US3779776A - Fogged, direct-positive silver halide emulsion containing a color coupler and a heterocyclic mercaptan desensitizer - Google Patents

Fogged, direct-positive silver halide emulsion containing a color coupler and a heterocyclic mercaptan desensitizer Download PDF

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Publication number
US3779776A
US3779776A US00269861A US3779776DA US3779776A US 3779776 A US3779776 A US 3779776A US 00269861 A US00269861 A US 00269861A US 3779776D A US3779776D A US 3779776DA US 3779776 A US3779776 A US 3779776A
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US
United States
Prior art keywords
direct
silver halide
element according
positive
photographic element
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Expired - Lifetime
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US00269861A
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English (en)
Inventor
W Vanassche
R Pollet
H Borginon
H Pattyn
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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
    • G03C1/485—Direct positive emulsions
    • G03C1/48515—Direct positive emulsions prefogged
    • G03C1/48523—Direct positive emulsions prefogged characterised by the desensitiser

Definitions

  • R is hydrogen or C -C alkyl
  • n 1, 2, or 3.
  • the desensitizing agents are highly compatible with color couplers.
  • the above desensitizing agents were found to be fully compatible with color couplers in that they favourably resist desorption from the silver halide grains by color forming couplers.
  • a direct-positive photographic emulsion comprising fogged silver halide grains, a colorforming coupler and a desensitizing agent corresponding to one of the above general formulae, a corresponding disulphide thereof or such desensitizing agent precursor compound.
  • the present invention further provides a method of producing direct-positive color images, which method comprises image-wise exposing a direct-positive element having prefogged silver halide grains and comprising a desensitizing agent according to one of the above general formulae, a corresponding disulphide thereof or such desensitizing agent precursor compound, and developing said element by means of an aromatic primary amino color developing agent in the presence of a co1orforming coupler.
  • the amount of desensitizing compounds used according to the present invention may vary within very wide limits. They are preferably used in amounts ranging from about mg to about 2 g per mole of silver halide.
  • color-forming couplers include cyan-forming color couplers of the phenol or naphthol type, magenta forming color couplers of the pyrazolone or indazolone type and yellow forming open-chain reactive methylene compounds containing the COCH -CO group, e.g., benzoylacetanilide couplers. They include polymeric as well as non-polymeric color couplers.
  • the color-forming couplers can be incorporated into the direct-positive photographic silver halide emulsion any suitable technique, e.g., from aqueous alkaline solutions or by techniques of the type shown in US. Pat. Nos. 2,186,849 of Gustave Wilmanns, Kreis Bitterfield, Karl Kumetat, Alfred Friihlich, Wilhelm Scheider and Richard Brodersen issued Jan. 9, 1940; 2,269,158 of Michele Martinez issued Jan. 6, 1942; 2,284,887 of Emil Vollenweider issued June 2, 1942; 2,304,939 of Emil Vollenweider issued Dec. 15, 1942; 2,304,940 of Leopold D.Mannes and Leopold Godowsky Jr. issued Dec.
  • tion is not critical and may consist of any of the known silver halides suitable for the formation of directpositive silver halide emulsions, e.g., silver bromide, silver chloride, silver chlorobromide, silver bromoiodide and silver chlorobromoiodide.
  • Especially suitable for use according to the present invention are direct-positive silver halide emulsions, the silver halide grains of which have an average grain size of less than about 1 micron.
  • the silver halide grains may be regular and have one of the commonly known shapes, e.g., cubic, octahedral or rhombohedral as described in British Pat. Application No. 14,224/71 filed May 1 l, 1971 by Gevaert-Agfa N.V. They preferably have a substantially uniform diameter.
  • Fogging of the silver halide emulsions may occur by exposure before or after coating of the emulsion, to actinic radiation but preferably fogging occurs by chemical means.
  • Chemical fogging can be effected by chemical sensitization to fog and any of the usual chemical sensitizing methods may be used.
  • Fogging can be effected successfully by means of reducing agents, e.g., hydrazine, hydroxylamine, tin(ll) salts such as tin(ll) chloride, ascorbic acid, formaldehyde, thiourea dioxide also called formamidine sulphinic acid, polyamines, phosphonium salts etc.
  • the direct positive silver halide emulsions may further comprise all kinds of known emulsion ingredients, e.g., wetting agents, development accelerators, optical brightening agents, hardeners, such as formaldehyde and mucochloric acid, stabilizers, spectral sensitizing dyes, which include cyanines, meroeyanines, complex (trinuclear) cyanines, complex (trinuclear) meroeyanines, styryls, and hemicyanines, etc.
  • known emulsion ingredients e.g., wetting agents, development accelerators, optical brightening agents, hardeners, such as formaldehyde and mucochloric acid, stabilizers, spectral sensitizing dyes, which include cyanines, meroeyanines, complex (trinuclear) cyanines, complex (trinuclear) meroeyanines, styryls, and hemicyanines, etc.
  • Gelatin is preferably used as a vehicle for the silver halide but like in other silver halide emulsions the gelatin may be replaced wholly or partly by other hydrophilic colloids, e.g., colloidal albumin, zein, agar-agar, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose ethers, partly hydrolyzed cellulose esters, e.g., partly hydrolyzed cellulose acetate etc.
  • hydrophilic colloids e.g., colloidal albumin, zein, agar-agar, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose ethers, partly hydrolyzed cellulose esters, e.g., partly hydrolyzed cellulose acetate etc.
  • the emulsions may be coated on any of a wide variety of supports in accordance with usual practice to provide light-sensitive silver halide materials.
  • the supports include glass, paper, baryta-coated paper, polyolefin-coated paper, e.g., coated with polyethylene and polypropylene, which in order to promote adhesion of the emulsion may be electron-radiated, film supports of cellulose acetate, cellulose acetatebutyrate, polyesters, e.g., polyethylene terephthalate,
  • the emulsion was reductionand gold-fogged by adjustment of the pAg to 5.3 and the pH to 7, by heating for 90 minutes at 60C and by the addition of 30 mg of chloroaurate per mole of silver halide. Heating was continued for minutes at 60C whereupon the pAg was adjusted to 8.2 at 35C.
  • the emulsion was divided into several samples and to each sample one of the desensitizing agents listed in the table below was added in an amount of 600 mg per mole of silver halide.
  • a magentaforming color coupler of the formula t-CsHn C N m5 lLNHCo was added also in an amount of 4() g. per mole of silver halide.
  • the values of the speed obtained after exposure and conventional black-and-white or color processing are listed in the table below.
  • the values given for the speed are relative log exposure values. An increase of these values by 0.30 means a doubling of the speed.
  • Example 1 was repeated with the difference that the magenta-forming color coupler was replaced by the cyan forming color coupler corresponding to the formula
  • the values of the speed obtained are listed in the following table.
  • Example 1 was repeated with the difference that the magenta-forming color coupler was replaced by a yellow-forming color coupler corresponding to the formula 0 (CH1) GB:
  • Example 1 was repeated with the difference that 5-mnitrobenzylidene rhodanine was used as comparative desensitizing agent instead of pinacryptol yellow.
  • Example 4 was repeated with the difference that the magenta-forming color coupler was replaced by the color coupler of the formula The values of the speed obtained are listed in the foll.
  • a direct-positive photographic color element which comprises uniformly fogged radiation-sensitive silver halide, a color forming coupling product capable of forming a dye on coupling with an oxidized aromatic primary amino color developing agent and a desensitizing agent or a desensitizing agent precursor wherein said desensitizing agent has one of the following general formulae, a tautomeric form thereof, or is a corresponding disulphide R is hydroxyl or C,C alkyl,
  • R is hydrogen or C C alkyl
  • R is C -C alkyl or aryl
  • A is a single bond or NH
  • B is phenyl or diphenyl sulphone group in which the or both phenyl group(s) is (are) substituted with one or more nitro groups
  • n 1, 2, or 3.
  • a direct-positive photographic element wherein the said desensitizing agent precursor is a compound corresponding to one of the general formulae of claim 1, or a tautomeric form thereof, wherein the tautomeric hydrogen atom is replaced by a COX group in which X represents alkyl, aralkyl, aryl, or a group identical to the diazine group linked to the carbonyl group of COX, by a SO Y group in which Y is alkyl, aryl, or aralkyl, or by a COOZ group wherein Z is alkyl or aryl.
  • a direct-positive photographic element according to claim 1, wherein the silver halides of the emulsion have a substantially uniform diameter.
  • a method of producing a direct-positive image which comprises exposing image-wise to radiation a direct-positive element according to claim 1, and developing the exposed material in a silver halide developer comprising an aromatic primary amino color developing agent.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
US00269861A 1971-07-30 1972-07-07 Fogged, direct-positive silver halide emulsion containing a color coupler and a heterocyclic mercaptan desensitizer Expired - Lifetime US3779776A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB3601771A GB1388847A (en) 1971-07-30 1971-07-30 Direct-positive silver halide emulsions

Publications (1)

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US3779776A true US3779776A (en) 1973-12-18

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US (1) US3779776A (Direct)
BE (1) BE785847A (Direct)
CA (1) CA1000100A (Direct)
DE (1) DE2237036A1 (Direct)
FR (1) FR2147985B1 (Direct)
GB (1) GB1388847A (Direct)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3980481A (en) * 1973-01-25 1976-09-14 Afga-Gevaert N.V. Direct-positive super-sensitized silver halide emulsions
US4273862A (en) * 1977-06-11 1981-06-16 Mitsubishi Paper Mills, Ltd. Direct-positive silver halide photographic sensitive materials
US4444871A (en) * 1981-10-08 1984-04-24 Konishiroku Photo Industry Co., Ltd. Method for forming a direct positive color image

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2901351A (en) * 1954-12-10 1959-08-25 Gavaert Photo Producten N V Direct positive photographic material
US3501305A (en) * 1966-03-11 1970-03-17 Eastman Kodak Co Monodispersed photographic reversal emulsions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2901351A (en) * 1954-12-10 1959-08-25 Gavaert Photo Producten N V Direct positive photographic material
US3501305A (en) * 1966-03-11 1970-03-17 Eastman Kodak Co Monodispersed photographic reversal emulsions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3980481A (en) * 1973-01-25 1976-09-14 Afga-Gevaert N.V. Direct-positive super-sensitized silver halide emulsions
US4273862A (en) * 1977-06-11 1981-06-16 Mitsubishi Paper Mills, Ltd. Direct-positive silver halide photographic sensitive materials
US4444871A (en) * 1981-10-08 1984-04-24 Konishiroku Photo Industry Co., Ltd. Method for forming a direct positive color image

Also Published As

Publication number Publication date
CA1000100A (en) 1976-11-23
BE785847A (nl) 1973-01-05
DE2237036A1 (de) 1973-02-08
GB1388847A (en) 1975-03-26
FR2147985A1 (Direct) 1973-03-11
FR2147985B1 (Direct) 1978-03-24

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