US3730721A - Photographic intensification process and composition - Google Patents

Photographic intensification process and composition Download PDF

Info

Publication number
US3730721A
US3730721A US00502389A US3730721DA US3730721A US 3730721 A US3730721 A US 3730721A US 00502389 A US00502389 A US 00502389A US 3730721D A US3730721D A US 3730721DA US 3730721 A US3730721 A US 3730721A
Authority
US
United States
Prior art keywords
silver
cupric
copper
developer
ascorbic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00502389A
Other languages
English (en)
Inventor
J Williams
P Gilman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Application granted granted Critical
Publication of US3730721A publication Critical patent/US3730721A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/58—Processes for obtaining metallic images by vapour deposition or physical development
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/40—Chemically transforming developed images
    • G03C5/42—Reducing; Intensifying
    • 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

Definitions

  • a physical developer for latent images in silver sensitized photographic materials comprises a cupric salt and a reducing agent such as ascorbic acid for this onpric salt.
  • a silver salt solvent transfer developer also contains a silver halide solvent. Latent image nuclei are physically developed or intensified by the cupric salt physical developer.
  • This invention relates to a novel method for preparing photographically useful images by physical or chemical development of latent image specks or nuclei, produced in an imagewise pattern by an exposure to light, using developing solutions comprising a soluble copper salt and an appropriate reducing agent whereby metallic copper in visible amounts is selectively deposited on the image specks or nuclei.
  • a solution of silver ion in combination with a reducing agent can be used to physically develop latent image specks or nuclei which remain after exposing and fixing an emulsion layer of silver halide.
  • a physical developer frequently used comprises an aqueous solution containing silver nitrate and a reducing agent such as hydroquinone, Elon, p-phenylenediamine, and the like.
  • a reducing agent such as hydroquinone, Elon, p-phenylenediamine, and the like.
  • An especially useful developer of the invention comprises .an aqueous solution of cupric nitrate and ascorbic acid or its alkali metal salts.
  • electroless copper plating solutions or baths are also operable in the process of the invention, but are usually less desirable for one reason or another, but principally because of their prolonging the developing time. Such solutions are described in a number of publications represented, for example, by ffElectroless Plating of Metals by Chemical Reduction, Natl. Bur. of Standards, Tech. Bull, 31, 111 (1957).
  • an object of the invention to provide a novel process of intensification or development of various photoproduced latent images in photographic layers by treating the layers with a physical and chemical developer comprising a solution of a soluble cupric salt and an appropriate reducing agent whereby metallic copper is selectively deposited in the exposed regions.
  • Anotherobject is to provide a process of the above kind wherein the physical and chemical developer comprises an aqueous solution of cupric nitrate and ascorbic acid. Another object is to provide a novel process of the above kind wherein a silver, zinc or lead type of latent image is intensified or developed. Another object is to provide a novel solvent transfer method of intensification or development of latent images using copper developers of the invention containing in addition a solvent for silver halide. Another object is to provide novel photographic products having intensified or developed visible images produced in accordance with the above processes of the invention. Another object is to provide novel copper con taining solutions which function. effectively as physical, chemical and solvent transfer developers for photoproduced latent images. Other objects will become apparent hereinafter. i
  • the copper developers of the invention are not only useful as physical, chemical and solvent transfer developers for the intensification or development of latent images formed by exposure of conventional gelatino-silver halide emulsion layers, but in addition also function eifectively as physical developers of latent images produced with other kinds of photosensitive materials such as any of those described in copending application of Gilman et aL, Ser. No. 244,456, filed Dec.
  • the photosensitive layer comprises a light insensitive nucleating agent, e.g., particles of silver, metal sulfides, metal selenides, silver proteinates, zinc oxide, zinc hydroxide, lead iodide, etc, and a sensitizer, e.g., a light sensitive dye, a photoreactive sulfur compound, and the like, which inhibits physical development of the nuclei until exposure to light causes the nuclei to form active sites for physical development.
  • v 0 Still other photosensitive materials that give on exposure physically developable latent images can with advantage be intensified or developed by using the copper developers of the invention, for example, photosensitive materials such as described in copending application of Gilman et al, Ser. No. 411,594, filed Nov. 16, 1964, wherein the photographic element comprises a light-sensitive layer containing a silver complex of a conventional sensitizing dye and having sensitivity only in the region of absorption by the silver-dye complex and which on exposure to radiation form active sites for physical development.
  • the copper developers of the invention can-be used, as previously-indicated, as physical, chemical and solvent transfer developers.
  • a solvent for silver halide is also incorporated in the developer composition.
  • a particularly useful copper developer for carrying out the physical and chemical development procedures of the invention has the following formulation:
  • any other reducing agenttor cupric salts preferably by an alkali metal salt of ascorbic acid, e.g., sodium ascorbate, etc.
  • the Z-aminoethanol component acts to control the alkalinity and also functions as a complexing agent for the vcupric salt.
  • any other aminoalkanol containing from 2 to 4 carbon atoms e.g., propanolamine, butanolamine, diethanolamine, etc., primary, secondary or tertiary amines, e,-.g., methylamine, ethylamine, butylamine, diethylamine, triethylamine, piperidine, pyridine, etc., alkane diamines, e.g., ethylenediamine, 1,3- pr opanediamine, -1,2-propanediamine, etc., sodiumfsalt of. ethylenediamine tetraacetic acid, or with a.
  • water-soluble amines such as any other aminoalkanol containing from 2 to 4 carbon atoms, e.g., propanolamine, butanolamine, diethanolamine, etc., primary, secondary or tertiary amines, e,-.g., methylamine, ethylamine, but
  • the sodium. sulfite component acts primarily as an antioxidant and can be substituted by a like amount of other alkalimetal sulfites, e.g., lithium sulfite, potassium sulfite, etc., or ,with ammonium sulfite.
  • the cupric salt and the reducing agent are critical components in the above formulation, and that the preferred combination. is cupricfnitrateand ascorbic acid.
  • the above formulation modified by the addition of about from 5 to 20 grams of a compound which is a solvent for silver halides, e.g., alkali metal thiosulfates, ammonium thiosulfates. an alkali metal thiocyanate, ammonium thiocyamate, and the like.
  • a compound which is a solvent for silver halides e.g., alkali metal thiosulfates, ammonium thiosulfates. an alkali metal thiocyanate, ammonium thiocyamate, and the like.
  • the preferred combination includes cupric nitrate, ascorbic acid and sodium thiosulfate.
  • Suitable unexposed photographic films or papers for carrying out the solvent transfer development procedure of the invention include any of the conventional photographic materials comprising a suitable film support material, e.g., cellulose esters such as cellulose nitrate, cellulose acetate, cellulose acetate-propionate, etc., polystyrene, polyesters, such as polyethylene terephthalate, etc., polyethylene, polyamides, paper, glass, metal, and the like, having thereon a gelatino silver halide developing-out emulsion layer, e.g., gelatino silver chloride, -chlorobromide, -chloroiodide, -chlorobromoiodide, -bromide and -bromoiodide.
  • a suitable film support material e.g., cellulose esters such as cellulose nitrate, cellulose acetate, cellulose acetate-propionate, etc., polystyrene, polyesters, such as polyethylene ter
  • emulsion layers can also contain sensitizers or other addenda for improving the character of the emulsion layer as is well known in the art.
  • Emulsions of the above kind can be prepared according to known methods, for example, such as those described in Hewitson and McClintock, US. Pat. No.- 2', 61'8,556, issued Nov. 18, 1952.
  • EXAMPLE 1 This example illustrates physical development of photoproduced nuclei originating from exposure of a photosensitive layer containing a silver complex of a sensitiz ing dye.
  • This mixture was then coated 10 grams per square foot onto a cellulose triacetate film support.
  • cupric nitrate is first dissolved in water and to this are then added the other components.
  • the whole layer was then fixed for two minutes and washed withwater.
  • the fixing bath had' the following composition:
  • V fixed part'of one-half was'immer'sed in the copper developer II ofabove Example 1 for 30 seconds;
  • the dudeveloped, fixed part'of the remaining half was immersed in a 1:1 ratio of water and developersolution of the above composition III for a period of 2 minutes.
  • a sensitometric comparison of a two minute development in 1:2 water and conventional developer of composition .III of above Example 2 with a 20-second development in the copper developer of composition II of above Example 1 was made using a conventional microfile film and a conventional silver halide film. Analyses of the sensitometric strips processed with the copper developer indicate both copper and silver are developed in the image areas. Also, the copper developed images show comparable uniform densities over the exposure range with those developed with the conventional developer.
  • EXAMPLE 4 This example illustrates that the usefulness of the copper developers of the invention can be extended to solvent transfer processes by the inclusion of a silver halide solvent in the developer formulation.
  • a processing web material containing a mixture of nickel and silver nuclei was prepared as follows:
  • a nickel sulfide dispersion was produced by adding 19 cc. of 1.0 N sodium sulfide to a precipitation vessel containing 50 grams of i 10 percent gelatin solution and 1435 cc. of water at a pH of. about 5.7 and a temperature of about 104 F. About seconds after the addition of the sodium sulfide solution, -a solution containing 20.8 cc. of- 1.0 N nickelous nitrate and 535 cc. of water was dumped into the reaction mixture over a period of seconds with rapid mechanical agitation. At the end of the addition, the mixture was stirred for 30 seconds at 104 F. Four hundred fifty grams of a 10 percent gelatin solution was then added and the dispersion obtained stirred at 104 F. for an additional minutes. i
  • a silver iodide dispersion was prepared as in above (1) except that potassium iodide was substituted for the sodiumsulfide and silver nitrate was substituted for the nickelous nitrate. f
  • a coating dispersion was prepared by mixing together 500 grams of the nickel sulfide dispersion of above (1), 100 grams of the silver iodide dispersion of above (2), 380 grams of a 10 percent gelatin solution and 1783 cc. distilled water. To this dispersion, whilestirring at 104 F., was added 30 cc. as a' 1 percent solution in methanol of l-methyl-l,2,3,6-tetrahydro-4-thiol, 60 cc. as a 1 percent solution inmethanol of 3- mercapto-l,2,4-triazole, and 44 cc.
  • the coated cellulose acetate receiving sheet prepared as above described was soaked for 30 seconds in a copper developer of the following composition:
  • the copper physical developers of the invention can also be used to develop latent images produced in zinc hydroxide photosensitive layers as illustrated in this example.
  • the zinc hydroxide coating emulsion was prepared by the following steps: I
  • EXAMPLE 6 This example illustrates the physical development of latent images produced in lead iodide photosensitive layers with the copper developers of the invention.
  • the lead iodide coating emulsion was prepared by the following steps:
  • the above emulsion was then coated 0.005 inch wet thickness on a suitable cellulose acetate support.
  • the dry coating was exposed imagewise, dipped in a 1% aqueous silver nitrate solution for 5 seconds, rinsed with water for 20 seconds, and then immersed in a copper developer of composition II of above Example 1 for 1-5 seconds to obtain a dense photographic image in the area of exposure.
  • the methylene blue coating emulsion was prepared by steps as follows:
  • latent images produced with any other of the photosensitive materials previously mentioned as being suitable can be effectively intensified by using the copper developers of the invention in the specified manner as physical, chemical and solvent transfer developers.
  • a process'for the intensification of photoproduced developable latent image nuclei in an exposed photosensitive layer selected from the class consisting of silver halide, zinc hydroxide, lead iodide, methylene blue and silver-dye complex layers comprising contacting said layer with an aqueous developing solution comprising a cupric saltand a reducing agent for said cupric salt selected from the class consisting of ascorbic acid and salts of ascorbic acid.
  • a process for the intensification of photoproduced developable latent image nuclei in an exposed photosensitive layer comprising contacting said layer with an aqueous developing solution comprising cupric nitrate and ascorbic acid.
  • a process for the intensification of photoproduced developable latent image nuclei in an exposed silver halide photosensitive layer comprising contacting said layer With an aqueous developing solution comprising a cupric salt and an ascorbic acid reducing agent.
  • a process for the intensification of photoproduced latent image nuclei in an exposed photosensitive zinc hydroxide emulsion layer comprising contacting said layer with an aqueous developing solution comprising a cupric salt and an ascorbic acid reducing agent.
  • a process for the intensification of photoproduced latent image nuclei in an exposed photosensitive lead iodide emulsion layer comprising contacting said layer with an aqueous developing solution comprising a cupric salt and an ascorbicacid reducing agent.
  • a process forthe intensification of photoproduced latentimage nuclei in an exposed photosensitive methylene blue emulsion layer comprising contacting said layer with an aqueous developing solution comprising a cupric salt and an ascorbic acid reducing agent.
  • a process for the intensification of photoproduced latent image nuclei in an exposed silver-dye complex emulsion layer comprising contacting said layer with an aqueous developing solution comprising a cupric salt and an ascorbic acid reducing agent.
  • a process for the intensification of photoproduced developable latent image nuclei in an exposed photosensitive layer comprising contacting said layer with an aqueous developing solution comprising a cupric salt and a reducing agent for said cupric salt selected from the class consisting of ascorbic. acid and ascorbic acid salts.
  • the method of amplifying a metallic image of a metal at least as noble as copper comprises contacting a physically developable copy medium comprising said metallic image with ascorbic acid and cupric ion to deposit selectively metallic copper in image areas of said copy medium Where metal is already present.
  • a solvent transfer process for the intensification- 8 of latent layer comprising (a) contacting said layer with an aqueous developing solution comprising a cupricsalt, an ascorbic acid reducing agent and a solvent for silver halide,and (b) then contacting said layer while still wet with said developing solution with a silver precipitating receiving sheet.
  • cupric salt is cupric nitrate
  • said reducing agent is ascorbic acid
  • silver halide solvent is sodium thiosulfate
  • the method of amplifying a latent metallic image in a copy medium which comprises contacting a copy medium comprising a latent metallic image with a developer comprising ascorbic acid and cupric ion to deposit selectively metallic copperin areas containing the latent image.
  • a developed'copy medium having'avisible image therein, said medium comprising a carrier and an image formed therein by a first metallic latent silver image a second, heavier, visible overlying metallic copper image.
  • An aqueous solution effective for the intensification of photoproduced latent images by a solvent transfer method comprising a cupric salt, an ascorbic acid, re* ducing agent for said cupric salt and a solvent for silver halides v 30.
  • cupric'salt is selected fromthe group consisting of cupric chloride, cupric bromide, cupric nitrate," cupric sulfate, cupric acetate, cupric benzoate, and cupric lactate
  • said reducing agent is selected from the group consisting of ascorbic acid and an alkali metal salt of ascorbic acid
  • said solvent for silver halidea is selected-from the group consisting of an alkali metal-1 thiosulfate, ammonium thiosulfate, an alkali metal thiocyanate and am monium thiocyanate.
  • composition for the amplification of images OTHER REFERENCES formed in a copy medium by the presence therein of a metal which composition comprises a solution of cupric ion, an acid acceptor, and ascorbic acid in a common solvent and wherein the acid acceptor is an organic amine.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US00502389A 1965-10-22 1965-10-22 Photographic intensification process and composition Expired - Lifetime US3730721A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US50238965A 1965-10-22 1965-10-22

Publications (1)

Publication Number Publication Date
US3730721A true US3730721A (en) 1973-05-01

Family

ID=23997596

Family Applications (1)

Application Number Title Priority Date Filing Date
US00502389A Expired - Lifetime US3730721A (en) 1965-10-22 1965-10-22 Photographic intensification process and composition

Country Status (4)

Country Link
US (1) US3730721A (enrdf_load_html_response)
BE (1) BE678170A (enrdf_load_html_response)
FR (1) FR1471718A (enrdf_load_html_response)
GB (1) GB1157330A (enrdf_load_html_response)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4254214A (en) * 1975-11-27 1981-03-03 Fuji Photo Film Co., Ltd. Photographic materials for non-silver images and process for forming non-silver images
EP2610366A2 (en) * 2011-12-31 2013-07-03 Rohm and Haas Electronic Materials LLC Plating catalyst and method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4254214A (en) * 1975-11-27 1981-03-03 Fuji Photo Film Co., Ltd. Photographic materials for non-silver images and process for forming non-silver images
EP2610366A2 (en) * 2011-12-31 2013-07-03 Rohm and Haas Electronic Materials LLC Plating catalyst and method

Also Published As

Publication number Publication date
GB1157330A (en) 1969-07-09
FR1471718A (enrdf_load_html_response) 1967-05-10
BE678170A (enrdf_load_html_response) 1966-09-01

Similar Documents

Publication Publication Date Title
US2592368A (en) Gelatine silver halide emulsion layer containing a dihydroxy diphenyl tanning developing agent
US4336321A (en) Silver halide photographic materials
US3457072A (en) Photographic element and process
US3632340A (en) Cored direct positive silver halide emulsion developed with polyhydroxybenzene
US3404980A (en) Silver images in light-sensitive print-forming layers
US3446619A (en) Radiation sensitive silver-dye complexes
US4054457A (en) Silver halide emulsions containing hexathiocane thiones as sensitizers
US4029509A (en) Positive process using a low coating weight silver halide
US3260605A (en) Method for preparing light-sensitive silver halide emulsions suitable for print-out recording materials
US3149970A (en) Production of photographic silver images by physical development
US3730721A (en) Photographic intensification process and composition
US3615510A (en) Silver halide complexing agents
US3320064A (en) Non-silver halide light sensitive materials
US3586505A (en) Sensitizing silver halide emulsion layers
US3615490A (en) Photographic overcoat comprising a benzotriazole toning agent and a silver salt of 5-mercapto-1-substituted tetrazole
CA1063855A (en) Photosensitive composition containing cadmium iodide and cuprous iodide in a binder
US3600177A (en) Liquid amides as silver halide developer solvents
US3852072A (en) Photographic products and processes comprising synthetic nuclear isotopes
US3287129A (en) Light-sensitive photographic elements containing developing agent precursors
US5141845A (en) Process for the spectral sensitization of photographic silver halide emulsions and products thereof
US3326687A (en) Photographic colloid transfer system
US3345170A (en) Light sensitive photographic elements containing developing agent precursors
US3260604A (en) Photographic colloid transfer system
US3752674A (en) Silver halide emulsion fogged with a boron hydride and a gold compound
US3600175A (en) Argentohalide complex film construction