferable that 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. Examples of the 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.
Various organic or inorganic chelate agents may be added to the developer. Examples of the inorganic chelate agent can include sodium tetrapolyphosphate or sodium hexametaphosphate. On the other hand, examples of the organic chelate can include organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid, and phosphonocarboxylic acid.
Examples of the 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.
Examples of the 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.
Examples of the 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.
For the purpose of reducing developer transporting cost, packing material cost and space, 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. In the fixing process of the present invention, 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.
Preferable components of the fixing solution used for the fixing process include the following. That is, 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. In view of recent environmental protection consideration, it is preferable that 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.
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. Examples of the wetting agent can include an alkanolamine or an alkylene glycol. Examples of 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. 4,126,459, a mesoion compound disclosed in JP-A No. 4-229860, or a compound disclosed in JP-A No. 2-44355. Examples of 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. Examples of 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/m2 or less, more preferably 500 ml/m2 or less, and most preferably 300 ml/m2 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. In the cleaning process or the stabilizing process, the amount of cleaning water is generally 20 liters per 1 m2 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). Thus, water can be saved, and it is not necessary to provide piping in an automatic developing machine. As a method for reducing the amount of the cleaning water, a multi-step counter flow method (for example, two steps or three steps) has been conventionally known. When the multi-step counter flow method is applied to the present invention, 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. When the cleaning process is performed with a small amount of water, 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. In order to reduce environmental pollution caused when performing the cleaning process in a small amount of water, addition of oxidizers and/or filtration may be incorporated into the process. In the above-described method, 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. In order to prevent a treating component attached to the squeeze roller from being conveyed onto the film and/or prevent spots due to foam that is prone to be generated upon cleaning with a small amount of water, an aqueous surface active agent or an antifoam agent may be added.
In the cleaning process or the stabilizing process, 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. In the stabilizing process following the cleaning process, 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. In the same process, if necessary, 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). In addition, tap washing water containing compounds disclosed in JP-A Nos. 4-39652 and 5-241309 may be used. In the cleaning process or the stabilizing process, 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. In order to reduce the replenished amount, 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.
In each 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. Such 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/cm3 and more preferably 1.0 to 5.0 g/cm3 in view of solubility.
When manufacturing the solid treating agent, 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. The term “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. For example, 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. Further, 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. When 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. When 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. As a means for maintaining the gradation of 0.4 or more, for example, the above-described doping of rhodium ions or iridium ions may be used.
[Physical Development and Plating Process]In the present invention, for the purpose of applying conductivity to a metal silver portion formed by the exposing and developing processes, physical development and/or a plating process for immersing conductive metal particles in the metal silver portion is performed. In the present invention, 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.
EXAMPLESIn the following examples, properties were measured by the methods described below.
(1) Thickness of Plated Layer
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.
(2) Conveyance Tension
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. In the specification thereof, 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.
Example 1 Formation of Plated LayerFive roll-shaped films of 650 mm by 400 m with a conductive layer attached thereto were prepared by dividing a roll-shaped film of 2000 in with a developed silver mesh pattern attached thereto, which was obtained in the process described in the above-described embodiment, into five roll-shaped films of 400 in. One of them was passed through a plating machine described below, thereby forming a plated layer.
By using the machine shown in
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 101A to the cathode roller 1B from the cathode roller 1A 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. In the copper plating, 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
The conveyance speed was 4 m/min and the rotation of the motors driving the cathode rollers 1A to 1Q 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.
Silver was not deposited on the surface of the cathode rollers 1A to 1Q, and the conveyance was performed stably. Thus, a roll-shaped film having an excellent winding shape was obtained.
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 2In 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.
(1) Preparation of a Film with Conductive Surface
A film with a conductive surface that was completely the same as that of the Example 1 was prepared.
(2) Formation of Plated layer
One of the roll-shaped films with a conductive layer attached thereto, which were obtained by dividing the roll-shaped film obtained in (1) into five, was passed through a plating machine described below to form a plated layer.
By using any one machine shown in
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 1A to the cathode roller 1B 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. In the copper plating, 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
The conveyance speed was 4 m/min and the rotation of the motors driving the cathode rollers 1A to 1Q 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.
Silver was not deposited on the surface of the cathode rollers, and the conveyance status was very stable. Thus, a roll-shaped film having an excellent winding shape was obtained.
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 embodiments of the present invention described above are intended to explain and describe the present invention, but it is not intended that the present invention is limited to the embodiments. It can be obviously understood by those skilled in the art that the embodiments can be variously modified. The embodiments are selected and described so as to best explain the basic principle of the present invention and the practical application thereof. Accordingly, it can be understood by those skilled in the art that the present invention can be modified in various embodiments and can be variously changed so as to be suitable for specific uses. It is intended that the scope of the present invention is determined only by the appended claims and equivalents thereof.
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.
Claims
1-12. (canceled)
13. 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 and the film is conveyed;
- a plurality of cathode rollers being disposed above the plating bath;
- a moisture removing device for removing the plating solution and moisture on the conductive surface so that the moisture content of the plated layer of the film is 7 g/m2 or less right before the film that has passed through the plating bath comes in contact with the subsequent cathode roller.
14. 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 and the film is conveyed;
- a plurality of cathode rollers being disposed above the plating bath;
- an air knife device for removing the plating solution and moisture on the conductive surface before the film that has passed through the plating bath comes in contact with the subsequent cathode roller.
15. 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 and the film is conveyed;
- a plurality of cathode rollers being disposed above the plating bath;
- a squeeze blade for removing the plating solution and moisture on the conductive surface before the film that has passed through the plating bath comes in contact with the subsequent cathode roller.
16. 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 with which the film that has passed through the plating bath contacts at the side of the conductive surface thereof; and
- a water-absorbing roller 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.
17. The apparatus of claim 13, wherein the moisture removing device cleans both surfaces of the film and then removes the plating solution and the moisture on the conductive surface before the film that has passed through the plating bath comes in contact with the subsequent cathode roller.
18. The apparatus of claim 14, wherein the air knife device cleans both surfaces of the film and then removes the plating solution and the moisture on the conductive surface before the film that has passed through the plating bath comes in contact with the subsequent cathode roller.
19. The apparatus of claim 15, wherein the squeeze blade cleans both surfaces of the film and then removes the plating solution and the moisture on the conductive surface before the film that has passed through the plating bath comes in contact with the subsequent cathode roller.
20. The apparatus of claim 16, wherein the water-absorbing roller removing device cleans both surfaces of the film and then removes the plating solution and the moisture on the conductive surface before the film that has passed through the plating bath comes in contact with the subsequent cathode roller.
21. The apparatus of claim 13 or 17, 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.
22. The apparatus of any one of claims 13 to 20, 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.
23. The apparatus of claim 21, 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.
24. The apparatus of claim 22, wherein the light-transmitting conductive film has the patterned conductive metal portion that is formed of mesh-shaped lines having a size of 1 μm to 40 μm, and the pattern is a 3 m or more continuous mesh pattern.
25. The apparatus of claim 23, wherein the light-transmitting conductive film has the patterned conductive metal portion that is formed of mesh-shaped lines having a size of 1 μm to 40 μm, and the pattern is a 3 m or more continuous mesh pattern.
26. The apparatus of claim 22, wherein the conductive metal portion is formed of developed silver obtained by developing a silver halide photosensitive material.
27. The apparatus of claim 23, wherein the conductive metal portion is formed of developed silver obtained by developing a silver halide photosensitive material.
28. The apparatus of claim 24, wherein the conductive metal portion is formed of developed silver obtained by developing a silver halide photosensitive material.
29. The apparatus of claim 25, wherein the conductive metal portion is formed of developed silver obtained by developing a silver halide photosensitive material.
30. The apparatus of any one of claims 13 to 20, wherein the plated layer is a copper layer.
31. The apparatus of any one of claims 13 to 20, wherein the transparent support member comprises polyimide resin or polyester resin.
32. The apparatus of any one of claims 13 to 20, wherein the anode is provided along the path of the film in the plating bath and comprising a case and a group of copper balls filled therein.
33. The apparatus of any one of claims 13 to 20, 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.
34. A method for manufacturing a plated film in which a desired thickness of a plated layer is obtained by repeating plural times a process of bringing a conductive surface of a film into contact with a cathode roller and forming the plated layer on the conductive surface in a plating solution conveying the film having the conductive surface,
- wherein the plating solution and moisture on the plated layer formed on the conductive surface is removed so that the moisture content of the plated layer is 7 g/m2 or less right before the film that has passed through the plating solution comes in contact with a subsequent cathode roller.
Type: Application
Filed: Jun 20, 2006
Publication Date: Apr 1, 2010
Applicant: FUJIFILM CORPORATION (Minato-ku, Tokyo)
Inventor: Tomoyoshi Hyodo (Minami-Ashigara-shi)
Application Number: 11/993,709
International Classification: C25D 7/06 (20060101); C25D 17/12 (20060101); C25D 17/02 (20060101);
