US3189453A - Photographic emulsions containing thio derivatives as fixers and method of using same - Google Patents

Photographic emulsions containing thio derivatives as fixers and method of using same Download PDF

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Publication number
US3189453A
US3189453A US133770A US13377061A US3189453A US 3189453 A US3189453 A US 3189453A US 133770 A US133770 A US 133770A US 13377061 A US13377061 A US 13377061A US 3189453 A US3189453 A US 3189453A
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United States
Prior art keywords
silver halide
photographic
compound
emulsion
radical
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Expired - Lifetime
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US133770A
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English (en)
Inventor
Arthur H Herz
Norman W Kalenda
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to BE621607D priority Critical patent/BE621607A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US133770A priority patent/US3189453A/en
Priority to FR907407A priority patent/FR1331244A/fr
Priority to DEE23428A priority patent/DE1175074B/de
Priority to GB32856/62A priority patent/GB1019223A/en
Application granted granted Critical
Publication of US3189453A publication Critical patent/US3189453A/en
Anticipated expiration legal-status Critical
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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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/43—Processing agents or their precursors, not covered by groups G03C1/07 - G03C1/42
    • 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
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing

Definitions

  • thioether compound having a sulfur atom attached to two carbon atoms and which thioether has substantial stability in photographic silver halide emulsion at pHs of 7 or less and liberates a compound having a thiol radical (%H) capable of forming a substantially light stable complex with silver halide under aqueous conditions at pHs greater than 7.
  • thioether addenda of the invention have attached to an alpha carbon atom, with reference to the sulfur atom, a radical containing a second sulfur atom, a nitrogen atom or an oxygen atom.
  • thioether addenda of the invention have attached to a beta carbon atom, with reference to the sulfur atom, an electron-withdrawing group or an unsaturated group, such as an amide radical, a keto radical, a nitrile radical, a sulfonyl radical, a carboxyl radical and the like.
  • thiazoline derivatives including ortho and meta thiazoles and thiazolines.
  • thiazoline derivatives have the formula Typical suitable Certain of such derivatives have corresponding tautomeric forms, such tautomeric forms being included in our
  • R R, R and R can be either hydrogen atoms or hydrocarbon radicals such as alkyl radicals or aryl radicals, typical suitable alkyl radicals having 1 to 20 carbon atoms and generally 1 to 8 carbon atoms such as methyl, n-propyl, Z-ethylhexyl, n-decyl, stearyl, n-eicosyl, etc., and typical suitable aryl radicals being phenyl and alkyl-substituted phenyl radical.
  • R and R can be hydrogen atoms, hydrocarbon radicals as described above for R R R and R hydrocarbon radicals containing such substituents as hydroxyl radicals, or R and R together can be the necessary carbon and hydrogen atoms to form an aryl radical which includes the adjacent carbon atoms on the thiazoline nucleus.
  • X in combination with the adjacent nitrogen atom on the thiazoline nucleus forms a covalent quaternary salt having no hydrogen atom attached to the nitrogen atom.
  • the quaternary salt can include an electro-negative group such as sulfonate, carboxylic acid groups or the like to form an inner salt such as is illustrated by the quaternary salt group or alkyl quaternary salts including an anion or negatively charged ion such as a chloride ion, a perchlorate ion, a
  • thioether addenda are described in detail in our application titled Photographic 3 Silver Halide Emulsions Containing Isothiourca Derivatives, U.S. Serial No. 133,769, which. was also filcd concurrently herewith.
  • Typical thioether addenda of this copending application have the formulas wherein R, R and R can be hydrogen atoms or hydrocarbon radicals. R and R can also be acyl radicals or the necessary carbon and hydrogen atoms to form an alkylene radical linking both adjacent nitrogen atoms to form a cyclic nucleus.
  • the letter )1 can be an integer of 1 to 10.
  • the letter Z can be a carboxyl radical, a sulfonate radical, a hydroxyl radical or an amino radical, Z being other than a carboxyl radical when .n is 1 and R H;
  • thioether addenda of the invention include wherein X is an anion and wherein R is an organic radical including such hydrocarbons as alkyl or aryl, and heterocyclic radicals, which can be substituted with hydroxyl, carbonyl, amino, sulfonyl and the like radicals.
  • R is an organic radical including such hydrocarbons as alkyl or aryl, and heterocyclic radicals, which can be substituted with hydroxyl, carbonyl, amino, sulfonyl and the like radicals.
  • thioethers as thiomethyl esters as illustrated by fi-morpholino-cthylthiomethyl acetate hydrochloride are included in our invention.
  • the photographic silver halide emulsion addenda of the invention serve as incorporated fixing .or image stabilizing agents. These addenda do not prevent development of exposed areas of the emulsion but protect the unexposed areas against print out after development of the emulsion. Thus with emulsions containing the addenda of the invention silver images can be formed and stabilized without the use of a conventional fixing process.
  • the subject addenda are stable and do not act as fixing agents in acidic or neutral media. However, under aqueous alkaline conditions, such as conventionally prevail during the developing of photographic emulsions, the subject addenda are active fixing agents. Generally alkaline developing pH's of 9 or higher are utilized for rapid fixing.
  • the subject thioethers liberate a thiol compound which reacts with the unexposed and undeveloped silver halide of the emulsion forming a product which is more stable than silver halide to light, atmosphere and reducing conditions, and which complex does not decompose to silver or silver sulfide.
  • the subject addenda are used in photographic silver halide emulsions and utilized at a concentration of at least one mole of the addendum per mole of silver halide in the emulsion.
  • the preparation of photographic silver halide emulsions such as are used with the addenda of the invention involves three separate operations: (1) emulsification and digestion of silver halide, (2) the freeing of the emulsion of excess water-soluble salts, suitably by washing with water, and (3) the second digestion or after-ripening to 4 obtain increased emulsion speed or sensitivity.
  • the addenda of the invention can be added to the emulsion before the final digestion or utter-ripening, or they can be added immediately prior to the coating.
  • the addenda of the invention can be added to photographic emulsions using any of the well-known techniques in emulsion making. For example, they can be dissolved in a suitable solvent and added to the silver halide emulsion, or they can be added to the emulsion in the form of a dispersion similar to the technique used to incorporate certain types of color forming compounds (couplers) in a photographic emulsion. Techniques of this type are described in Jelley et al. U.S. Patent 2,322,027, issued June 15, 1943, and Fierke et a1. U.S. Patent 2,801,171, issued July 30, 1957.
  • the solvent should be selected so that it has no harmful efiect upon the emulsion in accordance with usual practice, and generally solvents or diluents which are miscible with water are to be preferred.
  • Water alone is a dispersing medium for some of the sensitizers of the invention.
  • the subject sensitizers can be dissolved in solvents, such as ethanol, acetone, pyridine, N,N-dimethylformamide, etc., and added to the emulsion in this form.
  • the emulsions of the invention can include the usual photographic addenda such as chemical sensitizers, optical sensitizers, stabilizers or antifoggants, plasticizers, hardeners, coating aids, and the like.
  • silver salts can be used as the sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide.
  • gelatin In the preparation of the silver halide dispersions employed for preparing silver halide emulsions, there can be employed as the dispersing agent for the silver halide in its preparation, gelatin or some other colloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound, although gelatin is preferred.
  • colloids which can be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe U.S. Patent 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester suchas cellulose acetate hydrolyzed to an acetyl content of 1926% as described in U.S.
  • Patent 2,768,- 154 issued October 23, 1956; or containing cyano-acetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in Unruh, Smith and Priest U.S. Patent 2,808,331, issued October 1, 1957', or a polymeric material which results from polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group as described in Illingsworth, Dann and Gates U.S. Patent 2,852,382, issued September 19, 1958. If desired, compatible mixtures of two or more of these colloids can be employed for dispersing the silver halide in its preparation.
  • Typical supports for photographic elements of the invention include cellulose nitrate film, ,cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethyleneterephthalate film and related films of resinous materials, as well as glass, paper, wood, metals and others.
  • Illustrative emulsion addenda bf the invention have the following structural formulas:
  • COMPOUND 14 COMPOUND 15 s E 5g/ JH -CH -CH; C1
  • COMPOUND 16 COMPOUND 17 7
  • COMPOUND 19 COMPOUND 20
  • the invention is illustrated by the following examples wherein representative members of the above-described compounds were utilized as incorporated fixers in photo graphic silver halide emulsions.
  • Example 1 To a photographic gelatino-silve-r bromide emulsion containing .05 mole of silver bromide per 400 cc. of 6.25% aqueous gelatain solution was added Compound 1 described above in an amount equal to about 2 moles thereof per mole of silver bromide which was then coated on a cellulose acetate film support at an amount of 10 cc. of emulsion per 5 inch by 14 inch area of support. The resulting film was then exposed through a negative for seconds at 34 inches with a 60 watt light bulb. The film was then developed for 10 minutes at 68 F. in a developer having the formula:
  • Example 2 Example 1 was repeated except that 4 moles. of Compound 2 described above per mole of silver bromide were utilized in lieu of Compound 1. Without an additional processing, the unexposed and undeveloped areas of the developed film did not darken and remained substantially clear on prolonged exposure to ordinary room illumination. Similar results are obtained when equivalent molar proportions of Compounds 3 to are substituted for Compound 1.
  • Example 3 Example 1 was repeated except that 2 moles of Compound 8 described above per mole of silver bromide were utilized in lieu of Compound 1. Without additional processing, the unexposed and undeveloped areas of the developed film had a slight yellow cast which did not darken on prolonged exposure to ordinary room illumination.
  • Example 4 Example 1 was repeated except that 2 moles of Compound 9 described above per mole of silver bromide were utilized in lieu of Compound 1. Without additional proc essing, the unexposed and undeveloped areas of the developed film had a slight yellow cast which did not darken on prolonged exposure to ordinary room illumination.
  • Example 5 Example 1 was repeated except that 432 grams of Compound 10 described above per mole of silver bromidewere utilized in lieu of Compound 1. Without additional processing, the unexposed and undeveloped areas of the developed film did not'darken and remained substantially clear on prolonged exposure to ordinary room illumination.
  • the present invention thus provides new and useful photographic silver halide emulsions, and which emulsions can be stabilized or fixed during development in aqueous alkaline solutions to form chemically and photolytically stable silver derivatives with the unexposed and undeveloped silver halide in the emulsion. No additional or separate fixing step is necessary When processing our emulsions.
  • R R R and R are selected from the group consisting of a hydrogen atom, a phenyl radical and an alkyl radical; R and R are selected from the group consisting of a hydrogen atom, a phenyl radical, an alkyl radical, an alkyl radical containing a hydroxyl group and together the necessary carbon and hydrogen atoms to form a phenyl radical; and X, in combination with the adjacent nitrogen atom, is selected from the group consisting of a covalent quaternary salt group containing an electronegative group and an alkyl quaternary salt group including an anion group.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US133770A 1961-08-25 1961-08-25 Photographic emulsions containing thio derivatives as fixers and method of using same Expired - Lifetime US3189453A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE621607D BE621607A (en)van) 1961-08-25
US133770A US3189453A (en) 1961-08-25 1961-08-25 Photographic emulsions containing thio derivatives as fixers and method of using same
FR907407A FR1331244A (fr) 1961-08-25 1962-08-21 Nouvelle émulsion photographique contenant certains thioéthers à titre de fixateurs
DEE23428A DE1175074B (de) 1961-08-25 1962-08-23 Photographisches Material mit einer Halogen-silberemulsionsschicht, die das Fixierenueberfluessig macht
GB32856/62A GB1019223A (en) 1961-08-25 1962-08-27 Improvements in or relating to silver halide photographic materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US133770A US3189453A (en) 1961-08-25 1961-08-25 Photographic emulsions containing thio derivatives as fixers and method of using same

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US3189453A true US3189453A (en) 1965-06-15

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BE (1) BE621607A (en)van)
DE (1) DE1175074B (en)van)
GB (1) GB1019223A (en)van)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3271154A (en) * 1961-11-30 1966-09-06 Gen Aniline & Film Corp Antifogging and stabilizing agents for photography
US3301678A (en) * 1964-05-28 1967-01-31 Eastman Kodak Co Process for stabilizing photographic images with heat
US3326681A (en) * 1963-08-30 1967-06-20 Polaroid Corp Photographic products and processes
US3342596A (en) * 1964-03-11 1967-09-19 Eastman Kodak Co Benzothiazolium compounds for controlling overdevelopment
US3434842A (en) * 1964-08-08 1969-03-25 Agfa Gevaert Ag Photographic silver halide emulsions stabilized with 2-imino-thiazolones
US3502467A (en) * 1967-12-12 1970-03-24 Eastman Kodak Co High temperature processing in dyedeveloper diffusion transfer systems
US3506444A (en) * 1964-05-28 1970-04-14 Eastman Kodak Co Dry stabilization of photographic images
US3844788A (en) * 1973-04-02 1974-10-29 Eastman Kodak Co Incorporation of sulfonyl derivatives of isothiourea in light-sensitive elements
US20030170382A1 (en) * 2000-08-11 2003-09-11 Masanori Tomonari Colloidal metal solution, process for producing the same, and coating material containing the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2597915A (en) * 1949-09-24 1952-05-27 Eastman Kodak Co Stabilization of photographic emulsions sensitized with gold compounds
FR1009385A (fr) * 1948-06-11 1952-05-28 Cie Ind Des Telephones Perfectionnements aux systèmes diviseurs et multiplicateurs de fréquence
US2728667A (en) * 1952-11-08 1955-12-27 Eastman Kodak Co Molecular compounds of mercury salts with benzothiazoles as fog inhibitors in a silver halide emulsion
US2798067A (en) * 1954-03-29 1957-07-02 Eastman Kodak Co 2-imino-4-thiazolidones and preparation
US3057724A (en) * 1959-12-11 1962-10-09 Eastman Kodak Co Internal amide, nonpolymeric thioether sensitizers for photographic emulsions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1009385A (fr) * 1948-06-11 1952-05-28 Cie Ind Des Telephones Perfectionnements aux systèmes diviseurs et multiplicateurs de fréquence
US2597915A (en) * 1949-09-24 1952-05-27 Eastman Kodak Co Stabilization of photographic emulsions sensitized with gold compounds
US2728667A (en) * 1952-11-08 1955-12-27 Eastman Kodak Co Molecular compounds of mercury salts with benzothiazoles as fog inhibitors in a silver halide emulsion
US2798067A (en) * 1954-03-29 1957-07-02 Eastman Kodak Co 2-imino-4-thiazolidones and preparation
US3057724A (en) * 1959-12-11 1962-10-09 Eastman Kodak Co Internal amide, nonpolymeric thioether sensitizers for photographic emulsions

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3271154A (en) * 1961-11-30 1966-09-06 Gen Aniline & Film Corp Antifogging and stabilizing agents for photography
US3326681A (en) * 1963-08-30 1967-06-20 Polaroid Corp Photographic products and processes
US3342596A (en) * 1964-03-11 1967-09-19 Eastman Kodak Co Benzothiazolium compounds for controlling overdevelopment
US3506444A (en) * 1964-05-28 1970-04-14 Eastman Kodak Co Dry stabilization of photographic images
US3301678A (en) * 1964-05-28 1967-01-31 Eastman Kodak Co Process for stabilizing photographic images with heat
US3434842A (en) * 1964-08-08 1969-03-25 Agfa Gevaert Ag Photographic silver halide emulsions stabilized with 2-imino-thiazolones
US3502467A (en) * 1967-12-12 1970-03-24 Eastman Kodak Co High temperature processing in dyedeveloper diffusion transfer systems
US3844788A (en) * 1973-04-02 1974-10-29 Eastman Kodak Co Incorporation of sulfonyl derivatives of isothiourea in light-sensitive elements
US20030170382A1 (en) * 2000-08-11 2003-09-11 Masanori Tomonari Colloidal metal solution, process for producing the same, and coating material containing the same
US20070098909A1 (en) * 2000-08-11 2007-05-03 Masanori Tomonari Colloidal metal solution, process for producing the same and paint using the same
US20070098608A1 (en) * 2000-08-11 2007-05-03 Masanori Tomonari Colloidal metal solution, process for producing the same and paint using the same
US7557149B2 (en) * 2000-08-11 2009-07-07 Ishihara Sangyo Kaisha, Ltd. Colloidal metal solution, process for producing the same, and coating material containing the same
US7897675B2 (en) 2000-08-11 2011-03-01 Ishihara Sangyo Kaisha, Ltd. Colloidal metal solution, process for producing the same and paint using the same
US7902292B2 (en) 2000-08-11 2011-03-08 Ishihara Sangyo Kaisha, Ltd. Colloidal metal solution, process for producing the same and paint using the same

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GB1019223A (en) 1966-02-02
BE621607A (en)van)
DE1175074B (de) 1964-07-30

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