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

• Photographic materials comprising a support and at least one layer of light-sensitive silver halide emulsion containing a water-soluble mercury(II) compound having one of the following formulae:
• X is a bivalent organic radical
• X stands for an aliphatic or aromatic bivalent group
• M represents hydrogen, alkali metal, alkaline earth metal,
• Y stands for an aliphatic, alicyclic, aromatic or heterocyclic radical, said radicals including the substituted derivatives thereof are described.
• the photographic material has improved stability and fogging characteristics.
• 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 elfecting a desired improvement or reuslt.
• Addenda to the emulsion, which are of particular importance 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) compounds corresponding to one of the following general Formulae I and II X represents a bivalent organic radical e.g. an aliphatic, aromatic or heterocyclic bivalent radical such as alkylene including substituted alkylene, arylene including substituted aralkylene and a bivalent radical comprising a heterocyclic nucleus including a substituted heterocyclic nucleus,
• X stands for an aliphatic or aromatic bivalent group such as alkylene including substituted alkylene, arylene including substituted arylene, and aralkylene including substituted aralkylene,
• M represents hydrogen, an alkali metal or alkaline earth metal, ammonium, guanidine, an organic amine, etc.
• Y stands for an organic aliphatic, alicyclic, aromatic or heterocyclic radical said radicals including the substituted alkyl, aryl including substituted aryl and a heterocyclic nucleus including a substituted heterocyclic nucleus,
• mercury(II) compounds 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 high-water-solubility obtained by the presence of the sulphonic acid group in the mercury(II) compounds of the above general formula guarantees a homogeneous distribution of the stabilizer in the emulsion.
• the watersoluble mercury(II) mercaptides of use according to the present invention can be prepared by allowing to react a mercury (II) salt such as mercury(II) acetate or mercury(II) chloride with the corresponding mercapto compound.
• a mercury (II) salt such as mercury(II) acetate or mercury(II) chloride
• the said mercury(II) mercaptides can also be obtained in a very pure form by reaction of mercury(II) oxide with the corresponding mercapto compound.
• the mercury(II) compounds corresponding to the above general Formula II can be prepared by allowing to react the corresponding organo-mercury salts such as the chlorides, bromides or acetates or the corresponding organomercury hydroxides with the sulphonated mercaptans.
• PREPARATION l.COMPOUND 1 (a) To a solution of 10.75 g. (0.05 mole) of the guanidine salt of 3-mercapto-propane sulphonic acid in 55 ccs. of water a solution of 7.95 g. (0.025 mole) of mercury(II) acetate in 35 ccs. of water was added. The water was distilled off under reduced pressure and the mercury(II) mercaptide formed was recrystallized from methanol.
• PREPARATION 3.COMPOUND 4 To a solution of 12.8 g. (0.05 mole) of the guanidine salt of Z-mercapto-4-methyl-4-sulpho-pentane in 400 ccs. of water a solution of 7.95 g. (0.025 mole) of mercury(II) acetate in 50 ccs. of water was added. After evaporation of the water the residue was digested with methanol and dried.
• PREPARATION 6.COMPOUND 8 A solution of 10 g. of allylurea in ccs. of methanol, 31.9 g. of mercury(II) acetate and 6 ccs. of acetic acid were refluxed for 6 hours. The excess of methanol and the acetic acid formed were distilled off under reduced pressure.
• PREPARATION 7.-COMPOUND 12 (a) To a solution of 13.5 g. of mercury(II) chloride in 200 ccs. of water a solution of 6 g. of sodium hydroxide in 25 ccs. of water was added. The precipitate formed was filtered 01f by suction and washed with water until no chloride ions could be indicated anymore.
• the product was suspended in 50 ccs. of water and then an aqueous solution of 22 g. of salicylic acid was added with stirring. After some hours the suspension formed was concentrated by evaporation and the resi due digested with ethanol.
• 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 cornpounds which sensitize the emulsion by development ac celeration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in United States Pat. 2,531,832 and 2,533,990, in United Kingdom Pat. 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 US patent application Ser. No. 573,801, filed Aug. 22, 1966, and now pending.
• the polyoxyalkylene type such as alkylene oxide condensation products as described among others in United States Pat. 2,531,832 and 2,533,990, in United Kingdom Pat. 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 US patent application Ser. No. 573,801, filed
• the stabilizers according to the inventions can also be used in combination with other known stabilizers for instance with heterocyclic nitrogen containing thioxo compounds such as benzothiazoline-Z-thione and 1-phenyl-2- tetrazoline-S-thione 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 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, X-ray emulsion layer, and an emulsion layer sensitive to infra-red 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 lightsensitive salt e.g. silver bromide, silver iodide, silver chloride, or mixed silver halides e.g. silver chloro-bromoide 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 being however favoured.
• the common hydrophilic colloids such as gelatin, casein, zein, polyvinyl alcohol, carboxymethylcellulose, alginic acid, etc., 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 mat ter 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 accord ing 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.
• a water-permeable layer e.g. a gelatin covering layer or 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 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.
• the light-sensitive emulsions may be chemically as well as optically sensitized. They may be chemically sensitized by eifecting 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-aminomethane 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.
• reductors for instance tin compounds as described in our French patent specification 1,146,955 and in our Belgian patent specification 568,687, imino-aminomethane 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.
• 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 (:4.5 mole percent of iodide) is divided into six aliquot portions A, B, C, D, E and F.
• emulsion portion B is added per mole of silver halide 1.2 l0 millimole (3 mg.) of mercury (II) cyanide, to emulsion portion C 0.6 10- millimole (3.8 mg.) of compound 1, to emulsion portion D 1.2 10- millimole (7.5 mg.) of compound 1, to emulsion portion E 2.0 10- millimole (10 mg.) of compound 7 and to emulsion portion F l.2 10- millimole (6.6 mg.) of compound 8.
• the six emulsions are then coated on a subbed cellulose triacetate support and dried whereupon the six materials thus obtained are stored for 5 days in an atmosphere of 57 C. and 34% of relatively humidity.
• x has a value of about and 2 g. of saponin as coating aid, is divided into 4 aliquot portions.
• the four 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 four materials A, B, C and D obtained are then stored for 36 hours in an atmosphere of 57 C. and 34% of relative humidity.
• Example 3 A gelatino silverbromoiodide emulsion as described in Example 2 is divided into 4 aliquot portions.
• Example 2 The four emulsions are then coated as described in Example 2 on a cellulose triacetate support and the resulting materials A, B, C and D are further treated as described in Example 2 with the difference, however, that the development now takes place at 26 C.
• Photographic material comprising a support and at ll lliiiiiilll llll lllll l l llllllllll lillllllllllll i llllillll till least one light-sensitive silver halide emulsion layer comprising in said emulsion layer or in at least one waterpermeable layer coated at the same side of the support as the said emulsion layer at least one water-soluble mercury(II) compound corresponding to one of the general Formulae I and II:
• X is a bivalent organic radical
• X stands for an aliphatic or aromatic bivalent group
• M represents hydrogen, alkali metal, alkaline earth metal, 15 ammonium, guanidine or an organic amine
• Y stands for an aliphatic, alicyclic, aromatic or heterocyclic radical, said radicals including the substituted derivatives thereof,
• said mercury(II) compound being present in an amount 20 sufficient to improve the stability or fogging characteristics of said material without appreciable desensitization thereof.
• X stands for alkylene including substituted alkylene, arylene including substituted arylene, aralkylene including substituted aralkylene or a bivalent group conprisin a heterocyclic nucleus including a substituted heterocyclic nucleus
• M represents hydrogen, alkali metal, alkaline earth metal, ammonium, guanidine or an organic amine.
• X stands for alkylene including substituted alkylene
• arylene including substituted arylene
• aralkylene including substituted aralkylene
• Y stands for alkyl including substitute dalkyl, aryl including substituted aryl or a heterocyclic nucleus including a substituted heterocyclic nucleus, and
• M stands for hydrogen, alkali metal, alkaline earth metal
• ammonium guanidine or an organic amine.
• Photographic light-sensitive silver halide material according to claim 1, wherein said material also includes a stabilizer of the hydroxytriazolopyrimidine type.
• Photographic light-sensitive silver haldie material according to claim 1, wherein said material also includes a development accelerator of the polyoxyalkylene type.
• Photographic light-sensitive silver halide material according to claim 1, wherein said emulsion is a gelatino silver halide emulsion.

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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)

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• 1966
  • 1966-12-12 GB GB55445/66A patent/GB1173609A/en not_active Expired
• 1967
  • 1967-11-21 US US684622A patent/US3567454A/en not_active Expired - Lifetime
  • 1967-12-01 BE BE707386D patent/BE707386A/xx unknown
  • 1967-12-11 DE DE19671597501 patent/DE1597501A1/de active Pending

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