US3554758A - Photographic light-sensitive material - Google Patents

Photographic light-sensitive material Download PDF

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Publication number
US3554758A
US3554758A US688659A US3554758DA US3554758A US 3554758 A US3554758 A US 3554758A US 688659 A US688659 A US 688659A US 3554758D A US3554758D A US 3554758DA US 3554758 A US3554758 A US 3554758A
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US
United States
Prior art keywords
emulsion
compounds
mercury
silver halide
light
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
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US688659A
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English (en)
Inventor
Jozef Frans Willems
Robrecht Julius Thiers
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Agfa Gevaert NV
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Agfa Gevaert NV
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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
    • G03C1/34—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

  • Y represents an anion and X represents a halogen atom having an atomic number greater than 9 is described.
  • the iodonium compound stabilizes the emulsion against any increase in fog without substantial desensitization of the emulsion.
  • This invention relates to improved light-sensitive silver halide emulsions.
  • Light-scnsitive silver halide emulsions are in general silver halide emulsions against spontaneous formation and growth of fog known as chemical fog during prolonged storage or storage at high temperatures and humidities or during development to maximum contrast and speed. Indeed, the fog increases with the degree and temperature of development, and, in constant development circumstances, with the time the light-sensitive emulsion is stored and with the temperature and the relative humidity of the atmosphere wherein the emulsion is stored. It is evident that a light-sensitive emulsion should be obtained which is as stable as possible at high temperature and highrelative humidity for instance in view of its use in tropical countries.
  • Y- represents an anion e.g. a halogen anion, a nitrate anion, a bisulphate anion, etc.
  • X represents a halogen atom
  • the aromatic nuclei of said compounds include the substituted derivatives thereof e.g. substituted with an alkyl radical, a halogen atom, an alkoxy radical, a cyano radical, an acyl radical or an acylamino radical.
  • the compounds of use according to the present invention can be prepared by reaction of the iodonium compound with the mercury(II) halide as is illustrated by the following preparations.
  • the mercury(II) compounds according to the present invention when used in the appropriate concentration do not cause or only to a slight extent a decrease in sensitivity.
  • the antifoggants according to the present invention are particularly suitable for use in combination with compounds which sensitize the emulsion by development acceleration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in United States Pats. 2,531,832 and 2,533,990, in United Kingdom Pats. 920,637, 940,051, 945,340 and 991,608 and in Belgian Pat. 648,710 and onium derivatives of amino-N-oxides.
  • compounds which sensitize the emulsion by development acceleration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in United States Pats. 2,531,832 and 2,533,990, in United Kingdom Pats. 920,637, 940,051, 945,340 and 991,608 and in Belgian Pat. 648,710 and onium derivatives of amino-N-oxides.
  • the stabilizers according to the inventions can also be used in combination with other known stabilizer for instance with heterocyclic nitrogen containing thioxo compounds such as benzothiazoline-Z-thione and 1-phenyl-2- tetrazoline-S-thione, with other mercury compounds, and, as said above, preferably with compounds of the hydroxytriazolopyrimidine type (azaindolizines).
  • heterocyclic nitrogen containing thioxo compounds such as benzothiazoline-Z-thione and 1-phenyl-2- tetrazoline-S-thione
  • other mercury compounds and, as said above, preferably with compounds of the hydroxytriazolopyrimidine type (azaindolizines).
  • the stabilizers 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 emulsion layer, an X-ray emulsion layer or an emulsion layer sensitive to infrared radiation. They may be incorporated into high-speed negative materials 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 chloro-bromide 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 however, being favoured.
  • the common hydrophilic colloids such as gelatin, casein, zein, polyvinyl alcohol, carboxymethylcellulose, alginic acid, etc., gelatin however, being favoured.
  • the stabilizing agents are generally incorporated into the silver halide emulsion layer of the light-sensitive material; they may be added to the emulsion during no matter what step of emulsion preparation; however, they are preferably added to the photographic emulsion after the chemical ripening and just before coating of the emulsion.
  • the addenda according to the present invention are incorporated into the photographic emulsions according to the methods well known in emulsion preparation. For instance they can be added to the emulsion in the form of a solution or of a dispersion according to the methods applied for incorporating colour couplers in the emulsion.
  • the compounds of the invention can also be incorporated into a water-permeable layer e.g. a gelatin covering layer or an intermediate layer.
  • the amount of mercury(II) compound 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 of mercury(II) compound to be added can be determined for each particular type of material in a very simple way by application of the usual tests.
  • said compounds are employed in a ratio of about 0.1 mg. to about 30 mg. per mole of silver halide, preferably from 0.5 mg. to 10 mg. per mole of silver halide.
  • 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 allylthiocyanate, allyl thiourea, sodium thiosulphate, etc.
  • the emulsions may also be sensitized by means of reductors for instance tin compounds as described in our French patent specification 1,146,955 and in our Belgian patent specification 568,687, imino-amino methane sulphinic acid compounds as described in our British patent specification 789,823 and small amounts of noble metal compounds such as of gold, platinum, palladium, iridium, ruthenium and rhodium.
  • addcnda such as hardening agents, wetting agents, plasticizers, colour couplers, developing agents and optical sensitizers can be incorporated into the emulsion in the usual way.
  • Example 1 A high sensitive gelatino silver bromoiodide emulsion (i4.5 moles percent of iodide) is divided into four aliquot portions A, B, C and D.
  • emulsion portion B is added per mole of silver halide 0.6 l0 millimole (1.5 mg.) of mercury(II) cyanide, to emulsion portion C 0.6 10 millimole (3.5 mg.) of compound 1 and to emulsion portion D 0.6 10 millimole (4.6 mg.) of compound 3.
  • the four emulsions are then coated on a subbed cellulose triacetate support and dried whereupon the four materials thus obtained are stored for 5 days in an atmosphere of 57 C. and 34% of relative humidity.
  • x has a value of about 135 and 2 g. of saponin as coating aid, is divided into 3 aliquot portions.
  • the three emulsions are coated on both sides of a cellulose triacetate support, which has been provided on both sides with a subbing layer, in such a way that per sq. m. an amount of silver halide equivalent to 36 g. of silver nitrate (both sides taken together) is present.
  • the emulsion layers are then overcoated with a gelatin antistress layer.
  • the three materials, A, B and C obtained are then exposed to X-rays with an X-ray radiation source of 80 kv. and developed for 8 min. at 26 C. in a common X- ray developer having the following composition:
  • a gelatino silver bromoiodide emulsion as described in Example 2 is divided into 3 aliquot portions.
  • a photographic light-sensitive silver halide emulsion including at least one compound corresponding to one of the general formulae:
  • Y- represents an anion and X represents a halogen atom having an atomic number greater than 9, said compound being present in an amount sufficient to stabilize said emulsion with regard to fogging.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US688659A 1967-03-06 1967-12-07 Photographic light-sensitive material Expired - Lifetime US3554758A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB00373/67A GB1189129A (en) 1967-03-06 1967-03-06 Stabilised Silver Halide Materials

Publications (1)

Publication Number Publication Date
US3554758A true US3554758A (en) 1971-01-12

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US688659A Expired - Lifetime US3554758A (en) 1967-03-06 1967-12-07 Photographic light-sensitive material

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US (1) US3554758A (en)van)
BE (1) BE709197A (en)van)
GB (1) GB1189129A (en)van)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3982947A (en) * 1974-03-14 1976-09-28 Agfa-Gevaert, N.V. Fog-inhibitors for silver halide photography silver halide photographic material containing an iodo benzene compound as antifoggant
US5605789A (en) * 1994-12-22 1997-02-25 Eastman Kodak Company Iodochloride emulsions containing iodonium salts having high sensitivity and low fog
US5714311A (en) * 1997-01-08 1998-02-03 Eastman Kodak Company Thermally processable imaging element comprising aryliodonium compounds
US5733717A (en) * 1997-01-08 1998-03-31 Eastman Kodak Company Silver halide photographic elements containing aryliodonium compounds
US5750324A (en) * 1997-01-08 1998-05-12 Eastman Kodak Company High chloride emulsions with improved reciprocity
US5851753A (en) * 1995-10-13 1998-12-22 Konica Corporation Silver halide photographic light-sensitive material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3982947A (en) * 1974-03-14 1976-09-28 Agfa-Gevaert, N.V. Fog-inhibitors for silver halide photography silver halide photographic material containing an iodo benzene compound as antifoggant
US5605789A (en) * 1994-12-22 1997-02-25 Eastman Kodak Company Iodochloride emulsions containing iodonium salts having high sensitivity and low fog
US5851753A (en) * 1995-10-13 1998-12-22 Konica Corporation Silver halide photographic light-sensitive material
US5714311A (en) * 1997-01-08 1998-02-03 Eastman Kodak Company Thermally processable imaging element comprising aryliodonium compounds
US5733717A (en) * 1997-01-08 1998-03-31 Eastman Kodak Company Silver halide photographic elements containing aryliodonium compounds
US5750324A (en) * 1997-01-08 1998-05-12 Eastman Kodak Company High chloride emulsions with improved reciprocity

Also Published As

Publication number Publication date
GB1189129A (en) 1970-04-22
BE709197A (en)van) 1968-07-11

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