US2592368A - Gelatine silver halide emulsion layer containing a dihydroxy diphenyl tanning developing agent - Google Patents

Gelatine silver halide emulsion layer containing a dihydroxy diphenyl tanning developing agent Download PDF

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Publication number
US2592368A
US2592368A US783912A US78391247A US2592368A US 2592368 A US2592368 A US 2592368A US 783912 A US783912 A US 783912A US 78391247 A US78391247 A US 78391247A US 2592368 A US2592368 A US 2592368A
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United States
Prior art keywords
developing agent
silver halide
emulsion
dihydroxy diphenyl
emulsion layer
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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
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US783912A
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English (en)
Inventor
Edward C Yackel
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
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Priority to US783912A priority Critical patent/US2592368A/en
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Publication of US2592368A publication Critical patent/US2592368A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B15/00—Special procedures for taking photographs; Apparatus therefor
    • 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
    • G03C5/29—Development processes or agents therefor
    • G03C5/315—Tanning development
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S101/00—Printing
    • Y10S101/29—Printing involving a color-forming phenomenon

Definitions

  • This invention relates to light-sensitive photographic materials and particularly to improved types of sensitized materials suitable for making images in tanned colloid vehicle.
  • a tanning developing agent into a photographic emulsion on a support such as tracing cloth and after exposure and development to form relief images by washing the unexposed emulsion away with water.
  • veloping agent such as pyrocatechol or hydro- .quinone is used, because of solubility, vapor pressure, etc., the developing agent does not remain in the emulsion layer during long periods of keeping. Instead, it wanders throughout the gelatin and waterproofing layer of a material such as tracing cloth and from one piece of material to another when the two are in close contact. This Wandering of the developing agent results in undesirable stain, poor developability, etc.
  • a light-sensitive silver'salt emulsion layer containing a substantially water insoluble tanning developing agent is prepared.
  • a support such as'tracing cloth, a cellulose ester film baseglass, or paper.
  • Fine-grain gelatino-silver bromide emulsions are preferably used but silverchloride or other silver halide emulsions may be used in gelatin or other vehicles such as polyvinyl alcohol, which can be differentially tanned with tanning developing agents.
  • the developing agent may be any substantially water-insoluble developing agent which tans the gelatin or other carrier, for the silver halide, upon development in an alkaline solution.
  • tanning developing agents specially useful because of their non-wandering characteristics, high rate of development, high tanning efliciency, and solubility in the preferred range, are those having a solubility of from about .005 to 1.0 gram per hundredcc. of a phosphate citric acid buffer solution of pH 5.0 prepared from a 1.5 per cent solution of sodium dihydrogenphosphate and sufficient citric acid to bring the pH to 5.0.
  • the preferred developing agent has the solubility of from about .01 to 0.2 gram per hundred cc. of buffer solution.
  • Developing agents following within the above classification arepfor example, 3,4-dihydroxy diphenyl; 2,5-dihydroxy diphenyl; 2,3-dihydroxy diphenyl; and 5,6,'7,8-tetrahydro napthohydroquinone.
  • Compounds like 2-hydroxy-5-amino-diphenyl or 3,4-diaminodipheny1 are not especially useful because of their poor stability characteristics or failure to differentially tan the emulsion vehicle.
  • the developing agents are substantially water-insoluble this is defined as meaning tanning developing agents having solubility within the above range of buffer solution.
  • the emulsion vehicle is substantially unhardened this is defined as meaning not harder than would be the case with gelatin containing 0.25 ounce of formaldehyde (40 per cent solution diluted 1 to 3 with water) per pound, when freshly coated, or 0.1 ounce of the solution per pound for a sample aged three to six months.
  • Emulsion layers appreciably harder are not very satisfactory for use in my process or that of the above oopending application. 7
  • the emulsion layer prepared as above is exposed in the usual manner under a line drawing and is "developed by immersion in an aqueous solution of an alkali such as sodium or potassium carbonate, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide, or an amine.
  • an alkali such as sodium or potassium carbonate
  • an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide, or an amine.
  • the addition to the alkaline solution, of other materials, is also helpful in obtaining a satisfactory relief image.
  • the addition of sodium hydroxide to a sodium carbonate solution improves the sensitometric characteristics of the material as well as the relief properties.
  • reducing agents such as ascorbic acid, hydrazine hydrochloride, sodium sulfite, in small quantities, sodium bicarbonate and urea, are also advantageous.
  • warm water I mean water at a temperature of about 90 F. to 100 F. or higher
  • Example I while stirring the latter over a period of about 10 minutes; Solution B preferably not being allowed to run in faster than C. Thereafter, 150 grams of gelatin in 1500 cc. of water at 40 C. are added. The emulsion is then adjusted to pH of 5.0. If desired, the emulsion may then be chilled, set, and washed in the usual manner. It is then remelted and 25 grams of 3,4-dihydroxy diphenyl dissolved in 250 cc. of methyl alcohol is slowly added to the above emulsion with stirring. As a result the developing agent becomes dispersed in the emulsion in minute crystals. Preparatory to coating an emulsion layer, in case a gelatin having poor physical properties has been used, 2 cc. of 10% formaldehyde may be added and this composition is coated on a prepared tracing cloth support over an area of about 500 square feet and dried.
  • 2 cc. of 10% formaldehyde may be added and this composition is coated on a prepared tracing cloth support
  • Example II Another emulsion suitable for use in my invention is made from the following solutions-(A) 25 grams gelatin in 1 liter water at 40 C.; (B) grams silver nitrate dissolved in 500 cc. water at 20 C.; (C) '72 grams potassium bromide in 500 cc. water at 20 C. Solutions B and C are simultaneously run into Solution A with stirring and afterwards a solution of 200 grams gelatin in 2 liter water at 40 C. is added. A suitable surface-active agent may then be added and the pH adjusted to 5.0. Thereafter a solution of 25 grams of 4-phenyl catechol in 250 cc. of methyl alcohol is added with stirring. Preparatory to coating the emulsion on a support as tracing cloth, a small quantity of hardener may be added as in Example I following which the emulsion is coated over an area of about 300 square feet.
  • the concentration of developing agent in the emulsion is dependent in part on the result desired but can be of the order of 350 grams per kg. of silver nitrate, converted to silver halide. used in making the emulsion, to obtain good density, or about 250 grams per kg. of silver nitrate to obtain adequate density and an emulsion having optimum keeping properties.
  • a typical tracing cloth at various stages in my process.
  • a support ill of sized tracing cloth is coated with a gelatinosilver halide emulsion II containing a substantially water insoluble tanning developing agent.
  • This material is exposed and developed by immersion in an alkaline solution to form images of silver and hardened gelatin as shown at I 2 in Fig. 2.
  • the remaining unhardened gelatin and silver halide I3 in Fig. 2 is then washed off by treatment of the tracing cloth with warm water to leave images ll of hardened gelatin on the support III as shown in Fig. 3.
  • a photographic emulsion layer comprising a substantially unhardened gelatin vehicle and dispersed in said vehicle a silver halide and a tanning developing agent of the class consisting of 2,3-dihydroxy diphenyl, 2,5-dihydroxy diphenyl, and 3,4-dihydroxy diphenyl.
  • a photographic emulsion layer comprising Number gelatin, silver halide, and 2,3-dihydroxy diphenyl. 1,535,700 3.
  • a photographic emulsion layer comprising 1,709,569 gelatin, silver halide, and 2,5-dihydroxy diphenyl. 1,812,981 4.
  • a photographic emulsion layer comprising 5 2,039,730 gelatin, silver halide, and 3,4-dihydroxy diphenyl. 2,090,484

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Printing Plates And Materials Therefor (AREA)
US783912A 1947-11-04 1947-11-04 Gelatine silver halide emulsion layer containing a dihydroxy diphenyl tanning developing agent Expired - Lifetime US2592368A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US783912A US2592368A (en) 1947-11-04 1947-11-04 Gelatine silver halide emulsion layer containing a dihydroxy diphenyl tanning developing agent

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US783912A US2592368A (en) 1947-11-04 1947-11-04 Gelatine silver halide emulsion layer containing a dihydroxy diphenyl tanning developing agent
US783914A US2596756A (en) 1947-11-04 1947-11-04 Photomechanical copy method
US267446A US2675313A (en) 1947-11-04 1952-01-21 Photographic reproduction process
US267482A US2763553A (en) 1947-11-04 1952-01-21 Lithographic offset printing process

Publications (1)

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US2592368A true US2592368A (en) 1952-04-08

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US783912A Expired - Lifetime US2592368A (en) 1947-11-04 1947-11-04 Gelatine silver halide emulsion layer containing a dihydroxy diphenyl tanning developing agent
US783914A Expired - Lifetime US2596756A (en) 1947-11-04 1947-11-04 Photomechanical copy method
US267446A Expired - Lifetime US2675313A (en) 1947-11-04 1952-01-21 Photographic reproduction process
US267482A Expired - Lifetime US2763553A (en) 1947-11-04 1952-01-21 Lithographic offset printing process

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US783914A Expired - Lifetime US2596756A (en) 1947-11-04 1947-11-04 Photomechanical copy method
US267446A Expired - Lifetime US2675313A (en) 1947-11-04 1952-01-21 Photographic reproduction process
US267482A Expired - Lifetime US2763553A (en) 1947-11-04 1952-01-21 Lithographic offset printing process

Country Status (5)

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US (4) US2592368A (en(2012))
BE (4) BE485609A (en(2012))
DE (2) DE874704C (en(2012))
FR (4) FR980399A (en(2012))
GB (4) GB655274A (en(2012))

Cited By (11)

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US2716059A (en) * 1952-01-21 1955-08-23 Eastman Kodak Co Photographic transfer process
US2740717A (en) * 1952-05-03 1956-04-03 Eastman Kodak Co Photographic transfer process
US2843485A (en) * 1952-05-03 1958-07-15 Eastman Kodak Co Transfer process of photographic printing
US3146104A (en) * 1959-12-21 1964-08-25 Eastman Kodak Co Silver halide sensitized lithographic printing plate
US3287129A (en) * 1963-01-16 1966-11-22 Eastman Kodak Co Light-sensitive photographic elements containing developing agent precursors
US3312550A (en) * 1959-04-10 1967-04-04 Eastman Kodak Co Processing photographic elements containing developing agent
US3345170A (en) * 1964-06-05 1967-10-03 Eastman Kodak Co Light sensitive photographic elements containing developing agent precursors
US4283479A (en) * 1979-02-26 1981-08-11 Fuji Photo Film Co., Ltd. Silver halide photographic materials and a process forming relief images
US4299909A (en) * 1979-08-07 1981-11-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US5037734A (en) * 1989-12-28 1991-08-06 Eastman Kodak Company Stabilized photographic element containing infrared sensitizing dye

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US2756143A (en) * 1953-12-24 1956-07-24 Eastman Kodak Co Photographic reproduction process
US3010390A (en) * 1954-06-29 1961-11-28 Buskes Willem Marie Planographic printing plates
US3010391A (en) * 1954-06-29 1961-11-28 Grinten Chem L V D Light-sensitive sheets and process for producing transfer images
US2903964A (en) * 1955-01-24 1959-09-15 Eastman Kodak Co Photographic spirit duplicating process
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US2865745A (en) * 1955-08-25 1958-12-23 Eastman Kodak Co Photographic reproduction process
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US2856283A (en) * 1956-05-07 1958-10-14 Eastman Kodak Co Photographic emulsion
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US3091528A (en) * 1958-08-19 1963-05-28 Chem Fab L Van Der Grinten N V Process and light-sensitive sheets for the production of pigment images by transfer
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US3060022A (en) * 1959-07-13 1962-10-23 Gen Aniline & Film Corp Image transfer process
US3152969A (en) * 1960-07-28 1964-10-13 Eastman Kodak Co Photoconductolithography employing hydrophobic images
US3106516A (en) * 1960-07-28 1963-10-08 Eastman Kodak Co Photoconductography employing electrolytic images to harden or soften films
US3106517A (en) * 1960-07-28 1963-10-08 Eastman Kodak Co Photoconductography employing spongy images containing gelatin hardeners
US3295969A (en) * 1961-04-12 1967-01-03 Eastman Kodak Co Photographic spirit duplicating process
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US3189448A (en) * 1962-08-22 1965-06-15 Eastman Kodak Co Developing compositions used in photographic transfer processes
US3189449A (en) * 1962-10-01 1965-06-15 Eastman Kodak Co Colloid stratum transfer process
US3240600A (en) * 1963-01-16 1966-03-15 Eastman Kodak Co Colloid transfer process
DE1256541B (de) * 1963-01-23 1967-12-14 Eastman Kodak Co Kopierapparat mit einer Entwicklungsvorrichtung fuer Matrizen mit Griffrand
US3326687A (en) * 1964-11-10 1967-06-20 Eastman Kodak Co Photographic colloid transfer system
US3751161A (en) * 1965-10-01 1973-08-07 Itek Corp Photographic image transfer apparatus
US3650742A (en) * 1968-07-01 1972-03-21 Eastman Kodak Co Oleophilizing gelatinous images
JPS5619277B2 (en(2012)) * 1973-10-03 1981-05-06
DE2832530C2 (de) * 1978-07-25 1984-08-02 Du Pont de Nemours (Deutschland) GmbH, 4000 Düsseldorf Lichtempfindliches Material für die Gerbentwicklung
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Cited By (11)

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Publication number Priority date Publication date Assignee Title
US2716059A (en) * 1952-01-21 1955-08-23 Eastman Kodak Co Photographic transfer process
US2740717A (en) * 1952-05-03 1956-04-03 Eastman Kodak Co Photographic transfer process
US2843485A (en) * 1952-05-03 1958-07-15 Eastman Kodak Co Transfer process of photographic printing
US3312550A (en) * 1959-04-10 1967-04-04 Eastman Kodak Co Processing photographic elements containing developing agent
US3146104A (en) * 1959-12-21 1964-08-25 Eastman Kodak Co Silver halide sensitized lithographic printing plate
US3287129A (en) * 1963-01-16 1966-11-22 Eastman Kodak Co Light-sensitive photographic elements containing developing agent precursors
US3345170A (en) * 1964-06-05 1967-10-03 Eastman Kodak Co Light sensitive photographic elements containing developing agent precursors
US4283479A (en) * 1979-02-26 1981-08-11 Fuji Photo Film Co., Ltd. Silver halide photographic materials and a process forming relief images
US4299909A (en) * 1979-08-07 1981-11-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US5037734A (en) * 1989-12-28 1991-08-06 Eastman Kodak Company Stabilized photographic element containing infrared sensitizing dye

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BE517064A (en(2012)) 1954-11-26
US2675313A (en) 1954-04-13
US2763553A (en) 1956-09-18
DE874704C (de) 1953-04-27
GB655273A (en) 1951-07-18
FR1089934A (fr) 1955-03-24
GB726543A (en) 1955-03-23
BE485609A (en(2012)) 1942-11-12
BE517066A (en(2012)) 1954-11-26
GB725667A (en) 1955-03-09
FR980399A (fr) 1951-05-11
DE927307C (de) 1955-05-23
US2596756A (en) 1952-05-13
FR980401A (fr) 1951-05-11
FR1092963A (fr) 1955-04-28
BE485611A (en(2012)) 1948-11-13
GB655274A (en) 1951-07-18

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