US3822127A - Process of producing metal images by amplification of diffusion transfer images - Google Patents

Process of producing metal images by amplification of diffusion transfer images Download PDF

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Publication number
US3822127A
US3822127A US00213542A US21354271A US3822127A US 3822127 A US3822127 A US 3822127A US 00213542 A US00213542 A US 00213542A US 21354271 A US21354271 A US 21354271A US 3822127 A US3822127 A US 3822127A
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images
silver
metal
solution
hydrophilic
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M Tsuboi
H Kamata
Y Suganuma
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/06—Silver salts
    • G03F7/07—Silver salts used for diffusion transfer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
    • G03C8/06—Silver salt diffusion transfer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
    • H05K3/106—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam by photographic methods

Definitions

  • the present invention relates to a process for producing a photographic image forming base plate and, in more detail, to a process for producing metal images which comprises carrying out electroless plating corresponding to silver images formed on a plastic surface.
  • Such metal images can be produced by a process which comprises exposing a photographic image-forming base plate prepared by applying a photosensitivesilver halide photographic emulsion onto a hydrophilic surface of a plastic rlilm which contains a nucleus substance for a diffusion transfer process, producing reversal silver images of the original on said hydrophilic surface part by the diffusion transfer process, removing the silver halide photographic emulsion layer, and intensifying the reversal silver images by electroless plating.
  • the present inventors have thus found that the electroless plating can be carried out on silver images photographically produced on a hydrophilic part of a plastic having a hydrophilic surface part. Furthermore, they have 3,822,127 Patented July 2, 1974 ICC found that such silver images can be produced on plastics having an oleophilic surface whereafter electroless plating can be practiced on said silver images.
  • One object of the present invention is to provide a process producing metal images by producing silver images photographically on a surface of a plastic, and thereafter practicing the electroless plating on said silver images (hereinafter, to plate the silver images with metal by electroless plating is called intensiication).
  • Another object of the present invention is to produce electrically conductive surface images by intensifying the silver images produced on the surface of a plastic.
  • a further object of the present invention is to produce metal images having a good thermal conductivity by intensifying the silver images produced on the surface of a plastic.
  • FIG. l is a sectional view of a photographic imageforming base plate used in the present invention.
  • FIG. 2 shows a state of exposing this base plate
  • FIG. 3 shows a photographic image forming base plate after treating with a diffusion transfer developer
  • FIG. 4 shows a photographic image forming base plate after electroless plating treatment.
  • any plastic is applicable provided that a diffusion transfer developing solution is permeable to silver halide photographic emulsion and that alkali solution is chemically permeable.
  • the degree of the hydrophilicity at the hydrophilic surface of the plastic lm or the plastic laminating layer can be indicated by, for example, a static contact angle toward the distilled water.
  • the following data is obtained by determining the static contact angle of the liquid drop of the distilled water fallen on a film at 25 C. in one minute using a microscope.
  • PET film passed through a propane gas-oxygen 48 ame at a rate of :1L/min. 8-.-.- Polyethylene (PE) film 93 9- PE hlm treated with corona discharge at 70 W. using 55 n electrode having 30 cm. in width at a distance of mm. 10. TAC film processed with coating and hardening. 27 11.
  • PE polyethylene
  • the hydrophilic lm includes partially saponitied polyvinyl alcohol hn, partially saponilied hydroxyethyl polyvinyl alcohol film, cellophane, polyethylene laminated cellophane, anti-humidity cellophane, polyethylene oxide films, methyl cellulose lms and gelatin film.
  • the hydrophilic portion must be thick more than 0.05, preferably more than 0.1;, which was confirmed by an electron microscope.
  • hydrophilic surface part includes the following three cases.
  • Plastic films wherein only the surface is treated to render the same hydrophilic, e.g., with a chemical agent, by corona discharge processing or by flame treatment.
  • Example (1a) A cellulose organic acid ester sheet which is originally oleophilic (cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate and cellulose acetate butyrate) is contacted with an aqueous solution of an alkali, a mixture of alkali containing water or a solvent or an alkali containing solvent. There will result a cellulose organic acid ester sheet only the surface of which becomes hydrophilic. In this case, the degree of hydrophilic property in the thickness direction of the sheet is not uniform, but lowers continuously from the surface to the interior of the sheet.
  • Example l-b Polyethylene terephthalate film is treated by flame treatment to give the same decreasing hydrophilic property.
  • Example (l-c) A polyethylene film is treated by corona discharging to give the same decreasing hydrophilic property.
  • Example (2-a) A cellulose triacetate film to which gelatin or polyvinyl alcohol is applied.
  • Example (2-b) A polyester film to which a vinyl chloride-vinyl acetate copolymer is initially applied and casein thereafter applied.
  • Hydrophilic plastic films For example, a polyvinyl alcohol film.
  • hydrophilic surface parts are made to contain diffusion transfer nuclei.
  • diffusion transfer nuclei are, for example, colloidal heavy metals such as colloidal silver, sulfur compounds such as silver sulfide, nickel sulfide, cadmium sulfide and zinc sulfide and selenium compounds such as silver selenide and nickel selenide, which are known substances commonly used in diffusion transfer processes.
  • the diffusion transfer nuclei may be introduced after production of the hydrophilic surface or may be added at the film forming process before carrying out the hydrophilic treatment.
  • the diffusion transfer nuclei may be introduced into the hydrophilic surface part after application of a hydrophilic
  • binder such as gelatin, gelatin derivatives, polyvinyl alcohol, casein, carboxymethyl cellulose and alginic acid, or the above-mentioned hydrophilic binder to which the diffusion transfer nuclei are added may be applied onto a surface of the oleophilic plastic films.
  • the minimum thickness of the hydrophilic layer containing diffusion transfer nucleus material is equal to the thickness of the hydrophilic layer or less than the thickness of the hydrophilic layer.
  • the thickness of the hydrophilic layer is more than 0.25/2, preferably more than 0.4p., it is confirmed by an electron microscope.
  • FIG. 1 shows a sectional view of a photographic image forming base plate used in the present invention, in which an oleophilic plastic sheet (for example, a cellulose organic acid ester sheet) 1 has a hydrophilic surface part 4 containing diffusion transfer nuclei 2 and a photosensitive silver halide photographic emulsion layer 3 applied thereto.
  • an oleophilic plastic sheet for example, a cellulose organic acid ester sheet
  • FIG. 2 shows the exposed state of the photographic image forming base plate of FIG. 1 which has been exposed to light through an original.
  • 3A represents an exposed part, that is a part corresponding to a non-image part of the original
  • 3B represents a non-exposed part, that is, a part corresponding to an image part of the original.
  • line drawings or half-tone images may be used.
  • Exposure may be carried out directly from a continuous gradation original using a screen. Exposure may be practiced by contact printing or enlarging.
  • the exposed photographic image forming base plate is then treated by a diffusion transfer development.
  • the developer which is used in the common diffusion transfer process contains a silver halide solvent together with a developing agent.
  • Representative silver halide solvents are, for example, thiosulfate compounds, thiocyanate compounds, and sodium sulfite.
  • FIG. 3 shows the photographic image forming base plate after treating with the diffusion transfer developer, in which silver images are formed on exposed parts 3A of the emulsion layer. These images are negative to the original.
  • silver images 1B are formed on the hydrophilic surface part 4 underneath unexposed parts 3B of the emulsion layer. These images are positive to the original, and are produced by diffusion of the complex salt of silver halide from the non-exposed parts 3B to the hydrophilic surface part 4 containing the diffusion transfer nuclei material 2 by silver halide solvent included in the developer, by which the complex salt is reduced at the site of the nuclei material 2 by the developing agent to produce metallic silver 1B.
  • the developed photographic image base plate is treated with warm water to remove the emulsion layer 3.
  • Complex salt of silver halide means silver complex compound, that is, soluble silver complex salt, for example, Ag(S2O3)-, Ag(S2O3)23-, Ag (S203 )a5-a Ag (SCN 2, etc-
  • FIG. 4 shows the state of the photographic image forming base plate after plating following removal of the emulsion layer 3. By the electroless plating, metal silver images 1B formed in the hydrophilic surface 4 are intensified by metal images 5.
  • gelatin or other natural or synthetic colloidal binders may 'be used.
  • the binder having a generic criteria is alkali permeable binder, hydrophilic binder or gelatin compatible binder.
  • Such binders include water-permeable or water-soluble polyvinyl alcohol and derivatives thereof, for example, partially saponified polyvinyl acetate [the one part of polyvinyl alcohol is saponified, and the other parts of polyvinyl alcohol are formed hydroxyl group. See the following.
  • Polyvinyl ether and acetals which contain many grafted groups -CH2CHOH- [graft-copolyymerized to many functional groups in polymer chain] and interpolymers of vinyl acetate and an addition-polymerizable unsaturated compounds such as maleic anhydride, ethyl acrylate, ethyl methacrylate and styrene.
  • the colloids lastly described type are disclosed in U.S. Pats. 2,276,322, 2,276,323 and 2,347,811.
  • Preferred polyvinyl acetals include polyvinyl acetaldehyde acetal, polyvinyl butyraldehyde acetal and polyvinyl sodium o-sulfobenzaldehyde acetal.
  • Other useful colloidal binders include poly-n-vinyl lactams as described in U.S. Pat. 2,495,918, copolymers of N-acrylamide alkylbetaine as described in U.S. Pat. 2,833,050, cellulose ethers and esters, colloidal albumin, zein and polyacrylamide.
  • the silver halide emulsions can contain silver chloride, silver bromide, silver iodide or mixtures thereof, and can be selected from the known emulsions containing optical sensitizers, chemical sensitizers, antifogging compounds, emulsion hardening agents, plasticizing compounds, wetting agents, toning agents and frosting agents.
  • an antihalation layer can be applied to the back of the support.
  • the metal images produced as above may be electrically conductive surface images and thermally conductive surface images.
  • the conductivity of the metal images is less than ⁇ 6 'K2/square, preferably less than 2 Q/square.
  • the difference is preferably 100 times between the con- ⁇ ductivity of the metal images and that of the backgrounds (non-image parts).
  • the silver images formed as shown in FIG. 3 are sometimes electrically conductive, but the electrical conductivity thereof is inferior to that of metal images produced by intensification, and the surface of the silver is easily injured.
  • the conductivity of the metal images produced by intensification can be controlled by conditions of the electroless plating treatment and the metal images are dicult to injure.
  • the plating thickness is important criterion, and is controlled by composition of the electroless plating bath, pH and temperature of bath. That composition contains an amount of the metal salt, a kind of the reducing agent and -an amount of the reducing agent, pH control-agent, complexing agent, reaction accelerator, etc.
  • electroless plating is also called chemical plating, and any metal such as nickel, copper, chromium, cobalt and tin may be used for intensifying the silver images of the invention.
  • Silver images produced by the prior art as described in,U.S. Pat. 3,033,765, Jap. Pat. Pub. No. Sho 45-25234 and British Pat. 1,183,907, or silver images formed on a multi-layer lm as described in Jap. Pat. P-ub. No. Sho 45-29876 have the faults that it is diicult to intensify with metal images by electroless plating, that the backg-round is soiled at intensification and intensiiication is weak.
  • metal Salt is palladium (II) chloride [PdCl2], hydrogen gold (IV) chloride [HAuCl4], diaminesilver nitrate [As(NH3)2N0-31, ete;
  • the present invention may not require sensitizing and hardly requires activating.
  • the activating will result in easy plating on the silver metal.
  • plating bath includes electroless plating bath of plastics, preferably electroless plating bath of low temperature type, and said temperature is less than the softening point of plastics.
  • Examples of the said electroless plating bath are as follows.
  • NICKEL PLATING BATH I. Nickel electroless plating bath (1) A. Brenners bath:
  • Nickel sulfate ..-g/l-- 40 Sodium citrate g./l 24 Sodium acetate g./1 14 Sodium hypophosphite ..g./l.. 20 Ammonium chloride g./1 5 pH 5.5 Temperature C 40 to 60 (2) H. Narcuss bath:
  • Nickel sulfate g./l 30 Sodium citrate g./l 10 Sodium succinate g./1 20 Sodium acetate g./l 20 Diethylaminoborazane ml 3 Methanol ml 50 Stabilizer g ll..- 0.01
  • Nickel sulfate g./l 50 Lactic acid g /1 25 Sodium citrate g./l 25 N-dimethylborazane g./l 2.5 Wetting agent (bubble-less) g./l 0.1 Thioglycol acid ..g./l 1.5 pH (by NH4OH) 7.0
  • Nickel sulfate g./l 30 Ethylenediamine g./l 60
  • Sodium boron hydroxide g./l 0.6 stabilizer (1) pH Temperature C-- 90 to 95 1 A small amount.
  • Copper sulfate g./1 30 l15 29 29 5 Sodium carbonate, g. 30 2 10 25 Potassium sodium tartr 100 30 140 140 25 Sodium hydroxide, g./l 50 20 40 40 7 Foi-malin 37% solution, m1./1. 30 10o 166 166 10 Versene T, g./l.*.-. 17 pH 11.5 11.5 11.5 Temperature C.) 24 24 21 21 l Copper nitrate. 2 Sodium bicarbonate. Mixture of EDTA and triethylamine at equal mol.
  • Narcuss bath Furthermore, the present invention can be utilized for A solution: G./l. producing a base plate for thermoprinting and thermo- Copper sulfate 60 copying, if the metal images are produced on the surface Nickel sulfate 16 of a plastic which is a thermal nonconductor. Hydraziue sulfate 45 As described above, the present invention has many B solution: industrial uses and many advantages. The metal images Sodium hydroxide 45 20 produced are very sharp and have a high electric cOn- Potassium sodium tartrate 180 ductivity and a good thermal conductivity. Sodium carbonate 15 The present invention will be explained in more detail by the following examples: (All thickness in the Exam- Mixing A and B solution before using. ples are dry thickness.)
  • the metal images produced by the present invention have many advantages. These advantages are as follows: (1) a high electric conductivity and a good thermal conductivity in the metal image area; (2) a high electric resistivity in the non-metal image area (background); (3) rapidness, that is, exposure is rapidly practiced and subsequent treatments are easily carried out; and (4) the metal image area is not injured and a circuit consisting of a narrow metal image area is not easily broken.
  • the present invention is useful for producing an electric circuit plate and can be used for the correction of circuit designs on circuit plates.
  • Hydrophilic surface used as follows:
  • the element was then dipped in warm water at 40 C. to remove the emulsion layer. At this stage, a positive image of the original formed on the element.
  • the element was dipped in a 15% aqueous formalin solution for 8 minutes at 25 C. and then in a 0.8% aqueous palladium chloride solution having a pH of 2.0 for 60 seconds at 50 C.
  • the element was then dipped in a Cahills copper electroless plating at 24 C. for one minute, by which beautiful plating of copper was formed according to the pattern of the original.
  • the electric conductiivty was below 0.2 Q/square.
  • Q/square had a value of 1,400 of the resistivity (Q) of a resistance Wire which had the length of times the width thereof.
  • EXAMPLE 2 A cellulose triacetate iilm 135,4 thick was dipped in a solution having the following composition at 20 C. for 3 minutes. i
  • a silver chlorobromide emulsion containing 1.2 mols of silver per kg. of the emulsion was applied to provide a 4p. thickness.
  • the sheet was exposed to reiiection rays using an original having a positive pattern of a circuit by means of a process camera at 16 of iris, 8 seconds, (diaphragm f:16, exposure time 8 seconds) and developed using a developer having the following composition at 20 C. for 20 seconds.
  • the resulting electric circuit consisting of the positive silver image was dipped into an aqueous solution of palladium chloride having an adjusted pH of 1.5 (palladium chloride content: 3.5%) at 30 C. for 40 seconds and then into a copper electroless solution (commercial name: Top Metalate Bath, produced by Okuno Seiyaku Co.) at for 3 minutes to plate the silver image with copper.
  • the electric conductivity of the circuit obtained by this process was below 0.1 Q/square.
  • EXAMPLE 3 A sheet element having a 3-layer sandwiched structure was prepared by laminating a polyethylene of g./m.2 in weight with paper having a 100 g./m.2 weight, and laminating the resulting paper with a cellulose acetate butyrate film p thick (161-40, produced by Eastman Kodak Co.). This sheet element was dipped into a solution (prepared by dissolving 50 g. of sodium hydroxide in 500 ml. of methyl alcohol) at 35 C. for 2 minutes to saponify the surface of the cellulose.
  • a solution prepared by dissolving 50 g. of sodium hydroxide in 500 ml. of methyl alcohol
  • the sheet element having a hydrophilic surface was dipped at 25 C. for 2 minutes into a solution prepared by dissolving 10 g. of silver nitrate in 500 ml. of water, adding 500 ml. of a 0.5 N sodium hydroxide solution thereto, and adding an aqueous ammonium solution till the produced silver oxide precipitate dissolved. Then the sheet element was dipped in a 3.7% aqueous formalin solution at 25 C. for 30 seconds, followed by squeezing and drying. By these treatments, a sheet element which contained colloidal silver in the part near the surface of the hydrophilic surface part was produced, the colloidal silver serving as the diffusion transfer nucleus material.
  • This sheet element was exposed to light through a positive original and developed by a developer having the composition of Example 1 at 25 C. for 30 seconds.
  • a developer having the composition of Example 1 at 25 C. for 30 seconds.
  • silver images were produced according to the positive original. These were intensified with copper images by the electroless plating treatment of Example 1.
  • the thus produced sheet element in which the images were oleophilic and the surface part of the cellulose was hydrophilic, could be used as a lithographie offset printing plate. Using an available wetting solution and inks, more than 10,000 copies of printed material of good quality were obtained.
  • EXAMPLE 4 A polyethylene terephthalate film g thick was treated by passage through a fiame jet produced from propane gas and air so as to have a hydrophilic surface. [passing PET film base in the dame of propane gas and air running at 70 m./min., the surface is made oxidated and hydrophilic]. This film was dipped in a 0.2 mol aqueous solution of sodium sulfide at 40 C. for 10 minutes and then the solution on the surface was removed by squeezing. The film was then dipped in a 0.1 mol aqueous solution of nickel chloride at 25 C. for 3 minutes, followed by washing and drying.
  • a polyethylene terephthalate film containing nickel sulfide as diffusion transfer nuclei was produced.
  • a silver bromoiodide emulsion containing 1.3 mols of silver per kg. of the emulsion (1.5% silver iodide) was applied to provide a 3p thickness.
  • the sheet element was exposed to light through a positive original and developed using a developer having the following composition at 25 C. for 45 seconds.
  • the emulsion layer was removed by dipping in warm water at 45 C.
  • the element was then dipped into an aqueous formalin solution (25%) at 25 C. for 5 minutes, into a 3% aqueous solution of palladium chloride at 45 C. for 20 seconds and then into a copper electroless solution at 20 C. for 3 minutes to intensify the images with copper.
  • thermosensitive copying paper On the pattern of copper images formed on the sheets, a thermosensitive copying paper was laid. By uniformly applying infrared rays of an intensive luminous flux at the side of the polyethylene terephthalate film free of copper, a duplicated pattern was formed on the thermosensiti've copying paper according to the metal images. -Infrared ray was applied to the side free of copper. The infrared ray is absorbed in black image of silver and transmitted copper.
  • the copper electroless solution in Example 4 is as follows:
  • EXAMPLE 5 To a polyethylene terephthalate film support (thickness 135p), a solution which contained 48 parts vinyl chloride (70 mol percent)vinyl acetate (30 mol percent) copolymer and (polymerization degree is 400) 2.65 parts by weight of titanium dioxide pigment (based on parts by weight of the vinyl chloride-vinyl acetate copolymer) was applied so as to provide a 0.2 g./decimeter2 thickness. A solution of this pigment in 52 parts methylethylketone was applied to the polyester support and dryed at F. for 5 minutes. A composition containing finelydivided colloidal silica and colloidal silver having the following composition was applied to the resulting layer so as to provide a 1pl thickness.
  • This photographic image forming base plate was exposed by reflection rays to a positive original by means of a plate making camera at 16 of iris for 6 seconds.
  • the plate was treated with using the same diffusion transfer developer as in Example 1 at 25 C. for 30 seconds.
  • the photographic emulsion layer was removed by warm water at 45 C.
  • the silver images were intensified with metal images by electroless plating as described in Example 1.
  • the metal images obtained had an excellent electrical conductivity which was below 1.5 tl/ square.
  • This invention is used to manufacture printed circuits, oiset printing plates, master plates of heat-printing, master plates of heat duplicating, name plates, etc.
  • a process for producing metal images comprising image-exposing, through an original image, a photosensitive element which comprises a photosensitive silver halide photographic emulsion laid on a hydrophilic surface of a plastic which has a surface containing a diffusion transfer nucleus material, forming reversal silver images of the original on the surface of said plastic by a diiusion transfer developing process, removing said emulsion, activating said silver images with a solution of a metal salt, and intensifying said silver images by electrolessly plating a metal thereon.
  • a process for producing metal image as claimed in claim 1 wherein said silver halide is silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver iodochloride, or silver chlorobromoiodide.

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  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
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US00213542A 1970-12-29 1971-12-29 Process of producing metal images by amplification of diffusion transfer images Expired - Lifetime US3822127A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3935013A (en) * 1973-11-12 1976-01-27 Eastman Kodak Company Electroless deposition of a copper-nickel alloy on an imagewise pattern of physically developable metal nuclei
US4059445A (en) * 1974-08-01 1977-11-22 Fuji Photo Film Co., Ltd. Noble metal image forming method
US4129445A (en) * 1975-10-13 1978-12-12 Fuji Photo Film Co., Ltd. Metal image formation process
US4157262A (en) * 1976-04-28 1979-06-05 Fuji Photo Film Co., Ltd. Intensification of photographic silver images by physical development and improvement in physical developer solution for use therein
US4192640A (en) * 1975-08-06 1980-03-11 Winter Park Associates Multiple transfer process and article resulting therefrom
US5043244A (en) * 1990-09-10 1991-08-27 E. I. Du Pont De Nemours And Company Process for defined etching of substrates
US5322763A (en) * 1992-05-06 1994-06-21 E. I. Du Pont De Nemours And Company Process for making metal ledge on stencil screen
US5536617A (en) * 1993-09-21 1996-07-16 Agfa-Gevaert, N.V. Method for making a lithographic printing plate
US5573815A (en) * 1994-03-07 1996-11-12 E. I. Du Pont De Nemours And Company Process for making improved metal stencil screens for screen printing
US20060115636A1 (en) * 2002-07-12 2006-06-01 Taro Yoshida Electromagnetic wave shield material and process for producing the same

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50130412U (enExample) * 1974-04-09 1975-10-27
JPS51148122U (enExample) * 1975-05-21 1976-11-27
JPS54145405U (enExample) * 1978-03-30 1979-10-09
JPS57194349U (enExample) * 1981-06-03 1982-12-09
JPS6060958U (ja) * 1983-10-05 1985-04-27 トヨタ自動車株式会社 自動車用座席の背もたれ装置
EP0432493A3 (en) * 1989-11-16 1992-02-26 E.I. Du Pont De Nemours And Company Electronic circuitry utilizing silver diffusion transfer imaging

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3935013A (en) * 1973-11-12 1976-01-27 Eastman Kodak Company Electroless deposition of a copper-nickel alloy on an imagewise pattern of physically developable metal nuclei
US4059445A (en) * 1974-08-01 1977-11-22 Fuji Photo Film Co., Ltd. Noble metal image forming method
US4192640A (en) * 1975-08-06 1980-03-11 Winter Park Associates Multiple transfer process and article resulting therefrom
US4129445A (en) * 1975-10-13 1978-12-12 Fuji Photo Film Co., Ltd. Metal image formation process
US4157262A (en) * 1976-04-28 1979-06-05 Fuji Photo Film Co., Ltd. Intensification of photographic silver images by physical development and improvement in physical developer solution for use therein
EP0475287A3 (en) * 1990-09-10 1992-07-08 E.I. Du Pont De Nemours And Company Process for defined etching of substrates
US5043244A (en) * 1990-09-10 1991-08-27 E. I. Du Pont De Nemours And Company Process for defined etching of substrates
US5322763A (en) * 1992-05-06 1994-06-21 E. I. Du Pont De Nemours And Company Process for making metal ledge on stencil screen
US5447757A (en) * 1992-05-06 1995-09-05 E. I. Du Pont De Nemours And Company Process for making improved metal stencil screens for screen printing
US5536617A (en) * 1993-09-21 1996-07-16 Agfa-Gevaert, N.V. Method for making a lithographic printing plate
US5573815A (en) * 1994-03-07 1996-11-12 E. I. Du Pont De Nemours And Company Process for making improved metal stencil screens for screen printing
US20060115636A1 (en) * 2002-07-12 2006-06-01 Taro Yoshida Electromagnetic wave shield material and process for producing the same
US7749620B2 (en) 2002-07-12 2010-07-06 Fujimori Kogyo Co., Ltd. Electromagnetic wave shield material and process for producing the same

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JPS492621B1 (enExample) 1974-01-22

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