US3625689A - High-contrast photographic elements and method for processing same - Google Patents

High-contrast photographic elements and method for processing same Download PDF

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Publication number
US3625689A
US3625689A US661530A US3625689DA US3625689A US 3625689 A US3625689 A US 3625689A US 661530 A US661530 A US 661530A US 3625689D A US3625689D A US 3625689DA US 3625689 A US3625689 A US 3625689A
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US
United States
Prior art keywords
mole percent
contrast
bromide
coated
silver halide
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Expired - Lifetime
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US661530A
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English (en)
Inventor
Eugene D Salesin
Thomas E Whiteley
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Eastman Kodak Co
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Eastman Kodak Co
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Publication of US3625689A publication Critical patent/US3625689A/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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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

Definitions

  • the low level of sulfite ion partially stabilizes the developer solution for a short period of time and is achieved 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 3,625,689 Patented Dec. 7, 1971 ice 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 (50-90% dots) which are adjacent to areas of low development (dot area of 20% 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.
  • high-contrast photographic elements comprising a support coated with a silver halide emulsion, said silver halide emulsion containing a dispersed polymerized vinyl compound, and said halide comprising at least about mole percent chloride, about 0.1 to about 5 mole percent iodide and the balance bromide.
  • I also provide a continuous process for processing such elements after exposure wherein said element is processed in one continuous motion by transporting it into, through and out of at least one processing solution in the manner shown, for example, by US. Patents 3,025,779 of Russell and Kunz issued Mar. 20, 1962; 3,078,024 of Sardeson issued Feb.
  • the developing agents which can be employed in the instant invention can be any of those suitable for the intended purpose.
  • Useful silver halide developing agents include the dihydroxybenzenes such as hydroquinone; chlorohydroquinone; bromohydroquinone; isopropylhydroquinone; toluhydroquinone; methylhydroquinone; 2,3-dichlorohydroquinone; 2,5-dimethylhydroquinone; 2,3 dibromohydroquinone; 1,4 dihydroxy-2- acetophenone 2,5 dimethylhydroquinone; 2,5-diethylhydroquinone; 2,5-di p phenethylhydroquinone; 2,5-dibenzoylaminohydroquinone; 2,5 diacetaminohydroquinone; etc.
  • Esters of such compounds 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 0.50 mole per liter of developer composition and is preferably from about 0.10 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 bisulfiteamine condensation products such as sodium-Z-hydroxyethylaminomethane sulfonate;
  • 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 dislosed, for example, in US. Pat. 2,388,- 816 of Bean issued 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 of the instant invention comprise a support coated with a silver halide emulsion layer in which the halide comprises at least about 85 mole percent chloride, about 0.1 to about 5 mole percent iodide and the balance bromide.
  • the halide in said silver halide emulsion comprises at least about 90 mole percent chloride, about 0.5 to about 2 mole percent iodide and the balance bromide, since such preferred emulsions provide particularly good results in eliminating drag streaks and dot distortions.
  • the silver halide emulsion layer of the high-contrast photographic elements of the instant invention can contain any of the hydrophilic water-permeable binding materials suitable for this purpose in combination with a dispersed polymerized vinyl compound.
  • Suitable binding materials include, for example, gelatin, colloidal albumin, cellulose derivatives, etc. Mixtures of these binding agents can also be employed.
  • the vinyl compound in the silver halide emulsion must be a dispersed polymerized vinyl compound, e.g., a polymeric latex or hydrosol. Such vinyl compounds are to be distinguished from watersoluble polymerized vinyl compounds which will not function in the same manner in my invention. Dispersed polymerized vinyl compounds are disclosed, for example, in US. Pats.
  • vinyl polymers are generally employed in concentrations in the range of about 20 to about percent, preferably at least 50 percent, by weight, based on the weight of the binding agent. Further details concerning these polymers can be found in copending application Ser. No. 454,683 of Dykstra filed May 10, 1965, now Pat. No. 3,411,911, and application Ser. No. 625,593 of Smith filed Mar. 24, 1967 now Pat. No. 3,488,708.
  • the silver halide emulsion of the high-contrast photographic elements of 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.
  • the silver halide emulsions of the high-contrast photographic elements of 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, ployethylene glycols, thioether sensitizers or combinations thereof.
  • the silver halide emulsion of the high-contrast photographic elements of the instant invention can conveniently be ortho-sensitized or pan-sensitized 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. Patents 2,526,632 of Brooker and White issued Oct. 24, 1950, and 2,503,776 of Sprague issued Apr. 11, 1950.
  • Spectral sensitizers which can be used are the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls, and hemicyanines.
  • sion containing 90 mole percent chloride, 9 mole percent bromide and 1 mole percent iodide is chemically sensi- Grams 9 wltllisulfur a gold compounds and coated on a Sodium 3-hydroxyethylaminomethane sulfonate 322 polyethylene terephthalate support at a coverage of 456 10 Hydroquinone bromide 90 milligrams. of silver per square foot'and 452 milligrams potassium bromide 63 per square foot.
  • a gelatin overcoat is coated Water to make11iter over the emulsion layer at a coverage of 82.6 milligrams pH k 10 0 1 per square. foot. n i
  • (C) A coated element similar to (A) is prepared but with 296-,milligrams per square foot of copoly(methyl acrylate-sulfopropyl acrylate-Z-acetoacetoxyethyl methacrylate)land 296 milligrams of gelatin per square foot in Coated element Curve Shape the emuls on layer.
  • a Ont ol n i did 1 H T a e elements are then exposed, 118mg tungsten B (Emailsiofiifiai:::::::::::::::::::::::I: 3 b i e? illumination, to a step wedge through a magenta contact screen.
  • the coated elements are processed using the various E MPLE 3 development times llsted below with the following results:
  • (A) A fine-grain silver chlorobromoiodide gelatin emul- Relative speed change Etfective contrast 1 1 I 3 I l I 1 Drag Curve Coated element l/ dev. 1A dev. 2 dev. 2/ dev. l/ dev. 1%dev. 2dev. 2%dev. streaks shape A g 100 +114 +176 +317 0.8 2.4 3.1 2.95 s v P 550 e +18 +35 +51 8.0 8.2 9.2 8.5 ivi od tir iiiellI Gail 468 +26 +48 +66 7.0 8.6 9.5 9.5 Do Do.
  • a gelatin overcoat is coated over the emul- Effect of iodide content sion layer at a coverage of 83 milligrams per square foot.
  • (B) A coated element similar to (A) is prepared but with 80 mole percent chloride, 19 mole percent bromide and 1 mole percent iodide.
  • a coated element similar to (A) is prepared but (A) A silver chlorobromide gelatin emulsion containing 90 mole percent chloride and 10 mole percent bromide is chemically sensitized with sulfur and gold compounds and coated on a polyethylene terephthalate support at a coverage of 470 milligrams of silver per square foot, 300 70 mole Percenf m 29 mole Pefcfillt bromlde milligrams of gelatin per square foot and 300 milligrams and 1 mole Percent lodlde: of a methylacrylate-sulfopropyl acrylate latex per square A coated element slmllaf t0 is P p t foot. A gelatin overcoat is coated over the emulsion with 40 mole pe chloride. 59 mole percent bromide layer at a coverage of 80 milligrams per square foot. and 1 mole percent iodide.
  • Example 7 The coated elements are then exposed and processed as in Example 1 employing a 1% minute development time with the following results:
  • said silver halide containing a dispersed waterinsoluble polymer of an alkyl acrylate, methacrylate, sulfoalkyl acrylate, sulfoalkylmethacrylate or acrylic acid, and
  • said halide comprising at least about 85 mole percent chloride, about 0.1 to about 5 mole percent iodide and the balance bromide.
  • said dispersed waterinsoluble polymer is a polymer of an alkyl acrylate 'or an alkyl methacrylate.
  • halide comprises about 90 mole percent chloride, about 1 mole percent iodide and about 9 mole percent bromide.
  • a high-contrast, photographic element comprising a support coated with a silver halide emulsion, said silver halide emulsion containing a dispersed water-insoluble polymer of an alkyl acrylate, methacrylate, sulfoallg l acrylate, sulfoalkylmethacrylate-or acrylic acid, and said halide comprising at least about mole percent chloride, about 0.1 to about 5 mole percent iodide and the balance bromide.
  • said dispersed water-insoluble polymer is a polymer of an alkyl acrylate or alkyl methacrylate.
  • the photographic element of claim 12 wherein said halide comprises about mole percent chloride, about 1 mole percent iodide and about 9 mole percent bromide.
  • dispersed water-insoluble polymer is present in an amount ranging from about 20 to about 80 percent by weight based on the weight of total binding agent in said silver halide emulsion.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US661530A 1967-08-18 1967-08-18 High-contrast photographic elements and method for processing same Expired - Lifetime US3625689A (en)

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US (1) US3625689A (enrdf_load_stackoverflow)
BE (1) BE719512A (enrdf_load_stackoverflow)
DE (1) DE1797088A1 (enrdf_load_stackoverflow)
FR (1) FR1575382A (enrdf_load_stackoverflow)
GB (1) GB1228868A (enrdf_load_stackoverflow)

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* Cited by examiner, † Cited by third party
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IT1179519B (it) * 1984-12-17 1987-09-16 Minnesota Mining & Mfg Materiale fotosensibile agli alogenuri d'argento per l'ottenimento di immagini in bianco e nero a mezza tinta e metodo per la riproduzione a mezza tinta ad alto contrasto

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BE719512A (enrdf_load_stackoverflow) 1969-01-16
GB1228868A (enrdf_load_stackoverflow) 1971-04-21
DE1797088A1 (de) 1970-11-05
FR1575382A (enrdf_load_stackoverflow) 1969-07-18

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