US3709689A - Surface development of an imagewise exposed emulsion containing silver halide grains with cores chemically ripened in two stages - Google Patents

Surface development of an imagewise exposed emulsion containing silver halide grains with cores chemically ripened in two stages Download PDF

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Publication number
US3709689A
US3709689A US00025091A US3709689DA US3709689A US 3709689 A US3709689 A US 3709689A US 00025091 A US00025091 A US 00025091A US 3709689D A US3709689D A US 3709689DA US 3709689 A US3709689 A US 3709689A
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United States
Prior art keywords
emulsion
process according
silver halide
solution
fogging
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Expired - Lifetime
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US00025091A
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English (en)
Inventor
R Florens
F Claes
F Moisar
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Agfa Gevaert NV
Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C1/485—Direct positive emulsions
    • G03C1/48515—Direct positive emulsions prefogged
    • 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
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • 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
    • 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03511—Bromide content
    • 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03535—Core-shell grains

Definitions

  • ABSTRACT Light-sensitive silver halide emulsion adapted for producing either negative or direct positive photographic images and containing composite grains of silver bromide having internal core portions of chemically ripened silver bromide and external shell portions surrounding such core portions of chemically fogged silver bromide, such emulsion on development with a surface developing agent having a characteristic curve which exhibits a knee portion connecting a generally rectilinear portion of positive gradient and a generally rectilinear portion of negative gradient and is preferably of generally symmetrical configuration.
  • the present invention relates to the production of photographic images by means of a photographic silver halide recording material, which depending on the intensity of the image-wise exposure yields a negative or positive image.
  • silver halide grains having a different interior and surface structure are prepared by interrupted precipitation and by chemically modifying the interior part of the grains by adding, e.g., hydrazine as reducing agent after a first precipitation stage.
  • a silver halide emulsion comprising composite silver halide grains, which consist of a chemically modified -core covered with a layer of unripened silver halide, is obtained.
  • a photographic silver halide emulsion comprising silver halide grains that contain in the interior part ripening nuclei or sensitivity specks can be fogged externally to such an extent that when said grains are incorporated into a photographic colloid layer and are image-wise exposed in a range of rather low exposure intensities, a negative image is formed, whereas by image-wise exposure in a range of higher exposure intensities a positive image is obtained, the developing conditions of both differently exposed photographic materials being the same.
  • Silver halide emulsions which are particularly suited for use according to the present invention are obtained by the following steps:
  • noble metal compounds e.g., gold compounds, sulphur compounds, reducing compounds, or mixtures of said compounds may be used.
  • the interior ripening of the grains is preferably carried out by means of a gold sensitizing agent or a reducing agent or with mixtures of both.
  • thiourea dioxide known also as formamidine sulphinic acid and mixtures of water-soluble gold salts and thiocyanates forming complexes with gold and having a solvent action on the silver'halide grains, e.g., alkali thiocyanates and ammonium thiocyanate.
  • the precipitation of the silver bromide is preferably accomplished by simultaneously adding the bromide solution and silver salt solution to the gelatin solution and keeping the pAg-value during the precipitation as constant as possible.
  • the emulsions containing ripening nuclei in the interior of the silver halide grains are fogged uniformly at the surface of the grains.
  • the fogging can be performed with the aid of suitable reducing agents, e.g., hydrazine, tin(lI) salts, ascorbic acid, or formamidine sulphinic acid.
  • suitable reducing agents e.g., hydrazine, tin(lI) salts, ascorbic acid, or formamidine sulphinic acid.
  • formamidine sulphinic acid thiourea dioxide
  • derivatives as sulphur sensitizers with reducing properties is described in the United Kingdom Patent Specification 789,823 and the U.S. Pat. Nos. 2,983,609 and 2,983,610.
  • the chemical fogging is the very critical step in the preparation of photographic silver halide emulsions suited for use according to the present invention. Different concentrations of fogging agent must be tried be fore it can be decided which concentration is the best for obtaining a negative or a positive image depending on a properly chosen exposure intensity.
  • the development of the exposed silver halide emulsion layers is preferably carried out by means of a surface developer, e.g., a lith-developer, which gives a particularly pronounced differentiation between the negative and positive image formation.
  • a surface developer e.g., a lith-developer
  • a lith-developer is a developing composition for active-radiation-exposed silver halide, which composition contains an addition compound of an aliphatic aldehyde or ketone with a hydrogen sulphite e.g., formaldehyde hydrogen sulphite, and hydroquinone as the sole developing substance.
  • a hydrogen sulphite e.g., formaldehyde hydrogen sulphite
  • EXAMPLE 1 An aqueous solution of ammonia was added to 650 ml of a 4 percent by weight aqueous gelatin solution at 45C to obtain a pH value of 9.3.
  • a precipitating flask were introduced ml of 3N aqueous solution of potassium bromide and 75 ml of 3N aqueous solution of silver nitrate, at a rate of 10 ml per minute, the pAg value during precipitation being adjusted to and maintained at a value corresponding to an E.M.F. of mV (Ag/saturated calomel electrode).
  • pAg value during precipitation being adjusted to a value corresponding to an E.M.F. of +100 mV (Ag/saturated calomel electrode).
  • the emulsion was allowed to gel after the addition of 84 g of gelatin and washed in the usual manner.
  • Portion B was treated for 1 hour at 55C with 3 ml of 10- molar aqueous solution of formamidine sulphinic acid
  • Portion C was treated for 1 hour at 55C with 4.5 ml
  • gelatin was added and the pAg was adjusted to avalue corresponding to an E.M.F. of 20 mV (Ag/saturated calomel electrode).
  • the emulsion ready for coating contained per kg 110 g of silver halide, 80 g of gelatin and l g of saponine as wetting agent.
  • 500 mg of formaldehyde (hardening agent) was added per kg of emulsion.
  • the emulsion was applied to a polyethylene terephthalate support at a ratio of 7.5 g of silver bromide per sq.m and dried.
  • Test strips were then exposed to incandescent light through a gray test wedge (constant 0.15) and developed for 135 sec at 20C in a developing solution comprising:
  • EXAMPLE 2 An emulsion was prepared, divided in three portions and fogged as described in Example 1.
  • Test strips were exposed and developed for 135 sec at 20C in the following developer composition:
  • a process of producing negative or direct positive images from the same light-sensitive photographic material which comprises:
  • the silver bromide cores with a reducing agent in alkaline medium, lowering the pH to stop that reduction sensitization and continuing the chemical ripening by noble metal compounds in acid medium,

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00025091A 1969-04-02 1970-04-02 Surface development of an imagewise exposed emulsion containing silver halide grains with cores chemically ripened in two stages Expired - Lifetime US3709689A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB1716169 1969-04-02

Publications (1)

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US3709689A true US3709689A (en) 1973-01-09

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US00025091A Expired - Lifetime US3709689A (en) 1969-04-02 1970-04-02 Surface development of an imagewise exposed emulsion containing silver halide grains with cores chemically ripened in two stages

Country Status (5)

Country Link
US (1) US3709689A (nl)
JP (1) JPS5036569B1 (nl)
BE (1) BE748059A (nl)
DE (1) DE2015070A1 (nl)
GB (1) GB1306801A (nl)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4619889A (en) * 1983-01-24 1986-10-28 Fuji Photo Film Co., Ltd. Image forming method

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5551780U (nl) * 1978-10-02 1980-04-05
JPS57120242U (nl) * 1981-01-20 1982-07-26
JPS57166169U (nl) * 1981-04-14 1982-10-20
DE3229999A1 (de) * 1982-08-12 1984-02-16 Agfa-Gevaert Ag, 5090 Leverkusen Fotografische silberhalogenidemulsion
GB8624704D0 (en) * 1986-10-15 1986-11-19 Minnesota Mining & Mfg High contrast scanner photographic elements

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3294540A (en) * 1963-12-17 1966-12-27 Eastman Kodak Co Lith-type emulsions with block co-polymers
US3367778A (en) * 1965-04-15 1968-02-06 Eastman Kodak Co Silver salt direct positive emulsion
US3501307A (en) * 1966-03-11 1970-03-17 Eastman Kodak Co Photographic reversal materials containing organic desensitizing compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3294540A (en) * 1963-12-17 1966-12-27 Eastman Kodak Co Lith-type emulsions with block co-polymers
US3367778A (en) * 1965-04-15 1968-02-06 Eastman Kodak Co Silver salt direct positive emulsion
US3501307A (en) * 1966-03-11 1970-03-17 Eastman Kodak Co Photographic reversal materials containing organic desensitizing compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Photolithography, Associated General Publications Pty, Ltd, Sydney, Australia, 1953, p. 45 46 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4619889A (en) * 1983-01-24 1986-10-28 Fuji Photo Film Co., Ltd. Image forming method

Also Published As

Publication number Publication date
JPS5036569B1 (nl) 1975-11-26
GB1306801A (en) 1973-02-14
DE2015070A1 (de) 1970-10-15
BE748059A (nl) 1970-09-28

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