EP1251395B1 - Photographisches Silberhalogenidmaterial enthaltend einen Methinfarbstoff - Google Patents

Photographisches Silberhalogenidmaterial enthaltend einen Methinfarbstoff Download PDF

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Publication number
EP1251395B1
EP1251395B1 EP01124350A EP01124350A EP1251395B1 EP 1251395 B1 EP1251395 B1 EP 1251395B1 EP 01124350 A EP01124350 A EP 01124350A EP 01124350 A EP01124350 A EP 01124350A EP 1251395 B1 EP1251395 B1 EP 1251395B1
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EP
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Prior art keywords
group
emulsion
sample
ring
atom
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English (en)
French (fr)
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EP1251395A1 (de
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Tetsuo Nakamura
Takanori Hioki
Katsuhisa Ohzeki
Naoyuki Hanaki
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Fujifilm Corp
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Fujifilm Corp
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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
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/22—Methine and polymethine dyes with an even number of CH groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/16—Methine and polymethine dyes with an odd number of CH groups with one CH group
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/127—Methine and polymethine dyes the polymethine chain forming part of a carbocyclic ring
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/20—Methine and polymethine dyes with an odd number of CH groups with more than three CH groups

Definitions

  • the present invention relates to a silver halide photographic material and more particularly relates to a silver halide photographic material which is high sensitive and generates less residual colors after processing.
  • sensitizing dye which is used for spectral sensitization exerts a great influence on the capabilities of a silver halide photographic material.
  • a trace of structural difference of a sensitizing dye largely affects photographic capabilities such as sensitivity, fog, storage stability and residual colors after processing.
  • Photographic performances are also largely influenced by the combined use of two or more kinds of sensitizing dyes but it is difficult to foresee its effect.
  • Many engineers have hitherto synthesized various kinds of sensitizing dyes, examined the combined use of sensitizing dyes and endeavored to investigate photographic capabilities thereof, however, it is not possible to know photographic capabilities in advance yet.
  • the present durability is deteriorated by adsorbing onto the surface of silver halide grains the sensitizing dye used for the spectral sensitization. Accordingly, a sensitizing dye in which the pressure durability is not deteriorated is desired.
  • EP-A-341 958 describes a silver halide photographic material containing at least one cyanine dye with a *H-pyrrolopyridine, 4H-thienopyrrole, 6H-thienopyrrole, 4H-furopyrrole or 6H-furopyrrole nucleus.
  • EP-A-1139164 which is prior art in accordance with Article 54(3) EPC, discloses a silver halide photographic material containing a methine dye represented by the formula
  • An object of the present invention is to provide a silver halide photographic material which is high speed and generates less residual colors after processing, and also is to provide a silver halide photographic material not deteriorating the pressure durability.
  • the present invention provides a silver halide photographic material which comprises at least one methine dye represented by the following formula (XX): wherein Y 51 represents an atomic group necessary to form a furan ring or a pyrrole ring, and represents a structure selected from formulae (3a), (3b) and (3c) together with the rings including X 51 : wherein Xa represents an oxygen atom or a nitrogen atom (N-Rw); Rw represents a hydrogen atom or a monovalent substituent; Va represents a monovalent substituent selected from a methyl group, a methoxy group, a cyano group and a halogen atom; Vb represents a hydrogen atom; Vc and Vd each represents a hydrogen atom or a monovalent substituent, and at least one of Vc and Vd is a monovalent substituent selected from a methyl group, a methoxy group, a cyano group and a halogen atom; X 51 and X 52 each represents an oxygen atom
  • Y 51 represents an atomic group necessary to form a furan ring or a pyrrole ring, and represents a structure selected from formulae (3a), (3b) and (3c) together with the rings including X 51 : wherein Xa represents an oxygen atom or a nitrogen atom (N-Rw); Rw represents a hydrogen atom or a monovalent substituent; Va represents a monovalent substituent selected from a methyl group, a methoxy group, a cyano group and a halogen atom; Vb represents a hydrogen atom; Vc and Vd each represents a hydrogen atom or a monovalent substituent, and at least one of Vc and Vd is a monovalent substituent selected from a methyl group, a methoxy group, a cyano group and a halogen atom; X 51 and X 52 each represents an oxygen atom, a sulfur atom or a nitrogen atom; Y 52 represents an atomic group necessary to form a benzyl, a
  • Rw represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom, a substituted alkyl group or an unsubstituted alkyl group.
  • the substituents of the substituted alkyl group are preferably substituents having higher hydrophilicity than an iodine atom, more preferably substituents having the same or higher hydrophilicity than a chlorine atom, and particularly preferably substituents having the same or higher hydrophilicity than a fluorine atom.
  • Rw more preferably represents a hydrogen atom or an unsubstituted alkyl group, and particularly preferably a hydrogen atom or a methyl group.
  • an alkyl group e.g., methyl
  • an aryl group e.g., phenyl
  • an aromatic heterocyclic group e.g., 1-pyrrolyl
  • an alkoxyl group e.g., methoxy
  • an alkylthio group e.g., methylthio
  • a cyano group an acyl group (e.g., acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), and a halogen atom
  • the more preferred substituents are a methyl group, a methoxy group, a cyano group and a halogen atom
  • the still more preferred is a halogen atom
  • the particularly preferred are a fluorine atom, a chlorine atom and a bromine atom
  • the most preferred is a chlorine atom.
  • X 51 and X 52 each represents an oxygen atom, a sulfur atom, or a nitrogen atom, and preferably an oxygen atom or a sulfur atom.
  • Y 52 represents an atomic group necessary to form a benzene ring or a 5- or 6-membered unsaturated heterocyclic ring, which may further be condensed with other 5- or 6-membered carbocyclic or heterocyclic ring or may have a substituent, and two carbon atoms to which Y 52 is condensed may be bonded by a single bond or a double bond, preferably a double bond.
  • Y 52 represents an atomic group necessary to form a benzene ring or a 5- or 6-membered unsaturated heterocyclic ring.
  • Examples of the 5-membered unsaturated heterocyclic rings formed by Y 52 include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a furan ring, an oxazole ring, an isooxazole ring, a thiophene ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a selenophene ring, a selenazole ring, an isoselenazole ring, a tellurophene ring, a tellurazole ring, and an isotellurazole ring
  • examples of the 6-membered unsaturated heterocyclic rings formed by Y 52 include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyran ring, and a thio
  • Y 52 may further be condensed with other 5- or 6-membered carbocyclic ring or heterocyclic ring to form, e.g., an indole ring, a benzofuran ring, a benzothiophene ring, or a thienothiophene ring.
  • the preferred 5- or 6-membered unsaturated heterocyclic rings formed by Y 52 are a pyrrole ring, a furan ring, a thiophene ring, and a pyridine ring, and particularly preferred is a pyrrole ring, a thiophene ring or a furan ring.
  • the bond between two carbon atoms in which Y 52 is condensed may be a sigle bond or a double bond. Particularly, a double bond is preferred.
  • Y 52 is preferably a benzene ring, a pyrrole ring, a furan ring, or a thiophene ring (as the pyrrole and furan rings, the above-described (3a), (3b), and (3c) can be exemplified and the similar ones are preferred), particularly preferably a benzene ring, a furan ring or a pyrrole ring, and most preferably a benzene ring.
  • the substituents are not limited but preferably an alkyl group (e.g., methyl), an aryl group (e.g., phenyl), an aromatic heterocyclic group (e.g., 1-pyrrolyl), an alkoxyl group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group, an acyl group (e.g., acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), and a halogen atom (e.g.,fluorine,chlorine,bromine,iodine) are exemplified, more preferably a methyl group, a methoxy group, a cyano group and a halogen atom, still more preferably a halogen atom, particularly preferably a fluorine atom, a chlorine atom and a bromine atom, and most preferably a chlorine atom.
  • R 51 and R 52 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
  • the case where at least one of R 51 and R 52 represents an alkyl group substituted with an acid radical is preferred, the case where R 51 and R 52 both represent an alkyl group substituted with an acid radical is more preferred, the case where at least one of R 51 and R 52 , which are alkyl groups substituted with an acid radical, represents an alkyl group substituted with an acid radical other than a sulfo group is particularly preferred, and the case where one of R 51 and R 52 represents an alkyl group substituted with an acid radical other than a sulfo group and the other represents an alkyl group substituted with a sulfo group is most preferred.
  • the alkyl group represented by R 51 or R 52 may be substituted or unsubstituted, for example, an unsubstituted alkyl group having from 1 to 18, preferably from 1 to 7, and particularly preferably from 1 to 4, carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), and a substituted alkyl group having from 1 to 18, preferably from 1 to 7, and particularly preferably from 1 to 4, carbon atoms [examples of the substituents include, e.g.
  • an aryl group having from 6 to 12 carbon atoms e.g., phenyl, p-chlorophenyl, p-tolyl
  • an unsaturated hydrocarbon group having from 2 to 6 carbon atoms e.g., vinyl
  • an alkoxyl group having from 1 to 7 carbon atoms e.g., methoxy, ethoxy, 2-methoxyethoxy, benzyloxy
  • an aryloxy group having from 6 to 12 carbon atoms e.g., phenoxy, 1-naphthoxy
  • an alkylthio group having from 1 to 7 carbon atoms e.g., methylthio
  • the aryl group represented by R 51 or R 52 may be substituted or unsubstituted, for example, an unsubstituted aryl group having from 6 to 20, preferably from 6 to 15, and more preferably from 6 to 10, carbon atoms (e.g., phenyl, 1-naphthyl), and a substituted aryl group having from 6 to 26, preferably from 6 to 21, and more preferably from 6 to 16, carbon atoms [examples of the substituents include each substituent described above in the substituted alkyl group (an aryl group, an unsaturated hydrocarbon group, a carboxyl group, a sulfo group, a sulfato group, a cyano group, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), a hydroxyl group, a mercapto group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthi
  • the heterocyclic group represented by R 51 or R 52 may be substituted or unsubstituted, for example, an unsubstituted heterocyclic group having from 1 to 20, preferably from 1 to 15, and more preferably from 1 to 10, carbon atoms (e.g., pyrrole, furan, thiophene), and a substituted azole group having from 1 to 26, preferably 1 to 21, and more preferably 1 to 16, carbon atoms
  • substituents include each substituent described above in the substituted alkyl group (an aryl group, an unsaturated hydrocarbon group, a carboxyl group, a sulfo group, a sulfato group, a cyano group, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), a hydroxyl group, a mercapto group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group,
  • R 51 and R 52 preferably represent, an alkyl group substituted with a group having an acid radical or a dissociable proton (specifically, a carboxyl group, a sulfo group, a phosphoric acid group, a boric acid group, an alkylsulfonylcarbamoyl group (e.g., methanesulfonylcarbonyl), an acylcarbamoyl group (e.g., acetylcarbamoyl), an acylsulfamoyl group (e.g., acetylsulfamoyl), or an alkylsulfonylsulfamoyl group (e.g., methanesulfonylsulfamoyl)), and more preferably represents a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group
  • L 51 , L 52 and L 53 each represents a methine group, which may be a substituted or unsubstituted methine group.
  • Example of the substituents include the substituents described above in the substituted alkyl group represented by R 51 or R 52 .
  • n 51 represents 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and more preferably 0 or 1.
  • L 52 and L 53 are repeated but they may be or may not be the same.
  • L 51 preferably represents an unsubstituted methine group
  • L 51 and L 53 each preferably represents an unsubstituted methine group
  • L 52 preferably represents a methine group substituted with an unsubstituted alkyl group (e.g., methyl, ethyl, propyl).
  • L 52 more preferably represents a methine group substituted with an ethyl group.
  • M 51 represents a counter ion, which is required for neutralizing the ion charge.
  • M 51 is included in the formula for showing the presence of cation or anion. It is depended on the substituent whether a dye is cation or anion, or the dye has a net ion charge or not.
  • Examples of the cation include inorganic ions such as a hydrogen ion, alkali metal ions (e.g., Na, K, and Li ions) and alkaline earth metal ions (e.g., Ca ion), organic ions such as ammonium ions (e.g., ammonium, tetraalkyl ammonium, pyridinium and ethylpyridinium ions) .
  • inorganic ions such as a hydrogen ion, alkali metal ions (e.g., Na, K, and Li ions) and alkaline earth metal ions (e.g., Ca ion)
  • organic ions such as ammonium ions (e.g., ammonium, tetraalkyl ammonium, pyridinium and ethylpyridinium ions) .
  • anion may be either of inorganic and organic ions, and include halide ions (fluoride, chloride, bromide and iodide ions), substituted arylsulfonic acid ions (e.g., p-toluene sulfonic acid ion, p-chlorobenzene sulfonic acid ion), aryldisulfonic acid ions (e.g., 1, 3-benzene sulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfonic acid ions (e.g., methyl sulfuric acid ion), a sulfonic acid ion, a thiocyanic acid ion, a perchloric acid ion, a tetrafluoroboric acid ion, a picric acid ion, an acetic acid ion, a trifluoromethane sulfonic acid
  • Examples of the preferred cation include a sodium ion, a potassium ion, a triethylammonium ion, a tetraethylammonium ion, a pyridinium ion, an ethylpyridinium ion and a methylpyridinium ion.
  • Examples of the preferred anion include a perchloric acid, a iodide ion, a bromide ion, and a substituted arylsulfonic acid ion (e.g., p-toluen sulfonic acid ion).
  • m 51 represents a number of 0 or higher necessary to neutralize the charge in the molecule, and when an inner salt is formed, m 51 represents 0. m 51 preferably represents a number of from 0 to 4.
  • the methine dye represented by formula (XX) is more preferably represented by the following formula (XXI).
  • Y 71 represents an atomic group necessary to form a furan ring or a pyrrole ring as defined for Y 51 .
  • X 71 and X 72 each represents an oxygen atom, a sulfur atom, or a nitrogen atom.
  • R 71 and R 72 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
  • L 71 , L 72 and L 73 each represents a methine group.
  • n 71 represents 0, 1, 2, 3 or 4.
  • M 71 represents a counter ion, and m 71 represents a number of 0 or higher necessary to neutralize the charge in the molecule.
  • V 71 , V 72 , V 73 and V 74 each represents a hydrogen atom or a substituent.
  • Y 71 has the same meaning as Y 51 described above, and the similar ones are preferred, and two carbon atoms to which Y 71 is condensed may be bonded by a single bond or a double bond, preferably a double bond.
  • X 71 and X 72 each has the same meaning as X5 1 and X 52 described above, and the similar ones are preferred.
  • R 71 and R 72 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, each has the same meaning as R 51 and R 52 described above, and the similar ones are preferred.
  • L 71 , L 72 and L 73 each represents a methine group, each has the same meaning as L 51 , L 52 and L 53 described above, and the similar ones are preferred.
  • n 71 represents 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and more preferably 0 or 1.
  • LLa: CH- LLb: -wherein A represents a methyl group, an ethyl group or a propyl group, preferably an ethyl group.
  • M 71 represents a counter ion, and m 71 represents a number of 0 or higher necessary to neutralize the charge in the molecule, and they have the same meaning as M 51 and m 51 described above. It is particularly preferred that M 71 represents a cation, and preferred cations are a sodium ion, a potassium ion, a triethylammonium ion, a pyridinium ion and an N-ethylpyridinium ion.
  • V 71 , V 72 , V 73 and V 74 each represents a hydrogen atom or a substituent.
  • two contiguous substituents may be linked to each other to form a saturated or unsaturated condensed ring but it is not preferred particularly to form an unsaturated condensed ring in view of photographic performances. Further, it is also preferred not to form a saturated condensed ring.
  • V 71 and V 74 represent a hydrogen atom
  • V 72 and V 73 each represents a hydrogen atom, an alkyl group (e.g., methyl), an aryl group (e.g., phenyl), an aromatic heterocyclic group (e.g., 1-pyrrolyl), an alkoxyl group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group, an acyl group (e.g., acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), or a halogen atom (e.g., fluorine, chlorine, bromine, iodine) .
  • an alkyl group e.g., methyl
  • an aryl group e.g., phenyl
  • an aromatic heterocyclic group e.g., 1-pyrrolyl
  • an alkoxyl group e.g., meth
  • V 72 more preferably represents a hydrogen atom and V 73 more preferably represents a methyl group, a methoxy group, a cyano group, an acetyl group, a methoxycarbonyl group, or a halogen atom, still more preferably a halogen atom, particularly preferably a fluorine atom, a chlorine atom or a bromine atom, and most preferably a fluorine atom or a chlorine atom.
  • the methine dye represented by formula (XXI) when used in a red-sensitive emulsion layer, it is preferred that the methine chain (L 71 , L 72 , L 73 , n 71 ) represents theabove-describedLLb (wherein Apreferably represents an ethyl group), either X 71 or X 72 represents an oxygen atom and the other represents a sulfur atom, and Y 71 represents a pyrrole ring or a furan ring substituted with a halogen atom (preferably a chlorine atom or a bromine atom).
  • A preferably represents an ethyl group
  • X 71 or X 72 represents an oxygen atom and the other represents a sulfur atom
  • Y 71 represents a pyrrole ring or a furan ring substituted with a halogen atom (preferably a chlorine atom or a bromine atom).
  • R 71 and R 72 each represents a sulfoalkyl group, a carboxyalkyl group or an alkanesulfonylcarbamoylalkyl group, all of V 71 , V 72 and V 74 represent a hydrogen atom, V 73 represents an alkyl group (e.g., methyl), an alkoxyl group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group, an acyl group (e.g., acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), or a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably a methyl group, a methoxy group, a cyano group, an acetyl group, a methoxycarbonyl group or a halogen atom, particularly preferably a
  • the methine dye represented by formula (XXI) is used in a green-sensitive emulsion layer
  • the methine chain (L 71 , L 72 , L 73 , n 71 ) represents the above-described LLb (wherein A preferably represents an ethyl group), both of X 71 and X 72 represent an oxygen atom, and Y 71 represents a pyrrole ring or a furan ring substituted with a halogen atom (preferably a chlorine atom or a bromine atom).
  • R 71 and R 72 each represents a sulfoalkyl group, a carboxyalkyl group or an alkanesulfonylcarbamoylalkyl group, all of V 71 , V 72 and V 74 represent a hydrogen atom, V 73 represents an alkyl group (e.g., methyl), an aryl group (e.g., phenyl), an aromatic heterocyclic group (e.g., 2-thienyl), an alkoxyl group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group, an acyl group (e.g., acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), or a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably a methyl group, a methoxy group, a cyano
  • the methine dye represented by formula (XXI) is used in a blue-sensitive emulsion layer
  • the methine chain (L 71 , L 72 , L 73 , n 71 ) represents the above-described LLa
  • both of X 71 and X 72 represent a sulfur atom
  • Y 71 represents a pyrrole ring or a furan ring substituted with a halogen atom (preferably a chlorine atom or a bromine atom).
  • R 71 and R 72 each represents a sulfoalkyl group, a carboxyalkyl group or an alkanesulfonylcarbamoylalkyl group, all of V 71 , V 72 and V 74 represent a hydrogen atom, V 73 represents an alkyl group (e.g., methyl), an alkoxyl group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group, an acyl group (e.g., acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), or a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably a methyl group, a methoxy group, a cyano group, an acetyl group, a methoxycarbonyl group or a halogen atom, particularly preferably a
  • sensitizing dyes which are less in residual colors are poor in J-associative property and low in sensitivity, but the sensitizing dyes used according to the present invention are remarkably high in J-associative property and high in sensitivity, although they generate less residual colors.
  • the methine dyes may be directly dispersed in the emulsion, or they may be dissolved in water, a single or mixed solvent of methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N,N-dimethylformamide, and then added to the emulsion.
  • various methods can be used for incorporating dyes into the emulsion, for example, a method in which dyes are dissolved in a volatile organic solvent, the solution is dispersed in water or hydrophilic colloid and this dispersion is added to the emulsion as disclosed in U.S.
  • Patent 3,469,987 a method in which water-insoluble dyes are dispersed in a water-soluble solvent without being dissolved and this dispersion is added to the emulsion as disclosed in JP-B-46-24185 (the term "JP-B" as used herein means an "examined Japanese patent publication"), a method in which dyes are dissolved in acid and this solution is added to the emulsion, or dyes are added to the emulsion as an aqueous solution coexisting with acid or base as disclosed in JP-B-44-23389 , JP-B-44-27555 and JP-B-57-22091 , a method in which dyes are added to the emulsion as an aqueous solution or a colloidal dispersion coexisting with a surfactant as disclosed in U.S.
  • Patents 3,822,135 and 4,006,026 a method in which dyes are directly dispersed in a hydrophilic colloid and the dispersion is added to the emulsion as disclosed in JP-A-53-102733 and JP-A-58-105141 , or a method in which dyes are dissolved using a compound capable of red-shifting and the solution is added to the emulsion as disclosed in JP-A-51-74624 can be used. Further, ultrasonic waves can also be used for dissolution.
  • the time of the addition of the methine dyes to the silver halide emulsion used in the present invention may be at any stage of the preparation of the emulsion recognized as useful hitherto.
  • they may be added at any stage if it is before coating, i.e., before grain formation stage of silver halide grains and/or before desalting stage, during desalting stage and/or after desalting and before beginning of chemical ripening, as disclosed in U.S.
  • the dyes can be used as a single compound alone or in combination with compounds having foreign structures, and they may be divided and added separately, for example, one part of them is added during grain formation stage and the remaining is added during chemical ripening or after the completion of chemical ripening, otherwise one part is added prior to chemical ripening or during ripening stage and the remaining after completion of chemical ripening.
  • the kinds of compounds added separately and combinations of compounds may be varied.
  • the use amount of the methine dyes used according to the present invention varies in accordance with the shape and the size of silver halide grains, but is preferably from 1 ⁇ 10 -2 to 1 ⁇ 10 -8 mol per mol of the silver halide.
  • sensitizing dyes can be used in combination besides the methine dyes used according to the present invention.
  • Sensitizing dyes are often used in combination, in particular, for the purpose of supersensitization. Representative examples thereof are disclosed in U.S. Patents 2,688,545 , 2,977,229 , 3,397,060 , 3,522,052 , 3,527,641 , 3,617,293 , 3,628,964 , 3,666,480 , 3,672,898 , 3,679,428 , 3,703,377 , 3,769,301 , 3,814,609 , 3,837,862 , 4,026,707 , British Patents 1,344,281 , 1,507,803 , JP-B-43-4936 , JP-B-53-12375 , JP-A-52-110618 and JP-A-52-109925 .
  • silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride, and silver chloroiodobromide can be used as silver halide grains in the silver halide photographic material according to the present invention.
  • the silver halide grains contained in the silver halide emulsion for use in the present invention have an average grain size (the grain size herein refers to the diameter of the equivalent circle corresponding to the projected area of the grains, and the number average is taken as the average grain size) of preferably from 0.1 to 2 ⁇ m.
  • a so-called monodispersed emulsion having a variation coefficient (the value obtained by dividing the standard deviation of the grain size distribution by the average grain size) of 20% or less, preferably 15% or less, and more preferably 10% or less, is preferred.
  • a variation coefficient the value obtained by dividing the standard deviation of the grain size distribution by the average grain size
  • the silver halide grains contained in a photographic emulsion may have a regular crystal form, such as cubic, octahedral or tetradecahedral form, an irregular crystal form, such as spherical or plate-like form, or a composite form of these forms.
  • the grains having the above described regular crystal forms preferably account for 50% or more, preferably 70% or more, and more preferably 90% or more.
  • an emulsion in which the proportion of tabular grains having an average aspect ratio (equivalent-circle diameter/thickness) of 5 or more, preferably 8 or more, to the entire grains exceeds 50% as a projected area can also be preferably used.
  • the emulsion for use in the present invention can be prepared according to the methods disclosed, for example, in P. Glafkides, Chimie et Physique Photographique, Paul Montel (1967 ), G. F. Duffin, Photographic Emulsion Chemistry, Focal Press (1966 ), V.L. Zelikman, et al., Making and Coating Photographic Emulsion, Focal Press (1964 ). That is, any process, such as an acid process, a neutral process, and an ammoniacal process, can be used. A single jet method, a double jet method, and a combination of them may be used for reacting a soluble silver salt with a soluble halide, and any of these methods can be used.
  • a method in which silver halide grains are formed in the atmosphere of excessive silver ions may also be used.
  • a so-called controlled double jet method which is one form of a double jet method, in which the pAg of the liquid phase in which the silver halide is formed is maintained constant, may also be used. According to this method, a silver halide emulsion having a regular crystal form and substantially an almost uniform grain size can be obtained.
  • the silver halide emulsions for use in the present invention are generally chemically sensitized.
  • chemical sensitization chemical sensitization using chalcogen sensitizers (typically, sulfur sensitization represented by the addition of labile sulfur compounds, selenium sensitization by selenium compounds, and tellurium sensitization by tellurium compounds can be exemplified), noble metal sensitization represented by gold sensitization, and reduction sensitization are used alone or in combination.
  • chalcogen sensitizers typically, sulfur sensitization represented by the addition of labile sulfur compounds, selenium sensitization by selenium compounds, and tellurium sensitization by tellurium compounds can be exemplified
  • noble metal sensitization represented by gold sensitization
  • reduction sensitization reduction sensitization
  • the silver halide emulsions used according to the present invention can be used in both color photographic materials, such as color papers, color films for photographing, and color reversal films , and black-and-white photographic materials, such as X-ray films, general films for photographing, and photographic films for printing, and preferably used as color photographic materials.
  • color photographic materials such as color papers, color films for photographing, and color reversal films
  • black-and-white photographic materials such as X-ray films, general films for photographing, and photographic films for printing, and preferably used as color photographic materials.
  • a hydrophilic colloid layer for the purpose of preventing irradiation and halation and improving safelight stability.
  • water-soluble dyes which can be used as such a coloring substance, the dyes capable of decoloration by processing (oxonol dyes and cyanine dyes, above all) disclosed in EP-A-0337490 , pages 27 to 76, can be exemplified.
  • a coloring substance disperses regardless of the position where it is added and pervades over the entire constitutional layers of the photographic material by such coloration.
  • Cyan, magenta and yellow couplers are preferably impregnated in a loadable latex polymer (e.g., disclosed in U.S. Patent 4, 203, 716 ) in the presence (or absence) of the high boiling point organic solvents described in the above table, or dissolved in a polymer insoluble in water but soluble in an organic solvent and emulsified and dispersed in a hydrophilic colloid aqueous solution.
  • a loadable latex polymer e.g., disclosed in U.S. Patent 4, 203, 716
  • Cyan, magenta and yellow couplers are preferably impregnated in a loadable latex polymer (e.g., disclosed in U.S. Patent 4, 203, 716 ) in the presence (or absence) of the high boiling point organic solvents described in the above table, or dissolved in a polymer insoluble in water but soluble in an organic solvent and emulsified and dispersed in a hydrophilic colloid aqueous solution
  • polymers insoluble in water but soluble in an organic solvent which can preferably be used in the present invention include homopolymers or copolymers disclosed in U.S. Patent 4,857,449 , from pages 12 to 30.
  • Methacrylate based or acrylamide based polymers are more preferred, in particular, acrylamide based polymers are preferred in the light of color image stability.
  • color image preservability improving compounds disclosed in EP-A-0277589 in combination with the couplers.
  • the use in combination with pyrazoloazole couplers or pyrrolotriazole couplers is preferred.
  • the use of the compound disclosed in the above EP Patent which produces a chemically inactive and substantially colorless compound upon chemically bonding with an aromatic amine developing agent remaining after color development processing and/or the compound disclosed in the above EP Patent which produces a chemically inactive and substantially colorless compound upon chemically bonding with the oxidized product of an aromatic amine color developing agent remaining after color development processing, alone or in combination, is preferred for preventing the generation of stain due to the formation of a colored dye caused by the coupling reaction of the coupler with the color developing agent or the oxidized product thereof remaining in the film, or preventing other side reactions, during preservation after processing.
  • 5-Bromo-2-methylthieno[3,2-d]thiazole was obtained at a yield of 34% by reacting 3-acetylamino-2,5-dibromothiophene (synthesized according to J. Am. Chem. Soc, 1954, 76, 2447 ) with phosphorous pentasulfide in toluene under heat-reflux.
  • 5-Bromo-2-methylthieno[2,3-d]thiazole was obtained at a yield of 96% by adding dropwise bromine to 2-methylthieno[2,3-d]thiazole (synthesized according to J. Heterocyclic Chem., 1983, 20, 113 ) in the presence of sodium acetate in an acetic acid solvent.
  • 5-Chloro-2-methylthieno[2,3-d]thiazole was obtained by making trichloroisocyanuric acid act on the above 2-methylthieno[2,3-d]thiazole in a dichloromethane solvent. Yield: 98%.
  • Orange powder of S-97 was synthesized in the same manner as in Example 4 except for using 3-[5-fluoro-2-(2-ethoxy-1-butenyl)-3-benzoxazolio]propanesulfonate in place of 3-[5-chloro-2-(2-ethoxy-1-butenyl)-3-benzoxazolio]propanesulfonate.
  • oxime was prepared using 2-acetyl-3-hydroxythiophene and hydroxylamine (yield: 88%), and the oxime was further acetylated with acetic anhydride (yield: 69%).
  • the oxime acetate was subjected to treatment with sodium hydroxide in an N, N-dimethylformamide solvent at room temperature, thereby the objective 2-methylthieno[2,3-d]oxazole was obtained (yield: 57%).
  • 4-chloromethyl-2-methylthiazole was synthesized with 1,3-dichloroacetone and thioacetamide as starting materials.
  • the above-obtained 4-chloromethyl-2-methylthiazole was converted to a 4-hydroxymethyl body by dilute sulfuric acid, and then introduced into a 4-formyl body by oxidation of manganese dioxide (yield to this point: 62%).
  • 5-Ethoxycarbonyl-2-methylpyrrolo[3,2-d]thiazole was obtained by making ethyl azidoacetate act on the above product in the presence of sodium ethoxide and further heating in xylene (yield: 31%) .
  • a multilayer color photographic material was prepared as Sample No. 101 by coating each layer having the following composition on an undercoated cellulose triacetate film support having a thickness of 127 ⁇ m.
  • the numeral corresponding to each component indicates the addition weight per m 2 .
  • the functions of the compounds added are not limited to the use described.
  • First Layer Antihalation Layer Black Colloidal Silver silver amount: 0.28 g Gelatin 2.20 g Ultraviolet Absorber U-1 0.27 g Ultraviolet Absorber U-3 0.08 g Ultraviolet Absorber U-4 0.08 g High Boiling Point Organic Solvent Oil-1 0.29 g Coupler C-9 0.12 mg
  • Second Layer Interlayer Gelatin 0.38 g Compound Cpd-K 5.0 mg Ultraviolet Absorber U-2 3.0 mg High Boiling Point Organic Solvent Oil-3 0.06 g Dye D-4 10.0 mg
  • Third Layer Interlayer Yellow Colloidal Silver silver amount: 0.007 g Gelatin 0.40 g
  • Fourth Layer First Red-Sensitive Emulsion Layer Emulsion A silver amount: 0.55 g Emulsion B silver amount: 0.23 g Surface Fogged Fine Grain silver amount: Silver Iodobromide Emulsion (average grain size: 0.11 ⁇ m) 0.07 g Gelatin 1.11 g Coupler C-1 0.04 g Coupler C-2
  • Additives F-1 to F-11 were further added to every emulsion layer in addition to the above components.
  • Gelatin Hardener H-1 and Surfactants W-1, W-3, W-4, W-5 and W-6 for coating and emulsifying were added to every layer in addition to the above components.
  • Photosensitive emulsions used in Sample No. 101 are shown in Table 1 below.
  • Emulsions A, B, I and J comprise triple structure tabular grains having main planes comprising ⁇ 100 ⁇ faces and other emulsions comprise triple structure tabular grains having main planes comprising ⁇ 111 ⁇ faces.
  • Emulsions A, B, E, F, I and P are emulsions whose internal sensitivity is higher than surface sensitivity.
  • Emulsions E, I and P are emulsions comprising silver chloride grains epitaxially grown after chemical sensitization.
  • Emulsions other than A, E and F comprise grains having 50 or more dislocation lines per one grain observed by a transmission electron microscope.
  • Dye E-1 shown below was dispersed according to the following method. That is, water and 70 g of W-4 were added to 1,400 g of a wet cake of the dye containing 30% of water, and the mixture was stirred to obtain a slurry having 30% dye concentration. Next, 1,700 ml of zirconia beads having an average diameter of 0.5 mm was filled in an ultravisco mill (UVM-2) manufactured by Imex Co., the slurry was passed and pulverized at a peripheral speed of about 10 m/sec and discharge amount of 0.5 1/min for 8 hours.
  • UVM-2 ultravisco mill
  • Sample Nos. 102 to 130 were prepared in the same manner as in the preparation of Sample No. 101 except that Sensitizing Dye Sen-2 or Sen-7 in the emulsions used in Sample No. 101 were replaced in equimolar amount as shown in Tables 2 and 3.
  • Sample No. 100 i.e., blank sample
  • Each of the thus-obtained samples was subjected to 20 CMS white light exposure for 1/100 sec. through a gray wedge. The exposed sample was processed according to the processing step shown below and sensitometry was carried out. Further, residual colors were evaluated by subtracting the yellow stain density and magenta stain density of Sample No.
  • composition of each processing solution used was as follows. First Developing Solution Tank Solution Replenisher Pentasodium Nitrilo-N,N,N- 1.5 g 1.5 g trimethylenephosphonate Pentasodium Diethylene- 2.0 g 2.0 g triaminepentaacetate Sodium Sulfite 30 g 30 g Potassium Hydroquinone- 20 g 20 g monosulfonate Potassium Carbonate 15 g 20 g Sodium Bicarbonate 12 g 15 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Potassium Bromide 2.5 g 1.4 g Potassium Thiocyanate 1.2 g 1.2 g Potassium Iodide 2.0 mg Diethylene Glycol 13 g 15 g Water to make 1,000 ml 1,000 ml pH (adjusted with sulfuric acid or potassium hydroxide) 9.60 9.60 Reversal Solution Tank Solution Replenisher Pentasodium Nitrilo-N,N,N-
  • An aqueous solution (1,164 ml) comprised of 0.017 g of KBr and 0.4 g of oxidation-processed gelatin having an average molecular weight of 20,000 was stirred with maintaining the temperature at 35°C.
  • An aqueous solution containing 1.6 g of AgNO 3 , an aqueous solution of KBr and an aqueous solution containing 2.1 g of oxidation-processed gelatin having an average molecular weight of 20,000 were added to the above solution by a triple jet method over 48 seconds. At this time, the silver potential was maintained at 13 mV to the saturated calomel electrode.
  • An aqueous solution of KBr was added thereto, and the silver potential was adjusted to -66 mV, and the temperature was raised to 60°C. After 21 g of succinated gelatin having an average molecular weight of 100,000 was added to the above solution, an aqueous solution containing 5.1 g of NaCl was added. An aqueous solution containing 206.3 g of AgNO 3 and an aqueous solution containing KBr were added thereto by a double jet method over 61 minutes with accelerating the flow rate. At this time, the silver potential was maintained at -44 mV to the saturated calomel electrode.
  • succinated gelatin having an average molecular weight of 100 , 000 was added to the solution to adjust pH to 5.8 and pAg to 8.8 at 40°C, thus a seed emulsion was obtained.
  • the seed emulsion was tabular grain emulsion containing 1 mol of Ag and 80 g of gelatin per kg of the emulsion, and having an average equivalent-circle diameter of 1.46 ⁇ m, an equivalent-circle diametyer variation coefficient of 28%, an average thickness of 0.046 ⁇ m, and an average aspect ratio of 32.
  • An aqueous solution containing 43.9 g of AgNO 3 , an aqueous solution containing KBr, and an aqueous solution containing gelatin having a molecular weight of 20,000 were mixed just before addition in another chamber equipped with a magnetic coupling induction stirrer disclosed in JP-A-10-43570 , and added to the above emulsion over 25 minutes. At this time, the silver potential was maintained at -40 mV to the saturated calomel electrode.
  • an aqueous solution containing 43.9 g of AgNO 3 , an aqueous solution containing KBr, and an aqueous solution containing gelatin having a molecular weight of 20,000 were mixed just before addition in the same another chamber, and added to the above emulsion over 20 minutes. At this time, the silver potential was maintained at -40 mV to the saturated calomel electrode.
  • an aqueous solution containing 42.6 g of AgNO 3 , an aqueous solution containing KBr, and an aqueous solution containing gelatin having a molecular weight of 20,000 were mixed just before addition in the same another chamber, and added to the above emulsion over 17 minutes.
  • the silver potential was maintained at -20 mV to the saturated calomel electrode, and then the temperature was lowered to 55°C.
  • the silver potential was adjusted to -55 mV, and an aqueous solution containing 7.1 g of AgNO 3 , an aqueous solution containing 6.9 g of KI, and an aqueous solution containing gelatin having a molecular weight of 20,000 were mixed just before addition in the same another chamber, and added to the above emulsion over 5 minutes.
  • an aqueous solution containing 66.4 g of AgNO 3 and an aqueous solution containing KBr were added to the above emulsion by a double jet method over 30 minutes at constant flow rate.
  • Potassium iridium hexachloride and yellow prussiate of potash were added en route.
  • the silver potential was maintained at 30 mV to the saturated calomel electrode.
  • the emulsion was subjected to ordinary washing, and then gelatin was added to adjust pH to 5.8 and pAg to 8.8 at 40°C. The thus-obtained emulsion was designated Emulsion b.
  • Emulsion b was a tabular grain emulsion having an average equivalent-circle diameter of 3.3 ⁇ m, an equivalent-circle diameter variation coefficient of 21%, an average thickness of 0.090 ⁇ m and an average aspect ratio of 37. Tabular grains having an equivalent-circle diameter of 3.3 ⁇ m or more and a thickness of 0.090 ⁇ m or less accounted for 70% or more of the entire projected area of Emulsion b.
  • Emulsion b was heated at 56°C, and after the sensitizing dye shown in Table 4 was added in an amount of 1.1 ⁇ 10 -3 mol/mol Ag, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N,N-dimethylselenourea were added and the emulsion was optimally chemically sensitized, and stirred for 60 minutes.
  • the sensitizing dye was used as the solid fine particle dispersion prepared according to the method disclosed in JP-A-11-52507 . That is, 0.8 weight parts of sodium nitrate and 3.2 weight parts of sodium sulfate were dissolved in 43 parts of ion exchange water, 13 weight parts of the sensitizing dye was added to the above solution, and dispersed by means of dissolver blades at 2, 000 rpm for 20 minutes on the condition of 60°C, thereby a solid dispersion of the sensitizing dye was obtained.
  • the density of each processed sample was measured, i.e., Sample Nos. 201 to 206 were measured through a red filter, Sample Nos. 207 to 209 were measured through a green filter, and Sample Nos. 210 to 214 were measured through a blue filter respectively and sensitivity was evaluated.
  • the reciprocal of the exposure amount giving density of fog density + 0.2 is taken as sensitivity, and sensitivity of each sample is shown in a relative value taking the value of Sample No. 201 as 100 with Sample Nos. 201 to 206, taking the value of Sample No. 207 as 100 with Sample Nos. 207 to 209, and taking the value of Sample No. 210 as 100 with Sample Nos. 210 to 214.
  • the sensitizing dye formed a J-association body having absorption maximum at about 605 nm in Sample No. 206, and at about 487 nm in Sample No. 213, and each sensitizing dye showed similar spectral sensitivity distribution to that of absorption.
  • samples in Table 5 were subjected to color development processing in the same manner as above (ordinarily processed samples) as one group, and the samples were subjected to sufficient washing processing (that is, the same processing was performed except that the time of washing (2) in the processing step was changed to 30 minutes) to completely remove the remaining sensitizing dyes (washing-processed samples) as the other group, each sample was not subjected to exposure. Since the samples did not undergo exposure, development did not occur and image-forming dyes were not formed.
  • the spectrum by transmission mode of from 360 to 700 nm of each sample was recorded with a spectrophotometer.
  • the difference spectrum of the ordinarily processed sample and the washing-processed sample was taken.
  • the absorption of the difference spectrum means the amount of the retained dye, i.e., the residual color of the sensitizing dye.
  • the residual color of each sample is shown in a relative value of the absorbance of the peak wavelength of each sample taking the absorbance of the peak wavelength of Sample No. 201 as 100 with Sample Nos. 201 to 206, taking the absorbance of the peak wavelength of Sample No. 207 as 100 with Sample Nos. 207 to 209, and taking the absorbance of the peak wavelength of Sample No. 210 as 100 with Sample Nos. 210 to 214.
  • pressure resistance test was performed as follows. A needle having a diameter of 0.1 mm was put on the above sample before exposure and 5 g of load was applied to the needle and the needle was moved at a rate of 600 mm/min. (pressure processing). The difference in density between the part where pressure processing was performed and the part where pressure processing was not performed (pressure marks) of the sample which had been development-processed without undergoing exposure was measured with a micro-densitometer having an aperture diameter of 10 ⁇ m.
  • the sample containing the sensitizing dye used according to the present invention is also excellent in pressure marks (i.e., pressure resistance).
  • an aqueous solution of silver nitrate (containing 71 g of silver nitrate) and an NaCl aqueous solution (containing 24.2 g of NaCl, 1.39 g of KI and 12 mg of yellow prussiate of potash) were added to the reaction mixture at an accelerated flow rate over 14 minutes.
  • the temperature of the reaction solution was raised to 75 °C over 20 minutes, and an aqueous solution of silver nitrate (containing 2.9 g of silver nitrate) and a KBr aqueous solution (containing 2.25 g of KBr) were added to the reaction solution at a constant flow rate over 1 minute.
  • Emulsion A was optimally chemically sensitized at 60 °C using Sen-17, Sen-18, Sen-19, S-132 and S-78 shown in Table 6, sodium benzylthiosulfonate, sodium thiocyanate, 1-(5-methylureidophenyl)-5-mercaptotetrazole, sodium thiosulfate and chloroauric acid. TABLE 6 Sample No.
  • the surface of a paper support both surfaces of which were laminated with polyethylene resin was subjected to corona discharge treatment.
  • the support was provided with a gelatin undercoat layer containing sodium dodecylbenzenesulfonate, and further, photographic constitution layers, from the first layer to the seventh layer, described below were coated in order to prepare a silver halide color photographic material samples shown below.
  • the coating solution of each photographic constitution layer was prepared as described below.
  • Each coupler, color image stabilizer and ultraviolet absorber were dissolved in a solvent and ethyl acetate.
  • the solution was emulsified and dispersed in a 10 weight% gelatin aqueous solution containing a surfactant by means of a high speed dissolver, thus an emulsified dispersion was prepared.
  • Ab-1, Ab-2 and Ab-3 were added to each layer so that the total amount became 15.0 mg/m 2 , 60.0 mg/m 2 and 5.0 mg/m 2 , respectively.
  • High silver chloride emulsion used in each photosensitive emulsion layer was as follows.
  • Compound I was added to a red-sensitive emulsion layer in an amount of 3.0 ⁇ 10 -3 mol per mol of the silver halide.
  • 1-(3-methylureidophenyl)-5-mercaptotetrazole was added to a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer in an amount of 3.3 ⁇ 10 -4 mol, 1.0 ⁇ 10 -3 mol and 5.9 ⁇ 10 -4 mol, respectively, per mol of the silver halide.
  • 1-(3-methylureidophenyl)-5-mercaptotetrazole was added to the second layer, the fourth layer, the sixth layer and the seventh layer in an amount of 0.2 mg/m 2 , 0.2 mg/m 2 , 0.6 mg/m 2 and 0.1 mg/m 2 , respectively.
  • 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene was added to a blue-sensitive emulsion layer and a green-sensitive emulsion layer in an amount of 1x10 -4 mol and 2x10 -4 mol respectively, per mol of the silver halide.
  • Copolymer of methacrylic acid and butyl acrylate (weight ratio: 1/1, average molecular weight: from 200,000 to 400,000) was added to a red-sensitive emulsion layer in an amount of 0.05 g/m 2 . Further, disodium catechol-3,5-disulfonate was added to the second layer, the fourth layer and the sixth layer in an amount of 6 mg/m 2 , 6 mg/m 2 and 18 mg/m 2 , respectively.
  • the constitution of each layer is described below.
  • the numeral represents the coating amount (g/m 2 ).
  • the numeral for an emulsion represents the coating amount in terms of silver.
  • Polyethylene resin-laminated paper [a white pigment (TiO 2 , content: 16 weight%, ZnO, content: 4 weight%), a brightening agent (13 mg/m 2 of 4,4'-bis (5-methylbenzoxazolyl) stilbene), and 96 mg/m 2 of a bluish dye (ultramarine) were added to the polyethylene resin of the first layer side].
  • Coated Sample Nos. 301 to 304 were prepared by using emulsions shown in Table 6 in the blue-sensitive layer of the photographic material having the above layer constitution.
  • YAG solid state laser oscillation wavelength: 946 nm
  • GaAlAs oscillation wavelength: 808.5 nm
  • YVO 4 solid state laser oscillation wavelength: 1,064 nm
  • GaAlAs oscillation wavelength: 808.5 nm
  • AlGaInP oscillation wavelength: 680 nm, manufactured by Matsushita Densan Co., Ltd., Type No.
  • Each of three laser beams was made to be able to successively scanning expose a color photographic paper transferring vertically to scanning direction by a polygonal mirror the intensity of which was modulated by AOM.
  • the temperature of semiconductor laser was maintained constant using Peltier element.
  • scanning exposure was performed at 600 dpi, and every beam diameter of B, G and R measured with a beam diameter meter (1180GP manufactured by Beam Scan Co., U.S.A.) was 65 ⁇ m (circular beams showing the difference in diameters in the main scanning direction/sub scanning direction of within 1%).
  • the thus-exposed samples were processed by CP45X processing (manufactured by Fuji Photo Film Co., Ltd.).
  • the reflection density of each processed color sample was measured using a TCD type densitometer (manufactured by Fuji Photo Film Co., Ltd.). Sensitivity was expressed as the logarithm of the exposure amount required to give color density of fog density + 1.0. Sensitivity of the blue-sensitive layer of each sample is shown in Table 7. In Table 7, sensitivity of each sample is shown in a relative value taking the value of Sample No. 301 as 0.00. A positive value shows that sensitivity is high.
  • Pressuremarks (i.e., pressure resistance) test was performed as follows. A needle having a diameter of 0.1 mm was put on each of the above samples and 10 g of load was applied to the needle and the needle was moved at a rate of 600 mm/min. (pressure processing). The difference in density between the part where pressure processing was performed and the part where pressure processing was not performed (pressure marks) of the sample which had been development-processed without undergoing exposure was measured with a micro-densitometer having an aperture diameter of 10 ⁇ m. The results obtained are shown in Table 7. TABLE 7 Sample No.
  • a tabular silver iodobromide emulsion was prepared according to the method of preparing Emulsion D in Example 5 of JP-A-8-29904 and this was designated Emulsion Q.
  • Multilayer color photographic materials were prepared according to the method of preparation of Sample No. 101 in Example 5 of JP-A-8-29904 .
  • Sample Nos. 401 and 402 were prepared by replacing Emulsion D in the fifth layer of Sample No. 101 in Example 5 of JP-A-8-29904 with Emulsion Q, and further replacing ExS-1, 2 and 3 with Sensitizing Dye Sen-10 (5.0 ⁇ 10 -4 mol/Ag mol) or Sensitizing Dye S-31 (5.0 ⁇ 10 -4 mol/Ag mol).
  • each sample was exposed for 1/100 sec. through an optical wedge and a red filter with Fuji FW type sensitometer (a product of Fuji Photo Film Co., Ltd.), color development processing was performed using the same processing step and processing solutions as in Example 1 of JP-A-8-29904 and cyan density was measured.
  • Sensitivity was a reciprocal of exposure amount required to give density of fog density + 0.2 and expressed as a relative value.
  • Sample No. 402 showed high sensitivity of 113 as compared with sensitivity 100 (control) of Sample No. 401. Sample No. 402 also showed less residual colors after processing.
  • Emulsion 1 in Example 1 of JP-A-7-92601 the spectral sensitizing dyes were replaced with Sensitizing Dye Sen-10 (8 ⁇ 10 -4 mol/Ag mol) or Sensitizing Dye S-31 (8 ⁇ 10 -4 mol/Ag mol) to prepare tetradecahedral silver iodobromide emulsions, the thus-obtained emulsions were designated Emulsion R and Emulsion S.
  • Emulsion 1 in Example 1 of JP-A-7-92601 the silver potential during the second double jet was changed from +65 mV to +115 mV, further, the spectral sensitizing dyes were replaced with Sensitizing Dye Sen-12 (8 ⁇ 10 -4 mol/Ag mol) or Sensitizing Dye S-76 (8 ⁇ 10 -4 mol/Ag mol) to prepare cubic silver iodobromide emulsions, the thus-obtained emulsions were designated Emulsion T and Emulsion U.
  • Multilayer color photographic materials were prepared according to the method of preparation of Sample No. 401 in Example 4 of JP-A-7-92601 .
  • Emulsion 1 in the ninth layer of Sample No. 401 in Example 4 of JP-A-7-92601 was replaced with Emulsion R or Emulsion S, the thus-obtained samples were designated Sample Nos. 411 and 412.
  • Emulsion 1 in the ninth layer of Sample No. 401 in Example 4 of JP-A-7-92601 was replaced with Emulsion T or Emulsion U, and these samples were designated Sample Nos. 413 and 414.
  • Octahedral silver bromide internal latent image type direct positive emulsion and hexagonal tabular silver bromide internal latent image type direct positive emulsion were prepared in the same manner as in the preparation of Emulsions 1 and 5 in Example 1 of JP-A-5-313297 and these emulsions were named Emulsion V and Emulsion W.
  • Emulsion F in Example 2 of JP-A-4-142536 red-sensitive sensitizing dye (S-1) was not added before sulfur sensitization, in addition to sulfur sensitization using triethylthiourea, chloroauric acid was used in combination and optimally gold-sulfur sensitized, and after gold-sulfur sensitization, Sensitizing Dye Sen-10 (2 ⁇ 10 -4 mol/Ag mol) or Sensitizing Dye S-31 (2 ⁇ 10 -4 mol/Ag mol) was added, the thus-obtained silver chlorobromide emulsions were designated Emulsions X and Y.
  • Multilayer color photographic papers were prepared in the same manner as in the preparation of Sample No. 20 in Example 1 of JP-A-6-347944 .
  • the emulsion in the fifth layer of Sample No. 20 in Example 1 of JP-A-6-347944 was replaced with Emulsion X or Y, these samples were designated Sample Nos. 431 and 432.
  • Tabular silver chloride emulsions were prepared in the same manner as in the preparation of Emulsion A in Example 1 of JP-A-8-122954 .
  • Chemical sensitization (B) in Example 1 of the same patent Sensitizing Dye-1 and Dye-2 were replaced with Sensitizing Dye Sen-10 (2 ⁇ 10 -4 mol/Ag mol) or Sensitizing Dye S-31 (2 ⁇ 10 -4 mol/Ag mol), the thus-obtained emulsions were designated Emulsion ZA and Emulsion ZB.
  • Coated samples were prepared by replacing the emulsion in Example 1 of JP-A-8-122954 with Emulsion ZA or Emulsion ZB and an emulsion layer and a surface protective layer were coated in combination on both sides of the support by a simultaneous extrusion method similar to in Example 1, these samples were designated Sample Nos. 441 and 442.
  • the coated silver amount per one side was 1.75 g/m 2 .
  • Tabular silver chloride emulsion was prepared in the same manner as in the preparation of Emulsion D in Example 2 of JP-A-8-227117 except that Sensitizing Dye-2 and Dye-3 were not added. This emulsion was designated Emulsion ZC.
  • Coated samples were prepared in the same manner as in the preparation of Coated Sample No. F in Example 3 of JP-A-8-227117 .
  • Emulsion F in Coated Sample No. F in Example 3 of JP-A-8-227117 was replaced with Emulsion ZC, and Sensitizing Dye-1 in Coated Sample No. F in Example 3 was replaced with Sensitizing Dye Sen-12 (5 ⁇ 10 -4 mol/Ag mol) or Sensitizing Dye S-76 (5 ⁇ 10 -4 mol/Ag mol), the thus-obtained samples were designated Sample Nos. 451 and 452.
  • samples were exposed for 1/100 second through an optical wedge and a blue filter using Fuji FW type sensitometer (a product of Fuji Photo Film Co., Ltd.), subjected to Fuji Photo Film CN16 processing and photographic characteristics were compared.
  • Fuji FW type sensitometer a product of Fuji Photo Film Co., Ltd.
  • Sensitivity was a reciprocal of exposure amount required to give a density of fog + 0.2 and expressed as a relative value taking the sensitivity of Sample No. 451 as 100.
  • Sample No. 452 showed such high sensitivity of 124, and also showed less residual colors after processing.
  • Octahedral silver chloride emulsion was prepared in the same manner as in the preparation of Emulsion F in Example 3 of JP-A-8-227117 , this was designated Emulsion ZD.
  • Coated samples were prepared in the same manner as in the preparation of Coated Sample No . F in Example 3 of JP-A-8-227117 .
  • Emulsion F and Sensitizing Dye-1 in Coated Sample No. F in Example 3 of JP-A-8-227117 were replaced with Emulsion ZD and Sensitizing Dye Sen-12 (5 ⁇ 10 -4 mol/Ag mol) or Sensitizing Dye S-76 (5 ⁇ 10 -4 mol/Ag mol), the thus-obtained samples were designated Sample Nos. 461 and 462.
  • Tabular grain emulsions were prepared in the same manner as in the preparation of Emulsion CC disclosed in European Patent 0699950 , and in chemical sensitization Sensitizing Dye Sen-12 was added in an amount of 5 ⁇ 10 -4 mol/Ag mol and chemical sensitization was performed, then Sen-12 was added in an amount of 3 ⁇ 10 -4 mol/Ag mol, thereafter, further, Sen-12 was added in an amount of 3 ⁇ 10 -4 mol/Ag mol, this emulsion was designated Emulsion ZE, or S-76 was added in an amount of 5 ⁇ 10 -4 mol/Ag mol and chemical sensitization was performed, then S-76 was added in an amount of 3 ⁇ 10 -4 mol/Ag mol, thereafter, further, S-76 was added in an amount of 3 ⁇ 10 -4 mol/Ag mol, this emulsion was designated Emulsion ZF.
  • Coated samples were prepared in the same manner as in the preparation of the coated samples in the example of European Patent 0699950 , and a sample in which Emulsion ZE was used was designated Sample No. 471, and ZF was used was designated Sample No. 472.
  • the thus-prepared samples were subjected to exposure and development in the same manner as in European Patent 0699950 and photographic characteristics were compared.
  • Sensitivity was a reciprocal of exposure amount required to give a density of fog + 0.2 and expressed as a relative value taking the sensitivity of Sample No. 471 as 100.
  • Sample No. 472 showed such high sensitivity of 136, and also showed less residual colors after processing.
  • Sample No. 101 in Example 8 was prepared and designated Sample No. 501.
  • Sample Nos. 502 to 516 were prepared by replacing sensitizing dye Sen-2 or Sen-7 used in the emulsion of Sample No. 501 with equimolar amount of the dye shown in Table 8 and Table 9, and Sample No. 500 (blank sample) was prepared by excluding both dyes.
  • Each piece of the samples thus obtained was subjected to 20 CMS white light exposure for 1/100 sec. through a gray wedge, then processed by the same processing step and same processing solutions as in Example 8, and sensitometry was performed.
  • the yellow stain density and the magenta stain density of blank Sample No. 500 were subtracted from the yellow stain density and magenta stain density of each piece of the samples after processing and residual color was evaluated.
  • the stain density was measured using a densitometer Status A, a product of X-RITE Co.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Claims (5)

  1. Photographisches Silberhalogenidmaterial, umfassend mindestens einen Methinfarbstoff, dargestellt durch die folgende Formel (XX):
    Figure imgb0247
     worin Y51 eine Gruppe von Atomen ist, die erforderlich ist, um einen Furanring oder einen Pyrrolring zu bilden, wobei zusammen mit den Ringen, die X51 enthalten, eine Struktur gebildet wird, die durch die Formel (3a), (3b) oder (3c) dargestellt wird:
    Figure imgb0248
     worin Xa ein Sauerstoffatom oder ein Stickstoffatom (N-Rw) ist; Rw ist ein Wasserstoffatom oder ein einwertiger Substituent; Va ist ein einwertiger Substituent, ausgewählt aus einer Methylgruppe, einer Methoxygruppe, einer Cyanogruppe und einem Halogenatom; Vb ist ein Wasserstoffatom; Vc und Vd sind Wasserstoffatome oder einwertige Substituenten, wobei mindestens einer der Reste Vc und Vd ein einwertiger Substituent ist, ausgewählt aus einer Methylgruppe, einer Methoxygruppe, einer Cyanogruppe und einem Halogenatom; X51 und X52 bedeuten jeweils ein Sauerstoffatom, ein Schwefelatom oder ein Stickstoffatom; Y52 ist eine Gruppe von Atomen, die erforderlich ist, um einen Benzolring oder einen 5- oder 6-gliedrigen ungesättigten heterocyclischen Ring zu bilden, der mit einem anderen 5- oder 6-gliedrigen carbocyclischen oder heterocyclischen Ring kondensiert sein kann oder der substituiert sein kann, und zwei Kohlenstoffatome, an die Y52 kondensiert ist, können über eine Einfachbindung oder eine Doppelbindung gebunden sein; R51 und R52 bedeuten jeweils eine substituierte oder unsubstituierte Alkylgruppe, eine substituierte oder unsubstituierte Arylgruppe oder eine substituierte oder unsubstituierte heterocyclische Gruppe; L51, L52 und L53 bedeuten jeweils eine Methingruppe; n51 ist 0, 1, 2, 3 oder 4; M51 ist ein Gegenion; und m51 bedeutet 0 oder eine größere Zahl und ist eine Zahl, die erforderlich ist, um die Ladung in dem Molekül zu neutralisieren, mit der Maßgabe, dass der Methinfarbstoff nicht
    Figure imgb0249
     ist.
  2. Photographisches Silberhalogenidmaterial nach Anspruch 1, wobei R51 und R52 in der Formel (XX) jeweils eine Alkylgruppe bedeuten, die mit einem Säurerest substituiert ist.
  3. Photographisches Silberhalogenidmaterial nach Anspruch 2, wobei eine der Gruppen R51 und R52 eine Alkylgruppe ist, die mit einem Säurerest substituiert ist, der keine Sulfogruppe ist, und die andere Gruppe ist eine Alkylgruppe, die mit einer Sulfogruppe substituiert ist.
  4. Photographisches Silberhalogenidmaterial nach Anspruch 1, wobei Y52 in der Formel (XX) eine Gruppe von Atomen ist, die erforderlich ist, um einen Benzolring zu bilden.
  5. Photographisches Silberhalogenidmaterial nach einem der Ansprüche 1 bis 4, wobei Va ein Chloratom ist.
EP01124350A 2001-04-17 2001-10-23 Photographisches Silberhalogenidmaterial enthaltend einen Methinfarbstoff Expired - Lifetime EP1251395B1 (de)

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