US3595662A - Light-sensitive material - Google Patents

Light-sensitive material Download PDF

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Publication number
US3595662A
US3595662A US688670A US3595662DA US3595662A US 3595662 A US3595662 A US 3595662A US 688670 A US688670 A US 688670A US 3595662D A US3595662D A US 3595662DA US 3595662 A US3595662 A US 3595662A
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US
United States
Prior art keywords
mercury
emulsion
silver halide
light
poly
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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US688670A
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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
    • G03C1/08—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
    • 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

  • a light-sensitive material comprising a silver halide emulsion layer and containing a mercury(II) chelate of a (poly)amino(poly)carboxylic acid in the form of the acid or a water-soluble salt is described.
  • the chelate exerts a stabilizing and fog-inhibiting action upon the lightsensitive material without causing appreciable desensitization.
  • This invention relates to improved light-sensitive silver halide emulsions.
  • Light-sensitive silver halide emulsions are in general characterised by their sensitivity, gradation and fog.
  • sensitivity, gradation and fog are determined by the way in which the silver halide emulsion is prepared and by the use of special chemical ingredients effecting a desired improvement or result.
  • Addenda to the emulsion, which are of particular im portance for the stability of the light-sensitive characteristics of a silver halide emulsion are the so-called stabilizers.
  • Stabilizers or antifoggants protect the light-sensitive 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.
  • 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 high relative humidity for instance in view of its use in tropical countries.
  • mercury(II) chelates are very suitable for use in combination with stabilizers of the triazolopyrimidine type, particularly in extreme storage and development circumstances in order to reduce the fogging tendency of the light-sensitive emulsion without giving rise to an appreciable desensitization thereof.
  • the mercury(II) chelates of (poly)amino(poly)carboxylic acids can be prepared by allowing to react a water-soluble mercury (II) salt (chloride, cyanide, acetate, etc.) with a (poly) amino(poly)carboxylic acid or water-soluble salt thereof or by treating the sequestering compound, in acid form or in the form of a water-soluble salt, with mercury(II) oX- ide until the mercury oxide has dissolved completely (cf. H. Mohrle, Archiv der Pharmazie 299 (1966) 529).
  • a water-soluble mercury (II) salt chloride, cyanide, acetate, etc.
  • mercury(II) oX- ide mercury(II) oX- ide
  • L stands for alkylene including substituted alkylene e.g. hydroxyalkylene, cycloalkylene including substituted cycloalkylene or alkylene interrupted by one or more hetero atoms, such as an oxygen atom,
  • x 0, 1 or 2.
  • R stands for lower alkylene e.g. methylene and ethylene including substituted lower alkylene, e.g. alkylene substituted by alkyl, aryl, aralkyl, including substituted alkyl, aryl and aralkyl, and
  • each of R and R stands for hydrogen, lower alkyl including substituted lower alkyl, aralkyl including substituted aralkyl or aryl including substituted aryl;
  • substituted alkyl groups for R and for R are alkyl substituted with hydroxyl, halogen, alkoxy, carbamoyl, amino, substituted amino e.g. dihydroxyalkylamino, epoxy, carboxyl, sulpho, phosphono, mercapto, alkylmercapto, alkoxycarbonyl, a nitrogen-containing heterocyclic ring e.g.
  • pyridyl and examples of substituted aryl groups and aralkyl groups for R and/ or R are: aryl and aralkyl substituted by hydroxyl, halogen, alkyl, alkoxy, nitro, carboxyl and sulpho.
  • the mercury(II) oxide dissolves gradually. After 3 hours the aqueous solution formed is filtered, evaporated under reduced pressure at 50 C. and the solid product formed is dried under reduced pressure at 50 C. in a drying oven. The product obtained is a white amorphous powder which is soluble in water. Yield: 75 g.
  • the mercury(II) chelates 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 de scribed among others in US. Pats. 2,531,832 and 2,533,990, in U.K. Pats. 920,637, 940,051, 945,340 and 991,608 and in Belgian Pat. 648,710 and onium derivatives of amino-N-oxides as described in UK. patent application 42,592/ 65.
  • compounds which sensitize the emulsion by development acceleration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as de scribed among others in US. Pats. 2,531,832 and 2,533,990, in U.K. Pats. 920,637, 940,051, 945,340 and 991,608 and in Belgian Pat. 648,710 and onium derivatives of amino-N-oxides as described in UK. patent
  • the stabilizers according to the invention can also be used in combination with other known stabilizers for instance with heterocyclic nitrogen containing thioxo compounds such as benzothiaZoline-2-thione and 1- phenyl-Z-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-2-thione and 1- phenyl-Z-tetrazoline-S-thione
  • 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, and 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., a gelatin being however favoured.
  • the common hydrophilic colloids such as gelatin, casein, zein, polyvinyl alcohol, carboxymethylcellulose, alginic acid, etc., a gelatin being however 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 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, e.g. in the form of a solution in water.
  • the compounds of the invention can also be incorporated into a water-permeable layer e.g. a gelatin covering layer or intermediate layer.
  • the amount of mercury(II) chelate employed in the light-sensitive silver halide material depends on the particular type of emulsion and the desired eifect and can vary within very wide limits.
  • the optimum amount of mercury(II) chelate to be added can be determined for each particular type of emulsion 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 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.
  • 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
  • noble metal compounds such as of gold, platinum, palladium, iridium, ruthenium and rhodium.
  • addenda 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 (:45 moles percent of iodide) is divided into nine aliquot portions A, B, C, D, E, F, G, H and I.
  • emulsion B 0.6 l millimole (1.5 mg.) of mercury (II) cyanide emulsion C: 1.2 millimole (3 mg.) of mercury (II) cyanide emulsion D: 0.6 10* millimole (4 mg.) of the mercury (II) chelate of compound 8 trisodium salt emulsion E: 0.6 10- millimole (3 mg.) of the mercury (II) chelate of compound 4 sodium salt emulsion F: 0.6x 10 millimole (3.7 mg.) of the mercury (II) chelate of compound disodium salt emulsion G: 1.2x 10- millimole (7.5 mg.) of the mercury (II) chelate of compound 15 disodium salt emulsion H: 0.6 X 10 millimole (3.1 mg.) of the mercury (II) chelate of compound 1 disodium salt emulsion I: 1.2 10- millimole (6.2 mg.) of the mercury (II)
  • the nine emulsions are then coated on a subbed cellulose triacetate support and dried whereupon the nine materials thus obtained are stored for 5 days in an atmosphere of 57 C. and 34% of relative humidity.
  • EXAMPLE 2 A gelatino silver bromoiodide emulsion (0.20 mole percent of iodide) comprising per mole of silver halide 400 mg. of 5-methyl-7-hydroxy-s-triazolo-[l,5-a]-pyrimidine as stabilizer and per litre of emulsion 1 g. of saponin as coating aid, is divided into 3 aliquot portions.
  • the three emulsions are coated on a subbed cellulose triacetate support and the emulsion layers are then overcoated with a gelatin antistress layer.
  • Photographic material comprising a support and at least one light-sensitive silver halide emulsion layer comprising in said emulsion layer at least one mercury (II) chelate of a (poly)amino(po1y)carboxylic acid in acid form or in the form of a water-soluble salt, said chelate being present in an amount suflicient to stabilize said material with regard to fogging.
  • Photographic light-sensitive silver halide material according to claim 1, wherein said (poly)amino(poly)- carboxylic acid corresponds to the following general formula:
  • Photographic light-sensitive silver halide material according to claim 1, wherein said material also comprises a hydroxytriazolopyrimidine stabilizer.
  • Photographic light-sensitive silver halide material according to claim 1, wherein said material also comprises a polyoxyalkylene development accelerator.
  • Photographic light-sensitive silver halide material according to claim 1, wherein said emulsion layer is a gelatino silver halide emulsion layer.
  • Photographic material comprising a support and at least one light-sensitive silver halide emulsion layer comprising in a water permeable layer coated at the same side of the support as the emulsion layer at least one mercury (II) chelate of a (poly)amino(poly)carboxylic acid in acid form or in the form of a water-soluble salt, said chelate being present in an amount sufficient to stabilize said material with regard to fogging.
  • Photographic light-sensitive silver halide material according to claim 7, wherein said material also comprises a hydroXytriazolopyrimidine stabilizer.
  • Photographic light-sensitive silver halide material according to claim 7, wherein said material also comprises a polyoxyalkylene development accelerator.

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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)
US688670A 1967-03-06 1967-12-07 Light-sensitive material Expired - Lifetime US3595662A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB10372/67A GB1200188A (en) 1967-03-06 1967-03-06 Improvements in or relating to photographic light-sensitive material

Publications (1)

Publication Number Publication Date
US3595662A true US3595662A (en) 1971-07-27

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US688670A Expired - Lifetime US3595662A (en) 1967-03-06 1967-12-07 Light-sensitive material

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US (1) US3595662A (en, 2012)
BE (1) BE709196A (en, 2012)
DE (1) DE1622919A1 (en, 2012)
FR (1) FR1553434A (en, 2012)
GB (1) GB1200188A (en, 2012)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3930867A (en) * 1974-01-07 1976-01-06 E. I. Du Pont De Nemours And Company Macrocyclic polyamines as sensitizers for silver halide emulsions
US4036650A (en) * 1974-08-27 1977-07-19 Canon Kabushiki Kaisha Heat developable photosensitive material containing compounds of sulfur
JPS55500704A (en, 2012) * 1978-09-14 1980-09-25

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2619628B1 (en) 2010-09-17 2014-03-26 Fujifilm Manufacturing Europe BV Photographic paper and its use in a photo album
GB202006061D0 (en) 2020-04-24 2020-06-10 Fujifilm Mfg Europe Bv Photographic paper

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3930867A (en) * 1974-01-07 1976-01-06 E. I. Du Pont De Nemours And Company Macrocyclic polyamines as sensitizers for silver halide emulsions
US4036650A (en) * 1974-08-27 1977-07-19 Canon Kabushiki Kaisha Heat developable photosensitive material containing compounds of sulfur
JPS55500704A (en, 2012) * 1978-09-14 1980-09-25

Also Published As

Publication number Publication date
GB1200188A (en) 1970-07-29
FR1553434A (en, 2012) 1969-01-10
BE709196A (en, 2012) 1968-07-11
DE1622919A1 (de) 1970-12-17

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