WO2006036028A1 - Silver halide color photographic light-sensitive material - Google Patents
Silver halide color photographic light-sensitive material Download PDFInfo
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- WO2006036028A1 WO2006036028A1 PCT/JP2005/018578 JP2005018578W WO2006036028A1 WO 2006036028 A1 WO2006036028 A1 WO 2006036028A1 JP 2005018578 W JP2005018578 W JP 2005018578W WO 2006036028 A1 WO2006036028 A1 WO 2006036028A1
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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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
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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
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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
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/03517—Chloride content
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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
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/03535—Core-shell grains
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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
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/03558—Iodide content
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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
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/03594—Size of the grains
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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
- G03C2001/097—Selenium
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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
- G03C2200/00—Details
- G03C2200/39—Laser exposure
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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
- G03C2200/00—Details
- G03C2200/52—Rapid processing
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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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
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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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/34—Couplers containing phenols
- G03C7/346—Phenolic couplers
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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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/407—Development processes or agents therefor
Definitions
- the present invention relates to a silver halide color photographic light-sensitive material.
- silver halide emulsions with high-silver chloride content have been used, to cope primarily with the aforementioned demand for
- a silver halide color photographic light-sensitive material comprising, on a support, at least one silver halide emulsion layer containing a cyan dye forming coupler, at least one silver halide emulsion layer containing a magenta dye forming coupler, and at least one silver halide emulsion layer containing a yellow dye forming coupler, wherein at least one layer of said at least one silver halide emulsion layer containing a cyan dye forming coupler contains high-silver chloride emulsion grains, which are selenium-sensitized and have a silver chloride content of 90 mol% or more, and contains at least one coupler represented by the following formula (I):
- R' and R" each independently represent a substituent; and Z represents a hydrogen atom, or a group capable of being split-off upon a coupling reaction with an oxidized product of an aromatic primary amine color-developing agent;
- M 1 and M 2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, an alkoxy group, a hydroxy group, or a carbamoyl group;
- Q represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, -OM 3 , or -NM 4 M 5 , in which M 3 , M 4 , and M 5 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group; and any two groups of M 1 , M 2 , and Q may bond together, to form a ring structure;
- X 1 , X 2 , and X 3 each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group,- OJ 1 , or -NJ 2 J 3 , in which J 1 , J 2 , and J 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group;
- E 1 and E 2 which are the same or different from each other, each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group;
- the silver halide color photographic light-sensitive material according to any one of the above (1) to (8) which is a silver halide color photographic light-sensitive material for rapid processing, in which a color development processing is started within 9 seconds after imagewise exposure, and said color development processing is finished in a period time within 28 seconds, to form an image; and
- a silver halide emulsion that has high sensitivity, that is reduced in fogging, and that imparts contrasty gradation, can be obtained.
- the present invention can also provide a silver halide photographic light-sensitive material that is reduced in the change in performance with the lapse of time after materials to be used in said light-sensitive material are mixed and dissolved in a production process.
- the silver halide color photographic light-sensitive material of the present invention is high in sensitivity, low in fogging, excellent in gradation characteristics, and reduced in the change in performance with the lapse of time after materials to be used in said light-sensitive material are mixed and dissolved in a production process.
- the silver halide emulsion that can be used in the present invention comprises high-silver chloride emulsion grains, which are sensitized by selenium and have a silver chloride content of 90 mol% or more, and said at least one layer contains at least one coupler represented by formula (I).
- R' and R" each independently represent a substituent; and Z represents a hydrogen atom, or a group capable of being split-off upon a coupling reaction with an oxidized product of an aromatic primary amine color-developing agent.
- alkyl refers to an unsaturated or saturated, straight-chain or branched-chain alkyl group (including a alkenyl and aralkyl), including a cyclic alkyl group having 3 to 8 carbon atoms (including a cycloalkyl group and a cycloalkenyl group), and the term "aryl" specifically includes a condensed aryl.
- R 1 and R" each are preferably selected independently from an unsubstituted or substituted alkyl group, aryl group, amino group or alkoxy group, or a 5- to 10-membered heterocycle containing at least one heteroatom selected from nitrogen, oxygen and sulfur, which ring may be unsubstituted or substituted.
- R' and/or R" when R' and/or R" is an amino group or an alkoxy group, R' and/or R" may have a substituent (e.g., a halogen atom, an aryloxy group, or an alkyl- or aryl-sulfonyl group).
- R' and R" are independently selected from unsubstituted or substituted, alkyl or aryl groups having 1 to 50 carbon atoms (e.g., hexyl, phenyl, and tolyl), or five to ten-membered heterocyclic groups, such as a pyridyl, morpholino, imidazolyl, or pyridazolyl group.
- R' is more preferably an alkyl group substituted with a substituent; and examples of the substituent include a halogen atom, an alkyl group, an aryloxy group, and an alkyl- or aryl-sulfonyl group, each of which may be further substituted, and these are preferable.
- R" is an alkyl group, it may be likewise substituted in the same manner as described above.
- R" is preferably an unsubstituted aryl group, or an aryl group that is substituted with a substituent.
- substituent on said substituted aryl group include a cyano group, a halogen , atom (chlorine, fluorine, bromine, or iodine), an alkyl-.
- alkyl- or aryl-carbonyl group an alkyl- or aryl-oxycarbonyl group, an acyloxy group, a carbonamido group, an alkyl- or aryl-carbonamido group, an alkyl- or aryl- oxycarbonamido group, an alkyl- or aryl-sulfonyl group, an alkyl- or aryl-sulfonyloxy group, an alkyl- or aryl-oxysulfonyl group, an alkyl- or aryl-sulfoxido group, an alkyl- or aryl-sulfamoyl group, an alkyl- or aryl-sulfamoylamino group, an alkyl- or aryl-sulfonamido group, an aryl group, an alkyl group, an alkoxy group, an aryloxy group, a nitro group, an alkyl- or aryl-ureid
- a preferred substituent is a halogen atom, a cyano group, an alkoxycarbonyl group, an alkylsulfamoyl group, a sulfonamido group, an alkyl-sulfonamido group, an alkylsulfonyl group, a carbamoyl group, an alkylcarbamoyl group, or an aDcylcarbonamido group.
- R' is an aryl group or a heterocyclic group, it may also be substituted in the same manner as described above.
- R" is a 4-chlorophenyl group, a 3,4-dichlorophenyl group, a 3,4-difiuorophenyl group, a 4-cyanophenyl group, 3-chloro-4-cyano-phenyl group, a pentafluorophenyl group, or a 3- or 4- sulfonamido-phenyl group.
- Z represents a hydrogen atom, or a group that can split off upon a coupling reaction with an oxidized product of an aromatic primary amine color-developing agent.
- Z is preferably a hydrogen atom, a chlorine atom, a fluorine atom, or a substituted aryloxy group, more preferably a hydrogen atom or a chlorine atom.
- Z in formula (I) is not one which reacts with an oxidized color developing agent, to convert into a diffusible development inhibitor or a precursor thereof, and/or which reacts with an oxidized color developing agent, to form a cleft compound that can react with another one molecule of the oxidized color developing agent, to convert into a development inhibitor or a precursor thereof, i.e. a so-called DIR compound.
- development inhibitor examples include development inhibitors as described in Research Disclosure, vol. 76, No. 17643, (December, 1978), U.S. Patent Nos. 4,477,563, 5,021,332, 5,026,628, 3,227,554, 3,384,657, 3,615,506, 3,617,291, 3,733,201, 3,933,500, 3,958,993, 3,961,959, 4,149,886, 4,259,437, 4,095,984 and 4,782,012, and GB Patent Nos. 1450479 or 5034311.
- Typical examples of the development inhibitor or its precursor include heterocyclic thio groups, heterocyclic seleno groups, or triazolyl groups (monocyclic or condensed cyclic 1,2,3-triazolyl or 1,2,4- triazolyl), and particularly preferable examples include tetrazolylthio, tetrazolylseleno, 1,3,4- oxadiazolylthio, 1,3,4-thiadiazolylthio, l-(or 2-)benzotriazolyl, l,2,4-triazole-l-(or 4-)yl, 1,2,3-triazole-l-yl, 2-benzothiazolylthio, 2-benzooxazolylthio, 2-benzimidazolylthio, and derivatives of these.
- Z determines the chemical equivalent of the coupler, that is, whether it is a two-equivalent coupler or a four-equivalent coupler, and the reactivity of the coupler can be changed depending on the kind of Z.
- Such a group can give advantageous effects on the layers on which the coupler is coated or other layers in a photographic recording material, by exhibiting a function, for example, of dye formation, dye hue adjustment, acceleration of development or inhibition of development, acceleration of bleaching or inhibition of bleaching, facilitation of electron mobilization, color correction, or the like, after said group is released from the coupler.
- Examples of representative class of such a coupling split-off group include a halogen atom, an alkoxy, aryloxy, heterocyclic oxy, sulfonyloxy, acyloxy, acyl, heterocyclic, sulfonamido, heterocyclic thio, benzothiazolyl, phosphonyloxy, alkylthio, arylthio, or arylazo group.
- the coupling split-off group is particularly preferably a chlorine atom, a hydrogen atom, or a p- methoxyphenoxy group.
- the aforementioned exemplified compounds IC-22 to IC-24, IC-30, and IC-31 are particularly preferable.
- selenium compound any of compounds represented by formula (SEl), (SE2), or (SE3) is preferable.
- M 1 and M 2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, an alkoxy group, a hydroxy group, or a carbamoyl group;
- Q represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, -OM 3 , or -NM 4 M 5 , in which M 3 , M 4 , and M 5 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group; and any two groups of M 1 , M 2 , and Q may bond together, to form a ring structure;
- X 1 , X 2 , and X 3 each independently represent an alkyl group, an alkenyl group, an alkyny
- alkyl group as represented by any of M 1 to M 5 and Q means a straight-chain, branched or cyclic, substituted or unsubstituted alkyl group. Preferred examples thereof include a straight- chain or branched, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms (e.g., a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an n-butyl group, a t-butyl group, a 2-pentyl group, an n-hexyl group, an n-octyl group, a t-octyl group, a 2-ethylhexyl group, a 1,5-dimethylhexyl group, an n-decyl group, an n-dodecyl group, an n-tetradecyl group, an n-hexadecyl group
- Examples of the alkenyl group represented by any of M 1 to M 5 and Q include an alkenyl group having 2 to 16 carbon atoms (e.g., an allyl group, a 2-butenyl group, and a 3-pentenyl group).
- Examples of the alkynyl group represented by any of M 1 to M 5 and Q include an alkynyl group having 2 to 10 carbon atoms (e.g., a propargyl group, and a 3-pentynyl group).
- Examples of the aryl group represented by any of M 1 to M 5 and Q include a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, including a phenyl group and a naphthyl group (e.g. unsubstituted phenyl, unsubstituted naphthyl, 3,5-dimethylphenyl, 4-butoxyphenyl, and 4- dimethylaminophenyl).
- Examples of the heterocyclic group include pyridyl, furyl, imidazolyl, piperidyl and morpholyl.
- Examples of the acyl group represented by M 1 and M 2 include an acetyl group, a formyl group, a benzoyl group, a pivaloyl group, a caproyl group, and an n-nonanoyl group;
- examples of the amino group include an unsubstituted amino group, a methylamino group, a hydroxyethylamino group, an n-octylamino group, a dibenzylamino group, a dimethylamino group, and a diethylamino group;
- examples of the alkoxy group include a methoxy group, an ethoxy group, an n-butyloxy group, a cyclohexyloxy group, an n- octyloxy group, and an n-decyloxy group;
- examples of the carbamoyl group include an unsubstituted carbamoyl group, an N,N-diethy
- M 1 to M 5 and Q may have a substituent(s) as many as possible.
- substituents include a halogen atom (fluorine, chlorine, bromine, or iodine), an alkyl group (any of linear, branched, or cyclic alkyl groups including a bicycloalkyl group and an active methine group), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group (any substitution position is permitted), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, a carbamoyl group, an N-hydroxycarbamoyl group, an N-acylcarbamoyl group, an N-sulfonylcarbamoyl group, an N- carbamoylcarbamoyl group, a thiocarbamoyl group, an N-sulfamoylcarb
- the active methine group refers to a methine group substituted by two electron- withdrawing groups.
- the electron-withdrawing group which is explained in detail below, means to include, for example, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a trifluoromethyl group, a cyano group, a nitro group, and a carbonimidoyl group.
- These two electron-withdrawing groups may bond together, to form a ring structure.
- salt as used herein is intended to include cations of alkali metals, alkali earth metals, and heavy metals; and organic cations, such as ammonium ions, and phosphonium ions. Those substituents may further be substituted with any of those substituents.
- M 1 and M 2 each are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, or an acyl group;
- Q is an alkyl group, an alkenyl group, an aryl group, or -NM 4 M 5 ; and
- M 4 and M 5 each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.
- M 1 and M 2 each are a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group
- Q is an alkyl group, an aryl group, or -NM 4 M 5
- M 4 and M 5 each represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.
- M 1 and M 2 each are a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group
- Q is -NM 4 M 5
- M 4 and M 5 each represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.
- the compound represented by formula (SEl) can be synthesized, according to known methods, for example, the methods described in Chem. Rev., 55, 181-228 (1955); J. Org. Chem., 24, 470-473 (1959); J. Heterocycl. Chem., 4, 605-609 (1967); J. Drug (Yakushi), 82, 36-45 (1962); JP-B-39-26203, JP-A-63- 229449 ("JP-A” means unexamined published Japanese patent application), and German Patent Publication (OLS) No. 2,043,944.
- the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group as represented by any of X 1 to X 3 and J 1 to J 3 have the same meanings as those represented by M 1 to M 5 and Q in formula (SEl).
- X 1 to X 3 and J 1 to J 3 each may have a substiruent(s) up to its possible limit, and examples of the substituent include the same specific examples of the substituent as mentioned above.
- X 1 to X 3 each independently are an alkyl group, an aryl group, or a heterocyclic group.
- X 1 to X 3 each independently are an aryl group.
- the compound represented by formula (SE2) can be synthesized, according to known methods, for example, the methods described in Organic Phosphorus Compounds, vol. 4, pp. 1-73; J. Chem. Soc. B, p. 1416 (1968); J. Org. Chem., vol. 32, p. 1717 (1967); J. Org. Chem., vol. 32, p. 2999 (1967); Tetrahedron, vol. 20, p. 449 (1964); and J. Am. Chem. Soc, vol. 91, p. 2915 (1969).
- alkyl, alkenyl, alkynyl, aryl, and heterocyclic groups represented by E 1 and E 2 have the same meanings as those represented by M 1 to M 5 and Q in formula (SEl).
- Examples of the acyl group represented by E 1 and E 2 include an acetyl group, a formyl group, a benzoyl group, a pivaloyl group, a caproyl group, and an n-nonanoyl group;
- examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butyloxycarbonyl group, a cyclohexyloxycarbonyl group, an n- octyloxycarbonyl group, and an n-decyloxycarbonyl group;
- examples of the aryloxycarbonyl group include a phenoxycarbonyl group, and a napthoxycarbonyl group; and examples of the carbamoyl group include an unsubstituted carbamoyl group, an N,N-diethylcarbamoyl group, and an N-phenylcarbamoyl group.
- E 1 and E 2 each may further have a substituent(s) as far as possible.
- substituents have the same meaning as the substituents that M 1 to M 5 and Q in formula (SEl) may have, and examples of the substituent include the same specific examples of the substituent as mentioned above.
- either E 1 or E 2 is a group selected from the groups represented by any of the following formulae (Tl) to (T4). In these cases, E 1 and E 2 may be the same or different.
- Y 11 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, -OR 11 , or -NR 12 R 13 , in which R 11 , R 12 , and R 13 each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
- L 11 represents a divalent linking group
- EWG represents an electron- withdrawing group
- a 11 represents an oxygen atom, a sulfur atom, or -NR 17 ; and R 14 , R 15 , R 16 , and
- R 17 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
- a 12 represents an oxygen atom, a sulfur atom, or -NR 111 ;
- R 18 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, or an acyl group;
- R 19 , R 110 , and R 111 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
- Z 11 represents a substituent; n 11 is an integer from 0 to 4. When n 11 is 2 or more, plural Z 11 S may be the same or different.
- Y 11 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, -OR 11 , or -NR 12 R 13 , in which R 11 , R 12 , and R 13 each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
- the "alkyl group” as mentioned has the same meaning as one represented by M 1 to M 5 and Q in formula (SEl), and they are identical in the range of preferred one.
- alkenyl group, the alkynyl group, the aryl group, and the heterocyclic group have the same meanings as the alkenyl group, the alkynyl group, the aryl group, and the heterocyclic group represented by M 1 to M 5 and Q, and the ranges of preferred ones in regard to each of these groups are also identical.
- Y 11 is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group; and more preferably an alkyl group or an aryl group.
- the divalent linking group represented by L 1 preferably represents an alkylene, alkenylene, or alkynylene group having 2 to 20 carbon atoms; more preferably represents a straight-chain, branched or cyclic alkylene group having 2 to 10 carbon atoms (e.g., ethylene, propylene, cyclopentylene, and cyclohexylene), an alkenylene group (e.g., vinylene), or an alkynylene group (e.g., propynylene).
- L 11 is more preferably a group represented by formula (Ll) or (L2).
- Formula ( L I ) Formula ( L 2 )
- G 1 , G 2 , G 3 , and G 4 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heterocyclic group having 1 to 10 carbon atoms. Any two of G 1 , G 2 , and G 3 may bond together, to form a ring.
- G 1 , G 2 , G 3 , and G 4 each are preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.
- EWG represents an electron-withdrawing group.
- the term "electron- withdrawing group” so-called herein means a group having a positive value of Hammett's substituent constant ⁇ m value, and preferably a ⁇ m value of 0.12 or more, with its upper limit being 1.0 or less.
- the electron- withdrawing group having a positive ⁇ m value include an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a formyl group, an acyloxy group, an acylthio group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group, a diarylphosphono group, a dialkylphosphinyl group, a diarylphosphinyl group, a phosphoryl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, an acylthio group, a sulfamoyl group, a thiocyanato
- EWG is preferably an alkoxy group, an acyl group, a formyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group, a diarylphosphono group, a dialkylphosphinyl group, a diarylphosphinyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a thiocarbonyl group, an imino group, an imino group substituted with an N atom; a phosphoryl group, a carboxy group (or its salt), an alkyl group substituted with at least two or more halogen atoms; an aryl group substituted with other electron-withdrawing group having
- L 11 is represented by formula (Ll); G 1 to G 3 each are a hydrogen atom or an alkyl group; and EWG is an alkoxy group, an acyl group, a formyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a carboxy group, or an alkyl group substituted with at least two or more halogen atoms.
- EWG is an alkoxy group, an acyl group, a formyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a carboxy group, or an alkyl group substituted with at least two or more
- L 11 is represented by formula (Ll); G 1 to G 3 each are a hydrogen atom or an alkyl group; and EWG is an alkoxy group, an acyl group, a formyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, or an alkyl group substituted with at least two or more halogen atoms.
- R 14 to R 17 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
- the alkyl group so-called herein has the same meaning as the aforementioned alkyl group represented by any of M 1 to M 5 and Q in formula (SEl), and the preferable range is also the same.
- the alkenyl group, alkynyl group, aryl group, and heterocyclic group have the same meanings as the aforementioned alkenyl group, alkynyl group, aryl group, and heterocyclic group, represented by any of M 1 to M 5 and Q, and the preferable ranges are also the same.
- R 14 is preferably an alkyl group
- R 15 and R 16 each are preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, and most preferably one of R 15 and R 16 is a hydrogen atom and the other is a hydrogen atom or an alkyl group.
- R 17 is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, and most preferably an alkyl group.
- a 11 represents an oxygen atom, a sulfur atom, or -NR 17 .
- a 11 is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.
- the alkyl group represented by R 18 , R 19 , R 110 , and R 111 has the same meaning as the aforementioned alkyl group represented by any of M 1 to M 5 and Q in formula (SEl), and the preferable range is also the same.
- the alkenyl group, alkynyl group, aryl group, and heterocyclic group have the same meanings as the aforementioned alkenyl group, alkynyl group, aryl group, and heterocyclic group represented by any of M 1 to M 5 and Q, respectively, and the preferable ranges are also the same.
- Examples of the acyl group represented by R IS include an acetyl group, a formyl group, a benzoyl group, a pivaloyl group, a caproyl group, and an n-nonanoyl group.
- Z 11 in formula (T4) represents a substituent, and examples thereof include the same ones as the substituent described in the above.
- Z 11 include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an N-acylcarbamoyl group, an N-sulfonylcarbamoyl group, an N-carbamoylcarbamoyl group, a thiocarbamoyl group, N-sulfamoylcarbamoyl group, a carbazoyl group, a carboxy group (including a salt thereof), a cyano group, a formyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a nitro group, an amino group, an alkyl-, aryl- or heterocyclic- amino group, an acylamino group,
- More preferable examples thereof include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a carboxy group (including a salt thereof), a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an amino group, an alkyl-, aryl-, or heterocyclic-amino group, an acylamino group, a ureido group, a thioureido group, an alkylthio group, an arylthio group, a heterocyclic thio group, and a sulfo group (including a salt thereof).
- n represents an integer of from 0 to 4.
- n 11 is preferably an integer of from 0 to 2, and more preferably 0 or 1.
- a 12 represents an oxygen atom, a sulfur atom, or -NR 111 .
- a 12 preferably represents an oxygen atom or a sulfur atom, and more preferably an oxygen atom.
- a 12 is an oxygen atom or a sulfur atom
- R )8 is a hydrogen atom, an alkyl group or an acyl group
- R 19 and R 110 each are a hydrogen atom, an alkyl group or an aryl group
- n 11 is an integer of 0 to 2
- Z 11 is an alkyl group, an aryl group, a carboxy group (including its salt), a hydroxy group, an alkoxy group, an aryloxy group, an alkyl-, aryl- or heterocyclic-amino group, a ureido group, an alkylthio group, an arylthio group, or a sulfo group (including its salt).
- a 12 is an oxygen atom
- R 18 is a hydrogen atom or an alkyl group
- R 19 and R 110 each are a hydrogen atom or an alkyl group
- n 11 is an integer of 0 to 2
- Z 11 is an alkyl group, an aryl group, a carboxy group (including its salt), an alkoxy group, a ureido group or a sulfo group (including its salt).
- a 12 is an oxygen atom
- R 18 is an alkyl group
- R 19 and R 110 each are a hydrogen atom
- n 11 is an integer of 0 to 2
- Z 11 is an alkyl group, a carboxy group (including its salt), an alkoxy group or a sulfo group (including its salt).
- At least one of E 1 and E 2 is selected from the groups represented by any of formula (Tl) or (T4).
- at least one of E 1 and E 2 is selected from the groups represented by formula (Tl) and the other is selected from the groups represented by any of formulae (Tl), (T2) and (T4), or alternatively at least one of E 1 and E 2 is selected from the groups represented by formula (T4) and the other is selected from the groups represented by formula (T3) or (T4).
- At least one of E 1 and E 2 is selected from the groups represented by formula (Tl) and the other is selected from the groups represented by formula (T2) or (T4), or alternatively E 1 and E 2 each are selected from the groups represented by formula (T4).
- at least one of E 1 and E 2 is selected from the groups represented by formula (Tl) and the other is selected from the groups represented by formula (T2), or alternatively E 1 and E 2 each are selected from the groups represented by formula (T4).
- the compound represented by formula (SE3) can be synthesized, according to the methods described, for example, in the following documents: The Chemistry of Organic Selenium and Tellurium Compounds, Vol. 1 (1986), and ibid. Vol. 2 (1987), edited by S. Patai and Z. Rappoport; and Organoselenium Chemistry (1987) by D. Liotta.
- non-labile selenium compounds as described, for example, in JP-B-46-4553 and JP-B-52-34492, including selenous acid compounds, selenocyanic acid compounds (such as potassium selenocyanate), selenazoles, and selenides, can also be optionally used. Of these compounds, selenocyanic acid compounds are preferred over the others.
- the 3d-orbital electron of a selenium atom in the selenium compound that can be used in the present invention has bound energy of from 54.0 eV to 65.0 eV, as measured with an X-ray photoelectron spectroscope.
- the amount of a selenium sensitizer for use in the present invention is generally from about IxIO "8 to about IxIO "4 mole, preferably from about IxIO '7 to about IxIO "5 mole, per mole of silver halide.
- the present invention has no particular restriction as to conditions for chemical sensitization, but the pCl is preferably from 0 to 7, more preferably from 0 to 5, and further preferably from 1 to 3, and the temperature is preferably from 40 to 95°C, and more preferably from 50 to 85°C.
- the selenium compounds according to the present invention can be added at any stage during the period from the instant following the grain formation to the instant preceding the completion of chemical sensitization.
- the preferable addition timing is within a period between the instant following completion of desalting and the chemical sensitization process inclusive.
- gold selenium compound that can be used in the present invention a compound represented by any one of formulae (PFl) to (PF6) can be preferably used.
- R 210 , R 211 and R 212 each independently represent a hydrogen atom or a substituent, and at least one of R 210 and R 211 represents an electron attractive group;
- W 21 represents an electron attractive group
- R 213 , R 214 , and R 215 each independently represent a hydrogen atom or a substituent
- W 21 and R 213 may bond together, to form a cyclic structure
- a 22 represents -O-, -S-, -Se-, -Te-, or -NR 219 -;
- R 216 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, or an acyl group;
- R 217 , R 218 , and R 219 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group;
- Z 21 represents a substituent;
- n 22 represents an integer of from 0 to 4; when n 22 is 2 or more, Z 21 S may be the same or different, or may bond together to form a ring;
- Q 21 and Q 22 each independently represent a compound selected from those represented by any of formulae (SEl) to (SE3) mentioned in the above; the Se atoms in Q 21 and Q 22 each are coordinated with the Au; n 23 represents 0 or 1; J 21 represents a counter anion; when n 23 is 1, Q 21 and Q 22 may be the same or different; and the compound represented by formula (PF6) does not include the compounds represented by any of formulae (PFl) to (PF5).
- R 21 and R 22 each preferably represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group, a mercapto group, an alkylthio group, an arylthio group, or a heterocyclic thio group, more preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, most preferably a hydrogen atom or an alkyl group.
- R 23 preferably represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, more preferably an alkyl group, an aryl group, or a heterocyclic group, most preferably an alkyl group or an aryl group.
- R 24 preferably represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, an alkyl- or aryl-sulfonylamino group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, or a carbamoyl group, more preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
- R 23 may form a 5- to 7-membered ring structure together with R 21 or R 22 .
- the ring structure to be formed is a non-aromatic, oxygen-, sulfur- or nitrogen-containing hetero ring. Also, this ring structure may form a fused ring together with an aromatic or non-aromatic carbon ring or a hetero ring. In the present invention, it is more preferable that R 23 forms a 5- to 7-membered ring structure together with R 21 or R 22 .
- R and R ⁇ each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group or a heterocyclic thio group;
- R 23 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group; and
- R 24 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, an alkyl- or aryl-sulfonylamino group, an alkyl- or aryl-sulfonyl group, or an acyl group.
- a 21 represents -O- or -S-; R 21 and R 22 each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group; and R 23 represents an alkyl group, an aryl group, or a heterocyclic group. Still more preferred are those wherein A 21 represents -O- or -S-; R 21 and R 22 each represent a hydrogen atom, an alkyl group, or an aryl group; and R 2j represents an alkyl group or an aryl group.
- a ring structure formed by R 23 , together with R 21 or R 22 is, for example, glucose, mannose, galactose, gulose, xylose, lyxose, arabinose, ribose, fucose, idose, talose, allose, altrose, rhamnose, sorbose, digitoxose, 2-deoxyglucose, 2-deoxygalactose, fructose, glucosamine, galactosamine, or glucuronic acid, or a sugar derivative thereof (in the case where A 21 in formula (PFl) represents O), or a sulfur analogue thereof (in the case where A 21 in formula (PFl) represents S).
- sugar derivatives represent compounds each having a sugar structure in which any one or more of the hydroxy group, amino group or carboxy group is substituted with an alkoxy group (containing a group having an ethyleneoxy group or propylene oxy group unit repeatedly), an aryloxy group, a heterocyclic oxy group, an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a sulfonyloxy group, a silyloxy group, an (alkyl-, aryl- or heterocyclic-) amino group, an acylamino group, a sulfonamido group, a ureido group, a thioureido group, an N-hydroxyureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, a semicarbazido group, a
- ⁇ -isomers and ⁇ -isomers which are different from each other in the 1-position stereostructure
- D- isomers and L-isomers which are in a relation of mirror image with each other.
- these isomers are not discriminated from each other.
- preferable examples of the compound include selenoglucose gold (I) salts, selenomannose gold (I) salts, selenogalactose gold (I) salts, selenolyxose gold (I) salts, and sugar derivatives of these.
- Y 21 preferably represents an alkyl group containing 1 to 30 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, a 5- to 7-membered heterocyclic group containing at least one of an N atom, an O atom or an S atom, -OR 26 , -SR 27 , or -N(R 28 )R 29 ; preferably an alkyl group, an aryl group, a heterocyclic group, -OR 26 , - SR 27 , or -N(R 28 )R 29 ; more preferably an alkyl group, an aryl group, a heterocyclic group, or -N(R 28 )R 29 ; still more preferably an alkyl group, an aryl group or a heterocyclic group.
- R 25 to R 29 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, more preferably an alkyl group or an aryl group.
- X 21 and Y 21 may bond together to form a ring.
- the ring to be formed is a 3- to 7-membered, nitrogen-containing hetero ring, and examples thereof include a pyrrole ring, an indole ring, an imidazole ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, an isoxazole ring, an oxazole ring, a benzoxazole ring, an indazole ring, a purine ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring and a quinazoline ring.
- preferred compounds are those wherein
- Y 21 represents an alkyl group, an aryl group, a heterocyclic group, -OR 26 , -SR 27 or -N(R 28 )R 29
- R 210 and R 211 represents an electron attractive group.
- electron attractive group means a substituent group having a positive Hammett's substituent constant ⁇ p value, preferably a ⁇ p value of 0.2 or more, with the upper limit being 1.0.
- the electron attractive group having a ⁇ p value of 0.2 or more include an acyl group, a formyl group, an acyloxy group, an acylthio group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group, diarylphosphono group, a dialkylphosphinyl group, a diarylphosphinyl group, a phosphoryl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, an acylthio group, a sulfamoyl group, a thiocyanato group, a thiocarbonyl group, an imino group, an imino group substituted at N atom,
- acyl group preferably an acyl group, a formyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a dialkylphosphono group, a diarylphosphono group, a dialkylphosphinyl group, a diarylphosphinyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a thiocarbonyl group, an imino group, an imino group substituted at N atom, a phosphoryl group, a carboxy group (or its salt), an alkyl group substituted by at least two halogen atoms, an aryl group substituted by other electron attractive group having a ⁇ p value of 0.2 or more, a heterocyclic group,
- R 210 and R 211 each represent an electron attractive group.
- R 212 preferably represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group, an acylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, or a carbamoyl group, more preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group, or an acylamino group.
- R 210 R 211 and R 212 are also preferably such that any of two groups among these are bonded to each other, to form a ring.
- the ring to be formed is a non-aromatic carbon ring or hetero ring, and is preferably a 5- to 7-membered ring.
- R 210 forming the ring is preferably an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group or a sulfonyl group
- R 211 is preferably an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, a sulfonyl group, an imino group, an imino group substituted at N atom, an acylamino group or a carbonylthio group.
- R 210 and R 211 each represent an electron attractive group
- R 212 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group or an acylamino group. More preferred are those wherein R 210 and R 211 each represent an electron attractive group, and R 212 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Most preferred are those wherein R 210 and R 211 each represent an electron attractive group, and R 212 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
- R 210 and R 211 form a 5- to 7-membered non-aromatic ring are also preferred; and in this case, R 212 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group or an acylamino group. More preferred are those wherein R 210 and R 211 form a 5- to 7-membered non-aromatic ring, and R 212 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Most preferred are those compounds wherein R 210 and R 211 form a 5-to 7-membered non-aromatic ring, and R 212 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
- the electron attractive group represented by W 21 has the same meaning as the electron attractive group represented by the foregoing R 210 and R 211 , and its preferred range is also the same.
- preferred examples of R 213 to R 215 include a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfamoyl group, a sulfo group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and a carbamoyl group.
- More preferred examples thereof include a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and a carbamoyl group.
- W 21 and R 213 may bond together, to form a ring.
- the ring to be formed is a non-aromatic carbon ring or hetero ring, preferably a 5- to 7-membered ring.
- W 21 for forming the ring is preferably an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, or a sulfonyl group
- R 213 is preferably an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.
- R 213 to R 215 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group or a carbamoyl group.
- R 213 to R 215 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group or a carbamoyl group.
- R 213 to R 215 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group or a carbamoyl group.
- R 213 represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, or the like
- R 214 and R 215 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl- or aryl- sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, or the like.
- R 214 and R 215 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group or a carbamoyl group.
- R 214 and R 215 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group or a carbamoyl group.
- R 216 is preferably a hydrogen atom, an alkyl group, an aryl group or an acyl group, more preferably a hydrogen atom, an alkyl group or an acyl group, and most preferably an alkyl group.
- R 217 and R 218 each are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and most preferably such the case that one of R 217 and R 218 is a hydrogen atom and the other is a hydrogen atom or an alkyl group.
- R 219 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and most preferably an alkyl group.
- a 22 represents -O-, -S-, -Se-, -Te- or -NR 219 , preferably -O-, -S- or -NR 219 , more preferably -O- or -S-, and most preferably -O-, in the present invention.
- Z 21 represents a substituent.
- substituents include the same groups as the substituents explained in the above.
- preferable examples of Z 21 include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an N-acylcarbamoyl group, an N- sulfonylcarbamoyl group, an N-carbamoylcarbamoyl group, a thiocarbamoyl group, an N- sulfamoylcarbamoyl group, a carbazoyl group, a carboxy group (including its salts), a cyano group, a formyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group,
- Z 21 include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a carboxy group (including its salts), a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an amino group, an (alkyl-, aryl- or heterocyclic-)amino group, an acylamino group, a ureido group, a thioureido group, an alkylthio group, an arylthio group, a heterocyclic thio group, and a sulfo group (including its salts).
- Z 21 include an alkyl group, an aryl group, a carboxy group (including its salts), a hydroxy group, an alkoxy group, an aryloxy group, an (alkyl-, aryl- or heterocyclic-)amino group, a ureido group, an alkylthio group, an arylthio group, and a sulfo group (including its salts).
- n 22 represents an integer from 0 to 4. In the present invention, n 22 is preferably 0 to 2 and more preferably 0 or 1. In formula (PF5), preferable is the case in which A 22 represents -O-, -S- or -NR 219 -; R 216 represents a hydrogen atom, an alkyl group, an aryl group or an acyl group; R 217 and R 218 each represent a hydrogen atom, an alkyl group or an aryl group; R 219 represents a hydrogen atom, an alkyl group or an aryl group; n 22 denotes 0 to 2; and Z 21 represents an alkyl group, an aryl group, a carboxy group (including its salts), a hydroxy group, an alkoxy group, an aryloxy group, an (alkyl-, aryl- or heterocyclic-)amino group, a ureido group, an alkylthio group, an arylthio group,
- a 22 represents -O-, -S- or -NR 219 -;
- R 216 represents an alkyl group;
- R 217 and R 218 each represent a hydrogen atom or an alkyl group;
- R 219 represents an alkyl group or an aryl group;
- n 22 denotes 0 to 2;
- Z 21 represents an alkyl group, an aryl group, a carboxy group (including its salts), a hydroxy group, an alkoxy group, an aryloxy group, an (alkyl-, aryl- or heterocyclic-)amino group, a ureido group, an alkylthio group, an arylthio group, or a sulfo group (including its salts).
- a 22 represents -O-, -S- or -NR 219 -;
- R 216 represents an alkyl group;
- R 217 and R 218 each represent a hydrogen atom or an alkyl group;
- R 219 represents an alkyl group;
- n 22 denotes 0 to 2;
- Z 21 represents an alkyl group, an aryl group, a carboxy group (including its salts), a hydroxy group, an alkoxy group, an aryloxy group, an (alkyl-, aryl- or heterocyclic-)amino group, a ureido group, an alkylthio group, an arylthio group, or a sulfo group (including its salts).
- a 22 represents -O-;
- R 216 represents an alkyl group; one of R 217 and R 218 represent a hydrogen atom and the other represents a hydrogen atom or an alkyl group;
- n 22 denotes 0 to 1 ;
- Z 21 represents an alkyl group, an aryl group, a carboxy group (including its salts), a hydroxy group, an alkoxy group, an aryloxy group, an (alkyl-, aryl- or heterocyclic-)amino group, a ureido group, an alkylthio group, an arylthio group, or a sulfo group (including its salts).
- n 21 represents 0 or 1.
- L 21 represents a compound, which can be coordinated with gold through an N atom, S atom, Se atom, Te atom or P atom.
- L 21 include a substituted or unsubstituted amine (which means, preferably, a primary, secondary or tertiary alkylamine having 1 to 30 carbon atoms, or an arylamine), a five to six-membered nitrogen-containing hetero ring (preferably a five- or six-membered nitrogen-containing hetero ring composed of a combination of N, O, S and C, which hetero ring may have a substituent.
- This hetero ring may be coordinated with gold through a nitrogen atom in the ring, or through a substituent; and examples of the hetero ring include benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, benzoxazoline, oxazole, thiadiazole, oxadiazole, triazine, pyrrole, pyrrolidine, imidazolidine and morpholine), a meso-ion (a meso-ion compound so called herein is a five- or six-membered heterocyclic compound, which cannot be satisfactorily expressed by one covalent bond structural formula or polar structural formula, and in which the ring carries a positive charge partly due to a compound having a sextet of ⁇ -electron related to all atoms constituting the ring, to keep a balance with the equal negative charge
- Examples of the compound include dialkyl thioethers, diaryl thioethers, diheterocyclic thioethers, alkyl-aryl thioethers, alkyl-heterocyclic thioethers, and aryl-heterocyclic thioethers), a disulfide (preferably, a disulfide compound in which an alkyl group having 1 to 30 carbon atoms, aryl group or heterocyclic group is bonded with an S atom, which compound may be either symmetric or asymmetric.
- Examples of the compound include dialkyl disulfides, diaryl disulfides, diheterocyclic disulfides, alkyl-aryl disulfides, alkyl- heterocyclic disulfides, and aryl-heterocyclic disulfides; and a dialkyl disulfide, a diaryl disulfide or an alkyl-aryl disulfide is more preferable), a thioamide (the thioamide may be a part of the ring structure or non-cyclic thioamide. Useful one as the thioamide may be selected from those disclosed, for example, in U.S. Patent Nos.
- thioamide examples include thio urea, thiourethane, dithiocarbamate, 4-thiazoline-2-thion, thiazolidine-2-thion, 4-oxazoline-2-thion, oxazolidine-2-thion, 2-pyrazoline-5-thion, 4-imidazoline-2-thion, 2-thiohydantoin, rhodanine, isorhodanine, 2-thio-2,4-oxazolidi ⁇ edione, thiobarbituric acid, tetrazoline-5- thion, l,2,4-triazoline-3-thion, l,3,4-thiadiazoline-2-thion, l,3,4-oxadiazoline-2-thion, benzimidazoline-2- thion, benzoxazoline-2-thion, and benzothiazoline-2-thion, each of which may be substituted), a selenol (preferably, an alkyl selenol,
- selenoether examples include dialkyl selenoethers, diaryl selenoethers, diheterocyclic selenoethers, alkyl-aryl selenoethers, alkyl-heterocyclic selenoethers, and aryl-heterocyclic selenoethers.
- a dialkyl selenoether, a diaryl selenoether, or an alkyl-aryl selenoether is preferable.
- a diselenide preferably, a diselenide compound in which an alkyl group having 1 to 30 carbon atoms, aryl group or heterocyclic group is bonded with a Se atom, in which the substitution of the groups may be either symmetric or asymmetric with respect to the diselenido group.
- diselenide examples include dialkyl diselenides, diaryl diselenides, diheterocyclic diselenides, alkyl-aryl diselenides, alkyl-heterocyclic diselenides, and aryl-heterocyclic diselenides.
- a dialkyl diselenide, a diaryl diselenide or an alkyl-aryl diselenide is preferable.
- a selenoamide (a compound obtained by replacing the S atom with an Se atom in the aforementioned thioamide compound is given as an example)
- a tellurol (a compound obtained by replacing the Se atom with a Te atom in the aforementioned selenol compound is given as an example)
- a telluroether a compound obtained by replacing the Se atom with a Te atom in the aforementioned selenoether compound is given as an example
- a ditelluride (a compound obtained by replacing the Se atom with a Te atom in the aforementioned diselenide compound is given as an example)
- a telluroamide (a compound obtained by replacing the Se atom with a Te atom in the aforementioned selenoamide compound is given as an example)
- an alkylphosphine preferably, a primary, secondary or
- L 21 is preferably a 5- to 6-membered nitrogen-containing hetero ring, a meso-ion, a thiol, a thioether, a thioamide, a selenol, a selenoether, a selenoamide, an alkylphosphine or an arylphosphine, more preferably a 5- to 6-membered nitrogen-containing hetero ring, a meso-ion, a thiol, a thioether, a thioamide, a selenol, an alkylphosphine or an arylphosphine, and most preferably a meso-ion, a thiol, a thioether, a thioamide, a selenol, an alkylphosphine or an arylphosphine.
- Particularly preferable examples of L 21 are selected from compounds of any of the following formulae (PLl) to (PL
- Ch represents S, Se, or Te
- M 21 represents a hydrogen atom, or a counter cation that is necessary to neutralize the charge of the compound.
- a 23 represents -O-, -S-, or -NR 223 -; and R 220 , R 221 , R 222 and R 223 have the same meanings as the aforementioned R 21 , R 22 , R 23 and R 24 , respectively, and each preferable range is also the same.
- Y 22 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, -OR 225 , -SR 226 , or - N(R 227 )R 228 .
- R 224 , R 225 , R 226 , R 227 and R 228 have the same meanings as the above R 25 , R 26 , R 27 , R 28 and R 29 respectively, and each preferable range is also the same.
- R 229 , R 230 and R 231 have the same meanings as the above R 210 , R 211 and R 212 respectively, and each preferable range is also the same.
- W 22 , R 232 , R 233 and R 234 have the same meanings as the above W 21 , R 213 , R 214 and R 215 respectively, and each preferable range is also the same.
- a 24 represents -O-, -S-, -Se-, -Te- or -NR 238 -.
- R 235 , R 236 , R 237 , R 238 , Z 22 and n 23 have the same meanings as the above R 216 , R 217 , R 218 , R 219 , Z 21 and n 22 respectively, and each preferable range is also the same.
- the compound represented by any of formulae (PFl) to (PF5) may be a complex, which is either symmetric or asymmetric with respect to gold (I). Both the symmetric complex and the asymmetric complex are preferable in the present invention, but a complex symmetric with respect to gold (I) is more preferable.
- Ch represents S, Se or Te.
- S or Se is preferable, and S is more preferable.
- M 21 represents a hydrogen atom, or a counter cation that neutralizes the charge of the compound.
- M 21 represents a counter cation, it specifically represents an inorganic cation, including an alkali metal, such as Li, Na, K, Rb or Cs, or an alkali earth metal, such as Mg, Ca or Ba; or an organic cation, such as a substituted or unsubstituted ammonium ion or phosphonium ion.
- M 21 when M 21 is an inorganic cation, it represents neither an Ag + ion nor an Au + ion.
- M 21 is preferably a hydrogen atom, a cation of an alkali metal, a cation of an alkali earth metal, or a substituted or unsubstituted ammonium ion, more preferably a cation of an alkali metal or a substituted or unsubstituted ammonium ion, and still more preferably a cation of an alkali metal or a substituted or unsubstituted ammonium ion.
- M 21 represents a cation of alkali metal
- Ch represents S or Se
- a 23 represents -O- or -S-
- R 220 and R 221 each represent a hydrogen atom, an alkyl group or an aryl group
- R 222 represents an alkyl group or an aryl group.
- M 21 represents a cation of alkali metal
- Ch represents S
- a 23 represents -O- or -S-
- R 220 and R 221 each represent a hydrogen atom, an alkyl group or an aryl group
- R 222 represents an alkyl group or an aryl group.
- a ring structure formed by R 222 is glucose, mannose, galactose, gulose, xylose, lyxose, arabinose, ribose, fticose, idose, talose, allose, altrose, rhamnose, sorbose, digitoxose, 2- deoxyglucose, 2-deoxygalactose, fructose, glucosamine, galactosamine, or glucuronic acid, or a sugar derivative thereof (in the case where A 23 in formula (PLl) represents O), or a sulfur analogue thereof (in the case where A 23 in formula (PLl) represents S).
- Preferable examples of the compound used as L 21 include thioglucose, thiomannose, thiogalactose, thiolyxose, thioxylose, thioarabinose, selenoglucose, selenomannose, selenogalactose, selenolyxose, selenoxylose, selenoarabinose, telluroglucose, alkali metal salts thereof, their sulfur analogues, and derivatives of these compounds.
- M 21 represents a cation of alkali metal
- Ch represents S
- Y 22 represents an alkyl group, an aryl group or a heterocyclic group.
- M 21 represents a cation of alkali metal
- Ch represents S or Se
- R 229 and R 230 each represent an electron attractive group
- R 231 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group or an acylamino group.
- M 21 represents a cation of alkali metal
- Ch represents S or Se
- R 229 and R 230 each represent an electron attractive group
- R 231 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
- M 21 represents a cation of alkali metal
- Ch represents S
- R 229 and R 230 each represent an electron attractive group
- R 231 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
- R 229 and R 230 form a 5- to 7-membered non-aromatic ring are also preferred; and in this case, M 21 represents a cation of alkali metal; Ch represents S or Se; and R 231 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group or an acylamino group.
- R 229 and R 230 form a 5- to 7-membered non-aromatic ring
- M 21 represents a cation of alkali metal
- Ch represents S or Se
- R 231 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
- M 21 represents a cation of alkali metal
- Ch represents S
- R 229 and R 230 form a 5-to 7-membered non-aromatic ring
- R 231 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
- R 232 to R 234 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group or a carbamoyl group.
- R 232 to R 234 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group or a carbamoyl group.
- R 232 to R 234 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group or a carbamoyl group.
- W 22 and R 234 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group or
- R 232 bond together to form a non-aromatic 5- to 7-membered ring are preferred as well, and in this case, preferably, M 21 represents a cation of alkali metal, Ch represents S or Se, R 26 represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group or the like, and R 233 and R 234 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or the like.
- R 233 and R 234 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group or a carbamoyl group.
- R 233 and R 234 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a sulfo group, an alkyl- or aryl-sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group or a carbamoyl group.
- Ch is S or Se
- a 24 represents -O-, -S- or -NR 238 -
- R 235 represents a hydrogen atom, an alkyl group, an aryl group or an acyl group
- R 236 and R 237 each represent a hydrogen atom, an alkyl group or an aryl group
- R 238 represents a hydrogen atom, an alkyl group or an aryl group
- n 23 denotes 0 to 2
- Z 22 represents an alkyl group, an aryl group, a carboxy group (including its salts), a hydroxy group, an alkoxy group, an aryloxy group, an (alkyl-, aryl- or heterocyclic-)amino group, a ureido group, an alkylthio group, an arylthio group or a sulfo group (including its salts).
- Ch is S or Se
- a 24 represents -O-, -S- or - NR 238 -
- R 235 represents an alkyl group
- R 236 and R 237 each represent a hydrogen atom or an alkyl group
- R 238 represents an alkyl group or an aryl group
- n 23 denotes 0 to 2
- Z 22 represents an alkyl group, an aryl group, a carboxy group (including its salts), a hydroxy group, an alkoxy group, an aryloxy group, an (alkyl-, aryl- or heterocyclic-)amino group, a ureido group, an alkylthio group, an arylthio group or a sulfo group (including its.
- a 24 represents -O-, -S- or -NR 238 -
- R 235 represents an alkyl group
- R 236 and R 237 each represent a hydrogen atom or an alkyl group
- R 238 represents an alkyl group
- n 23 denotes 0 to 2
- Z 22 represents an alkyl group, an aryl group, a carboxy group (including its salts), a hydroxy group, an alkoxy group, an aryloxy group, an (alkyl-, aryl- or heterocyclic- )amino group, a ureido group, an alkylthio group, an arylthio group or a sulfo group (including its salts).
- Ch is S
- a 24 represents -O-
- R 235 represents an alkyl group
- one of R 236 and R 237 represent a hydrogen atom and the other represents a hydrogen atom or an alkyl group
- n 23 denotes 0 to 1
- Z 22 represents an alkyl group, an aryl group, a carboxy group (including its salts), a hydroxy group, an alkoxy group, an aryloxy group, an (alkyl-, aryl- or heterocyclic-)amino group, a ureido group, an alkylthio group, an arylthio group or a sulfo group (including its salts).
- L 21 is preferably a compound represented by formula (PLl), (PL2) or (PL5), more preferably a compound represented by formula (PLl) or (PL5), and most preferably a compound represented by formula (PLl).
- PF6 the compound represented by formula (PF6) will be explained.
- J 21 represents a counter anion.
- the counter anion examples include a halogen ion (e.g., F ' , Cl “ , Br “ and I “ ), tetrafluoroboronate ion (BF 4 " ), hexafluorophosphonate ion (PF 6 “ ), hexafluoroantimonate ion (SbF 6 " ), aryl sulfonate ion (e.g., p-toluene sulfonate ion), alkyl sulfonate ion (e.g., methane sulfonate ion, and trifluoromethane sulfonate ion), and carboxy ion (e.g., acetic acid ion, trifluoroacetic acid ion, and benzoic acid ion).
- a halogen ion e.g., F ' , Cl “ , Br “ and I “
- These counter anions preferably contain no adsorption group to gold, which group is typified by a mercapto group (-SH), thioether group (-S-), selenoether group (-Se-) or telluroether group (-Te-).
- group is typified by a mercapto group (-SH), thioether group (-S-), selenoether group (-Se-) or telluroether group (-Te-).
- J 21 is preferably a halogen ion, tetrafluoroboronate ion, hexafluorophosphonate ion, aryl sulfonate ion or alkyl sulfonate ion, more preferably a halogen ion, tetrafluoroboronate ion or hexafluorophosphonate ion, and still more preferably a halogen ion.
- halogen ions Cl “ , Br “ or I " is preferable, Cl “ or Br " is more preferable, and Cl " is still more preferable.
- Q 21 and Q 22 in formula (PF6) are selected from the compounds represented by any of formulae (SEl) to (SE3) which are explained before.
- M 1 and M 2 each are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group or an acyl group
- Q is an alkyl group, an alkenyl group, an aryl group or -NM 4 M 5
- M 4 and M 3 each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.
- M 1 and M 2 each are a hydrogen atom, an alkyl group, an alkenyl group or an aryl group
- Q is an alkyl group, an aryl group or -NM 4 M 5
- M 4 and M 5 each represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.
- M 1 and M 2 each are a hydrogen atom, an alkyl group or an aryl group
- Q is -NM 4 M 5
- M 4 and M 5 each represent a hydrogen atom, an alkyl group or an aryl group.
- V 1 to V 3 each represent an alkyl group, an aryl group or a heterocyclic group; and, in a more preferable case, V 1 to V 3 each represent an aryl group.
- E 1 and E 2 are selected from the compounds represented by any of formulae (T2) to (T4) in a preferable case, one of E 1 and E 2 is selected from the compounds represented by formula (T4) and the other is selected from the compounds represented by formula (T2), (T3) or (T4) in a more preferable case, one of E 1 and E 2 is selected from the compounds represented by formula (T4) and the other is selected from the compounds represented by formula (T3) or (T4) in a still more preferable case, and both E 1 and E 2 are selected from the compounds represented by formula (T4) in a most preferable case.
- n 23 is 0 or 1
- Q 21 and Q 22 each are independently selected from the compounds represented by formula (SEl) or (SE3)
- J 21 is a halogen ion, a tetrafluoroboronate ion or a hexafluorophosphonate ion, n 23 is 0, and Q 21 is selected from the compounds represented by formula (SE3); and still more preferable are those in which J 21 is a halogen ion, n 23 is 0, and Q 21 is selected from the compounds represented by formula (SE3).
- preferred compounds that can be used are those represented by any of formulae (PFl), (PF5) and (PF6), more preferred are those represented by formula (PFl) or (PF6), and most preferred are those represented by formula (PF6).
- the addition amount of the compound represented by any of formulae (PFl) to (PF6) that can be used in the present invention can widely vary depending upon the cases, but it is generally I x IO "7 to 5 ⁇ lO ⁇ 3 mol, preferably 5 x 10 "6 to 5 x 10 '4 mol, per mol of silver halide.
- the compound represented by any of formulae (PFl) to (PF6) may be dissolved in water, an alcohol (such as methanol or ethanol), a ketone (such as acetone), an amide (such as dimethylfomamide), a glycol (such as methylpropylene glycol) or an ester (such as ethyl acetate) to add to the system, or may be added as a solid dispersion (fine crystal dispersion) prepared by a known dispersing method.
- an alcohol such as methanol or ethanol
- a ketone such as acetone
- an amide such as dimethylfomamide
- a glycol such as methylpropylene glycol
- ester such as ethyl acetate
- Addition of the compound represented by any of formulae (PFl) to (PF6) that can be used in the present invention may be conducted at any stage in the production of photosensitive emulsion, but is preferably conducted after formation of silver halide grains and before completion of the chemical sensitization step.
- the exemplified compounds SE1-2, SE2-1, SE2-12, SE3-16 and SE3-31 are preferable, the exemplified compounds SE3-4, SE3-9, SE3- 17, SE3-29 and SE3-37 are more preferable, the exemplified compounds PF2-5, PF3-6, PF4-3 and PF5-7 are still more preferable, and the exemplified compounds PFl-I and PF6-1 are most preferable.
- Silver halide grains constituting the silver halide emulsion that can be used in the present invention are not particularly restricted as to their average side length.
- the average side length is preferably from 0.1 ⁇ m to 0.35 ⁇ m, more preferably from 0.1 ⁇ m to 0.30 ⁇ m, and most preferably from 0.1 ⁇ m to 0.27 ⁇ m.
- the projected area of silver halide grains ranging in side length from 0.1 ⁇ m to 0.35 ⁇ m makes up at least 50%, preferably at least 80%, particularly preferably at least 90%, of the sum total of projected area of all silver halide grains constituting the silver halide emulsion.
- the side lengths of silver halide grains can be determined from electron micrographs of the grains.
- the side lengths of cubes having the same volumes as silver halide grains are taken as side lengths of the grains.
- the average side length can be determined by measuring side lengths of silver halide grains so high in number as to be statistically significant (for instance, at least 600 silver halide grains), and then calculating the average of the side lengths measured.
- the silver halide emulsion that can be used in the present invention is required to have a silver chloride content of at least 90 mol%, and it is preferable that the silver chloride content therein be 95 mol% or above.
- the silver halide grains have no particular restriction as to their grain shapes. It is preferable that the grains are made up of cubic grains having substantially ⁇ 100 ⁇ faces, tetradecahedral crystal grains (which may be round in their vertexes and may have higher-order planes), octahedral crystal grains, or tabular grains having principal faces formed of ⁇ 100 ⁇ faces or ⁇ 111 ⁇ faces and an aspect ratio of 2 or more.
- the term "aspect ratio" as used herein refers to the value obtained by dividing the diameter of a circle whose area is equivalent to the projected area of an individual grain by the gain thickness.
- the silver halide grains be cubic or tetradecahedral grains.
- the silver halide grain in the silver halide emulsion for use in the present invention preferably has a silver bromide-containing phase and/or a silver iodide-containing phase.
- the silver bromide content therein is generally from 0.1 to 4 mol%, preferably from 0.5 to 2 mol%.
- the silver iodide content therein is generally from 0.05 to 1 mol%, preferably from 0.1 to 1 mol%, and more preferably from 0.1 to 0.40 mol%.
- the specific silver halide grains in the silver halide emulsion for use in the present invention each preferably have a silver bromide-containing phase and/or a silver iodide-containing phase.
- silver iodobromochloride grains having the above halogen composition are preferred.
- the term "silver bromide-containing phrase" or “silver iodide-containing phase” means a region where the content of silver bromide or silver iodide is higher than that in the surrounding regions.
- the halogen compositions of the silver bromide-containing phase or the silver iodide-containing phase and of the surrounding region (outer periphery) may vary either continuously or drastically.
- Such a silver bromide- containing phase or silver iodide-containing phase may form a layer which has an approximately constant concentration in a certain width at a portion in the grain, or it may form a maximum point having no spread.
- the local silver bromide content in the silver bromide-containing phase is preferably 3 mol% or more, more preferably from 5 to 40 mol%, and most preferably from 5 to 25 mol%.
- the local silver iodide content in the silver iodide-containing phase is preferably 0.3 mol% or more, more preferably from 0.5 to 8 mol%, and most preferably from 1 to 5 mol%.
- Such a silver bromide- or silver iodide-containing phase may be present in plural numbers in layer form, within the grain. In this case, the phases may have different silver bromide or silver iodide contents from each other.
- the silver bromide-containing phase or silver iodide-containing phase that the silver halide emulsion grains for use in the present invention have, are each formed in the layer form so as to surround the grain center.
- the silver bromide-containing phase or silver iodide-containing phase formed in the layer form so as to surround the grain has a uniform concentration distribution in the circumferential direction of the grain in each phase.
- the silver bromide or silver iodide concentration of a corner portion or of an edge of the grain can be different from that of a principal face of the grain.
- another silver bromide-containing phase and/or silver iodide-containing phase not surrounding the grain may exist in isolation at a specific portion of the surface of the grain.
- the silver halide emulsion for use in the present invention contains a silver bromide-containing phase
- said silver bromide-containing phase be formed in a layer form so as to have a concentration maximum of silver bromide inside the grain.
- the silver halide emulsion that can be used in the present invention contains a silver iodide-containing phase
- said silver iodide-containing phase be formed in a layer form so as to have a concentration maximum of silver iodide on the surface of the grain.
- Such a silver bromide-containing phase or silver iodide-containing phase is constituted preferably with a silver amount of 3% to 30%, more preferably with a silver amount of 3% to 15%, in terms of the grain volume, in the viewpoint of increasing the local concentration with a smaller silver bromide or silver iodide content.
- the silver halide grain of the silver halide emulsion for use in the present invention preferably contains both a silver bromide-containing phase and a silver iodide-containing phase.
- the silver bromide-containing phase and the silver iodide-containing phase may exist either at the same place in the grain or at different places thereof. It is preferred that these phases exist at different places, from a viewpoint that the control of grain formation may become easy.
- a silver bromide-containing phase may contain silver iodide.
- a silver iodide-containing phase may contain silver bromide.
- an iodide added during formation of high-silver chloride grains is liable to ooze to the surface of the grain more than a bromide, so that the silver iodide-containing phase is liable to be formed at the vicinity of the surface of the grain.
- a silver bromide-containing phase and a silver iodide-containing phase exist at different places in a grain, it is preferred that the silver bromide-containing phase be formed more internally than the silver iodide-containing phase.
- another silver bromide-containing phase may be provided further outside the silver iodide-containing phase in the vicinity of the surface of the grain.
- the silver bromide-containing phase and the silver iodide-containing phase are integrated, in the vicinity of the surface of the grain. Accordingly, it is preferred that the silver bromide-containing phase and the silver iodide-containing phase be placed adjacent to each other. From these points, it is preferred that the silver bromide-containing phase be formed at any of the position ranging from 50% to 100% of the grain volume measured from the inside, and that the silver iodide-containing phase be formed at any of the position ranging from 80% to 100% (preferably from 85% to 100%) of the grain volume measured from the inside.
- the silver bromide-containing phase be formed at any of the position ranging from 70% to 95% of the grain volume measured from the inside, and that the silver iodide-containing phase be formed at any of the position ranging from 90% to 100% of the grain volume measured from the inside.
- another preferable mode of the silver halide emulsion having a silver bromide-containing phase is a mode in which the silver halide emulsion has a region ranging in silver bromide content from 0.5 to 20 mol% at a depth of 20 nm or less below the emulsion grain surface. It is preferable for the silver bromide- containing phase to be situated at a depth of 10 nm or less below the emulsion grain surface and to range in silver bromide content from 0.5 to 10 mol%, more preferably from 0.5 to 5 mol%.
- the silver bromide-containing phase take a layer form.
- the silver bromide-containing phase be formed so as to take a layer form to surround the emulsion grain.
- another preferable mode of the silver halide emulsion having a silver iodide-containing phase is a mode in which the silver halide emulsion has a region ranging in silver iodide content from 0.3 to 10 mol% at a depth of 20 nm or less below the emulsion grain surface. It is preferable for the silver iodide- containing phase to be situated at a depth of 10 nm or less below the emulsion grain surface and to range in silver iodide content from 0.5 to 10 mol%, more preferably from 0.5 to 5 mol%.
- the silver iodide-containing phase take a layer form.
- the silver iodide-containing phase be formed so as to take a layer form to surround the emulsion grain.
- a bromide salt or iodide salt solution may be added singly, or it may be added in combination with both a silver salt solution and a high chloride salt solution.
- the bromide or iodide salt solution and the high chloride salt solution may be added separately, or as a mixture solution of these salts of bromide or iodide and high chloride.
- the bromide or iodide salt is generally added in a form of a soluble salt, such as an alkali or alkali earth bromide or iodide salt.
- bromide or iodide ion may be introduced by cleaving the bromide or iodide ion from an organic molecule, as described in U.S. Patent No. 5,389,508.
- fine silver bromide grains or fine silver iodide grains may be used.
- the addition of a bromide salt or iodide salt solution may be concentrated at one time of grain formation process, or may be performed over a certain period of time.
- the position of the introduction of iodide ion into a high chloride emulsion may be limited.
- the addition of an iodide salt solution is preferably started at 50% or outer side of the volume of the grain, more preferably 70% or outer side, particularly preferably 80% or outer side, and most preferably 85% or outer side.
- a bromide salt solution is preferably started at 50% or outer side, more preferably 70% or outer side of the volume of the grain.
- the distribution of a bromide ion concentration and iodide ion concentration in the depth direction of the grain can be measured, according to an etching/TOF-SIMS (Time of Flight - Secondary Ion Mass Spectrometry) method by means of, for example, TRIFT II Model TOF-SIMS apparatus (trade name, manufactured by Phi Evans Co.).
- a TOF-SIMS method is specifically described in, edited by Nippon Hyomen Kagakukai, "Hyomen Bunseki Gijutsu Sensho Niji Ion Shitsuryo Bunsekiho (Surface Analysis Technique Selection - Secondary Ion Mass Analytical Method)", Maruzen Co., Ltd. (1999).
- the emulsion that can be used in the present invention have the maximum concentration of iodide ions at the surface of the grain, that the iodide ion concentration decrease inwardly in the grain, and that the bromide ions have the maximum concentration in the inside of the grain.
- the local concentration of silver bromide can also be measured with X-ray diffractometry, as long as the silver bromide content is high to some extent.
- the specific silver halide grains in the silver halide emulsion that can be used in the present invention contains a hexacoordinate complex having at least two different kinds of ligands in one and the same complex and containing Ir as a central metal.
- hexacoordinate complex containing Ir as a central metal particularly preferably are hexacoordinate complexes containing Ir as a central metal and having both halogen ligands and organic ligands in one and the same complex, and hexacoordinate complexes containing Ir as a central metal and having both halogen ligands and inorganic ligands other than halogen ligands in one and the same complex.
- the hexacoordinate complex containing Ir as a central metal is preferably a metal complex represented by formula (II): Formula (II)
- X 1 represents a halogen, ion or a pseudohalogen ion other than a cyanate ion
- L 1 represents a ligand different from X 1
- n is 3, 4, or 5
- m is 5-, 4-, 3-, 2-, 1-, 0, or 1+, which represents an electric charge of the metal complex.
- X 1 S three to five of X 1 S may be the same or different from each other.
- these plural L 1 S may be the same or different from each other.
- the pseudohalogen (halogenoid) ion means an ion having a nature similar to that of halogen ion, and examples of the same include cyanide ion (CN ' ), thiocyanate ion (SCN ' ), selenocyanate ion (SeCN “ ), tellurocyanate ion (TeCN “ ), azide dithiocarbonate ion (SCSN 3 " ), cyanate ion (OCN “ ), fulminate ion (ONC “ ), and azide ion (N 3 " ).
- X 1 is preferably a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a cyanide ion, an isocyanate ion, a thiocyanate ion, a nitrate ion, a nitrite ion, or an azide ion.
- chloride ion and bromide ion are particularly preferable.
- L 1 is not particularly limited, and it may be an organic or inorganic compound that may or may not have electric charge(s), with organic or inorganic compounds with no electric charge being preferable.
- a metal complex represented by the following formula (HA) is preferred: Formula (HA) wherein X IA represents a halogen ion or a pseudohalogen ion other than a cyanate ion; L IA represents an inorganic ligand different from X IA ; n is 3, 4, or 5; and m is 5-, A-, 3-, 2-, 1-, 0, or 1+.
- X IA has the same meaning as X 1 in formula (II), and the preferred range is also the same.
- L IA is preferably water, OCN, ammonia, phosphine, and carbonyl, with water being particularly preferred.
- three to five of X IA s may be the same or different from each other.
- these plural L IA s may be the same or different from each other.
- LIrX n L (6 . n) J wherein X IB represents a halogen ion or a pseudohalogen ion other than cyanate ion; L IB represents a ligand having a chain or cyclic hydrocarbon as a basic structure, or a ligand in which a portion of carbon atoms or hydrogen atoms of the basic structure is substituted with other atom(s) or atomic group(s); n is 3, 4, or 5; m is 5-, 4-, 3-, 2-, 1-, 0, or 1+.
- X IB has the same meaning as X 1 in formula (II), and the preferable range is also the same.
- L IB represents a ligand having a chain or cyclic hydrocarbon as a basic structure, or a ligand in which a part of carbon atoms or hydrogen atoms of the basic structure is substituted with other atom(s) or atomic group(s), but it is not a cyanide ion.
- L IB is preferably a heterocyclic compound, more preferably a 5-membered heterocyclic compound ligand.
- a compound having at least one nitrogen atom and at least one sulfur atom in its 5-membered ring skeleton are further preferred.
- three to five of X 1B s may be the same or different from each other.
- these plural L IB s may be the same or different from each other.
- a metal complex represented by formula (IIC) is further preferred: Formula (IIC) r [ ⁇ I * r.Xv" ⁇ C n TL 1C (6-n) T]in wherein X IC represents a halogen ion or a pseudohalogen ion other than a cyanate ion; L IC represents a 5-membered ring ligand, which has at least one nitrogen atom and at least one sulfur atom in its ring skeleton, and which may have a substituent(s) on a carbon atom(s) in said ring skeleton; n is 3, 4, or 5; and m is 5-, 4-, 3-, 2-, 1-, 0, or 1+.
- X IC has the same meaning as X 1 in formula (II), and the preferable range is also the same.
- the substituent on the carbon atom in said ring skeleton in L IC is preferably a substituent having a volume smaller than an n-propyl group.
- Preferred examples of the substituent include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, a isothiocyanato group, a formyl group, a thioformyl group, a hydroxyl group, a mercapto group, an amino group, a hydrazino group, an azido group, a nitro group, a nitroso group, a hydroxyamino group, a carboxyl group, a carbamoyl group, and a halogen atom (fluoro, chloro, bromo, and iodo).
- formula (IIC) three to five of X Ic s may be the same or different from each other.
- these plural L ic s may be the same or different from each other.
- Preferable specific examples of the metal complex represented by formula (II) are shown below, but the present invention is not limited to these complexes.
- the specific silver halide grains in the silver halide emulsion for use in the present invention may contain, in stead of or alternatively in addition to the aforementioned iridium hexacoordinate complex represented by formula (II), another hexacoordinate complex containing Ir as a central metal and having 6 ligands, all of which are Cl, Br, or I; and in the present invention, the combination use of such another iridium hexacoordinate complex with the hexacoordinate complex of formula (II) is preferrred.
- any two or three kinds of Cl, Br, and I may be mixed and present in the 6-coordination complex.
- Br, or I is particularly preferably incorporated in a silver bromide-containing phase, in order to obtain hard gradation upon high illuminance exposure.
- Specific examples of the iridium complex (hexacoordination complex containing Ir as a central metal) in which the six ligands each are Cl, Br, or I are shown below, but the present invention is not limited to these complexes.
- metal complexes are anionic ions.
- counter cationic ions are preferably those easily soluble in water.
- Preferable examples thereof include an alkali metal ion, such as sodium ion, potassium ion, rubidium ion, cesium ion, and lithium ion; an ammonium ion, and an alkyl ammonium ion.
- These metal complexes can be used being dissolved in water or in a mixed solvent of water and an appropriate water-miscible organic solvent (such as an alcohol, an ether, a glycol, a ketone, an ester, or an amide).
- the iridium complex is added in an amount of, preferably 1 x 10 "10 mole to 1 x 10 "3 mole, and particularly preferably 1 x lO "8 mole to 1 x 10 "5 mole, per mole of silver, during grain formation.
- the above-mentioned iridium complex is preferably added directly to the reaction solution at the time of silver halide grain formation, or indirectly to the grain-forming reaction solution via addition to an aqueous halide solution for forming silver halide grains or other solution, so that the iridium complex is doped into the inside of the silver halide grains. Further, it is also preferable to employ a method in which the iridium complex is doped into a silver halide grain, by preparing fine grains doped with the complex in advance and adding the fine grains for carrying out physical ripening. Further, it is also possible that these methods may be combined, to incorporate the iridium complex into the inside of the silver halide grains.
- these metal complexes are doped to the inside of the silver halide grains, they are preferably uniformly distributed in the inside of the grains.
- they are also preferably distributed only in the grain surface layer.
- they are also preferably distributed only in the inside of the grain, while the grain surface is covered with a layer free of the complex.
- the silver halide grains be subjected to physical ripening in the presence of fine grains having the metal complexes incorporated therein, to modify the grain surface phase.
- Two or more kinds of complexes may be incorporated in the inside of an individual silver halide grain.
- the halogen composition at the site where the above-mentioned metal complex is incorporated but it is preferable that the hexacoordinate complex whose central metal is Ir and whose six ligands are all Cl, Br or I ions, be incorporated into the maximum silver-bromide concentration region(s).
- a metal ion other than the above-mentioned iridium can be doped in the inside and/or on the surface of the silver halide grains.
- the metal ions to be used are preferably ions of a transition metal.
- the transition metal are iron, ruthenium, osmium, and rhodium. It is more preferable that these metal ions are used in the form of a hexacoordination complex of octahedron-type having ligands.
- any of cyanide ion, halide ion, thiocyanate ion, hydroxide ion, peroxide ion, azide ion, nitrite ion, water (aquo), ammonio, nitrosyl ion, or thionitrosyl ion is preferably used.
- Such a ligand is preferably coordinated to any metal ion " selected from the group consisting of the above-mentioned iron, ruthenium, osmium, lead, cadmium and zinc. Two or more kinds of these ligands are also preferably used in one complex molecule.
- an organic compound can also be preferably used as a ligand.
- the organic compound include chain compounds having a main chain of 5 or less carbon atoms and/or heterocyclic compounds of 5- or 6-membered ring. More preferable examples of the organic compound are those having at least a nitrogen, phosphorus, oxygen, or sulfur atom in the molecule as an atom which is capable of coordinating to a metal. Most preferred organic compounds are furan, thiophene, oxazole, isooxazole, thiazole, isothiazole, imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine and pyrazine. Further, an organic compound which has a substituent introduced into a basic skeleton of any of the above- mentioned compounds is also preferred.
- a combination of the metal ion and the ligand a combination of an iron ion and a cyanide ligand and a combination of a ruthenium ion and a cyanide ligand are preferable.
- these metal complex compounds and the iridium complexes as mentioned above in combination.
- Preferred of these compounds are those in which the number of cyanide ions accounts for the majority of the coordination number (site) intrinsic to the iron or ruthenium that is the central metal.
- the remaining sites are preferably occupied by thiocyanate, ammonio, aquo, nitrosyl ion, dimethylsulfoxide, pyridine, pyrazine, or 4,4'-bipyridine.
- each of 6 coordination sites of the central metal is occupied by a cyanide ion, to form a hexacyano iron complex or a hexacyano ruthenium complex.
- Such metal complexes composed of these cyanide ion ligands are preferably added during grain formation in an amount of 1 x 10 ⁇ 8 mol to 1 x 10 "2 mol, most preferably 1 x 10 "6 mol to 5 x 10 "4 mol, per mol of silver atom.
- nitrosyl ion, thionitrosyl ion, or water molecule is also preferably used in combination with chloride ion, as ligands. More preferably these ligands form a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaquo complex. The formation of a hexachloro complex is also preferred. These complexes are preferably added during grain formation in an amount of 1 x 10 '10 mol to 1 x 10 "6 mol, more preferably 1 x 10 "9 mol to 1 x 10 "6 mol, per mol of silver atom.
- Various compounds or precursors thereof can be included in the silver ' halide emulsion for use in the present invention, to prevent fogging from occurring or to stabilize photographic performance, during manufacture, storage or photographic processing of the photographic material.
- Specific examples of the compounds are disclosed in JP-A-62-215272, pages 39 to 72, and they can be preferably used.
- 5-arylamino-l,2,3,4-thiatriazole compounds (the aryl residual group has at least one electron-withdrawing group) disclosed in European Patent No. 0447647 can also be preferably used.
- hydroxamic acid derivatives described in JP-A-11-109576 it is also preferred in the present invention to use hydroxamic acid derivatives described in JP-A-11-109576; cyclic ketones having a double bond adjacent to a carbonyl group, each end of said double bond being substituted with an amino group or a hydroxyl group, as described in JP-A-11-327094 (in particular, compounds represented by formula (Sl); the description at paragraph Nos. 0036 to 0071 of JP-A-11-
- the silver halide emulsion for use in the present invention can contain a spectral sensitizing dye, to impart sensitivity in a desired light wavelength region, i.e. so-called spectral sensitivity.
- a spectral sensitizing dye that can be used in spectral sensitization of blue, green, or red light region, include those disclosed by F. M. Harmer, in "Heterocyclic Compounds - Cyanine Dyes and Related Compounds", John Wiley & Sons, New York, London (1964).
- Specific examples of compounds and spectral sensitization methods that can be preferably used in the present invention include those described in JP-A-62-215272, from page 22, right upper column to page 38.
- the spectral sensitizing dyes described in JP-A-3-123340 are very preferred as red-sensitive spectral sensitizing dyes for silver halide emulsion grains having a high-silver chloride content, from the viewpoint of stability, adsorption strength, temperature dependency of exposure, and the like.
- the amount of these spectral sensitizing dyes to be added can vary in a wide range depending on the occasion, and it is preferably in the range of 0.5 x 10 "6 mole to 1.0 x 10 "2 mole, more preferably in the range of 1.0 x 10 '6 - mole to 5.0 x 10 "3 mole, per mole of silver halide.
- the silver halide color photographic light-sensitive material according to the present invention will be explained in below.
- the constitution of the silver halide color photographic light-sensitive material of the present invention has, on a support, at least one cyan dye-forming coupler-containing silver halide emulsion layer, at least one magenta dye-forming coupler-containing silver halide emulsion layer, and at least one yellow dye-forming coupler-containing silver halide emulsion layer.
- the silver halide emulsions contained in the above layers may have photo-sensitivities to mutually different wavelength regions of light (for example, light in a blue region, light in a green region, and light in a red region).
- the amount of the coupler to be used is preferably 0.6 equivalents or more, particularly preferably 0.7 equivalents or more, to silver, although it is ideally 1 equivalent to silver.
- the term “1 equivalent” means the amount of the coupler which develops a color when the coupler is reacted with all the amount of silver to be used; and the term “0.5 equivalents” means the amount of the coupler which develops a color when the coupler is reacted with half the amount of silver to be used.
- any of known materials for photography or additives may be used.
- a transmissive type support or a reflective type support may be used as a photographic support (base).
- a transmissive type support it is preferred to use a transparent film, such as a cellulose nitrate film, and a polyethylene terephthalate film; or a polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), or a polyester of NDCA, terephthalic acid, and EG, provided thereon with an information-recording layer such as a magnetic layer.
- NDCA 2,6-naphthalenedicarboxylic acid
- EG ethylene glycol
- an information-recording layer such as a magnetic layer.
- a reflective support having a substrate laminated thereon with a plurality of polyethylene layers or polyester layers, at least one of the water-proof resin layers (laminate layers) contains a white pigment such as titanium oxide.
- examples of more preferable reflective support includes a support having a paper substrate provided with a polyolefin layer having micropores (fine holes), on the same side as silver halide emulsion layers to be provided.
- the polyolefin layer may be composed of multi-layers.
- the support it is more preferable for the support to be composed of a micropore-free polyolefin (e.g., polypropylene, polyethylene) layer adjacent to a gelatin layer on the same side as the silver halide emulsion layers, and a micropore-containing polyolefin (e.g., polypropylene, polyethylene) layer closer to the paper substrate.
- a micropore-free polyolefin e.g., polypropylene, polyethylene
- a micropore-containing polyolefin e.g., polypropylene, polyethylene
- the density of the multi-layer or single-layer of polyolefin layer(s) existing between the paper substrate and photographic constituting layers is preferably in the range of 0.40 to 1.0 g/ml, more preferably in the range of 0.50 to 0.70 g/ml.
- the thickness of the multi-layer or single-layer of polyolefin layer(s) existing between the paper substrate and photographic constituting layers is preferably in the range of 10 to 100 ⁇ m, more preferably in the range of 15 to 70 ⁇ m.
- the ratio of thickness of the polyolefin layer(s) to the paper substrate is preferably in the range of 0.05 to 0.2, more preferably in the range 0.1 to 0.15.
- a polyolefin layer be provided on the surface of the foregoing paper substrate opposite to the side of the photographic constituting layers, i.e., on the back surface of the paper substrate.
- the polyolefin layer on the back surface be polyethylene or polypropylene, the surface of which is matted, with the polypropylene being more preferable.
- the thickness of the polyolefin layer on the back surface is preferably in the range of 5 to 50 ⁇ m, more preferably in the range of 10 to 30 ⁇ m, and further the density thereof is preferably in the range of 0.7 to 1.1 g/ml.
- preferable embodiments of the polyolefin layer to be provided on the paper substrate include those described in JP-A- 10-333277, JP-A-10-333278, JP-A-11-52513, JP-A-11-65024, European Patent Nos. 0880065 and 0880066.
- the above-described water-proof resin layer contain a fluorescent whitening agent.
- the fluorescent whitening agent may be dispersed and contained in a hydrophilic colloid layer, which is formed separately from the above layers in the light-sensitive material.
- Preferred examples of the fluorescent whitening agent that can be used include benzoxazole-series, coumarin-series, and pyrazoline-series compounds.
- fluorescent whitening agents of benzoxazolylnaphthalene- series and benzoxazolylstilbene-series are more preferably used.
- the amount of the fluorescent whitening agent to be used is not particularly limited, and it is preferably in the range of 1 to 100 mg/m 2 .
- a mixing ratio of the fluorescent whitening agent to be used in the water-proof resin is preferably in the range of 0.0005 to 3% by mass, and more preferably in the range of 0.001 to 0.5% by mass, to the resin.
- a transmissive type support or the foregoing reflective type support each having coated thereon a hydrophilic colloid layer containing a white pigment may be used as the reflective type support.
- a reflective type support having a mirror plate reflective metal surface or a secondary diffusion reflective metal surface may be employed as the reflective type support.
- a support of the white polyester type, or a support provided with a white pigment-containing layer on the same side as the silver halide emulsion layer may be adopted for display use. Further, it is preferable for improving sharpness that an antihalation layer be provided on the silver halide emulsion layer side or the reverse side of the support.
- the transmission density of support be adjusted to the range of 0.35 to 0.8, so that a display may be enjoyed by means of both transmitted and reflected rays of light.
- a dye that can be discolored by processing, as described in European Patent No. 0,337,490 A2, pages 27 to 76, is preferably added to the hydrophilic colloid layer, such that an optical reflection density at 680 nm in the light-sensitive material is 0.70 or more. It is also preferable to add 12% by mass or more (more preferably 14% by mass or more) of titanium oxide that is surface-treated with, for example, a dihydric to tetrahydric alcohol (e.g., trimethylolethane) to a water-proof resin layer of the support.
- a dihydric to tetrahydric alcohol e.g., trimethylolethane
- the light-sensitive material of the present invention preferably contains, in the hydrophilic colloid layer, a dye (particularly oxonole dyes and cyanine dyes) that can be discolored by processing, as described in European Patent No. 0337490A2, pages 27 to 76, in order to prevent irradiation or halation or to enhance safelight safety, and the like.
- a dye described in European Patent No. 0819977 may also be preferably used in the present invention.
- these water-soluble dyes some deteriorate color separation or safelight safety when used in an increased amount.
- Preferable examples of the dye which can be used and which does not deteriorate color separation include water-soluble dyes described in JP-A- 5-127324, JP-A-5-127325 and JP-A-5-216185.
- a colored layer which can be discolored during processing in place of the water-soluble dye, or in combination with the water-soluble dye.
- the colored layer that can be discolored with a processing, to be used may contact with an emulsion layer directly, or indirectly through an interlayer containing an agent for preventing color-mixing during processing, such as hydroquinone or gelatin.
- the colored layer is preferably provided as a lower layer (i.e. a layer closer to the support) with respect to the emulsion layer which develops the same primary color as the color of the colored layer. It is possible to provide colored layers independently, each corresponding to respective primary colors. Alternatively, only some layers selected from them may be provided.
- the optical density of the colored layer it is preferred that, at the wavelength which provides the highest optical density in a range of wavelengths used for exposure (a visible light region from 400 run to 700 nm for an ordinary printer exposure, and the wavelength of the light generated from the light source in the case of scanning exposure), the optical density is 0.2 or more but 3.0 or less, more preferably 0.5 or more but 2.5 or less, and particularly preferably 0.8 or more but 2.0 or less.
- the colored layer may be formed by a known method. For example, there are a method in which a dye in a state of a dispersion of solid fine particles is incorporated in a hydrophilic colloid layer, as described in JP-A-2-282244, from page 3, upper right column to page 8, and JP-A-3-7931, from page 3, upper right column to page 11 , left under column; a method in which an anionic dye is mordanted in a cationic polymer; a method in which a dye is adsorbed onto fine grains of silver halide or the like and fixed in the layer; and a method in which a colloidal silver is used, as described in JP-A- 1-239544.
- JP-A-2-308244 pages 4 to 13
- JP-A-2-308244 pages 4 to 13
- the method of mordanting anionic dyes in a cationic polymer is described, for example, in JP-A-2-84637, pages 18 to 26.
- U.S. Patent Nos. 2,688,601 and 3,459,563 disclose methods of preparing colloidal silver for use as a light absorber. Among these methods, preferred examples are the method of incorporating fine particles of dye, the method of using colloidal silver, and the like.
- the photographic material of the present invention can be used, for example, as a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, a display photosensitive material, a digital color proof, a motion picture color positive, or a motion picture color negative.
- a display photosensitive material, a digital color proof, a motion picture color positive, a color reversal photographic paper, and a color photographic paper are preferred over the others as use thereof, and the use as a color photographic paper is particularly preferable.
- the color photographic paper preferably contains at least one yellow-color-forming blue-sensitive silver halide emulsion layer, at least one magenta-color-forming green-sensitive silver halide emulsion layer, and at least one cyan-color- forming red-sensitive silver halide emulsion layer.
- the arranging order of these silver halide emulsion layers in the direction that goes away from a support is a yellow-color-forming blue-sensitive silver halide emulsion layer, a magenta-color-forming green-sensitive silver halide emulsion layer, and a cyan-color-forming red-sensitive silver halide emulsion layer.
- a layer arrangement which is different from the above, may be adopted.
- the blue-sensitive silver halide emulsion layer may be provided at any position on a support.
- the blue-sensitive silver halide emulsion layer be positioned more apart from a support than at least one of a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer.
- the blue-sensitive silver halide emulsion layer be positioned most apart from a support than other silver halide emulsion layers, from the viewpoint of color-development acceleration, desilvering acceleration, and reducing residual color due to a sensitizing dye.
- the red-sensitive silver halide emulsion layer be disposed in the middle of the other silver halide emulsion layers, from the viewpoint of reducing blix fading.
- the red-sensitive silver halide emulsion layer be the lowest layer, from the viewpoint of reducing light fading.
- each of the yellow-color-forming layer, the magenta-color-forming layer, and the cyan- color-forming layer may be composed of two or three layers.
- a color-forming layer be formed by providing a silver-halide-emulsion-free layer containing a coupler in adjacent to a silver halide emulsion layer, as described in, for example, JP-A-4-75055, JP-A-9-114035, JP-A- 10-246940, and U.S. Patent No. 5,576,159.
- cyan, magenta, and yellow couplers which can be used in the present invention or can used in combination with the specific coupler defined in the present invention, other than the above-mentioned ones, those disclosed in JP-A-62-215272, page 91, right upper column, line 4 to page 121, left upper column, line 6; JP-A-2-33144, page 3, right upper column, line 14 to page 18, left upper column, bottom line, and page 30, right upper column, line 6 to page 35, right under column, line 11; and European Patent No. 0355,660 (A2), page 4, lines 15 to 27, page 5, line 30 to page 28, bottom line, page 45, lines 29 to 31, page 47, line 23 to page 63, line 50, are also advantageously used.
- magenta dye-forming coupler (which may be referred to simply as "magenta coupler") that can be used in the present invention can be a 5-pyrazolone-series magenta coupler or a pyrazoloazole-series magenta coupler, such as those described in the patent publications in the above table.
- a pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly bonded to the 2-, 3-, or 6-position of the pyrazolotriazole ring, such as those described in JP-A-61-65245; a pyrazoloazole coupler having a sulfonamido group in its molecule, such as those described in JP-A-61-65246; a pyrazoloazole coupler having an alkoxyphenylsulfonamido ballasting group, such as those described in JP- A-61-147254; and a pyrazoloazole coupler having an alkoxy or aryloxy group at the 6-position, such as those described in European Patent Nos.
- a pyrazoloazole coupler represented by formula (M-I) described in JP-A-8-122984 is preferred.
- M-I pyrazoloazole coupler represented by formula (M-I) described in JP-A-8-122984
- the description of paragraph Nos. 0009 to 0026 of JP-A-8-122984 can be entirely applied to the present invention, and therefore is incorporated herein by reference.
- a pyrazoloazole coupler having each one steric hindrance group at both the 3- and 6-positions, as described in European Patent Nos. 854384 and 884640, can also be preferably used.
- yellow dye-forming coupler (which may be referred to simply as "yellow coupler”)
- acylacetamide-type yellow coupler in which the acyl group has a 3-membered to 5-membered ring structure, such as those described in European Patent No. 0447969 Al; a malondianilide-type yellow coupler having a ring structure, as described in European Patent No. 0482552 Al ; a pyrrol-2 or 3-yl or indol-2 or 3-yl carbonyl acetanilide-series coupler, as described in European Patent (laid open to public) Nos.
- couplers use can be preferably made of the acylacetamide- type yellow coupler whose acyl group is a 1-alkylcyclopropane-l -carbonyl group, the malondianilide-type yellow coupler in which one anilido forms an indoline ring, or the acetanilide-type yellow coupler which has a hetero ring substituted on the acyl group.
- the couplers may be used singly or in combination with two or more of these.
- coupler(s) for use in the present invention is pregnated into a loadable latex polymer (as described, for example, in U.S. Patent No. 4,203,716), in the presence (or absence) of the high- boiling-point organic solvent described in the foregoing table, or dissolved together with a polymer insoluble in water but soluble in an organic solvent, and then emulsified and dispersed into an aqueous hydrophilic colloid solution.
- a loadable latex polymer as described, for example, in U.S. Patent No. 4,203,716
- the high- boiling-point organic solvent described in the foregoing table or dissolved together with a polymer insoluble in water but soluble in an organic solvent, and then emulsified and dispersed into an aqueous hydrophilic colloid solution.
- water-insoluble but organic-solvent-soluble polymer which can be preferably used, include the homo-polymers and co-polymers as disclosed in U.S. Patent No.
- any of known color mixing-inhibitors may be used.
- these compounds those described in the following patent publications are preferred.
- redox compounds described in JP-A-5-333501 phenidone- or hydrazine-series compounds as described in, for example, WO 98/33760 and U.S. Patent. No. 4,923,787; and white couplers as described in, for example, JP-A-5-249637, JP-A-lO-282615/and German Patent No. 19629142 Al, may be used.
- 2,760,460 Al are also preferably used.
- an ultraviolet ray absorbent it is preferred to use a compound having a high molar extinction coefficient and a triazine skeleton.
- compounds described in the following patent publications can be used. These compounds are preferably added to the light-sensitive layer or/and the light-insensitive layer.
- JP-A-46-333 use can be made of those described in JP-A-46-3335, JP-A-55- 152776, JP-A-5- 197074, JP-A-5-232630, JP-A-5-307232, JP-A-6-211813, JP-A-8-53427, JP-A-8- 234364, JP-A-8-239368, JP-A-9-31067, JP-A-10-115898, JP-A-10-147577, JP-A- 10- 182621, German Patent No. 19,739,797 A, European Patent No. 0,711,804 A, and JP-T-8-501291 ("JP-T" means searched and published International patent application), and the like.
- gelatin is used advantageously, but another hydrophilic colloid can be used singly or in combination with gelatin. It is preferable for the gelatin that the content of heavy metals, such as Fe, Cu, Zn, and Mn, included as impurities, be reduced to 5 ppm or below, more preferably 3 ppm or below. Further, the amount of calcium contained in the light-sensitive material is preferably 20 mg/m 2 or less, more preferably 10 mg/m 2 or less, and most preferably 5 mg/m 2 or less.
- the film pH of the light- sensitive material is preferably in the range of 4.0 to 7.0, more preferably in the range of 4.0 to 6.5.
- a surfactant may be added to the light-sensitive material, in view of improvement in coating-stability, prevention of static electricity from being occurred, and adjustment of the charge amount.
- the surfactant mention can be made of anionic, cationic, betaine, and nonionic surfactants. Examples thereof include those described in JP-A-5-333492.
- a fluorine-containing surfactant is particularly preferred.
- the fluorine- containing surfactant may be used singly, or in combination with known other surfactant.
- the fluorine- containing surfactant is preferably used in combination with known other surfactant.
- the amount of the surfactant to be added to the light-sensitive material is not particularly limited, but it is generally in the range of 1 x 10 "5 to 1 g/m 2 , preferably in the range of 1 x 10 '4 to 1 x 10 "1 g/m 2 , and more preferably in the range of 1 x 10 "3 to 1 x 10 "2 g/m 2 .
- the photosensitive material of the present invention can form an image, as shown in the specific example of an image-forming arraratus for performing exposure to the photosensitive material, by undergoing an exposure step of irradiating the photosensitive material with light responsive to image information, and a development step of processing the light-irradiated photosensitive material.
- the light-sensitive material of the present invention can preferably be used in the digital scanning exposure system using monochromatic high density light, such as a gas laser, a light-emitting diode, a semiconductor laser, a second harmonic generation light source (SHG) comprising a combination of nonlinear optical crystal with a semiconductor laser or a solid state laser using a semiconductor laser as an excitation light source.
- monochromatic high density light such as a gas laser, a light-emitting diode, a semiconductor laser, a second harmonic generation light source (SHG) comprising a combination of nonlinear optical crystal with a semiconductor laser or a solid state laser using a semiconductor laser as an excitation light source.
- a semiconductor laser, or a second harmonic generation light source (SHG) comprising a combination of nonlinear optical crystal with a solid state laser or a semiconductor laser, to make a system more compact and inexpensive.
- use of a semiconductor laser is preferable; and it is preferred that at least one of exposure light sources uses a semiconductor laser.
- a blue laser with emission wavelength of 420 nm to 460 nm.
- a blue semiconductor laser can be used particularly preferably.
- the laser light source includes a blue-light semiconductor laser of wavelength 430 to 450 nm (Presentation by Nichia Corporation at the 48th Applied Physics Related Joint Meeting, in March of 2001); a blue laser at about 470 nm obtained by wavelength modulation of a semiconductor laser (oscillation wavelength about 940 nm) with a SHG crystal OfLiNbO 3 having a reversed domain structure in the form of a wave guide; a green-light laser at about 530 nm obtained by wavelength modulation of a semiconductor laser (oscillation wavelength about 1,060 nm) with SHG crystal Of LiNbO 3 having a reversed domain structure in the form of a wave guide; a red-light semiconductor laser of wavelength at about 685 nm (Type No. HL6738MG (trade name) manufactured by Hitachi, Ltd.); and a red-light semiconductor laser of wavelength at about 650 nm (Type No. HL6501MG (trade name) manufactured by Hitachi, Ltd.); and a red
- the maximum spectral sensitivity wavelength of the light-sensitive material of the present invention can be arbitrarily set up in accordance with the wavelength of a scanning exposure light source to be used. Since oscillation wavelength of a laser can be made half, using a SHG light source obtainable by a combination of a nonlinear optical crystal with a semiconductor laser or a solid state laser using a semiconductor as an excitation light source, blue light and green light can be obtained. Accordingly, it is possible to have the spectral sensitivity maximum of a light-sensitive material in usual three wavelength regions of blue, green, and red.
- the exposure time in such a scanning exposure is defined as the time period necessary to expose the size of the picture element (pixel) with the density of the picture element being 300 dpi, and a preferred exposure time is 1 x 10 "4 sec or less, more preferably 1 x 10 "6 sec or less.
- the silver halide color photosensitive material of the present invention can be preferably used in combination with the exposure and development system described in the following literatures.
- Example of the development system include the automatic print and development system described in JP-A-10-333253, the photosensitive material-conveying apparatus described in JP-A-2000- 10206, a recording system including image reading apparatus, as described in JP-A-11-215312, exposure systems with the color image recording methods, as described in JP-A-11-88619 and JP-A- 10-202950, a digital photo print-system including remote diagnosis method, as described in JP-A-10-210206, and a photo print system including image recording apparatus, as described in JP-A-2000-310822.
- the light-sensitive material of the present invention can also be preferably applied to a light-sensitive material having rapid processing suitability.
- the color-developing time is preferably 30 sec or less
- the blix time is preferably 30 sec or less, more preferably from 25 sec to 6 sec, and further preferably from 20 sec to 6 sec.
- the washing or stabilizing time is preferably 60 sec or less, and more preferably from 40 sec to 6 sec.
- color-developing time means a period of time required from the
- the color developing time is the sum total of a time in which a light-sensitive material has been dipped in a color developing solution (so-called "time in solution”) and a time in which the light-sensitive material has left the color developing solution and been conveyed in the air
- blix time means a period of time required from the beginning of dipping a light-sensitive material into a blix solution until the light-sensitive material is dipped into a washing or stabilizing bath in the subsequent processing step.
- washing or stabilizing time means a period of time required from the beginning of dipping a light-sensitive
- the color-developing time is preferably adjusted to 20 seconds or below (more preferably from 6 to 20 seconds, especially preferably from 6 to 15 seconds).
- 35 time of 20 seconds or below means that the above-mentioned color-developing time is 20 seconds or below (and does not mean performing the whole processing steps for color development processing within such a time).
- K 2 [IrCl 5 (H 2 O)] and K[IrCl 4 (H 2 O) 2 ] were added at the step of from 88% to 98% addition of the entire silver nitrate amount.
- Potassium iodide (0.4 mol%, per mol of the finished silver halide) was added, under vigorous stirring, at the step of completion of 93% addition of the entire silver nitrate amount.
- the thus-obtained emulsion grains were monodisperse cubic silver iodobromochloride grains of side length 0.25 ⁇ m and variation coefficient 9.5%.
- the re-dispersed emulsion was dissolved at 40°C, and thereto were added sodium benzenethiosulfate, p-glutaramidophenyldisulfide, Compound-1 as a gold-sulfur sensitizer, SE3-9 as a selenium sensitizer, and (bis(l,4,5-trimethyl-l,2,4-triazolium-3-thiorato) aurate (I) tetrafluoroborate) as a gold sensitizer, followed by repening to conduct chemical sensitization optimally.
- Potassium iodide (0.2 mol%, per mol of the finished silver halide) was added, under vigorous stirring, at the step of completion of 90% addition of the entire silver nitrate amount. Further, K 2 [IrCl 5 (H 2 O)] and K[IrCl 4 (H 2 O) 2 ] were added at the step of from 87% to 98% addition of the entire silver nitrate amount.
- the thus-obtained emulsion grains were monodisperse cubic silver iodobromochloride grains of side length 0.25 ⁇ m and variation coefficient 9.5%. The resultant emulsion was subjected to sedimentation desalting and re-dispersing in the same manner as in the above.
- This emulsion was dissolved at 40°C, and thereto sodium benzenethiosulfate, p- glutaramidophenyldisulfide, SE3-9 as a selenium sensitizer, and (bis(l,4,5-trimethyl-l,2,4-friazolium-3- thiorato) aurate (I) tetrafluoroborate) as a gold sensitizer were added, followed by ripening for optimal chemical sensitization.
- K 2 [IrCl 5 (5-methylthiazole)] was added at the step of from 88% to 93% addition of the entire silver nitrate amount.
- Potassium iodide (the amount of silver iodide would be 0.05 mol%, per mol of the finished silver halide) was added, under vigorous stirring, at the step of completion of 93% addition of the entire silver nitrate amount.
- K 2 [IrCl 5 (H 2 O)] and K[IrCl 4 (H 2 O) 2 ] were added at the step of from 93% to 98% addition of the entire silver nitrate amount.
- the thus-obtained emulsion grains were monodisperse cubic silver iodobromochloride grains of side length 0.25 ⁇ m and variation coefficient 9.5%.
- the resultant emulsion was subjected to sedimentation desalting and re-dispersing in the same manner as above.
- Sensitizing dye S-8 Compound-5, sodium benzenethiosulfate, p-glutaramidophenyldisulfide, SE3-9 as a selenium sensitizer, and (bis(l,4,5-trimethyl- l,2,4-triazoliuni-3-thiorato) aurate (I) tetrafiuoroborate) as a gold sensitizer were added, followed by ripening for optimal chemical sensitization.
- Emulsion RH-I Emulsion RH-I
- Emulsion RH-2 was prepared in the same manner as in the preparation of Emulsion RH-I, except that Compound-1 was added as a gold-sulfur sensitizer in place of the selenium sensitizer SE3-9, that the gold sensitizer (bis(l,4,5-trimethyl-l,2,4-triazolium-3-thiolato) aurate (I) tetrafluoroborate) was not added, and that amounts of the compounds to be added were changed from those in RH-I. (Preparation of Red-sensitive layer emulsion RH-3)
- Emulsion RH-3 was prepared in the same manner as in the preparation of Emulsion RH-I, except that SE3-29 was added in place of the selenium sensitizer SE3-9, and that amounts of the compounds to be added were changed from those in RH-I.
- Emulsion RH-4 was prepared in the same manner as in the preparation of Emulsion RH-I, except that PFl-I was added in place of the selenium sensitizer SE3-9, and that amounts of the compounds to be added were changed from those in RH-I.
- Emulsion RH-5 was prepared in the same manner as in the preparation of Emulsion RH-I, except that PF6-1 was added in place of the selenium sensitizer SE3-9, and that amounts of the compounds to be added were changed from those in RH-I .
- Emulsion RH-6 was prepared in the same manner as in the preparation of Emulsion RH-I, except that the amount of potassium iodide to be added was changed such that the amount of silver iodide would be 0.3 mol%, per mol of the finished silver halide.
- Emulsion RH-7 was prepared in the same manner as in the preparation of Emulsion RH-6, except that Compound- 1 was added as a gold-sulfur sensitizer in place of the selenium sensitizer SE3-9, that the gold sensitizer (bis(l,4,5-trimethyl-l,2,4-triazolium-3-thiolato) aurate (I) tetrafluoroborate) was not added, and that amounts of the compounds to be added were changed from those in RH-6.
- Compound- 1 was added as a gold-sulfur sensitizer in place of the selenium sensitizer SE3-9, that the gold sensitizer (bis(l,4,5-trimethyl-l,2,4-triazolium-3-thiolato) aurate (I) tetrafluoroborate) was not added, and that amounts of the compounds to be added were changed from those in RH-6.
- Emulsion RH-8 was prepared in the same manner as in the preparation of Emulsion RH-6, except that SE3-29 was added in place of the selenium sensitizer SE3-9, and that amounts of the compounds to be added were changed from those in RH-6.
- Emulsion RH-9 was prepared in the same manner as in the preparation of Emulsion RH-6, except that PF6-1 was added in place of the selenium sensitizer SE3-9, and that amounts of the compounds to be added were changed from those in RH-6.
- This solution was emulsified and dispersed in 205 g of a 20mass% aqueous gelatin solution containing 3 g of sodium dodecylbenzenesulfonate, with a high-speed stirring emulsifier (dissolver). Water was added thereto, to prepare 700 g of Emulsified dispersion A.
- the coating amount of the emulsion is in terms of silver.
- the coating solutions for the second layer to the seventh layer were prepared in the similar manner as that for the first-layer coating solution.
- As a gelatin hardener for each layer (H-I), (H-2), and (H-3) were used. Further, to each layer, were added Ab-I, Ab-2, Ab-3, and Ab-4, so that the total amounts would be 10.0 mg/m 2 , 45.0 mg/m 2 , 5.0 mg/m 2 , and 10.0 mg/m 2 , respectively.
- the fifth layer, and the sixth layer was added l-(3- methylureidophenyl)-5-mercaptotetrazole in amounts of 0.2 mg/m 2 , 0.2 mg/m 2 , and 0.6 mg/m 2 , respectively.
- l-(3- methylureidophenyl)-5-mercaptotetrazole in amounts of 0.2 mg/m 2 , 0.2 mg/m 2 , and 0.6 mg/m 2 , respectively.
- 4- hydroxy-6-methyl-l,3,3a,7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer, was added 4- hydroxy-6-methyl-l,3,3a,7-tetrazaindene in amounts of 1 x 10 '4 mol and 2 x 10 "4 mol, respectively, per mol of the silver halide.
- a copolymer latex of methacrylic acid and butyl acrylate (1:1 in mass ratio; average molecular weight, 200,000 to 400,000) in an amount of 0.05 g/m 2 .
- Disodium catecol-3,5-disulfonate was added to the third layer, the fifth layer, and the sixth layer so that coating amounts would be 6 mg/m 2 , 6 mg/m 2 , and .18 mg/m 2 , respectively.
- sodium polystyrene sulfonate was added to adjust viscosity of the coating solutions, if necessary. Further, in order to prevent irradiation, the following dyes (coating amounts are shown in parentheses) were added.
- each layer is shown below.
- the numerals show coating amounts (g/m 2 ).
- the coating amount is in terms of silver.
- Polyethylene resin laminated paper ⁇ The polyethylene resin on the first layer side contained white pigments (TiO 2 , content of 16 mass%; ZnO, content of 4 mass%), a fluorescent whitening agent
- Color-image stabilizer (Cpd- 18) . 0.12 .
- UV-A Color-image stabilizer 0.01 Solvent (Solv-4) 0.05
- Color-image stabilizer (Cpd-6) 0.020 ' Color-image stabilizer (UV-A) 0.020
- UV-A Color-image stabilizer
- Sample 101 The thus-prepared sample was designated to as Sample 101. Further, Samples 102 to 105 and 121 to 124 were prepared in the same manner as Sample 101, except that the structure of the fourth layer was changed, as shown in Table 2 below, but in the same amount of the coated silver as in Sample 101.
- Sample 111 was prepared in the same manner as Sample 101, except that the composition of the fourth layer of Sample 101 was changed as described below.
- Samples 112 to 116 and 125 to 128 were prepared in the same manner as Sample 111, except that the composition of the fourth layer was changed, as shown in Table 2, but not to change the amount of coated silver and the molar concentration ratio of the coated silver to the coupler.
- the aforementioned Sample 101 was made into a roll with width 127 mm; the resultant sample was exposed to light with a standard photographic image, using Digital Minilab Frontier 350 (trade name, manufactured by Fuji Photo Film Co., Ltd.); and then, the exposed sample was continuously processed (running test) in the following processing steps, until an accumulated replenisher amount of the color developing solution reached to be equal to twice the color developer tank volume.
- a processing with this running processing solutions was named processing A.
- a rinse cleaning system RC50D trade name, manufactured by Fuji Photo Film Co., Ltd., was installed in the above Rinse 3, and the rinse solution was taken out from Rinse 3 and sent to a reverse osmosis membrane module (RC50D) by using a pump.
- the permeated water obtained in that tank was supplied to Rinse 4, and the concentrated liquid was returned to Rinse 3.
- Pump pressure was controlled such that the permeated water in the reverse osmosis module would be maintained in an amount of 50 to
- compositions of each processing solution were as follows.
- Fluorescent whitening agent (FL-I) 2.2 g 5.1 g Fluorescent whitening agent (FL-2) 0.35 g 1.75 g Triisopropanolamine 8.8 g 8.8 g Polyethyleneglycol
- Ammonium thiosulfate (750 g/L) 107 mL - 386 mL Ammonium bisulfite (65%) 30.O g - 19O g Ethylenediamine tetraacetate iron (III) ammonium 47.O g 133 g _ Ethylenediamine tetraacetic acid 1.4 g 5 g 6 g Nitric acid (67%) 6.5 g 66.O g - Imidazole 14.6 g 50.0 g - m-Carboxybenzenesulfinic acid 8.3 g 33.0 g - Water to make 1,000 ml 1,000 ml 1,000 ml pH (25°C; adjusted using nitric acid and aqua ammonia) 6.5 6.0 6.0 6.0
- Deionized water (conductivity 5 ⁇ S/cm or less) 1,000 ml 1,000 ml pH (25 0 C) 6.5 6.5
- the aforementioned Sample 101 was made into a roll with width 127 mm; the resultant sample was exposed to light with a standard photographic image, using Digital Minilab Frontier 340 (trade name, manufactured by Fuji Photo Film Co., Ltd.); and then, the exposed sample was continuously processed (running test) in the following processing steps, until an accumulated replenisher amount of the color developing solution reached to be equal to twice the color developer tank volume.
- the processor was modified by modifying the processing racks thereby to change the conveyance speed, so as to set the following processing time conditions.
- a processing with this running processing solutions was named processing B.
- compositions of each processing solution were as follows. (Color developer) (Tank solution) (Replemsher) Water 80OmL 80OmL
- Fluorescent whitening agent FL-3 4.0g 10.0 g Residual-color-reducing agent (SR-I) 3.0g 3.0g m-Carboxybenzenesulfinic acid 2.Og 4.0g Sodium p-toluenesulfonate 10.0 g 10.0 g Ethylenediaminetetraacetic acid 4.0g 4.Og Sodium sulfite 0.10 g 0.10 g Potassium chloride 10.0 g -
- each sample was subjected to gradation exposure to impart gray in the above Processing B, with the following exposure apparatus; and then, at five seconds after the exposure was finished, the sample was subject to color-development processing by the above Processing A or B.
- the laser light sources used were a blue-light laser of wavelength about 470 nm which was taken out of a semiconductor laser (oscillation wavelength about 940 nm) by converting the wavelength by an SHG crystal Of LiNbO 3 having a waveguide-like inverse domain structure, a green-light laser of wavelength about 530 nm which was taken out of a semiconductor laser (oscillation wavelength about 1,060 nm) by converting the wavelength by an SHG crystal OfLiNbO 3 having a waveguide-like inverse domain structure, and a red-light semiconductor laser (Type No.
- HL6501 MG manufactured by Hitachi, Ltd.
- Each of these three color laser lights was moved in a direction perpendicular to the scanning direction by a polygon mirror so that it could be scanned to expose successively on a sample.
- Each of the semiconductor lasers is maintained at a constant temperature by means of a Peltier element, to obviate light intensity variations associated with temperature variations.
- the laser beam had an effective diameter of 80 ⁇ m and a scanning pitch of 42.3 ⁇ m (600 dpi), and an average exposure time per pixel was 1.7 x 10 "7 seconds.
- the temperature of the semiconductor laser was kept constant by using a Peltier device to prevent the quantity of light from being changed by temperature.
- the density of developed cyan color of each of the samples after processed was measured, to obtain a characteristic curve.
- the sensitivity (S) was the antilogarithm of the inverse number of an exposure amount giving a developed color density higher by 1.0 than the minimum developed color density, and it is expressed as a relative value when the sensitivity of Sample 101 in Processing A is set to 100. The larger the value is, the higher the sensitivity is, which is preferable.
- the gradation ( ⁇ ) is a difference between the sensitivity at density 0.5 and the sensitivity at density 1.5, and it is expressed as a relative value when the gradation of Sample 101 in Processing A is set to 100. The smaller the value is, the higher the gradation is, which is preferable.
- the fog density (Dmin) shows a value obtained by subtracting the density of the base from the cyan density of the unexposed portion. The smaller the value is, the clear and more attractive the white background is, which is preferable.
- the results of the sensitivity (S), gradation ( ⁇ ) and fog density (Dmin) are shown in Table 3.
- Samples 201 to 205 and Samples 211 to 215 were prepared in the same manner as Samples 101 to 105 and Samples 111 to 115 in Example 1, respectively, except that the silver halide emulsion and the emulsified dispersion for the red-sensitive layer were mixed and dissolved, followed by allowing the resultant solution to stand for 6 hours, and then applied.
- the density of developed cyan color of each sample after the sample was processed was measured, to obtain a characteristic curve.
- the sensitivity was the antilogarithm of the inverse number of an exposure amount giving a developed color density higher by 1.0 than the minimum developed color density, and it is expressed as a relative value when the sensitivity of Sample 101 in Processing B was set to 100.
- the difference in sensitivity of a sample from that of Sample 101 is defined as a difference in sensitivity, and as the value is closer to zero, the variation is smaller, which is preferable.
- a difference in fog density shows a difference obtained by subtracting the density of the base from the cyan density of the unexposed portion. The smaller the value is, the smaller the difference in fog density is, which is preferable.
- the results of the difference in sensitivity and the difference in fog density are shown in Table 5.
- the present invention is preferable as a silver halide color photographic light-sensitive material that can provide a silver halide emulsion high in sensitivity, low in fogging, and high in contrast, and that is reduced in the variation of performance with the lapse of time after the materials therefor are mixed and dissolved in its production process.
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Abstract
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EP05790419A EP1800184A4 (en) | 2004-09-30 | 2005-09-30 | Silver halide color photographic light-sensitive material |
US11/664,089 US7407740B2 (en) | 2004-09-30 | 2005-09-30 | Silver halide color photographic light-sensitive material |
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JP2004288299A JP2006106022A (en) | 2004-09-30 | 2004-09-30 | Silver halide color photographic sensitive material |
JP2004-288299 | 2004-09-30 |
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EP (1) | EP1800184A4 (en) |
JP (1) | JP2006106022A (en) |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1024402A2 (en) * | 1999-01-29 | 2000-08-02 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material and image forming method |
JP2004004144A (en) * | 2002-03-26 | 2004-01-08 | Fuji Photo Film Co Ltd | Silver halide photographic emulsion |
US20040157176A1 (en) * | 2003-02-06 | 2004-08-12 | Konica Minolta Holdings, Inc. | Silver halide emulsion, preparation method thereof and silver halide photographic material |
WO2004072730A1 (en) * | 2003-02-14 | 2004-08-26 | Konica Corporation | Silver halide photography photosensitive material |
JP2005181806A (en) * | 2003-12-22 | 2005-07-07 | Konica Minolta Photo Imaging Inc | Silver halide emulsion, silver halide photographic sensitive material and image forming method |
JP2005221815A (en) * | 2004-02-06 | 2005-08-18 | Konica Minolta Photo Imaging Inc | Silver halide emulsion, silver halide photographic sensitive material and image forming method |
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BE659479A (en) * | 1964-02-10 | 1965-05-28 | ||
BE667170A (en) * | 1964-07-22 | 1965-11-16 | ||
JPS51106424A (en) | 1975-03-17 | 1976-09-21 | Konishiroku Photo Ind | HAROGEN KAGINSHASHINNYUZAI |
JPH0545820A (en) * | 1991-08-20 | 1993-02-26 | Konica Corp | Color image forming method |
US5853951A (en) * | 1995-10-05 | 1998-12-29 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US6780579B2 (en) * | 2002-03-26 | 2004-08-24 | Fuji Photo Film Co., Ltd. | Silver halide emulsion and image-forming method using silver halide color photographic light-sensitive material containing the same |
WO2005088394A1 (en) * | 2004-03-11 | 2005-09-22 | Fuji Photo Film Co., Ltd. | Photosensitive material for silver halide color photograph |
-
2004
- 2004-09-30 JP JP2004288299A patent/JP2006106022A/en active Pending
-
2005
- 2005-09-30 CN CNA2005800330886A patent/CN101069128A/en active Pending
- 2005-09-30 WO PCT/JP2005/018578 patent/WO2006036028A1/en active Application Filing
- 2005-09-30 US US11/664,089 patent/US7407740B2/en not_active Expired - Fee Related
- 2005-09-30 EP EP05790419A patent/EP1800184A4/en not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1024402A2 (en) * | 1999-01-29 | 2000-08-02 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material and image forming method |
JP2004004144A (en) * | 2002-03-26 | 2004-01-08 | Fuji Photo Film Co Ltd | Silver halide photographic emulsion |
US20040157176A1 (en) * | 2003-02-06 | 2004-08-12 | Konica Minolta Holdings, Inc. | Silver halide emulsion, preparation method thereof and silver halide photographic material |
WO2004072730A1 (en) * | 2003-02-14 | 2004-08-26 | Konica Corporation | Silver halide photography photosensitive material |
JP2005181806A (en) * | 2003-12-22 | 2005-07-07 | Konica Minolta Photo Imaging Inc | Silver halide emulsion, silver halide photographic sensitive material and image forming method |
JP2005221815A (en) * | 2004-02-06 | 2005-08-18 | Konica Minolta Photo Imaging Inc | Silver halide emulsion, silver halide photographic sensitive material and image forming method |
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CN101069128A (en) | 2007-11-07 |
EP1800184A1 (en) | 2007-06-27 |
JP2006106022A (en) | 2006-04-20 |
US20070254248A1 (en) | 2007-11-01 |
US7407740B2 (en) | 2008-08-05 |
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