EP1251395A1 - Photographisches Silberhalogenidmaterial und Methinfarbstoff - Google Patents

Photographisches Silberhalogenidmaterial und Methinfarbstoff Download PDF

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Publication number
EP1251395A1
EP1251395A1 EP01124350A EP01124350A EP1251395A1 EP 1251395 A1 EP1251395 A1 EP 1251395A1 EP 01124350 A EP01124350 A EP 01124350A EP 01124350 A EP01124350 A EP 01124350A EP 1251395 A1 EP1251395 A1 EP 1251395A1
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Prior art keywords
group
ring
atom
substituted
condensed
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English (en)
French (fr)
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EP1251395B1 (de
Inventor
Tetsuo Nakamura
Takanori Hioki
Katsuhisa Ohzeki
Naoyuki Hanaki
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Fujifilm Corp
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Fuji Photo Film Co Ltd
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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.
  • 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.
  • Examples of the 5-membered unsaturated heterocyclic rings formed by Y 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 include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyran ring, and a thiopyran
  • Y 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 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 is condensed may be a sigle bond or a double bond. Particularly, a double bond is preferred.
  • the 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z may be condensed with a carbocyclic ring such as a benzene ring, a cyclohexene ring, or a naphthalene ring, or a heterocyclic ring such as a pyrazine ring or a thiophene ring.
  • Z preferably represents an oxazole ring, a thiazole ring, a selenazole ring, an imidazole ring, a 2-pyridine ring, or a 4-pyridine ring.
  • Z more preferably represents an oxazole ring, a thiazole ring, an imidazole ring, or a pyridine ring, still more preferably represents an oxazole ring or a thiazole ring, and particularly preferably a thiazole ring.
  • the alkyl group represented by R 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), a carboxyl group, a sulfo group,
  • the aryl group represented by R 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, carbonatoms (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
  • 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, an arylthi
  • the heterocyclic group represented by R 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, an an arylthi
  • R preferably represents 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, a
  • the methine group represented by L 1 or L 2 may have a substituent, and examples of the substituents include each substituent described above in the substituted alkyl group represented by R (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, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a heterocyclic group, an alkylsulfonylcarbamoyl group, etc.) , and an alkyl group (which
  • p preferably represents 0.
  • D represents a group necessary to form a methine dye, and every methine dye can be formed by D.
  • methine dyes include a cyanine dye, a merocyanine dye, a rhodacyanine dye, a trinuclear merocyanine dye, a holopolar dye, a hemicyanine dye, a styryl dye, etc. These dyes are described in detail in F.M. Harmer, Heterocyclic Compounds - Cyanine Dyes and Related Compounds , John Wiley & Sons, New York, London (1964), D.M. Sturmer, Heterocyclic Compounds - Special Topics in Heterocyclic Chemistry , Chap. 18, Clause 14, pp. 482 to 515.
  • Formulae (XI), (XII) and (XIII) disclosed in U.S. Patent 5,340,694, columns 21 and 22 are preferred as general formulae of the cyanine, merocyanine and rhodacyanine dyes, respectively.
  • the numbers of n12, n15 n17 and n18 are not limited, and they may be an integer of 0 or more (preferably 4 or less).
  • M 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-toluen 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 sufonic 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 tetraehtylammonium 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 represents a number of 0 or more (preferably 0 to 4) necessary for balancing the charge in the molecule.
  • the number is 0.
  • the methine dye represented by formula (I) is more preferably represented by the following formula (IX), (X), (XI) or (XII): wherein Y, R, Z, L 1 , L 2 and p each has the same meaning as in formula (I) ; L 11 , L 12 , L 13 , L 14 and L 15 each represents a methine group; p 11 represents 0 or 1; n 11 represents 0, 1, 2 or 3; Y 11 represents an atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, and Y 11 may further be condensed with other carbocyclic ring or heterocyclic ring; M 11 represents a counter ion; m 11 represents a number of from 0 to 4 necessary to neutralize the charge in the molecule; and R 11 represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group; wherein Y, R, Z, L 1 , L 2 and p each has the same
  • the 5- or 6-membered nitrogen-containing heterocyclic ring represented by Y 11 , Y 14 or Y 15 in formula (IX), (XI) or (XII) may further be condensed with other 5- or 6-membered carbocyclic ring or heterocyclic ring.
  • carbocyclic ring a benzene ring and a naphthalene ring
  • heterocyclic ring a pyrazine ring and a thiophene ring can be exemplified.
  • the heterocyclic rings exemplified as the examples of Z 1 described later are preferably used.
  • Y 12 represents an atomic group necessary to form an acidic nucleus and any form of an acidic nucleus of general merocyanine dyes can be used.
  • An acidic nucleus used in the present invention is defined, for example, by T.H. James, The Theory of the Photographic Process , 4th Ed., p. 198, Macmillan (1977). Specifically, those disclosed in U.S. Patents 3,567,719, 3,575,869, 3,804,634, 3,837,862, 4,002,480, 4,925,777 and JP-A-3-167546 (the term "JP-A" as used herein means an "unexamined published Japanese patent application”)can be exemplified.
  • nuclei When an acidic nucleus forms a 5- or 6-membered nitrogen-containing heterocyclic ring comprising carbon, nitrogen and chalcogen (typically, oxygen, sulfur, selenium, tellurium) atoms, the following nuclei can be exemplified: 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2- or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazolin-5-one, 2-thiooxazoline-2,4-dione, isooxazolin-5-one, 2-thiazolin-4-one, thiazolidin-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indane-1,3-dione, thiophen-3-one, thiophen-3-one-1
  • Y 12 preferably represents hydantoin, 2- or 4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid, and 2-thiobarbituric acid, more preferably hydantoin, 2- or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid, and 2-thiobarbituric acid, and particularly preferably 2- or 4-thiohydantoin, 2-oxazolin-5-one and rhodanine.
  • the 5- or 6-membered nitrogen-containing heterocyclic ring formed by Y 13 or Y 16 is a heterocyclic ring obtained by eliminating an oxo group or a thioxo group from the heterocyclic ring formed by Y 12 , preferably eliminating an oxo group or a thioxo group from hydantoin, 2- or 4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid, or 2-thiobarbituric acid, more preferably eliminating an oxo group or a thioxo group from hydantoin, 2- or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid, or 2-thiobarbituric acid, and particularly preferably eliminating an
  • R 11 , R 12 , R 13 , R 14 , R 15 and R 16 each represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, and examples of the substituents described above in R in the methine dye represented by formula (I) are preferred.
  • L 11 , L 12 , L 13 , L 14 , L 15 , L 16 , L 17 , L 18 , L 19 , L 20 , L 21 , L 22 , L 23 , L 24 , L 25 , L 26 , L 27 , L 28 , L 29 , L 30 and L 31 each represents a methine group, and each methine group may have a substituent, and examples of the substituents include each substituent described above in the substituted alkyl group represented by R in the methine dye represented by formula (I) (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 ary
  • L 11 to L 31 may form a ring together with other methine group, or may form a ring with Y 11 , Y 12 , Y 13 , Y 14 , Y 15 or Y 16 .
  • n 11 , n 12 , n 13 and n 15 preferably represents 0, 1 or 2, more preferably 0 or 1, and particularly preferably 1.
  • n 14 and n 16 preferably represents 0 or 1, more preferably 0 .
  • n 11 , n 12 , n 13 , n 14 , n 15 and n 16 each represents 2 or more, a methine group is repeated but it is not necessary to be the same group.
  • p 11 , p 12 and p 13 each represents 0 or 1, preferably 0.
  • M 11 , M 12 , M 13 , M 14 , m 11 , m 12 , m 13 and m 14 each has the same meaning and the same content, as M and m in the methine dye represented by formula (I).
  • the condensed ring containing Y and Z in the methine dye represented by formula (I) is preferably selected from Y-1 to Y-26, provided that Y-1 to Y-26 may further be condensed with other 5- or 6-membered carbocylic ring or heterocyclic ring, or may have a substituent. Of Y-1 to Y-26, Y-1 to Y-9 are particularly preferred.
  • the methine dye represented by formula (I) is more preferably represented by formula (II) or (III).
  • X 21 and X 22 each represents an oxygen atom, a sulfur atom, or a selenium atom, preferably an oxygen atom or a sulfur atom, and particularly preferably X 21 and X 22 both represent sulfur atoms.
  • V 21 and V 22 may be linked to form a condensed ring, e.g., a benzene ring, a cyclohexene ring, a naphthalene ring, or a thiophene ring, but it is preferred not to form the condensed ring.
  • a condensed ring e.g., a benzene ring, a cyclohexene ring, a naphthalene ring, or a thiophene ring, but it is preferred not to form the condensed ring.
  • V 21 and V 22 a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), a cyano group, a methyl group, a methoxy group, and a methylthio group are preferred, but it is preferred that V 21 and V 22 do not represent hydrogen atoms at the same time.
  • V 21 more preferably represents a hydrogen atom.
  • V 22 more preferably represents a chlorine atom, a bromine atom, an iodine atom, or a cyano group, particularly preferably represents a chlorine atom or a bromine atom, and most preferably a bromine atom.
  • the substituent represented by R is preferably a carboxyalkyl group, a sulfoalkyl group or an alkylsulfonylcarbamoylalkyl group, and particularly preferably a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group or a methanesulfonylcarbamoylmethyl group.
  • X 23 and X 24 each represents an oxygen atom, a sulfur atom, or a selenium atom, preferably an oxygen atom or a sulfur atom, and particularly preferably X 23 and X 24 both represent sulfur atoms.
  • V 23 and V 24 may be linked to form a condensed ring further, e.g., a benzene ring, a cyclohexene ring, a naphthalene ring, or a thiophene ring, but it is preferred not to form the condensed ring.
  • V 23 and V 24 a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), a cyano group, a methyl group, a methoxy group, and a methylthio group are preferred, but it is preferred that V 23 and V 24 do not represent hydrogen atoms at the same time.
  • X 23 represents a sulfur atom
  • V 23 is preferably not a phenyl group and V 24 is preferably not a methyl group.
  • V 24 more preferably represents a hydrogen atom.
  • V 23 more preferably represents a chlorine atom, a bromine atom, an iodine atom, or a cyano group, particularly preferably represents a chlorine atom or a bromine atom, and most preferably a bromine atom.
  • the substituent represented by R is preferably a carboxyalkyl group, a sulfoalkyl group or an alkylsulfonylcarbamoylalkyl group, and particularly preferably a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group or a methanesulfonylcarbamoylmethyl group.
  • Themethine dye representedby formula (II) is particularly preferably represented by formula (VII), and the methine dye represented by formula (III) is particularly preferably represented by formula (VIII).
  • X 31 and X 32 each represents an oxygen atom, a sulfur atom, or a selenium atom, preferably represents an oxygen atom or a sulfur atom.
  • X 31 particularly preferably represents a sulfur atom.
  • V 31 and V 32 each represents a hydrogen atom or a substituent but they do not represent hydrogen atoms at the same time.
  • substituents represented by V 31 and V 32 each substituent described above in the substituted alkyl group represented by R (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, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a heterocyclic group, an alkylsulfonylcarbamo
  • V 31 and V 32 a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine, iodine) , a cyano group, a methyl group, a methoxy group, and a methylthio group are preferred.
  • V 31 more preferably represents a hydrogen atom.
  • V 32 more preferably represents a chlorine atom, a bromine atom, an iodine atom, or a cyano group, particularly preferably represents a chlorine atom or a bromine atom, and most preferably a bromine atom.
  • Y 31 represents an atomic group necessary to form a benzene ring or a 5- or 6-membered unsaturated heterocyclic ring.
  • the 5- or 6-membered unsaturated heterocyclic ring formed by Y 31 each heterocyclic ring described above in Y of the methine dye represented by formula (I) can be exemplified.
  • Y 31 may further form a condensed ring with other 5- or 6-membered carbocyclic ring or heterocyclic ring, but it is preferred not to form the condensed ring.
  • the ring formed by Y 31 is preferably a benzene ring, a pyrrole ring, a furan ring, a thiophene ring, or a pyridine ring, and particularly preferably a benzene ring, a furan ring or a thiophene ring.
  • R 31 and R 32 each is selected from a carboxyalkyl group, a sulfoalkyl group or an alkylsulfonylcarbamoylalkyl group, and each particularly preferably represents a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, or a methanesulfonylcarbamoylmethyl group.
  • n 31 preferably represents 0 or 1.
  • the methine group represented by L 32 , L 33 and L 34 may be substituted or unsubstituted, and examples of the substituents include each substituent described above in the substituted alkyl group represented by R in the methine dye represented by formula (I) (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, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a heterocyclic group, an alkylsulfonyl
  • L 32 preferably represents an unsubstituted methine group.
  • n 31 represents 1
  • L 34 preferably represents an unsubstituted methine group.
  • the substituents of L 33 include an unsubstituted alkyl group, in particular, a methyl group or an ethyl group is preferred.
  • M 31 examples include the same ions as described in M in the methine dye represented by formula (I) .
  • Preferred cations include sodium, potassium, triethylammonium, pyridinium and N-ethylpyridinium ions, and preferred anions include bromide, iodide, p-toluenesulfonate and perchlorate ions.
  • n 31 represents a number of 0 or higher necessary to neutralize the charge in the molecule, and when an inner salt is formed, m 31 represents 0. m 31 preferably represents 0, 1, 2 or 3.
  • a preferred combination is a combination in which X 31 represents a sulfur atom, X 32 represents an oxygen atom or a sulfur atom, Y 31 represents a benzene ring, V 32 represents a chlorine atom, a bromine atom, an iodine atom, or a cyano group, V 31 represents a hydrogen atom, R 31 and R 32 each represents a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, or a methanesulfonylcarbamoylmethyl group, n 31 represents 0, L 32 represents an unsubstituted methine group, M 31 represents an inorganic or organic cation, and m 31 represents 0 or 1.
  • V 32 represents a chlorine atom or a bromine atom
  • R 31 or R 32 represents a 3-sulfopropyl group or a 4-sulfobutyl group, and the other represents a carboxymethyl group or a methanesulfonylcarbamoylmethyl group is particularly preferred.
  • a preferred combination is a combination in which X 31 represents a sulfur atom, X 32 represents an oxygen atom or a sulfur atom, Y 31 represents a benzene ring, V 32 represents a chlorine atom, a bromine atom, an iodine atom, or a cyano group, V 31 represents a hydrogen atom, R 31 and R 32 each represents a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, or a methanesulfonylcarbamoylmethyl group, n 31 represents 1, L 32 and L 34 each represents an unsubstituted methine group, L 33 represents a methine group substituted with a methyl group or an ethyl group, M
  • V 32 represents a chlorine atom or a bromine atom
  • R 31 or R 32 represents a 3-sulfopropyl group or a 4-sulfobutyl group, and the other represents a carboxymethyl group or a methanesulfonylcarbamoylmethyl group is particularly preferred.
  • X 33 and X 34 each represents an oxygen atom, a sulfur atom, or a selenium atom, preferably an oxygen atom or a sulfur atom.
  • X 33 particularly preferably represents a sulfur atom.
  • V 33 and V 34 each represents a hydrogen atom or a substituent but they do not represent hydrogen atoms at the same time.
  • substituents represented by V 33 and V 34 each substituent described above in the substituted alkyl group represented by R (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, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a heterocyclic group, an alkylsulfonylcarbamo
  • V 33 and V 34 a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine, iodine) , a cyano group, a methyl group, a methoxy group, and a methylthio group are preferred.
  • V 34 more preferably represents a hydrogen atom.
  • V 33 more preferably represents a chlorine atom, a bromine atom, an iodine atom, or a cyano group, particularly preferably represents a chlorine atom or a bromine atom, and most preferably a bromine atom.
  • Y 32 represents an atomic group necessary to form a benzene ring or a 5- or 6-membered unsaturated heterocyclic ring.
  • the 5- or 6-membered unsaturated heterocyclic ring formed by Y 32 each heterocyclic ring described above in Y of the methine dye represented by formula (I) can be exemplified.
  • Y 32 may further form a condensed ring with other 5- or 6-membered carbocyclic ring or heterocyclic ring, but it is preferred not to form the condensed ring.
  • the ring formed by Y 32 is preferably a benzene ring, a pyrrole ring, a furan ring, a thiophene ring, or a pyridine ring, and particularly preferably a benzene ring, a furan ring or a thiophene ring.
  • R 33 and R 34 each is selected from a carboxyalkyl group, a sulfoalkyl group or an alkylsulfonylcarbamoylalkyl group, and each particularly preferably represents a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, or a methanesulfonylcarbamoylmethyl group.
  • n 32 preferably represents 0 or 1.
  • the methine group represented by L 35 , L 36 and L 37 may be substituted or unsubstituted, and examples of the substituents include each substituent described above in the substituted alkyl group represented by R in the methine dye represented by formula (I) (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, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a heterocyclic group, an alkylsulfonyl
  • L 35 preferably represents an unsubstituted methine group.
  • L 37 preferably represents an unsubstituted methine group.
  • the substituents of L 36 include an unsubstituted alkyl group, in particular, a methyl group or an ethyl group is preferred.
  • M 33 examples include the same ions as described in M in the methine dye represented by formula (I) .
  • Preferred cations include sodium, potassium, triethylammonium, pyridinium and N-ethylpyridinium ions, and preferred anions include bromide, iodide, p-toluenesulfonate andperchlorate ions.
  • m 33 represents a number of 0 or higher necessary to neutralize the charge in the molecule, and when an inner salt is formed, m 33 represents 0.
  • m 33 preferably represents 0, 1, 2 or 3, more preferably 0 or 1.
  • a preferred combination is a combination in which X 33 represents a sulfur atom, X 34 represents an oxygen atom or a sulfur atom, Y 33 represents a benzene ring, V 33 represents a chlorine atom, a bromine atom, an iodine atom, or a cyano group, V 34 represents a hydrogen atom, R 33 and R 34 each represents a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, or a methanesulfonylcarbamoylmethyl group, n 32 represents 0, L 35 represents an unsubstituted methine group, M 32 represents an inorganic or organic cation, and m 32 represents 0 or 1.
  • V 33 represents a chlorine atom or a bromine atom
  • R 33 or R 34 represents a 3-sulfopropyl group or a 4-sulfobutyl group, and the other represents a carboxymethyl group or a methanesulfonylcarbamoylmethyl group is particularly preferred.
  • a preferred combination is a combination in which X 33 represents a sulfur atom, X 34 represents an oxygen atom or a sulfur atom, Y 33 represents a benzene ring, V 33 represents a chlorine atom, a bromine atom, an iodine atom, or a cyano group, V 34 represents a hydrogen atom, R 33 and R 34 each represents a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, or a methanesulfonylcarbamoylmethyl group, n 32 represents 1, L 35 and L 37 each represents an unsubstituted methine group, L 36 represents a methine group substituted with a methyl group or an ethyl group, M
  • V 33 represents a chlorine atom or a bromine atom
  • R 33 or R 34 represents a 3-sulfopropyl group or a 4-sulfobutyl group, and the other represents a carboxymethyl group or a methanesulfonylcarbamoylmethyl group is particularly preferred.
  • the methine dye represented by formula (I) is further preferably represented by formula (IV).
  • each heterocyclic ring described above in Y of the methine dye represented by formula (I) can be exemplified.
  • Y 1 may further form a condensed ring with other 5- or 6-membered carbocyclic ring or heterocyclic ring, but it is preferred not to form the condensed ring.
  • the ring formed by Y 1 is preferably a pyrrole ring, a furan ring, a thiophene ring, or a pyridine ring, and particularly preferably a pyrrole ring, a furan ring or a thiophene ring.
  • the 5- or 6-membered nitrogen-containing heterocyclic ring formed by Z 1 may be condensed with a carbocyclic ring such as a benzene ring, a cyclohexene ring, or a naphthalene ring, or a heterocyclic ring such as a pyrazine ring, a pyrrole ring, a furan ring or a thiophene ring.
  • a carbocyclic ring such as a benzene ring, a cyclohexene ring, or a naphthalene ring
  • a heterocyclic ring such as a pyrazine ring, a pyrrole ring, a furan ring or a thiophene ring.
  • Preferred examples of the rings represented by Z 1 include a thiazoline ring, a thiazole ring, a benzothiazole ring, an oxazoline ring, an oxazole ring, abenzoxazole ring, a selenazoline ring, a selenazole ring, a benzoselenazole ring, a 3,3-dialkylindolenine ring (e.g., 3,3-dimethylindolenine), an imidazoline ring, an imidazole ring, a benzimidazole ring, a 2-pyridine ring, a 4-pyridine ring, a 2-quinoline ring, a 4-quinoline ring, a 1-isoquinoline ring, a 3-isoquinoline ring, an imidazo[4,5-b]quinoxaline ring, an oxadiazole ring, a thiadiazole ring, a tetrazol
  • a benzoxazole ring a benzothiazole ring, a benzimidazole ring and a quinoline ring
  • a benzoxazole ring and a benzothiazole ring a benzothiazole ring
  • a benzothiazole ring a benzothiazole ring
  • R 1 and R 2 each group described above in R in the methine dye represented by formula (I) can be exemplified.
  • R 1 and R 2 each preferably represents 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., methanesulfonylsul
  • R 3 preferably represents an unsubstituted alkyl group, particularly preferably a methyl group or an ethyl group.
  • Each methine group represented by L a , L b , L 3 , L 4 , L 5 , L 6 and L 7 may be substituted or unsubstituted, and examples of the substituents include each substituent described above in the substituted alkyl group represented by R in the methine dye represented by formula (I) (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, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, a sulfamoyl group
  • L a and L b each preferably represents an unsubstituted methine group.
  • n 1 represents an integer of 0 or higher, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2, and still more preferably 0 or 1.
  • p 1 represents 0 or 1, preferably 0.
  • M 1 examples include the same ions as described in M in the methine dye represented by formula (I) .
  • Preferred cations include sodium, potassium, triethylammonium, pyridinium and N-ethylpyridinium ions, and preferred anions include bromide, iodide, p-toluenesulfonate and perchlorate ions.
  • n 1 represents a number of 0 or higher necessary to neutralize the charge in the molecule, and when an inner salt is formed, m 1 represents 0. m 1 preferably represents 0, 1, 2 or 3.
  • the methine dye represented by formula (IV) it is preferred that at least one of the atomic group constituting the heterocyclic ring Y 1 (exclusive of the substituents on the ring) and X 1 contains an oxygen atom.
  • the X 1 moiety may form an oxazole ring, or the Y 1 moiety may form a furan ring, an oxazole ring, an isooxazole ring, or a pyran ring.
  • Preferred is the case in which the X 1 moiety forms an oxazole ring or the case in which the Y 1 moiety form a furan ring.
  • the methine dye represented by formula (IV) is used as a blue-sensitive dye
  • the methine dye is more preferably represented by formula (V).
  • X 3 and X 4 each represents an oxygen atom, a sulfur atom, or a selenium atom, preferably an oxygen atom or a sulfur atom.
  • each heterocyclic ring described above in Y of the methine dye represented by formula (I) can be exemplified.
  • Y 4 may further form a condensed ring with other 5- or 6-membered carbocyclic ring or heterocyclic ring, but it is preferred not to form the condensed ring.
  • the ring formed by Y 4 is preferably a pyrrole ring, a furan ring, a thiophene ring, or a pyridine ring, and particularly preferably, pyrrole ring, a furan ring or a thiophene ring.
  • Y 4 may form a benzene ring or a naphthalene ring, preferably a benzene ring.
  • R 4 and R 5 each group described above in R in the methine dye represented by formula (I) can be exemplified.
  • R 4 and R 5 each preferably represents 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 group).
  • M 2 examples include the same ions as described in M in themethine dye representedby formula (I).
  • Preferred cations include sodium, potassium, triethylammonium, pyridinium and N-ethylpyridinium ions, and preferred anions include bromide, iodide, p-toluenesulfonate and perchlorate ions.
  • m 2 represents a number of 0 or higher necessary to neutralize the charge in the molecule, and when an inner salt is formed, m 2 represents 0. m 2 preferably represents 0, 1 or 2.
  • a preferred combination in formula (V) is a combination in which X 3 and X 4 each represents an oxygen atom or a sulfur atom, Y 3 represents a furan ring, Y 4 represents a furan ring, a thiophene ring or a benzene ring, R 4 and R 5 each represents a sulfoalkyl group, a carboxyalkyl group, or a methanesulfonylcarbamoylalkyl group, M 2 represents an inorganic or organic cation, and m 2 represents 0 or 1, more preferably X 3 and X 4 each represents a sulfur atom, and R 4 and R 5 each represents a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, or a methanesulfonylcarbamoylmethyl group.
  • R 4 or R 5 represents a 3-sulfopropyl group or a 4-sulfobutyl group, and the other represents a carboxymethyl group or a methanesulfonylcarbamoylmethyl group is particularly preferred.
  • the methine dye represented by formula (IV) is used as a green-sensitive dye or a red-sensitive dye
  • the methine dye is more preferably represented by formula (VI).
  • X 5 and X 6 each represents an oxygen atom, a sulfur atom, or a selenium atom, and preferably at least one represents an oxygen atom and the other represents an oxygen atom or a sulfur atom.
  • each heterocyclic ring described above in Y of the methine dye represented by formula (I) can be exemplified.
  • Y 5 or Y 6 may further form a condensed ring with other 5-or 6-membered carbocyclic ring or heterocyclic ring, but it is preferred not to form the condensed ring.
  • the ring formed by Y 5 or Y 6 is preferably a pyrrole ring, a furan ring, a thiophene ring, or a pyridine ring, and particularly preferably a pyrrole ring, a furan ring or a thiophene ring.
  • Y 6 may form a benzene ring or a naphthalene ring, preferably a benzene ring.
  • R 6 and R 7 each group described above in R in the methine dye represented by formula (I) can be exemplified.
  • R 6 and R 7 each preferably represents 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., methanesulfonyl)
  • a group having an acid radical or a dissociable proton specifically, a
  • R 8 preferably represents an unsubstituted alkyl group, in particular, a methyl group or an ethyl group.
  • M 3 examples include the same ions as described in M in the methine dye represented by formula (I).
  • Preferred cations include sodium, potassium, triethylammonium, pyridinium and N-ethylpyridinium ions, and preferred anions include bromide, iodide, p-toluenesulfonate and perchlorate ions.
  • n 3 represents a number of 0 or higher necessary to neutralize the charge in the molecule, and when an inner salt is formed, m 3 represents 0. m 3 preferably represents 0, 1 or 2.
  • a preferred combination in formula (VI) is a combination in which either of X 5 or X 6 represents an oxygen atom and the other represents a sulfur atom, Y 5 represents a furan ring or a thiophene ring, Y 6 represents a furan ring, a thiophene ring or a benzene ring, R 6 and R 7 each represents a sulfoalkyl group, a carboxyalkyl group, or a methanesulfonylcarbamoylalkyl group, R 8 represents a methyl group or an ethyl group, M 3 represents an inorganic or organic cation, and m 3 represents 1, particularly preferably Y 5 represents a thiophene ring, Y 6 represents a benzene ring, and R 6 and R 7 each represents a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobut
  • R 6 or R 7 represents a 3-sulfopropyl group or a 4-sulfobutyl group, and the other represents a carboxymethyl group or a methanesulfonylcarbamoylmethyl group is particularly preferred.
  • Y preferably represents a furan ring or a pyrrole ring, which may be condensed with other 5- or 6-membered carbocyclic or heterocyclic ring or may have a substituent.
  • the thiophene ring may further be condensed with other 5- or 6-membered carbocyclic or heterocyclic ring or may have a substituent, and the case where the thiophene ring is substituted with at least one substituent is preferred.
  • an alkyl group e.g., methyl, trifluoromethyl
  • 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 e.g., an acyl group (e.g., acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), and a halogen atom (e.g., fluorine, chlorine, bromine, iodine)
  • the more preferred substituents are 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., methyl,
  • D represents a group necessary to form a methine dye, preferably a group to form a cyanine dye, and more preferably to form a dye represented by the above formula (IX).
  • Y which represents a furan ring or a pyrrole ring
  • Z the rings including Z: wherein Xa represents an oxygen atom or a nitrogen atom (N-Rw).
  • the furan ring or pyrrole ring moiety may further be substituted, or may be condensed with a ring.
  • the preferred is the case where the furan ring or pyrrole ring moiety is substituted with a monovalent substituent.
  • (1a) and (1b) the case where only one monovalent substituent substitutes on the carbon atom contiguous to Xa is preferred.
  • (1c) the case where one monovalent substituent substitutes on at least either one carbon atom contiguous to Xa is preferred.
  • 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 e.g., an acyl group (e.g., acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), and a halogen atom (e.g.
  • fluorine, chlorine, bromine, iodine are exemplified, 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, and the most preferred is a chlorine atom.
  • 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.
  • the thiophene ring moiety may further be substituted, provided that the thiophene ring moiety is substituted with at least one substituent.
  • the case where only one monovalent substituent substitutes on the carbon atom contiguous to the S atom is preferred.
  • the case where one monovalent substituent substitutes on at least either one carbon atom contiguous to the S atom is preferred.
  • 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)
  • a halogen atom e.g., fluorine, chlorine, bromine, iodine
  • the more preferred substituents are a methoxy group, a cyano group, an acetyl group, a methoxycarbonyl group and a halogen atom
  • the still more preferred are a cyano group and a halogen atom
  • the still further preferred is a halogen atom
  • the particularly preferred are a fluorine atom, a chlorine atom and a bromine atom
  • the most preferred is
  • (2a), (2b) and (2c) are preferred.
  • a cyanine dye represented by formula (IX) is formed by D, and at this time, the case where at least one of R and R 11 represents an alkyl group substituted with an acid radical is preferred, and the case where both R and R 11 represent an alkyl group substituted with an acid radical is more preferred.
  • An acid racial is described below.
  • An acid racial is a group having a dissociable proton.
  • a sulfo group a carboxyl group, a sulfato group, a -CONHSO 2 - group (sulfonylcarbamoyl, carbonylsulfamoyl), a -CONHCO- group (carbonylcarbamoyl), an -SO 2 NHSO 2 - group (sulfonylsulfamoyl), a sulfonamido group, a sulfamoyl group, a phosphato group, a phosphono group, a phoronic acid group, and a phenolic hydroxyl group which dissociable protons by their pKa and the ambient pH can be exemplified.
  • proton-dissociable groups capable of dissociating 90% or more protons at pH 5 to 11 are preferred.
  • Preferred alkyl group ⁇ Qa ⁇ T 1 T 1 :
  • Qa may be any group so long as it satisfies the above condition, preferably comprised of an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom.
  • Qa preferably represents a linking group having from 0 to 10, preferably from 1 to 8, more preferably from 1 to 5 carbon atoms, consisting in combination of one or more of an alkylene group (e.g., methylene, ethylene, trimethylene, tetramethylene, pentamethylene, methyltrimethylene), an alkenylene group (e.g., ethenylene, propenylene), an alkynylene group (e.g., ethynylene, propynylene), an amido group, an ester group, a sulfoamido group, a sulfonic ester group, a ureido group, a sulfonyl group, a sulf
  • linking groups may further be substituted, or may contain a ring (e.g., an aromatic or non-aromatic hydrocarbon ring or a heterocyclic ring).
  • linking groups do not contain a hetero ring and that they are not substituted.
  • Qa represents a divalent linking group having from 1 to 5 carbon atoms consisting in combination of one or more of an alkylene group having from 1 to 5 carbon atoms (e.g., methylene, ethylene, trimethylene, tetramethylene, pentamethylene, methyltrimethylene), an alkenylene group having from 2 to 5 carbon atoms (e.g., ethenylene, propenylene), and an alkynylene group having from 2 to 5 carbon atoms (e.g., ethynylene, propynylene) , and particularly preferably an alkylene group having from 1 to 5 carbon atoms (preferably, e.g., methylene, ethylene, trimethylene, tetramethylene).
  • an alkylene group having from 1 to 5 carbon atoms e.g., methylene, ethylene, trimethylene, tetramethylene
  • an alkylene group having from 1 to 5 carbon atoms e.g., methylene
  • T 1 represents a sulfo group
  • Qa more preferably represents ethylene, trimethylene, tetramethylene, or methyltrimethylene, and particularly preferably trimethylene.
  • T 1 represents a carboxyl group
  • Qa more preferably represents methylene, ethylene, or trimethylene, and particularly preferably methylene.
  • Qa more preferably represents methylene, ethylene, or trimethylene, and particularly preferably methylene.
  • Ra, Rb, Rc and Rd each represents an alkyl group, an aryl group, a heterocyclic group, an alkoxyl group, an aryloxy group, a heterocyclic oxy group, or an amino group, and the following groups can be preferably exemplified.
  • Ra, Rb, Rc and Rd each more preferably represents a methyl group, an ethyl group, or a hydroxyethyl group, and particularly preferably a methyl group.
  • carboxyl groups and dissociable nitrogen atoms may be described in a form not dissociated (e.g., COOH, NH) or may be described in a dissociated form (e.g., COO - , N - ).
  • a dissociable group practically becomes a dissociating state or a non-dissociating state depending upon the atmosphere such as pH in which the dye is present.
  • a cation When a cation is present as the counter ion, it may be described as, e.g., (COO - , Na + ), (N - , Na + ). In a non-dissociated state, it is described as (COOH), (NH), but regarding a cationic compound of the counter ion as a proton, it can also be described as (COO - , H + ), (N - , H + ).
  • the case where at least one of R and R 11 represents an alkyl group substituted with an acid radical other than a sulfo group is particularly preferred, and the case where one of R and R 11 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 preferred alkyl groups substituted with an acid radical other than a sulfo group are alkyl groups substituted with a carboxyl group, a -CONHSO 2 - group, an -SO 2 NHCO- group, a -CONHCO- group or an -SO 2 NHSO 2 - group.
  • the preferred alkyl groups having a sulfo group are a 3-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group and a 2-sulfoethyl group, and the more preferred alkyl group is a 3-sulfopropyl group.
  • the preferred alkyl groups having an acid radical other than a sulfo group a carboxymethyl group and a methanesulfonylcarbamoylmethyl group are particularly preferred.
  • R and R 11 is the case where either one represents a carboxymethyl group or a methanesulfonylcarbamoylmethyl group, and the other represents a 3-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group or a 2-sulfoethyl group, and the more preferred combination is the case where either one represents a carboxymethyl group or a methanesulfonylcarbamoylmethyl group, and the other represents a 3-sulfopropyl group.
  • the methine dye represented by formula (I) is more preferably represented by formula (XX) or (XXX).
  • Y 51 represents a furan ring or a pyrrole ring which may be condensed with other 5- or 6-membered carbocyclic or heterocyclic ring or may have a substituent, and two carbon atoms to which Y 51 is condensed may be bonded by a single bond or a double bond, preferably a double bond.
  • a dye having a furan ring or a pyrrole ring as represented by formula (XX) has particularly excellent photographic performances.
  • Y 51 which represents a furan ring or a pyrrole ring are shown below together with the rings including X 51 : wherein Xa has the same meaning as Xa in the above formulae (1a) , (1b) and (1c), which represents an oxygen atom or a nitrogen atom (N-Rw) and the similar ones are preferred.
  • Va, Vb, Vc and Vd each represents a hydrogen atom or a monovalent substituent, Va and Vb may be bonded to each other to form a ring, and Va and Vb preferably represents a hydrogen atom or a monovalent substituent.
  • Va and Vb preferably represents a hydrogen atom or a monovalent substituent.
  • Va represents a monovalent substituent and Vb represents a hydrogen atom is preferred.
  • 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
  • (3a), (3b) and (3c) are preferred.
  • X 51 and X 52 each represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a nitrogen atom, or a carbon atom.
  • the nitrogen atom can be preferably expressed by -N (Rx) - and the carbon atomby -C (Ry) (Rz) -, wherein Rx, Ry andRz each represents a hydrogen atom or a monovalent substituent, preferably the same alkyl group, aryl group or heterocyclic group as represented by R, more preferably the alkyl group.
  • X 51 and X 52 each preferably represents an oxygen atom, a sulfur atom, or a nitrogen atom, and more 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, and as the 5- or 6-membered unsaturated heterocyclic ring formed by Y 52 , the heterocyclic rings described in Y in the methine dye represented by formula (I) above can be exemplified, which may further form a condensed ring together with other 5- or 6-membered carbocyclic or heterocyclic ring, but it is preferred that a third condensed ring should not be present.
  • Y 52 is preferably a benzene ring, a pyrrole ring, a furan ring, or a thiophene ring (as the pyrrole, furan and thiophene rings, the above-described (1a), (1b), (1c), (2a), (2b), (2c), (3a), (3b), (3c) and the later-described (4a), (4b) and (4c) 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.
  • halogen atom e.g., fluorine, chlorine, bromine, iodine
  • a halogen atom e.g., fluorine, chlorine, bromine, iodine
  • a halogen atom e.g., fluorine, chlorine, bromine, iodine
  • 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.
  • R 51 and R 52 represents an alkyl group substituted with an acid radical
  • 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
  • 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.
  • L 51 , L 52 and L 53 each represents a methine group, which may be a substituted or unsubstituted methine group, and each has the same meaning as L 11 , L 12 and L 13 described above.
  • 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 and has the same meaning as M described above.
  • the preferred examples of cations include a sodium ion, a potassium ion, a triethylammonium ion, a tetraethylammonium ion, a pyridinium ion, an ethylpyridinium ion and a methylpyridinium ion.
  • the preferred examples of anions include a perchloric acid ion, an iodide ion, a bromide ion, a substituted arylsulfonic acid ion (e.g., p-toluenesulfonic 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 a furan ring or a pyrrole ring which may be condensed with other 5- or 6-membered carbocyclic or heterocyclic ring or may have a substituent, and two carbon atoms to which Y 71 is condensed may be bonded by a single bond or a double bond.
  • X 71 and X 72 each represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a nitrogen atom, or a carbon 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 represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a nitrogen atom, or a carbon atom, each has the same meaning as X 51 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.
  • n71 - represents the following LLa or LLb is particularly preferred.
  • 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 and m 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) is used in a red-sensitive emulsion layer
  • the methine chain (L 71 , L 72 , L 73 , n 71 ) represents the above-described LLb (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).
  • 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
  • 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 halogen
  • 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
  • Y 61 represents a thiophene ring which may be condensed with other 5- or 6-membered carbocyclic or heterocyclic ring or may have a substituent but is substituted with at least one halogen atom, and two carbon atoms to which Y 61 is condensed may be bonded by a single bond or a double bond, preferably a double bond.
  • a dye having a thiophene ring substituted with at least one halogen atom as represented by formula (XXX) has particularly excellent photographic performances.
  • Y 61 which represents a thiophene are shown below together with the rings including X 61 : wherein Ve, Vf, Vg and Vh each represents a hydrogen atom or a monovalent substituent, provided that at least one of Ve and Vf and at least one of Vg and Vh each represents a halogen atom.
  • Ve represents a halogen atom
  • Vf represents a hydrogen atom.
  • at least one of Vg and Vh is substituted with a halogen atom.
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is preferred, a chlorine atom or a bromine atom is more preferred and a chlorine atom is particularly preferred.
  • 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 e.g., an acyl group (e.g., acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl)
  • a halogen atom e.g., fluorine, chlorine, bromine, iodine
  • a halogen atom e.g., fluorine, chlorine, bromine, iodine
  • (4a), (4b) and (4c) are preferred.
  • X 61 and X 62 each represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a nitrogen atom, or a carbon atom.
  • the nitrogen atom can be preferably expressed by -N (Rx) - and the carbon atomby-C (Ry) (Rz) -, wherein Rx, Ry andRz each represents a hydrogen atom or a monovalent substituent, preferably the same alkyl group, aryl group or heterocyclic group as represented by R, more preferably the alkyl group.
  • X 61 and X 62 each preferably represents an oxygen atom, a sulfur atom, or a nitrogen atom, and more preferably an oxygen atom or a sulfur atom.
  • Y 62 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 62 is condensed may be bonded by a single bond or a double bond, preferably a double bond.
  • Y 62 represents an atomic group necessary to form a benzene ring or a 5- or 6-membered unsaturated heterocyclic ring, and as the 5- or 6-membered unsaturated heterocyclic ring formed by Y 62 , the heterocyclic rings described in Y in the methine dye represented by formula (I) above can be exemplified, which may further form a condensed ring together with other 5- or 6-membered carbocyclic or heterocyclic ring, but it is preferred that a third condensed ring should not be present.
  • Y 62 is preferably a benzene ring, a pyrrole ring, a furan ring, or a thiophene ring (as the pyrrole, furan and thiophene rings, the above-described (1a), (1b), (1c), (2a), (2b), (2c), (3a), (3b), (3c), (4a), (4b) and (4c) 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 61 and R 62 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
  • R and R 11 the case where at least one of R 61 and R 62 represents an alkyl group substituted with an acid radical is preferred, the case where R 61 and R 62 both represent an alkyl group substituted with an acid radical is more preferred, the case where at least one of R 61 and R 62 , 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 61 and R 62 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.
  • L 61 , L 62 and L 63 each represents a methine group, and each has the same meaning as L 51 , L 52 and L 53 described above.
  • n 61 represents 0 or 1, preferably 1.
  • L 61 preferably represents an unsubstituted methine group
  • L 61 and L 63 each preferably represents an unsubstituted methine group
  • L 62 preferably represents a methine group substituted with an unsubstituted alkyl group (e.g., methyl, ethyl, propyl).
  • L 62 more preferably represents a methine group substituted with an ethyl group.
  • M 61 represents a counter ion
  • m 61 represents a number of 0 or higher necessary to neutralize the charge in the molecule, and they have the same meaning as M and m described above.
  • the methine dye represented by formula (XXX) is preferably represented by formula (XXXI) or (XXXII).
  • V 61 represents a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.
  • Y 61 , X 61 , X 62 , Y 62 , R 61 , R 62 , L 61 , L 62 , L 63 , n 61 , M 61 and m 61 each has the same meaning as defined in formula (XXX) and the similar ones are preferred.
  • L 61 preferably represents an unsubstituted methine group
  • L 61 and L 63 each preferably represents an unsubstituted methine group
  • L 62 preferably represents a methine group substituted with an unsubstituted alkyl group (e.g., methyl, ethyl, propyl).
  • L 62 more preferably represents a methine group substituted with an ethyl group.
  • the methine dye represented by formula (XXXI) is preferably represented by formula (XXXIa) or (XXXIb).
  • the methine dye represented by formula (XXXII) is preferably represented by formula (XXXIIa) or (XXXIIb), more preferably formula (XXXIIb).
  • V 85 represents a halogen atom
  • X 81 and X 82 each represents an oxygen atom or a sulfur atom
  • R 81 and R 82 each represents an alkyl group substituted with an acid radical
  • V 81 , V 82 , V 83 and V 84 each represents a hydrogen atom or a substituent
  • M 81 represents a counter ion
  • m 81 represents a number of 0 or higher necessary to neutralize the charge in the molecule.
  • V 85 represents a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.
  • a halogen atom e.g., fluorine, chlorine, bromine, iodine
  • R 81 and R 82 each represents an alkyl group substituted with an acid radical.
  • R and R 11 the case where at least one of R 81 and R 82 , which are alkyl groups substituted with an acid radical, represents an alkyl group substituted with an acid radical other than a sulfo group is preferred, and the case where one of R 81 and R 82 represents an alkyl group substituted with an acid radical other than a sulfo group (preferably a carboxyl group or an alkanesulfonylcarbamoyl group) and the other represents an alkyl group substituted with a sulfo group is more preferred.
  • R 81 and R 82 represent a carboxymethyl group or a methanesulfonylcarbamoylmethyl group
  • R 81 represents a carboxymethyl group or a methanesulfonylcarbamoylmethyl group
  • R 81 represents a methanesulfonylcarbamoylmethyl group
  • M 81 represents a counter ion, and m 81 represents a number of 0 or higher necessary to neutralize the charge in the molecule, and they have the same meaning as M and m described above. It is particularly preferred that M 81 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 81 , V 82 , V 83 and V 84 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 81 and V 84 represent a hydrogen atom
  • V 82 and V 83 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., me
  • V 82 more preferably represents a hydrogen atom and V 83 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.
  • V 95 represents a halogen atom
  • X 91 and X 92 each represents an oxygen atom or a sulfur atom
  • R 91 and R 92 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group
  • a 91 represents amethyl group, an ethyl group or a propyl group
  • V 91 , V 92 , V 93 and V 94 each represents a hydrogen atom or a substituent
  • M 91 represents a counter ion
  • m 91 represents a number of 0 or higher necessary to neutralize the charge in the molecule.
  • V 95 represents a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.
  • R 91 and R 92 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 61 and R 62 described above, and the similar ones are preferred.
  • a 91 represents a methyl group, an ethyl group or a propyl group, preferably a methyl group or an ethyl group, and particularly preferably an ethyl group.
  • M 91 represents a counter ion, and m 91 represents a number of 0 or higher necessary to neutralize the charge in the molecule, and they have the same meaning as M and m described above. It is particularly preferred that M 91 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 91 , V 92 , V 93 and V 94 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 91 and V 94 represent a hydrogen atom
  • V 92 and V 93 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., me
  • V 92 more preferably represents a hydrogen atom and V 93 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 (XXX) is used in a red-sensitive emulsion layer
  • the dye is represented by formula (XXXIb) or (XXXIIb) (A 91 preferably represents an ethyl group)
  • X 91 or X 92 represents an oxygen atom and the other represents a sulfur atom
  • V 95 represents a chlorine atom or a bromine atom.
  • R 91 and R 92 each represents a sulfoalkyl group, a carboxyalkyl group or an alkanesulfonylcarbamoylalkyl group, all of V 91 , V 92 and V 94 represent a hydrogen atom, V 93 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
  • the methine dye represented by formula (XXX) is used in a green-sensitive emulsion layer
  • the dye is represented by formula (XXXIb) or (XXXIIb) (A 91 preferably represents an ethyl group)
  • both of X 91 and X 92 represent an oxygen atom
  • V 95 represents a chlorine atom or a bromine atom.
  • R 91 and R 92 each represents a sulfoalkyl group, a carboxyalkyl group or an alkanesulfonylcarbamoylalkyl group, all of V 91 , V 92 and V 94 represent a hydrogen atom, V 93 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
  • the methine dye represented by formula (XXX) is used in a blue-sensitive emulsion layer, it is preferred that the dye is represented by formula (XXXIa) or (XXXIIa), both of X 81 and X 82 represent a sulfur atom, and V 85 represents a chlorine atom or a bromine atom.
  • Formula (XXXIa) is preferred to (XXXIIa).
  • R 81 and R 82 each preferably represents a sulfoalkyl group, a carboxyalkyl group or an alkanesulfonylcarbamoylalkyl group, more preferably either R 81 or R 82 represents an alkyl group substituted with a carboxyl group or an alkanesulfonylcarbamoyl group, and the other represents an alkyl group substituted with a sulfo group, still more preferably either R 81 or R 82 represents a carboxymethyl group or a methanesulfonylcarbamoylmethyl group, particularly preferably R 81 represents a carboxymethyl group or a methanesulfonylcarbamoylmethyl group, and most preferably R 81 represents a methanesulfonylcarbamoylmethyl group.
  • V 81 , V 82 and V 84 represent a hydrogen atom
  • V 83 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 halogen atom, and most preferably a fluorine atom or a chlorine atom
  • M 81 represents an organic or inorganic monovalent cation
  • m 81 represents 0 or
  • sensitizing dyes which are less in residual colors are poor in J-associative property and low in sensitivity, but the sensitizing dyes 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 represented by formula (I) , (II), (III), (IV), (V) , (VI), (VII), (VIII), (XX), (XXI), (XXX), (XXXI), (XXXIa), (XXXIb), (XXXII), (XXXIIa) or (XXXIIb) for use in the present invention can be synthesized according to the methods described in the following literature.
  • the methine dyes represented by formula (I), (II), (III), (IV) , (V), (VI), (VII), (VIII), (XX), (XXI), (XXX), (XXXI), (XXXIa), (XXXIb), (XXXII), (XXXIIa) or (XXXIIb) according to the present invention 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, etc., 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 represented by formula (I) , (II), (III), (IV), (V), (VI) , (VII), (VIII), (XX), (XXI), (XXX), (XXXI), (XXXIa), (XXXIb), (XXXII), (XXXIIa) or (XXXIIb) according to the present invention to the silver halide emulsion of 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. Patents 2,735,766, 3,628,960, 4,183,756, 4,225,666, JP-A-58-184142 and JP-A-60-196749, or immediately before or during chemical ripening, after chemical ripening and before coating as disclosed in JP-A-58-113920. Also, 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 represented by formula (I) , (II), (III) , (IV), (V) , (VI) , (VII) , (VIII) , (XX), (XXI), (XXX), (XXXI), (XXXIa), (XXXIb), (XXXII), (XXXIIa) or (XXXIIb) 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 represented by formula (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (XX), (XXI), (XXX), (XXXI), (XXXIa), (XXXIb), (XXXII), (XXXIIa) or (XXXIIb) 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.
  • 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), and so on. 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 according to the present invention 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 and reduction sensitization are used alone or in combination.
  • the compounds disclosed in JP-A-62-215272, from p. 18, right lower column to p. 22, right upper column are preferably used in the chemical sensitization of the present invention.
  • Various compounds and precursors thereof can be added to the silver halide emulsions of the present invention for the purpose of preventing generation of fog or stabilizingphotographic performances during production, storage or photographic processing of the photographic material.
  • the compounds disclosed in JP-A-62-215272, from pp. 39 to 72 are preferably used.
  • 5-arylamino-1,2,3,4-thiatriazole compounds (the aryl residue has at least one electron attractive group) disclosed in European Patent 0447647 are also preferably used.
  • the silver halide emulsions produced 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
  • 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.
  • 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 Iodobromide Emulsion (average grain size: 0.11 ⁇ m) silver amount: 0.07 g Gelatin 1.11 g Coupler C-1 0.04 g Coupler C-2 0.09 g
  • 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.
  • 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 l/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-trimethylenephosphonate 1.5 g 1.5 g Pentasodium Diethylene-triaminepentaacetate 2.0 g 2.0 g Sodium Sulfite 30 g 30 g Potassium Hydroquinone-monosulfonate 20 g 20 g 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
  • 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 1.1x10 -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 samples containing the sensitizing dyes according to the present invention are high sensitivity and conspicuously low in residual color as compared with the samples containing comparative dyes.
  • sensitivity is markedly improved in trimethyl cyanine dyes.
  • the samples containing the sensitizing dyes according to the present invention are 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.
  • the surface of a paper support both surfaces of which were laminatedwith 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 3.0x10 -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 3.3x10 -4 mol, 1.0x10 -3 mol and 5.9x10 -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
  • 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) testwasperformed 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. Sample No. Grains Blue Light Exposure Pressure Marks Remarks Fog Sensitivity 301 A 0.04 0.00 0.185 Comparison 302 A 0.04 0.02 0 160 Comparison 303 A 0.03 0.08 0.090 Invention 304 A 0.03 0.05 0.105 Invention
  • the emulsions according to the present invention are high sensitivity, pressure marks are suppressed and stability is improved.
  • 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 according to the present invention showed high sensitivity of 113 as compared with sensitivity 100 (control) of comparative 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. Fin 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 Comparative Sample No. 451 as 100.
  • Sample No. 452 according to the present invention 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/Agmol 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 addedin an amount of 5 ⁇ 10 -4 mol/Agmol 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 according to the present invention 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)
  • Plural Heterocyclic Compounds (AREA)
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  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
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JPH0792601A (ja) 1993-09-20 1995-04-07 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPH0829904A (ja) 1994-07-20 1996-02-02 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤の製造方法
EP0699950A1 (de) 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern und neuer Behandlung von Dotiermitteln
JPH08122954A (ja) 1994-08-30 1996-05-17 Fuji Photo Film Co Ltd ハロゲン化銀乳剤及びそれを用いた感光材料
JPH08227117A (ja) 1994-12-19 1996-09-03 Fuji Photo Film Co Ltd 写真用ハロゲン化銀乳剤の製造方法
JPH1043570A (ja) 1996-08-06 1998-02-17 Fuji Photo Film Co Ltd 撹拌装置
JPH1152507A (ja) 1997-07-31 1999-02-26 Fuji Photo Film Co Ltd 分光増感剤の分散方法及びこれにより得られた分散物
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JPH0792601A (ja) 1993-09-20 1995-04-07 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPH0829904A (ja) 1994-07-20 1996-02-02 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤の製造方法
EP0699950A1 (de) 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern und neuer Behandlung von Dotiermitteln
JPH08122954A (ja) 1994-08-30 1996-05-17 Fuji Photo Film Co Ltd ハロゲン化銀乳剤及びそれを用いた感光材料
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JPH1043570A (ja) 1996-08-06 1998-02-17 Fuji Photo Film Co Ltd 撹拌装置
JPH1152507A (ja) 1997-07-31 1999-02-26 Fuji Photo Film Co Ltd 分光増感剤の分散方法及びこれにより得られた分散物
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