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

• the present invention relates to a silver halide photographic material, and more particularly, to a silver halide photographic material having improved image quality.
• Methods are also known for rapidly processing silver halide photographic materials by either reducing the amount of gelatin (as binder) with respect to the silver halide or effecting development at an elevated temperature (30 - 40°C) in a developing bath of high pH value.
• an antifoggant or stabilizer is incorporated in a silver halide emulsion in order to inhibit the deterioration of image quality due to the coarsening of developed silver grains.
• Other methods are essentially the same in that they reinforce the film, on which developed silver grains are supported, by hardening the gelatin (binder) in the photographic material.
• Hardeners used for this purpose include inorganic compounds such as chrome alum; aldehyde compounds such as formaldehyde and glutaraldehyde; compounds having activated halogens as described in U.S. Patent No. 3,288,755; compounds having reactive ethylenically unsaturated bonds as described in U.S. Patent No. 3,635,718; epoxy compounds as described in U.S. Patent No. 3,091,537; and organic compounds such as halogenated carboxyaldehydes (e.g. mucochloric acid).
• inorganic compounds such as chrome alum
• aldehyde compounds such as formaldehyde and glutaraldehyde
• compounds having activated halogens as described in U.S. Patent No. 3,288,755
• compounds having reactive ethylenically unsaturated bonds as described in U.S. Patent No. 3,635,718
• epoxy compounds as described in U.S. Patent No. 3,091,537
• hardeners are incorporated in silver halide emulsion layers or protective layers to harden the gelatin (binder) to such a degree that it withstands processing under severe conditions such as rapidity and elevated temperatures.
• gelatin binder
• none of these methods are capable of improving the image quality satisfactorily without impairing the other properties of the silver halide photographic materials (e.g. sensitivity, contrast and maximum density).
• One object of the present invention is to provide a silver halide photographic material that produces an image of good quality even if it is processed to achieve high sensitivity subjected to rapid processing using less gelatin with respect to the silver halide.
• Another object of the present invention is to provide a silver halide photographic material that yields an image of good quality even if it is subjected to rapid processing under high pHs and temperatures.
• A is a carbonyl group or a sulfonyl group
• R 1 is an aliphatic group, an aromatic group or a heterocyclic group
• R 2 and R 3 are each a hydrogen atom, a hydroxyl group, an alkyl group, -S0 3 M (wherein M is a monovalent cation), a halogen atom or -COOR 4 (wherein R 4 is a monovalent cation or an aliphatic or aromatic group), provided that at least one of R 2 and R 3 is -COOR 4 : and n is an integer of 0 to 6.
• the objects of the present invention can be accomplished by incorporating the thioether compound of the formula in at least one element in a silver halide photographic material.
• the thioether compound incorporated in a photographic element according to the present invention is represented by the formula given hereinabove.
• Preferred aliphatic groups for R 1 and R 4 are straight-chain, branched-chain and cyclic aliphatic groups such as alkyl groups having 1 to 18 carbon atoms (e.g. methyl, n-butyl, 1-propyl, t-butyl and n-dodecyl), alkenyl groups having 2 to 18 carbon atoms (e.g. allyl, butenyl and octenyl), and cycloalkyl groups having 3 to 8 carbon atoms (e.g. cyclopentyl and cyclohexyl).
• alkyl groups having 1 to 18 carbon atoms e.g. methyl, n-butyl, 1-propyl, t-butyl and n-dodecyl
• alkenyl groups having 2 to 18 carbon atoms e.g.
• These aliphatic groups may have at least one substituent such as an alkoxy group (e.g. methoxy or ethoxy), aryl group (e.g. phenyl or tolyl), aryloxy (e.g. phenoxy), amino group, dialkylamino group (e.g. dimethylamino or diethylamino), heterocyclic group (e.g. N-morpholino or N-piperidino), halogen atom (e.g. chlorine, bromine or iodine), nitro group, hydroxyl group, carboxyl group, sulfo group, or alkoxycarbonyl group (e.g. methoxycarbonyl or ethoxycarbonyl).
• an alkoxy group e.g. methoxy or ethoxy
• aryl group e.g. phenyl or tolyl
• aryloxy e.g. phenoxy
• amino group e.g. dimethylamino or dieth
• Preferred aromatic groups for R 1 and R 4 include phenyl and naphthyl groups, and they may have at least one substituent such as an alkyl group (e.g. methyl or ethyl), alkoxy group (e.g. methoxy or ethoxy), hydroxyl group, halogen atom (e.g. chlorine, bromine or iodine), acylamino group (e.g. acetylamino or benzoylamino), alkoxycarbonyl group (e.g. methoxycarbonyl or ethoxycarbonyl), succinimido group, carbamoyl group or nitro group.
• substituent such as an alkyl group (e.g. methyl or ethyl), alkoxy group (e.g. methoxy or ethoxy), hydroxyl group, halogen atom (e.g. chlorine, bromine or iodine), acylamino group (e.g. acetylamino
• Preferred heterocyclic groups for R 1 are 5- or 6-membered heterocyclic groups having at least one hetero atom selected from among nitrogen, oxygen and sulfur atoms (e.g. pyrrolyl, pyridinyl, pyridyl, thiazolyl, morpholino and furanyl). These heterocyclic groups may have at least one substituent selected from among those listed as substituents for the above de- .. fined aliphatic and aromatic groups.
• Preferred monovalent cations for M in the group -S0 3 M for R 2 and R 3 , as well as for R 4 include hydrogen ion, alkali metal ion (e.g. sodium or potassium ion) and ammonium ion.
• Particularly preferred compounds having the formula defined above are those wherein R1 is an alkyl group having 1 to 8 carbon atoms, either R 2 or R 3 is a carboxyl group and the other is -COOR 4 (R 4 is an aliphatic or aromatic group), and A is a carbonyl group.
• the compounds according to the present invention are effective not only in increasing the sensitivity but also in inhibiting fog and minimizing the deterioration of image quality, and in this respect, the compounds are advantageous over conventional organic thioether compounds that can increase the photographic sensitivity only at the expense of other photographic characteristics.
• the silver halide photographic material comprising a support having formed thereon a photographic element that contains the compound of the formula is hereunder described in detail.
• the term "photographic element" as used in this specification includes silver halide emulsion layers formed on the support, as well as auxiliary layers formed on the same side of the support (e.g. a protective layer, an intermediate layer, a subbing layer and an anti-halation layer). According to the present invention, at least one of these layers contains the compound of the formula.
• the compound of the formula is preferably contained in the photographic element in an amount of from 0.1 to 1,000 mg per mol of silver halide. The range of from 1 to 100 mg is particularly preferred.
• the compound is usually employed in the form of a 0.1 to 1% solution of methanol or fluorine-containing alcohol. The compound may be added at any stage before the coating and drying of the photographic material.
• a particularly preferred photographic element for incorporation of this compound is a silver halide emulsion layer, but it may be incorporated in other elements such as the intermediate layer, the protective layer or the subbing layer.
• Silver halides that can be incorporated in the silver halide photographic emulsion according to the present invention are silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chloroiodobromide, and mixtures thereof. Silver iodobromide is the most preferred.
• Gelatin is the most preferred for use as a binder or hydrophilic colloid in the present invention. If necessary, gelatin may be used in combination with other polymers such as gelatin derivatives, colloidal albumin, agar, gum arabic, alginic acid, cellulose derivatives, acrylamide, imidated polyacrylamide, casein, vinyl alcohol polymers, polyvinyl alcohol, polyvinyl pyrrolidone and hydrolyzed polyvinyl acetate.
• other polymers such as gelatin derivatives, colloidal albumin, agar, gum arabic, alginic acid, cellulose derivatives, acrylamide, imidated polyacrylamide, casein, vinyl alcohol polymers, polyvinyl alcohol, polyvinyl pyrrolidone and hydrolyzed polyvinyl acetate.
• the silver halide photographic emulsion that is used in the present invention may contain various known photographic additives such as chemical sensitizers, spectral sensitizers, antifoggants, hard toning agents, gelatin hardeners, surfactants, agents to modify the film properties, thickeners and dot improving agents.
• Suitable chemical sensitizers include active gelatin; noble metal sensitizers such as water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, and water soluble-iridium salts; sulfur sensitizers; selenium sensitizers; and reduction sensitizers such as polyamines and stannous chloride. These chemical sensitizers may be used either alone or in combination.
• spectral sensitizers that can be used in the present invention.
• cyanine or merocyanine dyes such as zeromethine, monomethine, dimethine and trimethine dyes may be used either alone or in combination.
• cyanine or merocyanine dyes such as zeromethine, monomethine, dimethine and trimethine dyes may be used either alone or in combination.
• Suitable sensitizers should be selected depending upon the sensitization spectra, the sensitivity desired, and the object or use of the photographic material.
• the silver halide photographic emulsion according to the present invention may contain other additives such as stabilizers or antifoggants (e.g. azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts and polyhydroxy compounds); hardeners (e.g. aldehyde, aziridine, isoxazole, vinylsulfone, acryloyl, carbodiimide, maleimide, methan- sulfonate ester and triazine compounds); development accelerators (e.g. benzyl alcohol and polyoxyethylene compounds); image stabilizers (e.g.
• stabilizers or antifoggants e.g. azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts and polyhydroxy compounds
• hardeners e.g. aldehyde, aziridine, isoxazole, vinylsulfone
• chroman, chraman, bisphenol and phosphite ester compounds chroman, chraman, bisphenol and phosphite ester compounds
• lubricants e.g. wax, glycerides of higher aliphatic acids, and higher aliphatic acid esters of higher alcohols.
• Surfactants may be used as coating aids, agents to improve the penetrability of processing solutions, deforming agents or materials for controlling the physical properties of the photosensitive material.
• Anionic, cationic, nonionic or amphoteric surfactants may be used for these purposes.
• Effective antistats are diacetyl cellulose, styrene-per-fluoroalkyllidium maleate copolymer or alkali salt of the reaction product of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid.
• Latices may be added to improve the film properties, and suitable latices are copolymers of acryl acid esters or vinyl esters and other monomers having ethylene groups.
• Suitable gelatin plasticizers are glycerin and glycolic compounds.
• Suitable thickeners include styrene -sodium maleate copolymer and alkylvinyl ether-maleic acid copolymer.
• the silver halide photographic material of the present invention has the silver halide emulsion applied to a support by a known coating method, optionally through a subbing layer or an intermediate layer.
• Suitable supports are baryta paper, polyethylene coated paper, synthetic polypropylene paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester (e.g. polyethylene terephthalate) and polystyrene.
• the silver halide photographic material of the present invention may have a laminated structure of silver halide emulsion layers sensitive to different colors.
• each emulsion layer may contain a suitable photographic coupler. That is, a blue-sensitive emulsion layer may contain a yellow coupler, a green- sensitive emulsion layer may contain a magenta coupler, and a red-sensitive emulsion layer may contain a cyan coupler. If necessary, various combinations of emulsion layers and couplers may be used.
• the silver halide photographic material of the present invention may contain a known 2- or 4- equivalent coupler.
• Suitable yellow couplers are extended-chain ketomethylene couplers among which benzoyl acetanilde and pivaloyl acetanilide type yellow couplers are used to advantage.
• Illustrative yellow couplers are described in U.S. Patents Nos. 2,875,057, 3,265,506, 3,277,155, 3,408,194, 3,415,652, 3,447,928, 3,664,841, Japanese Patent Publication No. 13576/74, Japanese Patent Applications (OPI) Nos.
• magenta couplers include pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, indazolone and cyanoacetyl compounds.
• Illustrative magenta couplers are described in U.S. Patents Nos. 2,600,788, 3,061,432, 3,062,653, 3,127,269, 3,311,476, 3,419,391, 3,519,429, 3,558,319, 3,684,514, 3,888,680, British Patents Nos.
• the silver halide photographic material of the present invention may be used for processing by black-and-white or color photography. It may be used for general purposes, as well as for special purposes such as printing, X-ray photography and radiography. Especially good results are achieved if it is used as a high-sensitivity, silver iodobromide photographic material.
• the silver halide photographic material of the present invention may be subjected to ordinary exposure or it may be exposed for a shorter period or only for a flash of time.
• the material may be processed photographically by a conventional method.
• the two basic processing steps are development and fixing, which may be effected consecutively or simultaneously.
• each sample was exposed to white light with a sensitometer, Model KS-1 of Konishiroku Photo Industry Co., Ltd., according to the method specified in JIS, and subsequently processed with a processor of continuous transport type which could accomplish development, fixing, washing and drying automatically.
• the developing solution used had the following composition.
• the so processed samples were subjected to sensitometry to check for their photographic characteristics, which are summarized in Table 1, wherein the figures in the column of "sensitivity" are relative values, with the sensitivity of the control (sample No. 1) taken as 100.
• the quality of the image formed on each sample was evaluated by visually checking the deterioration of developed silver grains at a density of 0.8, and the indices of rating were ⁇ (good), ⁇ (moderate), and X (unacceptable).
• the combination of two indices means that the degree of deterioration was of a value between the two indices.
• Table 1 demonstrates the ability of the compounds of the formula to provide an image of improved quality without sacrificing other photographic characteristics.
• samples 2 to 19 according to the present invention were able to retain a good image quality during the 10-day storage at 23°C and 65% r.h. without causing adverse effects on other photographic characteristics, such as reduced sensitivity and maximum density, and increased fog.
• a cellulose triacetate film base having an anti-halation layer was coated with a high-sensitivity color photographic silver iodobromide emulsion layer (first layer in a dry thickness of 5 u) that contained 10 g of 4-chloro-l-hydroxy-2-n-octyl naphthamide (coupler) per kilogram of a negative silver halide emulsion and which was rendered sensitive to red light.
• first layer was formed a second layer in a dry thickness of 1 ⁇ that was prepared from a 3 % aqueous solution of gelatin.
• the second layer was overlaid with a high-sensitivity color photographic silver iodobromide emulsion layer (third layer in a dry thickness of 4 p) that contained 10 g of 1-(3-carboxyphenyl)-3-(4-stearoylaminophenyl)-5-pyrazolone (coupler) per kilogram of a negative silver emulsion and which was rendered sensitive to green light.
• a yellow colloidal silver layer was formed on the third layer having a dry thickness of 2 p.
• the fourth layer was overlaid with a high-sensitivity color photographic silver iodobromide emulsion layer (fifth layer in a dry thickness of 7 p) that contained 13 g of 2-dodecyloxybenzoyl acetanilide per kilogram of a negative silver halide emulsion and which was rendered sensitive to blue light.
• a sixth layer in a dry thickness of 1 p was prepared from a 4% aqueous solution of gelatin. Fifteen samples of this multilayer coupler-in-emulsion type negative film for color photography were prepared.
• samples 27 to 30 according to the present invention retained a good image quality wihtout increased fog or decreased sensitivity.
• Table 2 shows that samples 27 to 30 according to the present invention which contained compounds of the formula in a multilayer color photographic material provided a better image quality without sacrificing other photographic characteristics.
• the silver halide photographic material having the thioether compound of the formula in a photographic element according to the present invention can provide an improved image quality without having adverse effects on other photographic characteristics.

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• Engineering & Computer Science (AREA)
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• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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• 1983
  • 1983-06-22 EP EP83303599A patent/EP0097536A3/fr not_active Withdrawn

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