US3591385A - Silver halide emulsions sensitized with a combination of sulfur and selenium for color photography - Google Patents

Silver halide emulsions sensitized with a combination of sulfur and selenium for color photography Download PDF

Info

Publication number
US3591385A
US3591385A US818418A US3591385DA US3591385A US 3591385 A US3591385 A US 3591385A US 818418 A US818418 A US 818418A US 3591385D A US3591385D A US 3591385DA US 3591385 A US3591385 A US 3591385A
Authority
US
United States
Prior art keywords
selenium
silver halide
color
sulfur
photographic
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
Application number
US818418A
Other languages
English (en)
Inventor
Francis J Evans
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Application granted granted Critical
Publication of US3591385A publication Critical patent/US3591385A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
    • 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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising

Definitions

  • This invention relates to photography.
  • this invention relates to chemically sensitizing silver halide emulsions and photographic elements for color photography and to color-recording elements comprising recording layers of such emulsions.
  • Photographic color-recording elements typically comprise at least one and usually multiple layers of photographic silver halide, usually a silver chloride or silver chlorobromide emulsion.
  • Each layer is sensitive to a region of the spectrum, e.g., a red-sensitive layer, a greensensitive layer and a blue-sensitive layer, and each can contain a color coupler which forms by color development, as with a p-phenylenediamine or p-aminophenol developing agent, a color image usually complementary to the spectral region to which that layer is sensitive, e.g., cyan, magenta and yellow.
  • Typical color-recording photographic elements and processes of developing an image in such elements are described, for example, in Mees and James, The Theory of the Photographic Process, 3rd edition, 1966, pages 382396. It is known to employ labile sulfur compounds as chemical sensitizers for one or more of the silver halide layers in such a color-recording element. This is described, for example, in US. Pat. 2,956,879 of VanCampen, issued Oct. 18, 1960.
  • a further object is to provide a method of chemically sensitizing a photographic silver halide emulsion containing a color-forming coupler with a combination of sensitizers as described.
  • chemical sensitization of a photographic silver halide emulsion especially an emulsion comprising a photographic silver halide containing at least 10 mole percent chloride with any remainder consisting of bromide and not more than 10 mole percent iodide, containing a color-forming coupler, with a combination of labile sulfur with labile selenium, provides a synergistic increase in speed without adversely affecting the color-forming coupler and development of a color image.
  • Chemical sensitization of a photographic silver halide emulsion containing a color-forming coupler, as described can be carried outwith a combination of (a) 0.5 mg. to 50 mg. of sulfur sensitizer with (b) 0.05 mg. to 5 mg. of selenium sensitizer per mole of silver present in the emulsion.
  • a method of chemically sensitizing a photographic silver halide emulsion containing a color-forming coupler comprising Ostwald ripening said emulsion, adding a sulfur sensitizer and selenium sensitizer thereto, and finally digesting the resulting emulsion provides the described synergistic speed increase.
  • Selenium sensitizers that can be used according to the invention can be selected from a wide group of suitable selenium compounds, such as those described in US. Pat. 1,623,499 of Sheppard et al., issued Apr. 5, 1927, US. Pat. 1,574,944 of Sheppard, issued Mar. 2, 1926, US. Pat. 1,602,592 of Sheppard, issued Oct. 12, 1926 and US. Pat. 3,296,446 of Dunn, issued Jan. 10, 1967. Any selenium sensitizer commonly employed in the photographic art can be employed according to the invention.
  • selenium sensitizers are organic compounds having a selenium atom doubly bonded to a carbon atom by a covalent linkage. These include, for example, selenoamides, selenoketones (especially ketones having an alkyl radical attached to the moiety), selenocarboxylic acids and esters, etc.
  • Preferred selenium sensitizers are aliphatic selenoureas, e.g., alkyl selenoureas having alkyl radicals containing 1 to 8 carbon atoms, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl radicals.
  • Such selenourea compounds have at least one hydrogen atom on the nitrogen atom available for formation of an enol tautmer.
  • aromatic selenoureas having an aromatic radical, e.g., containing 6 to 20 carbon atoms, such as phenyl, tolyl, etc., or a heterocyclic radical such as benzothiazolyl, pyridyl, etc., and aliphatic isoselenocyanates, such as allyl isoselenocyanate.
  • Colloidal selenium is also a suitable selenium sensitizer as are selenophosphones and selenophosphates.
  • a suitable concentration of selenium sensitizer needed for optimum sensitization in accordance with the invention will vary according to several factors, such as the particular selenium sensitizer selected, the nature of the emulsion and time and temperature of digestion and the like. Depending on the particular conditions and other factors described, concentrations of selenium sensitizer can be in the range of about 0.01 mg. to about 20 mg. of selenium sensitizer per mole of silver in the emulsion in accordance -with the invention. In most cases the optimum concentration will fall in the range from about 0.1 mg. to about mg. of the selenium sensitizer per mole of silver.
  • Sulfur sensitizers useful in combination with the described selenium sensitizers can be selected from any of a variety of useful sulfur compounds known for use as chemical sensitizers, including, for instance, those described in US. Pat. 1,623,499 of Sheppard et al., issued Apr. 5, 1927, US. Pat. 1,574,944 of Sheppard, issued Mar. 2, 1926 and U.S. Pat. 2,410,689 of Sheppard et al., issued Nov. 5, 1946, as well as Mees and James, The Theory of the Photographic Process, 3rd edition, 1966, pages 113-116.
  • useful sulfur sensitizers include:
  • Colloidal sulfur is also a suitable sulfur sensitizer.
  • Concentrations of labile sulfur needed for optimum sensitization according to the invention will vary depending on the several factors described for the optimum concentration of selenium sensitizer, such as the particular sulfur sensitizer selected, the nature of the emulsion, time and temperature of digestion. Depending on the conditions and factors described concentrations of sulfur sensitizer can be about 0.5 mg. to about 50 mg. of sulfur sensitizer per mole of silver in the emulsion. In most cases the range will be about 2.0 mg. to about 20 mg. of sulfur sensitizer per mole of silver in the emulsion.
  • the ratio of selenium sensitizer to sulfur sensitizer in the described combination can vary depending on the desired contrast of the developed image, the particular selenium sensitizer and sulfur sensitizer, the nature of the emulsion, time and temperature of digestion and the like.
  • concentration of selenium sensitizer and concentration of sulfur sensitizer will preferably be within the described ranges.
  • labile has a meaning known in the art of photography and is defined, for example, in US. Pat. 3,408,196 of McVeigh, issued Oct. 29, 1968 and US. Pat. 3,297,446 of Dunn, issued Jan. 10, 1967. It means, for example, with regard to selenium, a material which yields a silver selenide that is insoluble in water at room temperature (20 C.) upon addition to an aqueous silver nitrate solution.
  • non-labile as used herein describing selenium compounds has a meaning known in the photographic art and is defined, for example, in US. Pat. 3,408,- 196 of McVeigh, issued Oct. 29, 1968. It means a material which does not yield a silver selenide that is insoluble in water at room temperature (20 C.) upon addition to an aqueous silver nitrate solution.
  • potassium selenocyanate and selenous acid are non-labile selenium compounds since silver selenide does not precipitate when these compounds are added to an aqueous silver nitrate solution.
  • One embodiment of the invention is a photographic silver halide emulsion comprising silver halide containing at least 10 mole percent chloride with any remainder consisting of bromide and not more than 10 mole percent iodide, a color-forming coupler and the silver halide emulsion being chemically sensitized with a combination of labile sulfur with labile selenium.
  • A. wide range of color-forming couplers and processes for forming color images can be employed according to the invention.
  • Suitable color-forming couplers are described, for example, in US. Pat. 3,297,446 of Dunn, ssued Jan. 10, 1967 and US Pat. 3,297,447 of McVeigh, issued Jan. 10, 1967, the disclosures of which are incorporated herein by reference.
  • Suitable color-forming couplers are also described in Mees and James. The Theory of the Photographic Process, 3rd edition, 1966, Chapter 17.
  • the sensitizing addenda and color couplers of the invention can be added to a silver halide emulsion in a variety of ways and at various stages in the preparation of the emulsion.
  • sensitizing addenda it is preferred to add the sensitizing addenda to an emulsion after completion of the Ostwald ripening and prior to a final digestion. It is preferable to add the sensitizing composition after the silver halide grains have reached substantially their final size and shape.
  • Water-soluble addenda may be added in aqueous solution; other solvents can be used as necessary for more diflicultly soluble sensitizers.
  • Useful organic solvents for this purpose include ethanol, methanol, pyridine, acetone, dioxane and the like; the more polar solvents are preferred.
  • Colloidal sensitizers such as colloidal sulfur or selenium are added as a suspension, such as a suspension in water of other suspending medium.
  • Another method is to first dissolve the sensitizer in a water immiscible liquid, e.g., tricresyl phosphate, dibutyl phosphate, triphenyl phosphate, etc., and then mechanically disperse the immiscible solvent in the emulsion as very small suspended particles carrying the sensitizer.
  • Dispersing agents for color couplers can be employed in the described emulsion, such as set out in US. Pat. 2,322,027 of Ielley and Vittum, issued June 15, 1943 and US. Pat. 2,304,940 of Mannes and Godowsky, issued Dec. 15, 1942.
  • a silver halide emulsion as described can contain conventional addenda, especially those known to be beneficial in photographic elements, 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 an oxypolysaccharides.
  • conventional addenda especially those known to be beneficial in photographic elements, 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 an oxypolysaccharides.
  • the described photographic emulsions can be nonspectrally sensitized emulsions, such as X-ray or other nonspectrally sensitized emulsions, or be orthochromatic, panchromatic, infrared and other emulsions. They are typically photographic emulsions containing spectral sensitizers, such as sensitizing dyes as described, for example, in US. Pat. 2,526,632 of Brooker et al., issued Oct. 24, 1950 and US. Pat. 2,503,776 of Sprague, issued Apr. 11, 1950. Spectral sensitizers which can be used include cyanines, merocyanines, styryls and hemicyanines.
  • photographic silver salts can be used in the practice of the invention. These include photographic silver halides, such as silver chloride, silver bromide, silver iodide, as well as mixed halides, such as silver bromoiodide, silver chloroiodide and the like.
  • a preferred photographic silver salt is one which comprises at least mole percent chloride with any remainder being bromide and not more than 10 mole percent iodide. This photographic silver salt has relatively low photographic speed and is typically employed in a photographic paper for producing prints.
  • the silver halide emulsion layer of a photographic element sensitized according to the invention can contain any of the 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 photographic element can also contain dispersed polymerized vinyl compounds and include, for example, the rwater-insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates and the like.
  • the silver halide emulsion of a photographic element which can be sensitized according to the invention can be coated on a Wide variety of supports.
  • a reflective white paper support is preferred, such as a baryta coated paper or the like, but the described emulsion can be coated on various reflective supports, such as 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, metal and the like.
  • Paper supports such as papers which are coated with alpha-olefin polymers, particularly polymers of alpha-olefins containing two or more carbon atoms, as exemplified by polyethylene, polypropylene, ethylene, butyl copolymers and the like, can also be employed.
  • the reflective support can be tinted with a color hue if desired.
  • Photographic emulsions sensitized according to the invention can contain speed-increasing compounds, such as quaternary ammonium compounds, polyethylene glycols or thioethers. Useful effects often can be obtained by adding the aforementioned speed-increasing compounds to the photographic developer solutions instead of, or in addition to, the photographic emulsions.
  • speed-increasing compounds such as quaternary ammonium compounds, polyethylene glycols or thioethers.
  • Another embodiment of the invention is in a method of developing a latent image in an exposed photographic silver halide emulsion containing a color-forming coupler with a silver halide developer the improvement comprising employing a photographic silver halide emulsion which is chemically sensitized with a combination of labile sulfur with labile selenium.
  • Suitable developing agents and processing conditions can be employed, typically those employed in the photographic art for developing a color image in a photographic silver halide emulsion containing a colorforming coupler. Suitable developing agents and processing conditions are set out, for example, in U.S. Pat. 2,956,879 of VanCampen, issued Oct. 18, 1960 and in Mees and James, The Theory of the Photographic Process, Chapter 17 (1966).
  • Example 1 A red-sensitive silver chlorobromide emulsion (86% bromide) containing a phenolic cyan coupler, 2-(alpha-di-tertiary aminophenoxy-n-butyrylamino)-4,6-dichloro-5-methyl phenol, is divided into portions and the separate portions are chemically sensitized to optimum sensitivity with, respectively, sodium thiosulfate, dimethyl selenourea, and with combinations of the two in the concentrations shown for each portion in Table I. Each portion is coated on white reflective baryta coated paper supports at 35 mg. silver and mg. gelatin per square foot and dried.
  • a sample of each coated portion is exposed through an intensity step wedge to light of daylight quality and then processed by a conventional negative-positive color print process using a phenylenediamine developer followed by stop, fix, bleach and hardener fixing steps.
  • the steps. of the negative color process are described in Example 1 of U8. Pat. 2,956,879 of VanCampen, used Oct. 18, 1960 and are as follows:
  • the photographic element is processed by immersion in a developer having the following cocposition:
  • the resulting element is then immersed in a stop bath for about two minutes.
  • the stop bath has the following composition:
  • a photographic element as in claim wherein said layer comprises silver halide containing at least mole TABLE I Sample Portion N 0. Chemical sensitization cone. in mg./mole Ag.
  • Example 2 Three color printing papers are made as described in Example 2 of US. Pat. 2,956,879 of Van- Campen, issued Oct. 18, 1960 but using for each of the color recording layers in each element a silver chlorobromide emulsion sensitized with a mixture of sulfur sensitizer and selenium sensitizer as described for samples 3 and 4 of Example 1 above. Results similar to those of Example 1 are obtained upon exposure and processing as set out in Example 1.
  • a photographic silver halide emulsion comprising silver halide containing at least 10 mole percent chloride with any remainder consisting of bromide and not more than 10 mole percent iodide, and a color-forming coupler; said silver halide emulsion being chemically sensitized with a combination of labile sulfur with labile selenium.
  • a photographic element comprising a support containing at least one layer of a silver halide emulsion comprising silver halide containing at least 10 mole percent chloride with any remainder consisting of bromide and not more than 10 mole percent iodide, and a color-forming coupler; said silver halide emulsion being chemically sensitized with a combination of labile sulfur with labile selenium.
  • a photographic element comprising a support containing (a) a layer of a photographic silver halide emulsion sensitive to the blue region of the spectrum and containing a color-forming coupler which forms a yellow image upon color development, (b) a layer of a photographic silver halide emulsion sensitive to the green region of the spectrum and containing a color-forming coupler which forms a magenta image upon color development and (c) a layer of a photographic silver halide emulsion sensitive to the red region of the spectrum and containing a color-forming coupler which forms a red image upon color development, the improvement comprising at least one of said layers comprising silver halide containing at least 10 mole percent chloride with any remainder consisting of bromide and not more than 10 mole percent iodide, and at least one of said layers being chemically sensitized with a combination of labile sulfur with labile selenium.
  • a method of chemically sensitizing a photographic silver halide emulsion containing a color forming coupler comprising Ostwald ripening said emulsion, adding a sulfur sensitizer and labile selenium thereto, and finally digesting the resulting emulsion.

Landscapes

  • 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)
US818418A 1969-04-22 1969-04-22 Silver halide emulsions sensitized with a combination of sulfur and selenium for color photography Expired - Lifetime US3591385A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US81841869A 1969-04-22 1969-04-22

Publications (1)

Publication Number Publication Date
US3591385A true US3591385A (en) 1971-07-06

Family

ID=25225490

Family Applications (1)

Application Number Title Priority Date Filing Date
US818418A Expired - Lifetime US3591385A (en) 1969-04-22 1969-04-22 Silver halide emulsions sensitized with a combination of sulfur and selenium for color photography

Country Status (5)

Country Link
US (1) US3591385A (enrdf_load_stackoverflow)
BE (1) BE748958A (enrdf_load_stackoverflow)
CA (1) CA929782A (enrdf_load_stackoverflow)
FR (1) FR2043359A5 (enrdf_load_stackoverflow)
GB (1) GB1305773A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0514675A1 (en) 1991-04-22 1992-11-25 Fuji Photo Film Co., Ltd. Silver halide photographic materials and method for processing the same
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
EP0693710A1 (en) 1994-07-18 1996-01-24 Konica Corporation Silver halide photographic element and processing method thereof
US5616446A (en) * 1994-09-29 1997-04-01 Konica Corporation Silver halide photographic light-sensitive material
US20060121397A1 (en) * 2003-01-31 2006-06-08 Konica Minolata Photo Imaging Inc. Silver halide emulsion silver halide photographic sensitive material and method of image formation

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0514675A1 (en) 1991-04-22 1992-11-25 Fuji Photo Film Co., Ltd. Silver halide photographic materials and method for processing the same
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
EP0693710A1 (en) 1994-07-18 1996-01-24 Konica Corporation Silver halide photographic element and processing method thereof
US5556738A (en) * 1994-07-18 1996-09-17 Konica Corporation Silver halide photographic element and processing method thereof
US5616446A (en) * 1994-09-29 1997-04-01 Konica Corporation Silver halide photographic light-sensitive material
US20060121397A1 (en) * 2003-01-31 2006-06-08 Konica Minolata Photo Imaging Inc. Silver halide emulsion silver halide photographic sensitive material and method of image formation
US7220537B2 (en) 2003-01-31 2007-05-22 Konica Minolta Photo Imaging, Inc. Silver halide emulsion silver halide photographic sensitive material and method of image formation

Also Published As

Publication number Publication date
BE748958A (fr) 1970-09-16
GB1305773A (enrdf_load_stackoverflow) 1973-02-07
FR2043359A5 (enrdf_load_stackoverflow) 1971-02-12
CA929782A (en) 1973-07-10

Similar Documents

Publication Publication Date Title
US3297446A (en) Synergistic sensitization of photographic systems with labile selenium and a noble metal
US3297447A (en) Stabilization of synergistically sensitized photographic systems
US3761270A (en) Photographic element composition and process
US3719492A (en) Complexed p-phenylenediamine containing photographic element and development process therefor
US3622318A (en) Photographic materials and processes
US2996382A (en) Photographic elements having improved sensitivity
US3628960A (en) Light sensitive halide material with variable contrast
US4292400A (en) Photographic silver halide development in the presence of thioether development activators
US3935014A (en) Direct-positive photographic emulsion containing, unfogged, monodispersed silver halide grains having a layered grain structure of specific silver chloride content
US3522052A (en) Photographic supersensitized silver halide emulsions
US3708303A (en) Photographic elements and processes lithographic silver halide element containing a 1-(amidophenyl)-5-mercaptotetrazole sensitizing agent and development process of using same
US3708298A (en) Method of producing direct positive images with photographic silver halide material containing compound releasing iodide ions
US3708302A (en) Silver halide emulsion sensitized with thioamine-glutaraldehyde or acrylic aldehyde adduct
US3784381A (en) High speed silver chloroiodide emulsions
US3582333A (en) Method for reducing color fog in color emulsions coated on electron bombarded supports
US3544336A (en) Phosphate antifoggants for photographic emulsions
US3708300A (en) Silver-dye-bleach photographic materials
US3536487A (en) Photographic elements and processes for producing therein interimage effects with diffusible 4 - thiazoline-2-thione
US3591385A (en) Silver halide emulsions sensitized with a combination of sulfur and selenium for color photography
US3730724A (en) Silver halide color photographic element containing a magenta color coupler and a carboxy substituted thiazoline compound
US3178292A (en) Direct-print photographic silver halide emulsions
JPH0810322B2 (ja) ハロゲン化銀カラ−写真感光材料
US3660099A (en) Light-sensitive supersensitized silver halide photographic emulsions
US3408196A (en) Sensitization of silver halide emulsion with labile selenium formed in situ
US3607278A (en) Photographic elements containing fogged and unfogged silver halide grains and a slow silver halide emulsion layer