US3728126A - Silver halide emulsion containing an organic selenium compound antifogging agent - Google Patents

Silver halide emulsion containing an organic selenium compound antifogging agent Download PDF

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Publication number
US3728126A
US3728126A US00017304A US3728126DA US3728126A US 3728126 A US3728126 A US 3728126A US 00017304 A US00017304 A US 00017304A US 3728126D A US3728126D A US 3728126DA US 3728126 A US3728126 A US 3728126A
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United States
Prior art keywords
emulsion
compound
silver halide
silver
light
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Expired - Lifetime
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US00017304A
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English (en)
Inventor
R Pollet
J Willems
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • 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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • 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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

  • the silver image formed after exposure undergoes a degradation, by which is meant a shift and a decrease of intensity of the image-tone during the finishing to a visible image e.g. under the influence of ingredients used in the developing bath, the fixing bath, the coloring'bath, and so on.
  • This degradation mainly appears on drying the developed images, whereby a decrease of density and of gradation takes Cl- -Se-Se- -Cl 4 COOH COOH HOOC- -SeSe- -COOH.
  • plumming an undesired color or metallic gloss of the developed silver
  • Compound 11 was prepared from the Grignard reagent of m-chloro-bromobenzene in anhydrous ether treated with an equimolecular amount of selenium by refluxing for 2 hours with stirring. The mixture was acidified with diluted hydrochloric acid whereupon the ether layer was separated, dried over sodium sulphate and filtered. An air current was conducted through the solution and the latter was distilled.
  • Compound 13 was prepared as follows 0.02 mole of phenylethylselenocyanate in 50 ml of methanol was admixed with a solution of 0.5 g of sodium in ml of methanol. The mixture was refluxed for 2 hours and an oil formed. After dilution with 75 ml of water, the mixture was extracted with ether. The ether extract was dried over sodium sulphate, filtered and concentrated by evaporation. Yield 1.7g of yellow oil.
  • the phenylethylsenocyanate used was prepared refluxing with stirring for 6 hours a mixture of 0.1 mole of bromethylbenzene and 0.1 mole of potassium selenocyanate in lOO ml of acetone.
  • the potassium bromide formed was filtered off by suction and the filtrate concentrated by evaporation.
  • the residual oil was distilled under reduced pressure. Yield 18 g.
  • the compounds according to the present invention are generally incorporated into the silver halide emulsion layer of the light-sensitive material.
  • the way in which the compounds of use according to the invention are added to the emulsions is not critical and the addition can be made during no matter what step of emulsion preparation; they can be added before or after the emulsion has been optically sensitized, preferably just before coating of the emulsion on a suitable support such as for example paper, glass or film.
  • the compounds of the invention can also be incorporated into another layer of the photographic material, e.g. a gelatin antistress layer or intermediate layer, which is in water-permeable relationship with the said emulsion layer.
  • a gelatin antistress layer or intermediate layer which is in water-permeable relationship with the said emulsion layer.
  • the compounds of use according to the present invention may be incorporated into any type of light-sensitive material comprising a silver halide emulsion layer e.g. a spectrally sensitized or non-sensitized silver halide emulsion layer, a silver halide emulsion layer of use in diffusion transfer processes for the production of silver images, an X-ray emulsion layer, and an emulsion layer sensitive to infra-red radiation. They may be incorporated into high speed negative material as well as into rather low speed positive materials.
  • Various silver salts may be used as light-sensitive salt e.g. silver bromide, silver iodide, silver chloride, or mixed silver halides e.g. silver chlorobromide or silver bromo-iodide.
  • the silver halides are dispersed in the common hydrophilic colloids such as gelatin, casein, zein, polyvinyl alcohol, carboxymethylcellulose, alginic acid, etc., gelatin being, however, favored.
  • the amount of compound according to the present invention employed in the light-sensitive silver halide material depends on the particular type of emulsion and the desired effect and can vary within very wide limits. The optimum amount to be added is best determined for each particular type of emulsion by trial.
  • the most suitable concentration of compound according to the present invention is generally comprised between 0.01 millimole and l millimole, preferably between 0.05 millimole and 0.25 millimole per mole of silver halide.
  • the compounds according to the present invention are preferably used in amounts from some mg to about 500 mg per sq.m. of light-sensitive printing material.
  • the light-sensitive emulsions may be chemically as well as optically sensitized. They may be chemically sensitized by effecting the ripening in the presence of small amounts of sulphur containing compounds such as allyl thiocyanate, allyl thiourea, sodium thiosulphate, etc.
  • the emulsions may also be sensitized by means of reductors for instance tin compounds as described in our British Patent Specification 789,823 and small amounts of noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium.
  • the emulsions may also comprise compounds which sensitize the emulsion by development acceleration for example alkylene oxide polymers.
  • alkylene oxide polymers may be of various type.
  • Various derivatives of alkylene oxides may be used to sensitize the silver halide emulsions e.g. alkylene oxide condensation products as described among others in US. Pat. Nos. 2,531,832 and 2,533,990 in U.K.Patent Specifications 920,637, 940,051, 945,340 and 991,608 and in Belgian Patent Specification 648,710.
  • Other compounds that sensitize the emulsion by development acceleration and that are suitable for use in combination with the compounds of use according to the invention are the onium derivatives of amino-N-oxides as described in U.K.Patent Specification 1,121,696.
  • stabilizers for instance heterocyclic nitrogen containing thioxo compounds such as benzothiazoline-Z-thione and l-phenyl-A tetrazoline-S-thione, mercury compounds such as those described in Belgian Patent Specifications 524,121 and 677,337 and in published Dutch Patent Application 67 15 932 and compounds of the hydroxytriazolo pyrimidine type (hydroxyazaindolizines), particularly in extreme storage and development circumstances.
  • addenda such as hardening agents, wetting agents, plasticizers, color couplers, developing agents and optical sensitizers can be incorporated into the emulsion in the usual way.
  • the values I and II given for the speed are exposure values corresponding with density 0.1 above fog and density 1 above fog respectively; a decrease of the value by 30 means a doubling of the speed.
  • Example 1 A conventional photographic gelatino silver bromoiodide emulsion (4.5 mole percent iodide) comprising per kg an amount of silver halide equivalent to 50 g of silver nitrate was divided into two portions A and B. To emulsion portion B was added per kg of emulsion 0.03 mmole of compound 2. Then the emulsions were coated on a conventional support and dried.
  • Example 4 A gelatino silver bromoiodide emulsion as described in example 3 was divided into four aliquot portions. To each portion, one of the compounds listed in the table below was added in the concentration given.
  • Example 5 Material 1 A gelatino silver chloroiodide emulsion (0.4 mole percent of iodide), prepared with aproportion of silver nitrate to gelatin of 1 to 3 was applied to a barytacoated paper support in such a way that after drying an amount of silver halide, equivalentto 1.9 g of silver nitrate was present per sq.m of light-sensitive material. The light-sensitive emulsion layer was overcoated with a thin gelatin covering layer which was hardened afterwards.
  • Material 2 -Material 2 was prepared as material 1 with the difference, however, that per kg of light-sensitive emulsion ready for coating, 1.8 mmol of compound 9 was added from a solution in ethylene glycol monomethyl ether.
  • Material 3 was prepared as material 1 with the difference, however, that per kg of light-sensitive emulsion ready for coating, 1.8 mmol of compound 10 was added from a solution in ethylene glycol monomethyl ether.
  • Material4 Material 4 was prepared as material 1 with the difference, however, that per kg of lightsensitive emulsion ready for coating, 1.8 mmol of compound 11 was added from a solution in ethylene glycol monomethyl ether.
  • Material 5 i i was prepared as material 1 with the difference, however, that per kg of light-sensitive emulsion ready for coating, 1.8 mmol of compound 3 was added from a solution in isopropylalcohol.
  • strips of each of these materials were exposedand developed for 5 minutes at 20C in a bath of the follow ing composition hydroquinone 6 g anhydrous sodium carbonate 32 g potassium bromide 2 g water up to 1000 ccs
  • the strips were rinsed and then fixed for minutes at room temperature in the following composition water 800 ccs anhydrous sodium thlosulphate 120 g potassium metabisulphite 25 g water to make 1000 ccs
  • the strips were then pressed for 6 minutes with their light-sensitive side to a polished plate of 80C.
  • the density of the various material strips was measured with a Macbeth densitometer before as well as after hot-glazing. The following results were attained.
  • Density before Density after hot-glazing hot-glazing 1st test material 1 2.04 1.59 material 2 2.05 1.96 2nd test material 1 1.96 1.67 material 3 1.99 1.86 3rd test material 1 1.98 1.64 material 4 2.01 1.89 material 5 1.96 1.82
  • Example 6 Material 1 A gelatino silver bromochloride emulsion (46 mole percent of chloride), prepared with a proportion of silver nitrate to gelatin of l to 3 was applied to a barytacoated paper support in such a way that after drying an amount of silver halide, equivalent to 2.6 g of silver nitrate was present per sq.m of light-sensitive material. The light-sensitive emulsion layer was overcoated with a thin gelatin covering layer which was hardened afterwards.
  • Material 2 was prepared as material 1 with the difference, however, that per kg of light-sensitive emulsion ready for coating, 1.8 mmol of compound 9 was added from a solution in ethylene glycol monomethyl ether.
  • Material 3 was prepared as material 1 with the difference, however, that per kg of light-sensitive emulsion ready for coating, 1.8 mmol of compound 10 was added from a solution in ethylene glycol monomethyl ether.
  • Material 4 was prepared as material 1 with the dif- Density before hot-glazing Density after hot-glazin g 1st test material 1 1.85 1.70 material 2 1.87 2.00 2nd test material 1 1.84 1.76 material 3 1.78 1.84 3rd test material 1 1.84 1.68 material 4 1.83 1.93 material 5 .8 1.78
  • Example 7 Material 1 A gelatino silver bromochloroiodide emulsion (9 mole percent of chloride and 1 mole percent of iodide), prepared with a proportion of silver nitrate to gelatin of l to 1.8 was applied to a baryta-coated paper support in such away that after drying an amount of silver halide, equivalent to 2.5 g of silver nitrate was present per sq.m of light-sensitive material. The light-sensitive emulsion layer was overcoated with a thin gelatin covering layer which was hardened afterwards.
  • Material 2a was prepared as material 1 with the difference, however, that per kg of light-sensitive emulsion ready for coating, 0.6 mmol of compound 9 was added from a solution in ethylene glycol monomethyl ether.
  • Material 2b was prepared as material 1 with thedifference, however, that per kg of light-sensitive emulsion ready for coating, 1.8 mmol of compound 9 was added from a solution in ethylene glycol monomethyl ether.
  • Photographic material comprising a support and at least one light-sensitive silver halide emulsion layer comprising in said emulsion layer and/or in at least one water-permeable layer coated at the same side of the support as the said emulsion layer and being in waterpermeable relation with said emulsion layer, at least one compound corresponding to the following general formula:
  • said emulsion layer is a gelatino silver halide emulsion layer.
  • Photographic material according to claim 1 according to according to according to claim claim claim claim claim claim claim claim claim ll) zo 10. Photographic material according to claim 1 wherein said compound has the formula:

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photoreceptors In Electrophotography (AREA)
US00017304A 1969-03-07 1970-03-06 Silver halide emulsion containing an organic selenium compound antifogging agent Expired - Lifetime US3728126A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB02234/69A GB1282303A (en) 1969-03-07 1969-03-07 Improved light-sensitive material

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BE (1) BE747012A (de)
DE (1) DE2010555C2 (de)
GB (1) GB1282303A (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120726A (en) * 1975-04-15 1978-10-17 Veb Filmfabrik Wolfen Silver-halide emulsion sensitized with an asymmetrical disulfide
US5028522A (en) * 1988-11-14 1991-07-02 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5292635A (en) * 1990-12-27 1994-03-08 Eastman Kodak Company Thiosulfonate-sulfinate stabilizers for photosensitive emulsions
US5910402A (en) * 1997-06-13 1999-06-08 Agfa-Gevaert, N.V. Photosensitive image-forming element with increased sensitivity-fog-relationship

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4607001A (en) * 1985-04-04 1986-08-19 Eastman Kodak Company Divalent chalcogenide fog inhibiting agents for silver halide photography
US4607000A (en) * 1985-04-04 1986-08-19 Eastman Kodak Company Amido substituted divalent chalcogenide fog inhibiting agents for silver halide photography
US4861703A (en) * 1988-08-15 1989-08-29 Eastman Kodak Company Cyclic dichalcogenide fog inhibiting agents for silver halide photography
US5219721A (en) * 1992-04-16 1993-06-15 Eastman Kodak Company Silver halide photographic emulsions sensitized in the presence of organic dichalcogenides

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1602592A (en) * 1924-06-06 1926-10-12 Eastman Kodak Co Photographic light-sensitive material containing selenium and process of making the same
US1623499A (en) * 1925-06-16 1927-04-05 A corpora
US2057764A (en) * 1933-07-22 1936-10-20 Agfa Ansco Corp Manufacture of stabilized silver halide emulsions
US2385762A (en) * 1944-07-01 1945-09-25 Gen Aniline & Film Corp Stabilized silver halide emulsions
US3226232A (en) * 1963-05-16 1965-12-28 Gen Aniline & Film Corp Fog reduction in silver halide emulsions with a diphenyldisulfide dicarboxylic acid
US3397986A (en) * 1964-12-29 1968-08-20 Eastman Kodak Co Photographic emulsion stabilized with bis (p-acylamidophenyl) disulfides

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE463879C (de) * 1925-07-26 1928-08-04 I G Farbenindustrie Akt Ges Verfahren zur Herstellung von photographischen Silbersalzemulsionen
DE606528C (de) * 1933-07-23 1934-12-04 I G Farbenindustrie Akt Ges Verfahren zur Stabilisierung photographischer Emulsionen
US2438716A (en) * 1944-10-06 1948-03-30 Gen Aniline & Film Corp Stabilized silver halide emulsions
US3409437A (en) * 1965-02-26 1968-11-05 Gaf Corp Silver halide emulsions containing antibronzing agents

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1602592A (en) * 1924-06-06 1926-10-12 Eastman Kodak Co Photographic light-sensitive material containing selenium and process of making the same
US1623499A (en) * 1925-06-16 1927-04-05 A corpora
US2057764A (en) * 1933-07-22 1936-10-20 Agfa Ansco Corp Manufacture of stabilized silver halide emulsions
US2385762A (en) * 1944-07-01 1945-09-25 Gen Aniline & Film Corp Stabilized silver halide emulsions
US3226232A (en) * 1963-05-16 1965-12-28 Gen Aniline & Film Corp Fog reduction in silver halide emulsions with a diphenyldisulfide dicarboxylic acid
US3397986A (en) * 1964-12-29 1968-08-20 Eastman Kodak Co Photographic emulsion stabilized with bis (p-acylamidophenyl) disulfides

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120726A (en) * 1975-04-15 1978-10-17 Veb Filmfabrik Wolfen Silver-halide emulsion sensitized with an asymmetrical disulfide
US5028522A (en) * 1988-11-14 1991-07-02 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5292635A (en) * 1990-12-27 1994-03-08 Eastman Kodak Company Thiosulfonate-sulfinate stabilizers for photosensitive emulsions
US5910402A (en) * 1997-06-13 1999-06-08 Agfa-Gevaert, N.V. Photosensitive image-forming element with increased sensitivity-fog-relationship

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DE2010555A1 (de) 1970-09-24
BE747012A (nl) 1970-09-07
GB1282303A (en) 1972-07-19
DE2010555C2 (de) 1983-10-13

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