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

Definitions

• ABSTRACT A photosensitive silver halide photographic emulsion containing at least one compound selected from the group consisting of compounds having the formula 9 Claims, No Drawings SILVER HALIDE EMULSION SENSITIZED WITH PENTATI-IIEPANE BACKGROUND OF THE INVENTION 1 Field of the Invention
• the present invention relates to a silver halide photographic emulsion. More particularly, the present invention relates to a silver halide photographic emulsion which is chemically sensitized with a sulfur-containing compound.
• An object of the present invention is to increase the sensitivity of photosensitive silver halide photographic emulsions.
• a chemically sensitizing process For example, compounds containing a labile sulfur (for example, sodium thiosulfate or thio-urea derivatives) are known as sulfur sensitizing agents. Also, a reducing agent, such as stannous chloride and hydrazine, is known as a reducing sensitizing agent. Some of these labile sulfur-containing compounds and reducing substances are considered to be contained in a natural gelatin for photography. Certain aurous or auric salts, for example aurous thiocyanate, have a chemically sensitizing action, and the method of utilizing this action is well known.
• a labile sulfur for example, sodium thiosulfate or thio-urea derivatives
• a reducing agent such as stannous chloride and hydrazine
• the present inventors have found that a compound represented by the general formula DETAILED DESCRIPTION OF THE INVENTION
• the above compound is a useful sensitizing agent regardless of whether the emulsion is a silver chloride emulsion, a silver bromide emulsion, a silver iodide emulsion, or a mixed silver halide emulsion, or, further, whether the emulsion is a waterwashed or a water-unwashed emulsion.
• Suitable chemical sensitizers having the above formula are However, the chemical sensitizers used in the present invention are not limited to these compounds.
• the optimum amount of the sulfur sensitizer having the above described formula to be used is dependent on the specific compound selected, the type of silver halide, the particle size ripening temperature, the ripening time, and the pH and the pAg of the silver halide emulsion. However, the amount generally used is in the range of from 0.01 to mg per 1 mole of silver halide. However, where the sensitizer is used in combination with other sensitizers, the amount used can be smaller; Where the sensitizer is used in combination with any appropriate antifoggant, the amount can be larger.
• the sulfur sensitizer used in the present invention can be used in combination with reducing sensitizers such as stannous chloride or thiourea dioxide, and also can be combined with auric or aurous salts, such as aurous thiocyanate, platinum salts, palladium salts, or sulfuncontaining compounds such as sodium thiosulfate, thiourea derivatives, and further can be used together with polyoxyalkylene compounds having a molecular weight of above 300 or onium compounds.
• reducing sensitizers such as stannous chloride or thiourea dioxide
• auric or aurous salts such as aurous thiocyanate, platinum salts, palladium salts, or sulfuncontaining compounds such as sodium thiosulfate, thiourea derivatives
• the sulfur-containing compound represented by the above described formula according to the present invention can be used not only in case of spectral sensitization but also without such sensitization. These can be usually applied to emulsions for black and white photography, for color photography, for X-ray, and for graphics.
• the sulfur-containing compound represented by the above formula can be added to the photographic emulsion without any deleterious effects on stabilizers, antifoggants, hardeners, color developing agents, coating agents, and other emulsion additives.
• the sulfur sensitizing agent represented by the above described formula is extremely useful for sensitizing a silver halide emulsion made of an inert gelatin and also can be used for sensitizing a silver halide emulsion in which at least one part of the protective colloid comprises other hydrophillic colloids such as a photographically labile gelatin or a polyvinylalcoho].
• the sulfur sensitizing agent is particularly valuable in that the sensitizing efi'ect is markedly increased in combination with a thiosulfate ion, Le. a compound giving rise to a thiosulfate ion.
• EXAMPLE 1 A highly sensitive neutral gelatino-silver bromo-iodide emulsion (5.0 percent silver iodide and 95.0 percent silver bromide) at the beginning of the chemical ripening was divided into five equal parts (Samples A to E). Samples C to E were mixed with Compound 1 in an alcohol solution and Sample B was mixed with a sensitizing natural gelatin, and were added with, as a metallic sensitizing agent, 7.5 mg of potassium chloroaurate (tetrahydrate) and 150 mg of potassium thiocyanate per 1 mole of silver halide in the form of an aqueous solution, and were chemically ripened under stirring at 50 C for 60 minutes.
• Samples C to E were mixed with Compound 1 in an alcohol solution and Sample B was mixed with a sensitizing natural gelatin, and were added with, as a metallic sensitizing agent, 7.5 mg of potassium chloroaurate (tetrahydrate) and 150 mg of potassium thiocyanate per 1 mole of silver
• EXAMPLE 2 A neutral gelatino-silver bromochloride emulsion (58.0 mole percent silver bromide and 42.0 mole percent silver chloride) for a fine grained positive film at the beginning of chemical ripening was divided into three equal parts (Samples I F to H). Compound 2 in a methyl alcohol solution was added to Sample H and a sensitive natural gelatin was added to Sample G in the amount as shown in Table 2.
• a highly sensitive neutral gelatino-silver bromoiodide emulsion for an outer type reverse color film at the beginning of chemical ripening was divided into five equal parts (Samples I to M) and Compound 2 in a methyl alcohol solution was 7 added to each of samples K to M, and a sensitizing natural gelatin was added to Sample J in the amount as shown in Table 3.
• Samples I to M Compound 2 in a methyl alcohol solution was 7 added to each of samples K to M, and a sensitizing natural gelatin was added to Sample J in the amount as shown in Table 3.
• To each of these five types of emulsions were added 7.5 mg of potassium chloroaurate tetrahydrate and 150 mg of potassium thiocyanate per 1 mole of silver halide in the form of an aqueous solution and was chemically ripened at 50 C under stirring for 70 minutes.
• N-Methyl-para-aminophcnol Sulfate 1.0 g Sodium Sulfite (anhydrous) 60.0 g Hydroquinone 10.0 g Potassium Bromide 5.0 g Potassium Thiocyanate 1.5 g Potassium lodide (0.1%) 5.0 ml Sodium Hydroxide 2.0 g Water to 1000 ml TABLE 3 Added Sulfur amount, Relative Sample sensitizer mole/AgX sensitivity Gamma For:
• EXAMPLE 4 A semi-ammonium process gelatino-silver bromoiodide emulsion (1.5 mole percent silver iodide and 98.5 mole percent silver bromide) at the beginning of chemical ripening was divided into three equal parts (Samples N to P) and to Sample 0 to P were respectively added compounds 1 and 2 in a methylalcohol solution in the amount shown in Table 4. Next, to Sample N were added 4.7 mg of sodium thiosulfate (pentahydrate) and 1.2 mg of sodium aurous thiosulfate (dihydrate) Na Au(S O .2l-l O in the form of an aqueous solution per 1 mole of silver halide.
• Sample O was added with 4.7 mg and 3.2 X10- mg of these salts per 1 mole of silver halide, respectively.
• Sample P was added with only 1.2 mg of sodium aurous thiosulfate (dihydrate) per 1 mole of silver halide.
• each of R R R and R is selected from the group consisting of a hydrogen atom, an alkyl group and an aralkyl group; and wherein R and R or R and R, can combine to form a cycloalkyl group.
• each of R R R R and R is selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group and a phenethyl group; and wherein R, and R or R and R, can combine to form a member selected from the group consisting of a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
• thiosulfate compound is selected from the group consisting of sodium thiosulfate, sodium aurous thiosulfate and mixtures thereof.
• a photosensitive element comprising a support having thereon at least a layer of the silver halide photographic emulsion as claimed in claim 1.

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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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Cited By (24)

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Citations (1)

• 0
  • BE BE755357D patent/BE755357A/xx unknown
• 1969
  • 1969-08-28 JP JP44068219A patent/JPS4912421B1/ja active Pending
• 1970
  • 1970-08-24 CA CA091,382A patent/CA942986A/en not_active Expired
  • 1970-08-26 DE DE2042359A patent/DE2042359C3/de not_active Expired
  • 1970-08-26 FR FR7031162A patent/FR2059245A5/fr not_active Expired
  • 1970-08-28 US US68041A patent/US3656955A/en not_active Expired - Lifetime
  • 1970-08-28 GB GB4161070A patent/GB1319548A/en not_active Expired

Patent Citations (1)

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