US3615524A - Method for processing high-contrast photographic elements - Google Patents

Method for processing high-contrast photographic elements Download PDF

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Publication number
US3615524A
US3615524A US661533A US3615524DA US3615524A US 3615524 A US3615524 A US 3615524A US 661533 A US661533 A US 661533A US 3615524D A US3615524D A US 3615524DA US 3615524 A US3615524 A US 3615524A
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US
United States
Prior art keywords
cadmium
chloride
silver halide
silver
halide emulsion
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
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US661533A
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English (en)
Inventor
Kirby M Milton
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
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Publication of US3615524A publication Critical patent/US3615524A/en
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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
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D499/00—Heterocyclic compounds containing 4-thia-1-azabicyclo [3.2.0] heptane ring systems, i.e. compounds containing a ring system of the formula:, e.g. penicillins, penems; Such ring systems being further condensed, e.g. 2,3-condensed with an oxygen-, nitrogen- or sulfur-containing hetero ring
    • 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
    • G03C5/305—Additives other than developers
    • 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
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/15—Lithographic emulsion

Definitions

  • One aspect of the invention relates to a continuous process for processing exposed high-contrast photographic elements in a continuous transport-processing machine wherein certain developers must be employed in combination with photographic elements containing a cadmium salt in order to increase speed and effective contrast, eliminate or reduce drag lines and improve the shape and spacing of its H and D curve.
  • the low level of sulfite ion partially stabilizes the developer solution for a short period of time and isachieved in all known commercial developers of this type by the use of sodium formaldehyde bisulfite, which acts as a sulfite ion buffer.
  • sodium formaldehyde bisulfite acts as a sulfite ion buffer.
  • a halftone photographic intermediate usually a film negative, in which the gradations in tone are represented by differing sizes of dots of uniform density.
  • the shape, density and uniformity of the halftone dots are closely correlated to the quality of the resulting picture.
  • the developer solutions for high-contrast films presently used in continuous transport processing machines also have a number of disadvantages.
  • the photographic quality obtained with a given film is usually inferior to that obtained in careful tray processing.
  • the sensitivity of high-contrast films to developer exhaustion products and variations in local developing agent concentration makes these films vulnerable to directional drag streaks in film halftone areas under conditions of machine processing. These drag streaks occur in areas of high development (5090 percent dots) which are adjacent to areas of low 90 (dot area of 20 percent or less).
  • the drag streaks are formed by more development occurring because the developer which is dragged in from the area of low development contains more developing agent and less exhaustion products (primarily bromide ion) than the developer that would normally be in that area.
  • the dots in a high-contrast film are also distorted and exhibit size changes depending on the orientation and direction of travel through the machine processor. This dot distortion is manifested by discontinuities or plateaus in the H and D curve of high-contrast films which are processed in continuous transport processing machines. The elimination or reduction of drag streaks and dot distortions would be a considerable advance in the art.
  • a continuous process for processing an exposed, high-contrast photographic element comprising a support coated with a silver halide emulsion wherein said element is processed in one continuous motion by transporting it into and out of at least one processing solution in the manner shown, for example, by U.S. Pat. Nos. 3,025,779 of Russell and Kunz issued Mar. 20, I962; 3,078,024 of Sardeson issued Feb. 19, I963; 3,122,086 of Fitch issued Feb. 25, 1964; 3,149,551 of Cramer issued Sept. 22, I964; 3,156,173 of Meyer issued Nov. I0, 1964; and 3,224,356 of Fleisher and Hixon issued Feb.
  • said element is developed in a liquid developer composition comprising a developing agent and a carbonyl bisulfite-amine condensation product, and wherein said photographic element contains at least about 10 grams of a cadmium salt per mole of silver in said silver halide emulsion.
  • the developing agents which can be employed in the instant invention can be any of those suitable for the intended purpose.
  • Useful silver halide developers include the dihydroxybenzenes such as hydroquinone; chlorohydroquinone; bromohydroquinone; isopropylhydroquinone; toluhydroquinone; methylhydroquinone; 2,3-dichlorohydroquinone; 2,5-dimethylhydroquinone; 2,3-dibromohydroquinone; l,4-dihydroxy-2-acetophenone-2,S-dimethylhydroquinone; 2,5-diethylhydroquinone; 2,S-di-p-phenethylhydroquinone; 2,S-dibenzoylamineohydroquinone; 2,5- diacetaminohydroquinone; etc.
  • Esters of such compounds e.g., formates and acetates can also be employed. These developing agents can be used alone or in any combination and can be employed in any concentration which is effective for development.
  • a suitable concentration for the developing agent is from about 0.05 to about 0.05 mole per liter of developer composition and is preferably from about 0.1 to about 0.30 mole per liter of developer composition.
  • the carbonyl bisulfite-amine condensation products which can be used in the developer composition employed in my invention are preferably formaldehyde bisulfite-amine condensation products such as sodium-2-hydroxyethylaminomethane sulfonate; sodium-2-hydroxypropylaminomethane sulfonate; sodium-l,1-dimethyl-2-hydroxyethylaminomethane sulfonate; sodium-l,l-bis(hydroxymethyl)ethylaminomethane sulfonate; sodium-tris-(hydroxymethyl)methylaminomethane sulfonate; sodium-3-hydroxypropylaminomethane sulfonate; sodium-bis(2-hydroxyethyl)aminomethane sulfonate; sodium- N,N-bis[ 2-( l-hydroxy)propyllaminomethane sulfonate; sodium-N-isopropyl-N-2-hydroxyethyl)-aminomethane sulf
  • the carbonyl bisulfite-amine condensation products can be used alone or in any combination and can be employed in any concentration which is effective to provide a low level of sulfite ion for the developer composition.
  • a suitable concentration for the carbonyl bisulfite-amine condensation product is from about 0.1 to about 1.0 mole per liter of liquid developer composition and is preferably from about 0.25 to about 0.50 mole per liter of liquid developer composition.
  • the carbonyl bisulfite-amine condensation product can be added to the developer composition as a separate compound or formed in situ. Methods for preparing these compounds are disclosed, for example, in U.S. Pat. No. 2,388,816 of Bean is sued Nov. '13, 1945. In this specification and claims, it is meant to include within the definition of carbonyl bisulfiteamine condensation product either the compound itself or the individual components which form the compound in situ.
  • the high-contrast photographic elements which can be processed according to the instant invention comprise a silver halide emulsion layer in which the halide comprises at least about 50 mole percent chloride.
  • the silver halide emulsion comprises at least about 90 mole percent chloride, the balance, if any, being bromide.
  • Such preferred emulsions provide particularly good results in eliminating drag streaks and dot distortions.
  • the silver halide emulsion can also contain a small amount of iodide, e.g., less than about 5 mole percent, if desired.
  • Silver halide emulsions comprising 100 mole percent chloride have also been found to be quite useful.
  • the silver halide emulsion layer of the high-contrast photographic elements which can be processed according to the instant invention can contain any of hydrophilic water-permeable binding materials suitable for this purpose. Suitable materials include gelatin, colloidal albumin, polyvinyl compounds, cellulose derivatives, acrylamide polymers, etc. Mixtures of these binding agents can also be used.
  • the binding agents for the emulsion layer of the high-contrast photographic element can also contain dispersed polymerized vinyl compounds. Such compounds are disclosed, for example, in U.S. Pats. Nos. 3,142,568 of Nottorf issued July 28, I964; 3,193,386 of White issued July 6, I965; 3,062,674 of Houck, Smith and Yudelson issued Nov.
  • the vinyl polymers are generally employed in concentrations in the range of about 20 to about 80 percent, most often concentrations at least about 50 percent, by weight, based on the weight of the binding agent.
  • Silver halide emulsions wherein the binding agent contains a dispersed polymerized vinyl compound provide particularly good results in eliminating drag streaks and dot distortions.
  • the high-contrast photographic elements processed according to the instant invention contain at least about grams of a cadmium salt per mole of silver in the silver halide emulsion. While the cadmium salt is generally present in the silver halide emulsion, it can be incorporated into a contiguous layer if desired. Any cadmium salt can be used in the instant invention which is effective for the intended purpose. Generally, good results are achieved with water-soluble salts of cadmium such as cadmium chloride, cadmium acetate, cadmium nitrate, cadmium sulfate, etc. Especially good results are achieved with cadmium chloride.
  • the concentration of the cadmium salt to be used depends, of course, upon the particular cadmium salt chosen as well as its location in the photographic element. Generally, at least about 10 grams of cadmium salt per mole of silver in the silver halide emulsion should be used. A useful concentration range for the cadmium salt is from about 10 to about 30, preferably about 13 to about 20, grams of cadmium salt per mole of silver in the silver halide emulsion.
  • the silver halide emulsion of the high-contrast photographic elements which can be processed according to the instant invention can be coated on a wide variety of supports. Hydrophilic colloid layers can be coated on one or both sides of the support, if desired.
  • Typical supports are cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, poly(ethylene terephthalate) film, and related films or resinous materials, as well as glass, paper, metal and the like.
  • Supports such as paper, which are coated with aolefin polymers, particularly polymers of a-olefins containing two or more carbon atoms, as exemplified by polyethylene, polypropylene, ethylene-butene copolymers and the like can also be employed.
  • aolefin polymers particularly polymers of a-olefins containing two or more carbon atoms, as exemplified by polyethylene, polypropylene, ethylene-butene copolymers and the like can also be employed.
  • the silver halide emulsions of the high-contrast photographic elements which can be processed according to the instant invention can be sensitized using any of the well-known techniques in emulsion making, for example, by digesting with naturally active gelatin or various sulfur, selenium, tellurium compounds and/or gold compounds.
  • the emulsions can be sensitized with salts of noble metals of Group VIII of the Periodic Table which have an atomic weight greater than 100.
  • the emulsions can also contain addenda which increase speed and/or contrast such as quaternary ammonium salts, polyethylene glycols, thioether sensitizers or combinations thereof.
  • the silver halide emulsion of the high-contrast photographic elements which can be processed according to the instant invention can conveniently be orthosensitized or pansensitized with spectral-sensitizing dyes.
  • these emulsions can be spectrally sensitized by treating with a solution of a sensitizing dye in an organic solvent.
  • Sensitizing dyes useful in sensitizing such emulsions are described, for example, in US. Pats. Nos. 2,526,632 of Brooker and White issued Oct. 24, 1950, and 2,503,776 of Sprague issued Apr. 11, I950.
  • Spectral sensitizers which can be used are the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls, and hemicyanines.
  • the silver halide emulsion of the high-contrast photographic elements which can be processed according to the instant invention can also contain conventional addenda such as gelatin plasticizers, coating aids, antifoggants such as the azaindines and hardeners such as aldehyde hardeners, e.g., formaldehyde, mucochloric acid, glutaraldehyde bis(sodium bisulfite), maleic dialdehyde, aziridines, dioxane derivatives and oxypolysaccharides.
  • additiveenda such as gelatin plasticizers, coating aids, antifoggants such as the azaindines and hardeners such as aldehyde hardeners, e.g., formaldehyde, mucochloric acid, glutaraldehyde bis(sodium bisulfite), maleic dialdehyde, aziridines, dioxane derivatives and oxypolysaccharides.
  • the coated elements are then exposed, using tungsten illumination, to a step wedge through a magenta contact screen.
  • the elements are then processed, using the development times listed below, in a Kodalith Roller Transport 324 Film Processor, of the type shown in US. Pat. No. 3,025,779 of Russell and Kunz issued Mar. 20, I962, employing the following developer which is disclosed and claimed in my coworker Masseths copending application, Ser. No. 661,532, filed concurrently herewith and entitled Photographic Developer Composition and Process of Using Same:
  • -lminodicthanol can be used to form this compound in situ.
  • a continuous process for processing an exposed, highcontrast, photographic element comprising a support coated with a silver halide emulsion layer, said halide comprising at least about 50 mole percent chloride, said element being processed in one continuous motion by transporting it into, through and out of at least one processing solution, the improvement comprising developing said element in a liquid developer composition comprising a developing agent and a carbonyl bisulfite-amine condensation product, said element containing in said silver halide emulsion at least about 10 grams of a cadmium salt per mole of silver.
  • formaldehyde bisulfite-amine condensation product is sodium bis(2-hydroxyethyl)aminomethane sulfonate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US661533A 1967-08-18 1967-08-18 Method for processing high-contrast photographic elements Expired - Lifetime US3615524A (en)

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Application Number Priority Date Filing Date Title
US66153367A 1967-08-18 1967-08-18

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US (1) US3615524A (enrdf_load_stackoverflow)
BE (1) BE719514A (enrdf_load_stackoverflow)
DE (1) DE1797087A1 (enrdf_load_stackoverflow)
FR (1) FR1575384A (enrdf_load_stackoverflow)
GB (1) GB1228869A (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3984243A (en) * 1972-12-21 1976-10-05 Fuji Photo Film Co., Ltd. Photographic developer compositions for obtaining high contrast images

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4946933B1 (enrdf_load_stackoverflow) * 1971-03-20 1974-12-12

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3984243A (en) * 1972-12-21 1976-10-05 Fuji Photo Film Co., Ltd. Photographic developer compositions for obtaining high contrast images

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Publication number Publication date
GB1228869A (enrdf_load_stackoverflow) 1971-04-21
BE719514A (enrdf_load_stackoverflow) 1969-01-16
DE1797087A1 (de) 1970-11-05
FR1575384A (enrdf_load_stackoverflow) 1969-07-18

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