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
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances

Definitions

• the present invention relates to a silver halide light-sensitive photographic material, and more particularly to a silver halide light-sensitive photographic material which is stable in the photographic characteristics against changes in the developing condition.
• Photographic film since it has generally a large coating amount of silver compared to photographic paper, tends to be processed at a high temperature or for a long period of time, and therefore, photographic paper, if processed at the same time in the same solution, is supposed to be processed under a much severe condition as compared to the conventional condition under which it should be processed, thus adversely affecting the paper, increasing a fog .
• Reducing the dependence of the photographic characteristics upon the processing condition is of course desirable for all light-sensitive materials as well as the photo-typesetting paper.
• a silver halide light-sensitive photographic material containing not less than 80 mole% silver bromide and silver halide grains whose average grain size is not less than 0.4 ⁇ m, since the developability of the silver halide grain itself is inferior, it is very difficult to lessen the dependence thereof on the processing.
• a silver halide light-sensitive photographic material comprising a support having on at least one side thereof at least one silver halide emulsion layer containing not less than 80 mole% silver bromide and silver halide grains whose average grain size is not less than 0.4 ⁇ m, the said silver halide light-sensitive photographic material wherein at least one of the photographic layers provided on the said silver halide emulsion layer-provided side comprises a 1-phenyl-3-pyrazolidone, and a nonlight-sensitive layer adjacent to the said silver halide emulsion layer comprises at least one heterocyclic compound having a mercapto group.
• the l-phenyl-3-pyrazolidones usable in this invention are those having the formula [1]: wherein R I is hydrogen or an acetyl group, and R 2 , R 3 and R 4 each is hydrogen or a substituted or unsubstituted alkyl group.
• 'average grain size' used herein means an average value of the whole grain sizes.
• the phrase 'having at least one silver halide photographic layer used herein implies a layer construction comprising a support provided on at least one side thereof directly or through a nonlight-sensitive layer with a silver halide photographic emulsion layer or a layer construction wherein the said emulsion layer has thereon, if necessary, further repeated nonlight-sensitive layers, emulsion layers, and the like. And on the topmost silver halide photographic emulsion layer a protective layer may be provided.
• the nonlight-sensitive layer adjacent to the silver halide photographic emulsion layer in this invention includes, e.g., a subbing (undercoat) layer, antihalation layer, intermediate layer, filter layer, protective layer and the like.
• the photographic layer is a general term for silver halide photographic emulsion layers and nonlight-sensitive layers mentioned above.
• the preferred adding amount range of any 1-phenyl-3-pyrazolidone is from 0.2g to 5 g per mole of silver halide. If the amount is less than 0.2g, the effect of the compound can lessen, while if it exceeds 5g, the shelf stability, i.e., stability with the passage of time can be deteriorated.
• the 1-phenyl-3-pyrazolidone may be added to any layer of the photographic layers on the emulsion layer side, and the addition of it to the emulsion layer is particularly effective.
• heterocyclic compound having a mercapto group to be used in this invention those having the following formula [21 may be suitably used: wherein Z is a group of nonmetallic atoms necessary to form a 5- to 6-member heterocyclic ring; and X is a hydrogen atom, an alkali metallic atom, ammonium or an organic amine residue.
• the 5- or 6-member heterocyclic ring including Z is preferably selected from the group consisting of an imidazole, a thiazole, an oxazole, a benzimidazole, a benzothiazole, a benzoxazole, an oxadiazole, a thiadiazole, a triazole, a tetrazole, a pyrimidine, a triazine, a tetrazaindene, or the like.
• mercapto group-having heterocyclic compounds usable in.this invention may be easily synthesized in accordance with those methods as described in, e.g., U.S. Patent Nos. 3,615,501, 2,324,123, 2,384,593, 2,496,940, 3,137,578, 2,496,940, 3,082,088, 3,473,924, 3,575,699, 3,687,660, 2,271,229 and 2,496,940, and British Patent Nos. 1,141,773 and 1,376,600, or in similar manner to these methods.
• these compounds may be easily synthesized in accordance with those methods as described in the 'Dai-Yuki-Kagaku' (Comprehensive Organic Chemistry), edited by Munio Kotake (published by Asakura Shoten, 1971) or A. Weissberger, 'The Chemistry of Heterocyclic Compounds,' (N. Y. Interscience, 1950-1964), or similar manner to these methods.
• any of these mercapto group-having heterocyclic compounds usable in this invention may be provided on the same side as the silver halide emulsion layer's and incorporated into a nonlight-sensitive layer adjacent to the emulsion layer.
• the nonlight-sensitive layer means, to be concrete, the subbing layer (undercoat layer), filter layer, or protective layer.
• the coating amount of the mercapto group-having heterocyclic compound to be used in this invention is desirable to be from 0.1 mg to 10 mg/m 2 . If the amount is less than 0.1 mg/m l , the effect of the compound can lessen, while if it exceeds 10 mg/m l , it tends to largely deteriorate the sensitivity.
• the mercapto group-having heterocyclic compound to be used in this invention may, if necessary, be incorporated also into the emulsion layer.
• the silver halide to be used in this invention is not subjected to any particular restriction; any silver halides, for example, silver bromide, silver chloride, silver iodidobromide, silver chloroiodobromide, etc., may be widely used.
• the crystal form or crystal habit of these silver halides is not placed under restriction either and can be freely selected, and further may be of either the surface latent image type or the internal latent image type.
• the pAg and pH of the silver halide emulsion may also be widely selected.
• the silver halide emulsion to be used in this invention may be prepared by any of various methods; e.g., the acid method, neutral method, alkaline method, ammoniacal method, and also, orderly mixing method, inversely mixing method, simultaneously mixing method, pAg-controlled double-jet method, conversion method, and the like. Further, a core/shell-type emulsion may also be used.
• the silver halide emulsion to be used in this invention in. the course of the formation of the grains thereof or of the physical ripening thereof, may be present together with a cadmium salt, zinc salt, lead salt, thalium salt, iridium salt or a complex salt thereof, rhodium salt or a complex salt thereof, iron salt or iron complex salt, or the like.
• Gelatin is usually used as a binder or protective colloid for the silver halide emulsion to be used in this invention, and in addition to gelatin, other materials may also be used which include, for example, proteins such as gelatin derivatives, graft polymers of gelatin with other high-molecular materials, albumin, casein, etc.; sugar derivatives such as agar-agar, sodium alginate, starch derivatives, etc.; and various synthetic hydrophilic high-molecular materials like homo- or copolymers such as polyvinyl alcohols, poly-N-vinylpyrolidones, polyacrylic acids, polyacrylamides, polyvinyl imidazoles, polyvinyl pyrazoles, etc.; and the like.
• proteins such as gelatin derivatives, graft polymers of gelatin with other high-molecular materials, albumin, casein, etc.
• sugar derivatives such as agar-agar, sodium alginate, starch derivatives, etc.
• the silver halide emulsion to be used in this invention may be chemically sensitized by using various sensitizers.
• the sensitization may be carried out by the single or combined use of, for example, sulfur sensitizers (e.g., hypo, thiourea, active gelatin), noble-metallic sensitizers (e.g., gold sensitizers such as gold chloride, gold thiocyanate, etc., platinum salt, palladium salt, iridium salt, rhodium salt, ruthenium salt), reduction sensitizers (e.g., stannous chloride, thiourea dioxide, hydrazine derivatives), those selenium sensitizers as desicribed in U.S. Patent No. 3,297,446, those polyalkylene-polyamine compounds as described in U.S. Patent No. 2,518,698, and the like.
• sulfur sensitizers e.g., hypo, thiourea, active gelatin
• the silver halide emulsion to be used in this invention may be sensitized by using appropriate sensitizing dyes to desired spectral wavelength regions.
• various-type sensitizing dyes may be used alone or in combination of two or more thereof.
• the sensitizing dye usable in this invention include methine dyes and styryl dyes, such as cyanines, merocyanines, hemicyanines, rhodacyanines, oxonoles, hemioxonoles, and the like.
• Hardening agents usable in this invention include organic hardening agents such as vinylsulfone-type, cyanur-chloride- type, acryloyl-type and ethylene-imine-type hardening agents, and inorganic hardening agents such as chrome alum, potassium alum, etc., which may be used alone or in combination of two or more thereof.
• the photographic light-sensitive material of this invention may use various-type surface active agents including nonionic surface active agents such as saponin, polyalkylene glycol ether, etc., and anionic surface active agents such as alkylbenzenesulfonates, alkyl sulfates, sulfosuccinates, etc.
• nonionic surface active agents such as saponin, polyalkylene glycol ether, etc.
• anionic surface active agents such as alkylbenzenesulfonates, alkyl sulfates, sulfosuccinates, etc.
• the photographic light-sensitive material of this invention may, if necessary, use various other photographic additives including, e.g., stabilizers, coating aids, layer's physical property improving agents, ultraviolet absorbing agents, brightening agents, oxidation inhibitors, antistain agents, metallic ion blocking agents, viscosity increasing agents, matting agents, antihalation agents, antiirradiation agents, and the like.
• various other photographic additives including, e.g., stabilizers, coating aids, layer's physical property improving agents, ultraviolet absorbing agents, brightening agents, oxidation inhibitors, antistain agents, metallic ion blocking agents, viscosity increasing agents, matting agents, antihalation agents, antiirradiation agents, and the like.
• Materials usable as the support for the photographic light-sensitive material of this invention include paper, glass, cellulose acetate, cellulose nitrate, polyester, polyamide, polystyrene, polypropylene, and two or more substrates-laminated materials such as paper-polyolefin (e.g., polyethylene, polypropylene) laminates, and the like.
• Developing agents for use in developing the silver halide light-sensitive photographic material of this invention include various discretional developing agents to be used according to the light-sensitive material produced.
• they are typified by the following:
• amino- pyrazolone such as 4-aminophenol, 2-amino-6-phenylphenol, 2-amino-4-chloro-6-phenylphenol, 4-amino-2-phenylphenol, 3,4-d
• heterocyclic-type developing agent examples include 3-pyrazolidones such as l-phenyl-3-pyrazolidone, l-phenyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, etc., and l-phenyl-4 - amino-5-pyrazolone, 1-(p-aminophenyl)-3-amino-2-pyrazoline, 1-phenyl-3-methyl-4-amino-5-pyrazolone, 5 - aminouracil, and the like.
• 3-pyrazolidones such as l-phenyl-3-pyrazolidone, l-phenyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, etc.
• those developing agents as described in T. H. James, 'The Theory of the Photographic Process,' Fourth Edition, pp. 291-334 and Journal of the American Chemical Society, Vol. 73, p. 3,100 (1951) may also be effectively used in this invention.
• These developing agents may be used either alone or in combination of two or more thereof, and the being used in combination is preferred.
• the effect of this invention will not be reduced even though, e.g., sodium sulfite or potassium sulfite, etc., as a preservative is added to the developing solution to be used for the light-sensitive material of this invention; this is one of the characteristics of this invention.
• hydroxylamine, hydrazide compounds may also be used as the preservative.
• the developer solution to be used in this invention may contain an alkanolamine or a glycol as an organic solvent.
• the pH value of the above-composition-having developer solution is preferably from 9 to 12, and more preferably from 10 to 11 from the standpoint of the preservability and photographic characteristics.
• the silver halide light-sensitive photographic material of this invention may be processed under various conditions.
• the processing temperature for example, the developing temperature is preferably not more than 50°C, and particularly preferably between 30°C and 40"C.
• the developing time is generally within 3 minutes, and particularly preferably within 2 minutes, which, in most cases, results in satisfactory results.
• Those processing steps other than the above development such as, e.g., washing, stopping, stabilizing, fixation, and further, if necessary, prehardening, neutralizing and the like processes, may be adopted arbitrarily, and some of these processes may be omitted according to circumstances. Further, these processes may be carried out either in manual way such as by tray development or frame development or in mechanical way such as by roller development, hanger development, or the like.
• a silver halide emulsion containing tetradecahedral silver halide crystalline grains comprised in composition of 90 mole% silver bromide, 9 mole% silver chloride and 1 mole% silver iodide, whose average grain size is 0.6 ⁇ m, was prepared and then subjected to gold sensitization and sulfur sensitization.
• a gelatin binder 30 mg/m of silica particles as a matting agent whose average particle size is 4 ⁇ m; 30 mg/m 2 of 2-sulfonate succinic acid bis(2-ethylhexyl) ester sodium salt as a coating aid; 20 mg/m 2 of the following compound [A] as a fluorine-containing surface active agent; 100 mg/m z of a styrene-maleic anhydride copolymer as a viscosity increasing agent; and 30 mg per gram of gelatin of the reaction product of tetrakis(vinylsulfonylmethyl)methane with taurine potassium salt (1:0.25) as a hardening agent, and further were added a mercapto group-having heterocyclic compound in a quantity as given in Table 1, and then the pH of the mixture was adjusted to 5.5, Whereby a protective layer coating liquid was prepared.
• Both the thus prepared emulsion coating liquid and protective layer coating liquid were coated superposedly on the nonbacking-layer-side surface of a 110 ⁇ m-thick polyethylene-coated paper having a hydrophilic colloid backing layer (provided on the reverse to the at least one silver halide emulsion layer-having side of the support) and an undercoat layer, provided that a mixture solution of a l-phenyl-3-pyrazolidone in a quantity as given in Table 1 and 4 g per mole of Ag of the following Compound [B] was added to the emulsion coating liquid immediately (within 10 seconds) before the coating.
• the coating amount of silver was 1.4 g/m 2
• the coating amount of gelatin was 2.5 g/m 2 for the emulsion layer and 1.2 g/m 2 for the protective layer.
• the thus obtained sample was subjected to 10 -6 second flash exposure by use of a xenon speed light unit through an optical wedge, and then developed under two different conditions: 15 seconds at 32 D C and 30 seconds at 38 C in a developer solution having the following composition [I]. The developing process was then followed by fixation, washing and drying in usual manner.
• a gelatin binder 0.1 g/m 2 of methyl methacrylate with an average particle size of 3.5 ⁇ m as a matting agent; 30 mg/m 2 of 2-sulfonate succinic acid bis(2-ethylhexyl)ester sodium salt as a coating aid; 20 mg/m 2 of a compound having the following Formula [A] as a fluorine-containing surface active agent; 100 mg/m 2 of a styrene-maleic anhydride copolymer as a viscosity increasing agent; 10 mg per gram of gelatin of formalin as a hardening agent; and further a mercapto group-having heterocyclic compound in an amount as given in Table 2, and then the pH of this mixture was adjusted to 5.5, whereby a protective layer coating liquid was prepared.
• Formula [A] as a fluorine-containing surface active agent
• 100 mg/m 2 of a styrene-maleic anhydride copolymer as a viscos
• Both the thus prepared emulsion coating liquid and protective layer coating liquid were coated superposedly on the nonbacking layer-side surface of a 100 wm-thick polyethylene terephthalate film support having a hydrophilic colloid backing layer, provided that a mixture solution of 15 g per mole of Ag of hydroquinon, a 1-phenyl-3-pyrazolidone in an amount as given in Table 2 and 8 g per mole of Ag of a compound having the following Formula [B] was added to the emulsion coating liquid immediately (within 10 seconds) before the coating thereof.
• the coating amount of silver was 3.8 g/m 2
• the coating amount of gelatin was 2.0 g/m 2 for the emulsion layer and 1.2 g/m 2 for the protective layer.
• the thus obtained sample was subjected to 10 6 second flash exposure by using a xenon speed light unit through an optical wedge, and then developed under two different conditions: 20 seconds at 35°C and 40 seconds at 38°C in the same developer solution [I] as in Example-1. The developing process was then followed by fixation, washing and drying in usual manner.

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• 1986
  • 1986-07-18 JP JP16807086A patent/JPS6325644A/ja active Pending
• 1987
  • 1987-07-10 EP EP19870306105 patent/EP0253585B1/de not_active Expired
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