EP0253585B1 - Silver halide light-sensitive photographic material - Google Patents
Silver halide light-sensitive photographic material Download PDFInfo
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- EP0253585B1 EP0253585B1 EP19870306105 EP87306105A EP0253585B1 EP 0253585 B1 EP0253585 B1 EP 0253585B1 EP 19870306105 EP19870306105 EP 19870306105 EP 87306105 A EP87306105 A EP 87306105A EP 0253585 B1 EP0253585 B1 EP 0253585B1
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- EP
- European Patent Office
- Prior art keywords
- silver halide
- phenyl
- pyrazolidone
- layer
- sensitive
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- 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.
- FR-A-2 119 508 describes photosensitive heat-developable recording materials in which the recording layer includes a photosensitive silver halide, a reducing agent and a thiol compound as a stabilising agent.
- the reducing agent may be a pyrazolidin-3-one developing agent.
- the mercapto compound forms a non-light-sensitive compound with the undeveoped silver halide and is preferably present in an amount from 15 to 60 g per mole of silver halide.
- DE-A-2 034 064 describes color photographic elements containing mercaptotetrazole compounds as anti-foggants in a silver halide emulsion layer and/or an auxiliary layer.
- a silver halide light-sensitive photographic material comprising a support and, provided on at least one side thereof, at least two photographic layers, at least one of the photographic layers being a silver halide emulsion layer containing silver halide grains, of which the silver bromide content is not less than 80 mol per cent and the average grain size is not less than 0.4 micrometres, and at least one other of said photographic layers being a non-light-sensitive layer provided contiguous to said silver halide emulsion layer, characterized in that at least one of said photographic layers contains a 1-phenyl-3-pyrazolidone compound and both said non-light-sensitive and said light sensitive layer contain a heterocyclic compound having therein a mercapto group and represented by the general formula [2]; in which Z is a group of non-metallic atoms necessary to form a five or six membered heterocyclic ring and X is a hydrogen atom, an alkali metal atom, an ammonium group or an organic
- the 1-phenyl-3-pyrazolidones usable in this invention those having the formula [1]: wherein R1 is hydrogen or an acetyl group, and R2, R3 and R4 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 and emulsion layers.
- a protective layer may be provided on the topmost silver halide photographic emulsion layer.
- 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 or protective layer.
- the photographic layer is a general term for silver halide photographic emulsion layers and nonlight-sensitive layers mentioned above.
- 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 or a tetrazaindene
- Typical compounds represented by the above general formula [2] will be given in the following [B-1] through [B-30]. It goes without saying that the compounds usable in this invention are not limited to the following exemplified compounds.
- 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/m2. If the amount is less than 0.1 mg/m2, the effect of the compound can lessen, while if it exceeds 10 mg/m2, it tends to largely deteriorate the sensitivity.
- the silver halide according to Claim 1 is to be used in this invention.
- 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 and conversion method. 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.
- 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, sugar derivatives such as agar-agar, sodium alginate, starch derivatives and various synthetic hydrophilic high-molecular materials like homo- or copolymers such as polyvinyl alcohols, poly-N-vinylpyrolidones, polyacrylic acids, polyacrylamides, polyvinyl imidazoles and polyvinyl pyrazoles.
- proteins such as gelatin derivatives, graft polymers of gelatin with other high-molecular materials, albumin, casein, sugar derivatives such as agar-agar, sodium alginate, starch derivatives and various synthetic hydrophilic high-molecular materials like homo- or copolymers such as polyvinyl alcohols
- 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, platinum salt, palladium salt, iridium salt, rhodium salt, ruthenium salt), reduction sensitizers (e.g., stannous chloride, thiourea dioxide, hydrazine derivatives), those selenium sensitizers as described in U.S. Patent No. 3,297,446, those polyalkylene-polyamine compounds as described in U.S. Patent No. 2,518,698.
- sulfur sensitizers e.g., hypo, thiourea, active gelatin
- noble-metallic sensitizers e.g.
- 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 and hemioxonoles.
- 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 and potassium alum, 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, and anionic surface active agents such as alkylbenzenesulfonates, alkyl sulfates, sulfosuccinates
- 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 and antiirradiation agents.
- 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.
- paper-polyolefin e.g., polyethylene, polypropylene
- 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:
- heterocyclic-type developing agent examples include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-amino-5-pyrazolone, 1-(p-aminophenyl)-3-amino-2-pyrazoline, 1-phenyl-3-methyl-4-amino-5-pyrazolone and 5-aminouracil.
- 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-amino-5-pyrazolone, 1-(p-aminophenyl)-3-amino-2
- 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, 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.
- a caustic alkali, carbonate alkali or amine which is usually used for general black-and-white developer solution
- an inorganic development restrainer such as potassium bromide
- an organic development restrainer such as benzotriazole
- a metallic ion capturing agent such as ethylenediaminetetraacetic acid
- a development accelerator such as methanol, ethanol, benzyl alcohol, or polyalkylene oxides, a surface active agent such as a sodium alkylarylsulfonate, natural saponin, saccharide, or an alkyl ester of the above compound
- a hardening agent such as glutaraldehyde, formalin or glyoxal, an ionic strength adjusting agent such as sodium sulfate may be carried out arbitrarily.
- 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 and neutralizing 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 or hanger development.
- 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 were added 30 mg/m of silica particles as a matting agent whose average particle size is 4 ⁇ m; 30 mg/m2 of 2-sulfonate succinic acid bis(2-ethylhexyl) ester sodium salt as a coating aid; 20 mg/m2 of the following compound [A] as a fluorine-containing surface active agent; 100 mg/m2 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 1-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/m2, and the coating amount of gelatin was 2.5 g/m2 for the emulsion layer and 1.2 g/m2 for the protective layer.
- [B] HO-CH2-SO3Na
- 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°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/m2 of methyl methacrylate with an average particle size of 3.5 ⁇ m as a matting agent; 30 mg/m2 of 2-sulfonate succinic acid bis(2-ethylhexyl)ester sodium salt as a coating aid; 20 mg/m2 of a compound having the following Formula [A] as a fluorine-containing surface active agent; 100 mg/m2 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/m2 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 ⁇ m-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/m2, and the coating amount of gelatin was 2.0 g/m2 for the emulsion layer and 1.2 g/m2 for the protective layer.
- [B] HO-CH2-SO3Na 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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Description
- 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.
- In recent years the processing of silver halide light-sensitive photographic materials has a tendency toward rapid processing, and at the same time the control procedure for the processing has a trend toward being simplified. It is because of saving the labors and expenses required for maintaining the development processes. Such trends can be seen in the movements toward the reduction of the replenishing amounts of developing and other processing solutions; extension of the time interval between renewals of the processing solutions; processing under the same condition of light-sensitive materials which had been conventionally processed independently under different conditions.
- Such movements to speed up and simplify the development processes have prompted devising means for light-sensitive materials to reduce the dependence of the photographic characteristics upon the processing: for example, the addition of those hydroquinone compounds as desicribed in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 39928/1975; the addition of those 1-phenyl-3-pyrazolidones as described in Japanese Patent O.P.I. Publication No. 19739/1982 are known as such means. These techniques all are of compounds for use as developing agents in ordinary photographic developing solutions, and, by incorporating such developing agents in advance into light-sensitive materials, are aimed at making light-sensitive materials hardly subject to changes in the developing condition.
- As has been mentioned, recently there is an increasing trend toward processing under the same condition light-sensitive materials which had been conventionally processed independently under different conditions: for example, there are cases where photo-typesetting films use and photo-sensitive papers for photo-typesettingr and other films or papers for graphic arts, are processed under the same conditions, respectively.
- 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.
- On the other hand, however, where photo-typesetting paper is processed alone, more rapid processing at a lower temperature is desired. Accordingly, in the case of photo-typesetting paper, it is strongly desired to reduce the dependence of the photographic characteristics upon the processing condition.
- 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. Particularly in the case of 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 0.4µm, since the developability of the silver halide grain itself is inferior, it is very difficult to lessen the dependence thereof on the processing.
- FR-A-2 119 508 describes photosensitive heat-developable recording materials in which the recording layer includes a photosensitive silver halide, a reducing agent and a thiol compound as a stabilising agent. The reducing agent may be a pyrazolidin-3-one developing agent. The mercapto compound forms a non-light-sensitive compound with the undeveoped silver halide and is preferably present in an amount from 15 to 60 g per mole of silver halide.
- DE-A-2 034 064 describes color photographic elements containing mercaptotetrazole compounds as anti-foggants in a silver halide emulsion layer and/or an auxiliary layer.
- According to the present invention there is provided a silver halide light-sensitive photographic material comprising a support and, provided on at least one side thereof, at least two photographic layers, at least one of the photographic layers being a silver halide emulsion layer containing silver halide grains, of which the silver bromide content is not less than 80 mol per cent and the average grain size is not less than 0.4 micrometres, and at least one other of said photographic layers being a non-light-sensitive layer provided contiguous to said silver halide emulsion layer, characterized in that at least one of said photographic layers contains a 1-phenyl-3-pyrazolidone compound and both said non-light-sensitive and said light sensitive layer contain a heterocyclic compound having therein a mercapto group and represented by the general formula [2];
in which Z is a group of non-metallic atoms necessary to form a five or six membered heterocyclic ring and X is a hydrogen atom, an alkali metal atom, an ammonium group or an organic amine residue. -
- The term '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 and emulsion layers.
- And on the topmost silver halide photographic emulsion layer a protective layer may be provided.
- As the support to be used in this invention those materials which will be mentioned hereinafter may be used.
- 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 or protective layer.
- The photographic layer is a general term for silver halide photographic emulsion layers and nonlight-sensitive layers mentioned above.
- Subsequently, the 1-phenyl-3-pyrazolidones to be used in this invention will be described below. Out of the compounds those having the foregoing formula [1] is preferred, of which typical examples will be given in the following (A-1) through (A-8). It goes without saying that the compounds usable in this invention are not limited to the following exemplified compounds.
- (A-1) 1-phenyl-3-pyrazolidone
- (A-2) 1-phenyl-4-methyl-3-pyrazolidone
- (A-3) 1-phenyl-4,4-dimethyl-3-pyrazolidone
- (A-4) 1-phenyl-5-methyl-3-pyrazolidone
- (A-5) 1-phenyl-4-methyl-4'-hydroxymethyl-3-pyrazolidone
- (A-6) 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone
- (A-7) 1-phenyl-4,4-di-n-propyl-3-pyrazolidone
- (A-8) 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone
- In the general formula [ 2 ] 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 or a tetrazaindene
Typical compounds represented by the above general formula [2] will be given in the following [B-1] through [B-30]. It goes without saying that the compounds usable in this invention are not limited to the following exemplified compounds. - These 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. Also, 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/m². If the amount is less than 0.1 mg/m², the effect of the compound can lessen, while if it exceeds 10 mg/m², it tends to largely deteriorate the sensitivity.
- The silver halide according to Claim 1 is to be used in this invention. 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 and conversion method. 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.
- 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, sugar derivatives such as agar-agar, sodium alginate, starch derivatives and various synthetic hydrophilic high-molecular materials like homo- or copolymers such as polyvinyl alcohols, poly-N-vinylpyrolidones, polyacrylic acids, polyacrylamides, polyvinyl imidazoles and polyvinyl pyrazoles.
- 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, platinum salt, palladium salt, iridium salt, rhodium salt, ruthenium salt), reduction sensitizers (e.g., stannous chloride, thiourea dioxide, hydrazine derivatives), those selenium sensitizers as described in U.S. Patent No. 3,297,446, those polyalkylene-polyamine compounds as described in U.S. Patent No. 2,518,698.
- The silver halide emulsion to be used in this invention may be sensitized by using appropriate sensitizing dyes to desired spectral wavelength regions. As the sensitizing dye various-type sensitizing dyes may be used alone or in combination of two or more thereof. Examples of the sensitizing dye usable in this invention include methine dyes and styryl dyes, such as cyanines, merocyanines, hemicyanines, rhodacyanines, oxonoles and hemioxonoles.
- 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 and potassium alum, 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, and anionic surface active agents such as alkylbenzenesulfonates, alkyl sulfates, sulfosuccinates
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 and antiirradiation agents. - 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.
- 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. For example, they are typified by the following: The most typical one as the HO-(CH=CH)n-OH-type developing agent is hydroquinone, and other examples representative of it include catechol, pyrogallol and derivatives thereof and ascorbic acid, such as chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone, 2,5-dihydroxyacetophenone, 2,5-diethylhydroquinone, 2,5-di-p-phenethylhydroquinone, 2,5-dibenzoylaminohydroquinone, catechol, 4-chlorocatechol, 3-phenylcatechol, 4-phenylcatechol, 3-methoxycatechol, 4-acetylpyrogallol, 4-(2-hydroxybenzoyl)pyrogallol, sodium ascorbate
Also, examples representative of the HO-(CH=CH)n-NH₂-type developing agent include o- and p-aminophenols and aminopyrazolone, such as 4-aminophenol, 2-amino-6-phenylphenol, 2-amino-4-chloro-6-phenylphenol, 4-amino-2-phenylphenol, 3,4-diaminophenol, 3-methyl-4,6-diaminophenol, 2,4-diaminoresorcinol, 2,4,6-triaminophenol, N-methyl-p-aminophenol, N-β-hydroxyethyl-p-aminophenol, and p-hydroxyphenylaminoacetic acid, 2-aminonaphthol. - Further, examples of the H₂N-(CH=CH)n-NH₂-type developing agent include, e.g., 4-amino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline, N-(4-amino-3-methylphenyl)-morpholine, p-phenylenediamine, 4-amino-N,N-dimethyl-3-hydroxyaniline, N,N,N,N-tetramethylparaphenylenediamine, 4-amino-N-ethyl-N-(β-hydroxyethyl)-aniline, 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline, 4-amino-N-ethyl-(β-methoxyethyl)-3-methyl-aniline, 4-amino-3-methyl-N-ethyl-N-(β-methylsulfonamidoethyl)-aniline, and 4-amino-N-butyl-N-γ-sulfobutylaniline, 1-(4-aminophenyl)-pyrolidine.
- Examples of the heterocyclic-type developing agent include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-amino-5-pyrazolone, 1-(p-aminophenyl)-3-amino-2-pyrazoline, 1-phenyl-3-methyl-4-amino-5-pyrazolone and 5-aminouracil.
- In addition to these compounds, 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, 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. In addition, hydroxylamine, hydrazide compounds may also be used as the preservative. Aside from the above, providing the developer solution with pH adjustment and buffer function by use of a caustic alkali, carbonate alkali or amine which is usually used for general black-and-white developer solution, and the addition to the developer solution of an inorganic development restrainer such as potassium bromide; an organic development restrainer such as benzotriazole; a metallic ion capturing agent such as ethylenediaminetetraacetic acid; a development accelerator such as methanol, ethanol, benzyl alcohol, or polyalkylene oxides, a surface active agent such as a sodium alkylarylsulfonate, natural saponin, saccharide, or an alkyl ester of the above compound; a hardening agent such as glutaraldehyde, formalin or glyoxal, an ionic strength adjusting agent such as sodium sulfate may be carried out arbitrarily.
- 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. As for 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 and neutralizing 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 or hanger development.
- The present invention will be further illustrated in detail by the following examples. It goes without saying that the invention is not limited to and by the examples.
- 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 0.6µm, was prepared and then subjected to gold sensitization and sulfur sensitization. To this emulsion were added 100mg each per mole of Ag of sensitizing dyes having the following Formulas (I) and (II), and further added 1 g per mole of Ag of a stabilizer 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene; a mercapto group-having heterocyclic compound as given in Table 1; 1 g per mole of Ag of a coating aid sodium tripropylnaphthalenesulfonate; 40 g per mole of Ag of liquid paraffin in the form of an emulsifiedly dispersed product and 20 g per mole of Ag of diethylene glycol both as layer's physical property improving agents; 5 g per mole of Ag of a styrene-maleic anhydride copolymer as a viscosity increasing agent; 30 mg per gram of gelatin of the reaction product of tetrakis(vinylsulfonylmethyl)methane and taurine potassium salt (1:0.25) as a hardening agent, and then the pH of the mixture was adjusted to 5.5, whereby an emulsion coating liquid was prepared.
- Subsequently, to a gelatin binder were added 30 mg/m of silica particles as a matting agent whose average particle size is 4 µm; 30 mg/m² of 2-sulfonate succinic acid bis(2-ethylhexyl) ester sodium salt as a coating aid; 20 mg/m² of the following compound [A] as a fluorine-containing surface active agent; 100 mg/m² 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 µm-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 1-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/m², and the coating amount of gelatin was 2.5 g/m² for the emulsion layer and 1.2 g/m² for the protective layer.
[B] HO-CH₂-SO₃Na
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°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. - The obtained resultes are shown in Table 1, wherein the sensitivity is of a value expressed in -log E when an exposure necessary to obtain a density of 1.0 is regarded as E.
-
- A silver halide emulsion having cubic silver halide crystalline grains comprised in composition of 98 mole% silver bromide and 2 mole% silver iodide, whose average grain size is 0.5 µm, was prepared, and then subjected to gold sensitization and sulfur sensitization treatments. To this emulsion were added 2 g per mole of Ag of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as a stabilizer; 150 mg per mole of Ag of a compound having the following Formula [III] as a sensitizing dye; a compound as given in Table 2 as a mercapto group-having heterocyclic compound; 10 g per mole of Ag of saponin as a coating aid; 80 g per mole of Ag of polyethylene acrylate latex as a layer's physical property improving agent; 5 g per mole of Ag of a styrene-maleic anhydride copolymer as a viscosity increasing agent; and 10 mg per gram of gelatin of formalin as a hardening agent, and the pH of this mixture was adjusted to 5.5, whereby an emulsion coating liquid was prepared.
- Subsequently, to a gelatin binder were added 0.1 g/m² of methyl methacrylate with an average particle size of 3.5 µm as a matting agent; 30 mg/m² of 2-sulfonate succinic acid bis(2-ethylhexyl)ester sodium salt as a coating aid; 20 mg/m² of a compound having the following Formula [A] as a fluorine-containing surface active agent; 100 mg/m² 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.
- Both the thus prepared emulsion coating liquid and protective layer coating liquid were coated superposedly on the nonbacking layer-side surface of a 100 µm-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/m², and the coating amount of gelatin was 2.0 g/m² for the emulsion layer and 1.2 g/m² for the protective layer.
[B] HO-CH₂-SO₃Na
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. - The obtained results are shown in Table 2, wherein the sensitivity is expressed in -log E when an exposure necessary to obtain a density of 3.0 is regarded as E.
-
Claims (7)
- A silver halide light-sensitive photographic material comprising a support and, provided on at least one side thereof, at least two photographic layers, at least one of the photographic layers being a silver halide emulsion layer containing silver halide grains, of which the silver bromide content is not less than 80 mol per cent and the average grain size is not less than 0.4 micrometres, and at least one other of said photographic layers being a non-light-sensitive layer provided contiguous to said silver halide emulsion layer, characterized in that at least one of said photographic layers contains a 1-phenyl-3-pyrazolidone compound and both said non-light-sensitive and said light sensitive layer contain a heterocyclic compound having therein a mercapto group and represented by the general formula [2];
- A silver halide light-sensitive photographic material according to claim 1, characterized in that the 1-phenyl-3-pyrazolidone compound is represented by the general formula :
- A silver halide light-sensitive photographic material according to claim 2, characterized in that the 1-phenyl-3-pyrazolidone is
1-phenyl-3-pyrazolidone,
1-phenyl-4-methyl-3-pyrazolidone,
1-phenyl-4,4-dimethyl-3-pyrazolidone,
1-phenyl-5-methyl-3-pyrazolidone,
1-phenyl-4-methyl-4'-hydroxymethyl-3-pyrazolidone,
1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone,
1-phenyl-4,4-di-n-propyl-3-pyrazolidone, or
1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone. - A silver halide light-sensitive photographic material according to any of the preceding claims, characterized in that said five or six membered heterocyclic ring in the general formula [2] is an imidazole, a thiazole, an oxazole, a benzimidazole, a benzothiazole, a benzoxazole, an oxadiazole, a thiadiazole, a triazole, a tetrazole, a pyrimidine, a triazine or a tetrazaindene ring.
- A silver halide light-sensitive photographic material according to any of the preceding claims, characterized in that said 1-phenyl-3-pyrazolidone compound is contained in said photographic layer in a quantity from 0.2 g to 5 g per mole of silver halide.
- A silver halide light-sensitive photographic material according to any of the preceding claims, characterized in that said compound of general formula [2] is contained in quantity from 0.1 mg/m² to 10 mg/m².
- A silver halide light-sensitive photographic material according to any of the preceding claims, characterized in that said non-light-sensitive layer is a protective layer, a subbing layer, an anti-halation layer, an intermdiate layer or a filter layer.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP168070/86 | 1986-07-18 | ||
JP16807086A JPS6325644A (en) | 1986-07-18 | 1986-07-18 | Silver halide photographic sensitive material adaptable to change of development condition |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0253585A2 EP0253585A2 (en) | 1988-01-20 |
EP0253585A3 EP0253585A3 (en) | 1989-03-29 |
EP0253585B1 true EP0253585B1 (en) | 1992-09-09 |
Family
ID=15861280
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19870306105 Expired - Lifetime EP0253585B1 (en) | 1986-07-18 | 1987-07-10 | Silver halide light-sensitive photographic material |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0253585B1 (en) |
JP (1) | JPS6325644A (en) |
DE (1) | DE3781615T2 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0329335A3 (en) * | 1988-02-12 | 1991-01-09 | Minnesota Mining And Manufacturing Company | Pattern free lithographic elements |
JP2784503B2 (en) * | 1988-12-12 | 1998-08-06 | 日本電信電話株式会社 | Guided optical waveguide and method of manufacturing the same |
DE69526734D1 (en) * | 1995-07-31 | 2002-06-20 | Agfa Gevaert Nv | Material for industrial radiography and development processes therefor |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4834170B1 (en) * | 1969-07-10 | 1973-10-19 | ||
GB1367459A (en) * | 1970-12-21 | 1974-09-18 | Agfa Gevaert | Photographic recording material |
JPS5943728B2 (en) * | 1980-10-30 | 1984-10-24 | 三菱製紙株式会社 | silver halide photographic materials |
JPS57144547A (en) * | 1981-03-03 | 1982-09-07 | Fuji Photo Film Co Ltd | Silver halide color photosensitive material and its processing method |
JPS60154247A (en) * | 1984-01-24 | 1985-08-13 | Fuji Photo Film Co Ltd | Silver halide photosensitive material |
JPS6165233A (en) * | 1984-09-06 | 1986-04-03 | Konishiroku Photo Ind Co Ltd | Photographic element |
JPS6191658A (en) * | 1984-10-11 | 1986-05-09 | Mitsubishi Paper Mills Ltd | Treatment of silver halide photographic sensitive material |
-
1986
- 1986-07-18 JP JP16807086A patent/JPS6325644A/en active Pending
-
1987
- 1987-07-10 EP EP19870306105 patent/EP0253585B1/en not_active Expired - Lifetime
- 1987-07-10 DE DE19873781615 patent/DE3781615T2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPS6325644A (en) | 1988-02-03 |
DE3781615D1 (en) | 1992-10-15 |
EP0253585A2 (en) | 1988-01-20 |
DE3781615T2 (en) | 1993-03-25 |
EP0253585A3 (en) | 1989-03-29 |
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