Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
  • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
  • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
  • G03C7/30523—Phenols or naphtols couplers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/34—Couplers containing phenols
  • G03C7/344—Naphtholic couplers

Definitions

• the present invention relates to a silver halide color photosensitive material containing a dye forming coupler which is little in the drop of color density even when a developing treatment is carried out with a weakly oxidative bleaching bath, bleach-fix bath or fatigued bleaching bath, bleach-fix bath and also is excellent in color image preservability after development; and more particularly, the present invention relates to said photosensitive material which is highly sensitive and excellent in graininess, sharpness and color reproducibility.
• a color image is formed by reacting a dye forming coupler with an aromatic primary amine developing agent oxidized by color development after light exposure to a silver halide color photosensitive material.
• a color reproduction method by a subtractive color process is used, and in order to reproduce blue, green and red, dye images of yellow, magenta and cyan (which are the complement colors of blue, green and red) are formed.
• phenol derivatives or naphthol derivatives are mostly employed as a coupler.
• couplers have defects in that a color image produced by color development is low in fastness to heat or light and the decrease in color density is caused when a developing treatment is carried out with a weakly oxidative bleaching bath or fatigued bleaching bath.
• a phenol type cyan coupler having a phenylureido group at 2-position and carbonamido group at 5-position has been proposed.
• These couplers are disclosed in, for example, JP-A-56-65134, JP-A-57-204543, JP-A-57-204544, JP-A-57-204545, JP-A-58-33249 and JP-A-58-33250.
• JP-A as used herein means an "unexamined published Japanese patent -application”
• the coupler having a phenylureido group at 2-position is excellent in the above respects compared with conventionally known phenol type cyan couplers and naphthol type cyan couplers. But it has become clear that these couplers are low in coupling activity with an oxidation product of a development agent to effect a sufficient color density.
• 1-naphthol type cyan couplers having a substituent such as carbonamido group, sulfonamido group and the like at 5-position have been proposed in JP-A-60-237448, JP-A-61-153640 and JP-A-61-145557. Admittedly, these couplers do not decrease in color density when the developing treatment is carried out with a weakly oxidative bleaching (bleach-fix) bath or fatigued bleaching (bleach-fix) bath, are excellent in image preservability after treatment, and are high to some extent in color developability, but are still insufficient in sharpness and graininess.
• a weakly oxidative bleaching (bleach-fix) bath or fatigued bleaching (bleach-fix) bath are excellent in image preservability after treatment, and are high to some extent in color developability, but are still insufficient in sharpness and graininess.
• JP-A-59-149364 discloses a combination of so-called monodispersed emulsion having little fluctuation coefficient in grain diameter of silver halide and a phenol type cyan coupler having phenylureido group at 2-position and acylamino group at 5-position, but it was not satisfactory in respect of sensitivity and graininess.
• JP-A-62-79449 proposes a combination of a naphthol type cyan coupler having arylcarbamoyl group at 2-position and a monodispersed emulsion, and it has become possible to provide the photosensitive material which is highly sensitive, is good in graininess and has no fluctuation of cyan density even when the weakly oxidative bleaching (bleach-fix) bath is used.
• weakly oxidative bleaching bleaching
• An object of the present invention is to provide a silver halide color photosensitive material which is little in the decrease of cyan image density even when a developing treatment is carried out with a weakly oxidative bleaching bath, bleach-fix bath or fatigued bleaching bath, bleach-fix bath.
• Another object of the present invention is to provide a silver halide color photosensitive material which is highly sensitive and excellent in graininess in all the exposure range.
• a further object of the present invention is to provide a silver halide color photosensitive material which is excellent in preservability of cyan image after development treatment.
• a still further object of the present invention is to provide a silver halide color photosensitive material which is excellent in sharpness.
• a still further object of the present invention is to provide a silver halide color photosensitive material which is excellent in color reproducibility.
• a silver halide color photosensitive material comprising a support having thereon at least one silver halide emulsion layer, characterized in that the photosensitive material is provided with at least one silver halide emulsion layer containing a substantially monodispersed silver halide grain and contains a cyan dye forming coupler represented by general formula (A): wherein R2 represents a halogen atom, hydroxyl group, carboxyl group, sulfo group, amino group, cyano group, nitro group, aliphatic group, aromatic group, carbonamido group, sulfonamido group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic sulfonyl group, aromatic sulfony
• the aliphatic group in the present invention indicates a straight, branched or cyclic alkyl group, alkenyl group or alkinyl group, and they may be substituted or unsubstituted.
• the aromatic group indicates a substituted or unsubstituted aryl group and may be a condensed ring.
• the heterocyclic group indicates a substituted or unsubstituted monocyclic ring or condensed ring type heterocyclic group.
• aliphatic group examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, cyclopentyl group, t-pentyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, 2-hexyldecyl group, adamantyl group, trifluoromethyl group, carboxymethyl group, methoxyethyl group, vinyl group, allyl group, hydroxyethyl group, heptafluoropropyl group, benzyl group, phenethyl group, phenoxyethyl group,
• aromatic group examples include phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 4-chlorophenyl group, 4-nitrophenyl group, 4-cyanophenyl group, 4-hydroxyphenyl group, 3-hydroxyphenyl group, 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, p-biphenylyl group, pentafluorophenyl group, 2-methoxyphenyl group, 2-ethoxyphenyl group, 4-methoxyphenyl group, 4-t-butylphenyl group, 4-t-octylphenyl group, 4-carboxyphenyl group, 4-methylsulfonamidophenyl group, 4-(4-hydroxyphenylsulfonyl)phenyl group , 2-n-tetradecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 2-chloroph
• heterocyclic group examples include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-furyl group, 2-thienyl group, 3-thienyl group, 4-quinolyl group, 2-imidazolyl group, 2-benzimidazolyl group, 4-pyrazolyl group, 2-benzothiazolyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, 5-tetrazolyl group, 1,3,4-thiadiazol-2-yl group, 2-prolyl group, 3-triazolyl group, 4-oxazolyl group, 4-thiazolyl group, 2-pyrimidyl group, 1,3,5-triazin-2-yl group, 1,3,4-oxadiazol-2-yl group, 5-pyrazolyl group, 4-pyrimidyl group, 2-pyrazinyl group, succinimido group, phthalimido group, morpholino group, pyrrolidino group, piperidino
• (A) represents an aliphatic group having 1 to 30 carbon atoms, aromatic group having 6 to 30 carbon atoms, heterocyclic group having 1 to 30 carbon atoms, amino group having 0 to 30 carbon atoms [e.g., amino, methylamino, dimethylamino, n-butylamino, anilino, N-(2-n-tetradecyloxyphenyl)amino, pyrrolidino, morpholino, piperidino, 2-ethylhexylamino, n-dodecylamino, N-methyl-N-dodecylamino, 3-dodecyloxypropylamino, 3-(2,4-di-t-pentylphenoxy)propylamino, 4-(2,4-di-t-pentylphenoxy)-butylamino], aliphatic oxy group having 1 to 30 carbon atoms [e.g., methoxy,
• R2 in the general formula (A) represents halogen atom (e.g., fluorine, chlorine, bromine or iodine), hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, amino group having 0 to 30 carbon atoms (e.g., amino, methylamino, dimethylamino, pyrrolidino, anilino), aliphatic group having 1 to 30 carbon atoms, aromatic group having 6 to 30 carbon atoms, carbonamido group having 1 to 30 carbon atoms (e.g., formamido, acetamido, trifluoroacetamido, benzamido), sulfonamido group having 1 to 30 carbon atoms (e.g., methylsulfonamido, trifluoromethylsulfonamido, n-butylsulfonamido, p-tolylsulfonamido), carbamoy
• R3 represents hydrogen atom or R6U wherein R6 represents a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, aromatic group having 6 to 30 carbon atoms, heterocyclic group having 1 to 30 carbon atoms, -OR7, -SR7, -COR8, -PO(R7)2, -PO(-OR7)2, -CO2R7, -SO2R7, -SO2OR7 or imido group having 4 to 30 carbon atoms (e.g., succinimido, maleinimido, phthalimido, diacetylamino), U represents ⁇ N-R9, -CO-, -SO2-, -SO- or a single bond, R7 represents an aliphatic group having 1 to 30 carbon atoms, aromatic group having 6 to 30 carbon atoms or heterocyclic group having 1 to 30 carbon atoms, R8 represents hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, aromatic
• T in the general formula (A) represents hydrogen atom or a group being releaseable upon a coupling reaction with an oxidation product of aromatic primary amine developing agent
• the letter examples are a halogen atom (e.g., fluorine, chlorine, bromine, or iodine), sulfo group, thiocyanato group, isothiocyanato group, selenocyanato group, aliphatic oxy group having 1 to 30 carbon atoms, aromatic oxy group having 6 to 30 carbon atoms, aliphatic thio group having 1 to 30 carbon atoms, aromatic thio group having 6 to 30 carbon atoms, heterocyclic thio group having 1 to 30 carbon atoms, heterocyclic oxy group having 1 to 30 carbon atoms, aromatic azo group having 6 to 30 carbon atoms, heterocyclic group having 1 to 30 carbon atoms, acyloxy group having 1 to 30 carbon atoms (e.g., acetoxy, benzoyloxy), s
• R2 and R3, R3 and T or plural R2's in the general formula (A) may be bonded to each other to form a ring, respectively.
• Bonded examples of R3 to T are -CH2C-, -COO-, etc.
• R4 is an amino group.
• -SO2R4 are sulfamoyl group, N-methylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-di-isopropylsulfamoyl group, N-(3-dodecyloxypropyl)-carbamoyl group, N-[3-(2,4-di-t-pentylphenoxy)propyl]-carbamoyl group, N-[4-(2,4-di-t-pentylphenoxy)butyl]-carbamoyl group, pyrrolidinosulfonyl group, N-phenyl-sulfonyl group, N-(2-butoxyphenyl)carbamoyl group and N-(2-tetradecyloxyphenyl)carbamoyl group.
• Preferable substitution position of R2 is 2- or 4-position in terms of the R3NH- group.
• R6 is an aliphatic group, aromatic group, -OR7 or -SR7, and preferable U is -CO- or -SO2-.
• the aliphatic group are methyl group, trifluoromethyl group, trichloromethyl group, ethyl group, heptafluoropropyl group, t-butyl group, 1-ethylpentyl group, cyclohexyl group, benzyl group, undecyl group, tridecyl group, and 1-(2,4-di-t-pentylphenoxy)propyl group
• examples of the aromatic group are phenyl group, 1-naphthyl group, 2-naphthyl group, 2-chlorophenyl group, 4-methoxyphenyl group, 4-nitrophenyl group, and pentafluorophenyl group
• examples of -OR7 are methoxy group, ethoxy group, is
• R3 is an aliphatic oxycarbonyl group (where R6 is R7O- and U is -CO-) and an aliphatic or aromatic sulfonyl group (where R6 is an aliphatic group or aromatic group and U is -SO2-), and aliphatic oxycarbonyl group is particularly preferable.
• T is hydrogen atom, a halogen atom, an aliphatic oxy group, aromatic oxy group, aliphatic thio group or heterocyclic thio group.
• the aliphatic oxy group are methoxy group, ethoxy group, 2-hydroxyethoxy group, 2-chloroethoxy group, carboxymethoxy group, 1-carboxyethoxy group, methoxyethoxy group, 2-(2-hydroxyethoxy)ethoxy group, 2-methylsulfonylethoxy group, 2-methylsulfonyloxyethoxy group, 2-methylsulfonamidoethoxy group, 2-carboxyethoxy group, 3-carboxypropoxy group, 2-(carboxymethylthio)ethoxy group, 2-(1-carboxytridecylthio)ethoxy group, 1-carboxytridecyl group, N-(2-methoxyethyl) carbamoylmethoxy group, 1-imi
• the coupler shown by the general formula (A) may form a dimer or higher polymer wherein substituent R4, R2, R3 or T is bonded to each other through a divalent or more valent group.
• substituent R4, R2, R3 or T is bonded to each other through a divalent or more valent group.
• carbon number of the above each substituent can be beyond its specified range.
• the coupler shown by the general formula (A) forms a polymer
• its typical example is a homopolymer or copolymer of ethylenic unsaturated addition polymerizable compounds (cyan color forming monomer) having a cyan dye forming coupler residue.
• the polymer contains a repeating unit of the following formula (B), one or more kinds of the cyan color forming repeating unit of the general formula (B) may be contained, and the copolymer may contain one or more kinds of non-color-forming ethylenic monomer as a copolymer component.
• R11 represents hydrogen atom, an alkyl group having 1 to 4 carbon atoms or chlorine atom
• H represents -CONH-, -COO- or a substituted or unsubstituted phenylene group
• I represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group
• J represents -CONH-, -NHCONH-, -NHCOO-, -NHCO-, -OCONH-, -NH-, -COO-, -OCO-, -CO-, -O-, -SO2-, -NHSO2- or -SO2NH-.
• K represents a cyan coupler residue removing a hydrogen atom other than the hydrogen atom of the hydroxyl group at the 1-position of the compound of the general formula (A).
• Copolymers of cyan color forming monomers which provide a coupler unit of general formula (B) and the non-color forming ethylenic monomers indicated below are the preferred polymers.
• non-color-forming ethylenic monomer which do not couple with the oxidation product of aromatic primary amine developing agent are acrylic acid, ⁇ -chloroacrylic acid, ⁇ -alkylacrylic acid (e.g., methacrylic acid), esters or amide derived from these acrylic acid (e.g., acrylamide, methacrylamide, n-butylacryamide, t-butylacrylamide, diacetonacrylamide, N-methylolacrylamide, N-(1,1-dimethyl-2-sulfonatoethyl)acrylamide, N-(3-sulfonatopropyl)acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, acetoacetoxyethyl acrylate, n-hexyl acrylate, 2-ethylhe
• acrylic acid esters, methacrylic acid esters and maleic acid esters are preferable.
• Two or more kinds of the non-color-forming ethylenic monomer used here can be used together.
• methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetonacrylic amide, N-(1,1-dimethyl-2-sulfonatoethyl)acrylic amide and acrylic acid, styrene sulfinic acid potassium salt and N-vinylpyrrolidone can be used.
• the ethylenic unsaturated monomer to be copolymerized with vinyl type monomer corresponding to the above general formula (B) can be selected in order that the physical property and/or chemical property such as solubility, compatibility with a binding agent (e.g., gelatin) of the photographic colloid composition, flexibility, thermostability, etc. of the copolymer to be formed should favorably be affected.
• a binding agent e.g., gelatin
• lipophilic polymer coupler soluble in an organic solvent
• lipophilic non-color-forming ethylenic monomers e.g., acrylic acid ester, methacrylic acid ester, maleic acid ester vinylbenzenes.
• a solution of a lipophilic polymeric coupler obtained by polymerizing a vinyl based monomer which provides a coupler unit which can be represented by the aforementioned general formula (B) in an organic solvent can be prepared by emulsification and dispersion, or by direct emulsification polymerization, in the form of a latex in an aqueous gelation solution.
• U.S. Patent 3,451,820 can be used for the emulsification and dispersion of a lipophilic polymeric coupler in the form of a latex in an aqueous gelatin solution, and the method disclosed in U.S. Patents 4,080,211 and 3,370,952 can be used for emulsion polymerization.
• hydrophilic non-color-forming ethylenic monomer as a copolymerization ingredient [e.g., N-(1,1-dimethyl-2-sulfonatoethyl)acrylic amide, 3-sulfonatopropyl acrylate, styrene sulfonic acid sodium salt, 2-styrene sulfinic acid potassium salt, acrylic amide, methacrylic amide, acrylic acid, methacrylic acid, N-vinyl-pyrrolidone and N-vinylpyridine].
• hydrophilic non-color-forming ethylenic monomer e.g., N-(1,1-dimethyl-2-sulfonatoethyl)acrylic amide, 3-sulfonatopropyl acrylate, styrene sulfonic acid sodium salt, 2-styrene sulfinic acid potassium salt, acrylic amide, methacrylic amide, acrylic acid, methacryl
• the hydrophilic polymer coupler can be added, in the form of aqueous solution, to a coating solution, and also can be added by dissolving into a mixed solvent comprising water and a water-miscible organic solvent (e.g., a lower alcohol, tetrahydrofuran, acetone, ethyl acetate, cyclohexane, ethyl lactate, dimethylformamide, dimethylacetamide). Moreover, they can be dissolved in aqueous alkaline solutions or in alkali containing organic solvents and added in this form. Also, a small amount of surface active agent can be added.
• a water-miscible organic solvent e.g., a lower alcohol, tetrahydrofuran, acetone, ethyl acetate, cyclohexane, ethyl lactate, dimethylformamide, dimethylacetamide.
• a small amount of surface active agent can be added.
• coupler represented by the general formula (A) in the present invention will be hereinafter be shown, but the present invention is not limited thereto.
• Examples other than the above examples of the coupler represented by the general formula (A) used in the present invention are described in JP-A-60-237448, JP-A-61-153640, and JP-A-61-145557. Synthesis of these couplers can also be carried out according to the methods described in JP-A-62-123157, and JP-A-123158 in addition to the methods according to the above patent specifications.
• couplers used in the present invention can be added to any layer in the photosensitive materials, but it is preferable to add them to a monodispersed emulsion containing layer.
• a monodispersed emulsion containing layer When the emulsion layer is divided into two or more layers having same color sensitivities and different photographic sensitivities, it is preferable to add 4-equivalents of the coupler to the layer of the lowest sensitivity and 2-equivalents of the coupler to the layer of the highest sensitivity.
• the coupler amount to be added is 5 x 10 ⁇ 6 to 3 x 10 ⁇ 3 mol/m2, preferable 1 x 10 ⁇ 5 to 2 x 10 ⁇ 3 mol/m2, and more preferably 3 x 10 ⁇ 5 to 1 x 10 ⁇ 3 mol/m2.
• a usable weight ratio of the below mentioned high boiling point organic solvent for coupler dispersion to the coupler is usually 1/1 or below but 1/2 or below is more preferable, and 1/3 or below is particularly preferable.
• the substantially monodispersed emulsion employed in the present invention is an emulsion which has a grain diameter distribution such that the fluctuation coefficient S/ r in the grain diameter of silver halide is 0.25 or less, wherein r is a mean grain diameter and S is a standard deviation. That is, when respective grain diameters are ri and grain number is ni, the mean grain diameter r is defined as and the standard deviation S is defined as The respective grain diameters mean a diameter corresponding to a projected area which occurs when the silver halide emulsion is subjected to a photographing according to a method (normally an electron microscope photographing) well known in this field as described in T.H.
• the silver halide grain diameter corresponding to the projected area is defined as a diameter of circle which area is equal to the projected area of silver halide grain, as shown in the above literature. Accordingly, the mean grain diameter r and its deviation S can also be obtained even when the grain form of silver halide is other than sphere, that is, for example, when the form is a cube, octahedron, tetradecahedron, tabular form, potato-like form or the like.
• the fluctuation coefficient in the grain diameter of silver halide is 0.25 or less, preferably 0.20 or less and more preferably 0.18 or less.
• the size of the silver halide grain is not particularly limited, but it is preferably 0.1 »m to 3,0 »m, more particularly 0.3 »m to 2.0 »m, and most preferably 0.5 »m to 1.2 »m.
• the form of the silver halide grain can be either a regular crystal form (normal crystal grain) such as hexahedron, octahedron, dodecahedron or tetradecahedron, or an irregular crystal form such as sphere, potato-like form, tabular form or the like, but a particularly desirable form is a normal crystal grain.
• regular crystal form normal crystal grain
• octahedron dodecahedron or tetradecahedron
• an irregular crystal form such as sphere, potato-like form, tabular form or the like
• the normal crystal grain having 50% or more of (111) face is particularly preferable. Even the irregular crystal form having 50% or more of (111) face is particularly preferable.
• a face ratio of the (111) face can be determined by a dye adsorption method of Kubelka Munk wherein the dye is preferentially adsorbed on either one of (111) face and (100) face and the dye associated states on (111) face and (100) face select respectively different dyes spectrometrically.
• the face ratio of (111) face can be determined by adding such a dye to an emulsion and examining in detail the spectrograph corresponding to the added amount of the dye. Reference of details of the above dye adsorption method can be made to Tadaaki Tani, Nihon Kagakukaishi ("Journal of Japan Chemical Society"), page 942 (1984).
• halogen composition of the silver halide grain it is preferable that 60 mol % or more of silver bromide is contained and 10 mol % or less of silver chloride is contained. More preferable grain contains 2 mol % to 40 mol % of silver iodide and particularly preferable one contains 5 mol % to 20 mol % of silver iodide.
• the halogen composition distribution of the grains is preferably uniform.
• halogen composition of the monodispersed emulsion used in the present invention is a grain which has substantially a clear layer structure having two layers comprising a core portion of high iodine content layer and a shell portion of low iodine content layer.
• This layer structure grain will hereinafter be illustrated.
• the core portion is silver halide of high iodine content, and preferable content of the iodine is between 10 mol % and 40 mol % of solid solution limit, that is, preferably 10 to 40 mol % and more preferably 15 to 40 mol %.
• the silver halide other than silver iodide in the core portion can be either one of silver chlorobromide and silver bromide, but it is preferable that the silver bromide ratio is high.
• Outermost layer composition is silver halide containing 8 mol % or less of silver iodide, more preferably 5 mol % or less of silver iodide.
• a silver halide other than silver iodide in the outermost layer can be any one of silver chloride, silver chlorobromide and silver bromide, but it is preferable that the silver bromide ratio is high.
• the above said clear layer structure can be decided by a method of X-ray diffraction.
• the width of slits (diverging slit, receiving slit, etc.), time constant of the apparatus, and scanning speed and recording speed of the goniometer be suitably selected and a measuring accuracy be confirmed by using a standard sample such as silicon, etc.
• the emulsion grain has a clear two layer structure, two peaks appear on the diffraction curve, that is, one diffraction maximum due to silver halide of high iodine content layer and the other diffraction due to silver halide of low iodine content layer.
• the substantially clear two layer structure means that, when a curve relating between a diffraction strength and a diffraction angle on (220) face of silver halide is obtained by using K ⁇ ray of Cu in the range of 38° to 42° of diffraction angle (2 ⁇ ), two diffraction maximums of a diffraction peak corresponding to a high iodine content layer containing 10 to 45 mol % of silver iodide and a diffraction peak corresponding to a low iodine content layer containing 5 or less mol % of silver iodide, and one minimum therebetween appear, and a ratio of the diffraction strength corresponding to the high iodine content layer peak to the diffraction strength corresponding to the low iodine content layer peak becomes 1/10 to 3/1, more preferably 1/5 to 3/1, and most preferably 1/3 to 3/1.
• the diffraction strength of minimum value between two peaks is 90% or less, more preferably 80% or less, most preferably 60% or less of weaker strength peak between two diffraction maximums (peaks).
• the technical method for analyzing a diffraction curve consisting of two diffraction components is well known as explained in, for example, Jikken Butsurigaku Koza (Lecture of Experimental Physics"), No. 11 (Lattice Flaw), published by Kyoritsu Shuppan. It is useful that the diffraction curve is analyzed by the use of a curve analyzer made by Du Dont de Nemours and Company assuming that the curve is a function such as Gauss function, Lorentz function or the like.
• the emulsion has a layer structure, when the halogen compositions in at least 50 grains are confirmed according to the EPMA method.
• the emulsions having a layer structure are preferable when the iodine contents of grains are uniform.
• Relative standard deviation when the iodine content distribution of granules is measured according to EPMA method is preferably 50% or less, more preferably 35% or less and most preferably 20% or less.
• the high iodine content silver halide in the core must sufficiently be covered by low iodine content silver halide in the shell.
• Necessary widths of the shell are different depending upon the grain size, but 0.1 »m or more width is desirable when the grain has a large size of 1.0 »m or more, and 0.05 »m or more width is desirable when the grain has a small size of less than 1.0 »m.
• the silver content ratio of shell portion to core portion is preferably in the range of 1/5 to 5, more preferably 1/5 to 3, most preferably 1/5 to 2.
• the silver halide grain substantially has clearly two layer structures is explained as that two regions different in halogen composition substantially exist in the grain wherein the central portion is a core portion and a surface portion is a shell portion.
• Substantially two layers means that the third region (for example, a layer existing between central core portion and outermost shell portion) may be exist. However, it also means that, even if such third region might be exist, the configurations of two peaks (corresponding to high iodine content portion and low iodine content portion) must not substantially be affected by the third region when the X-ray diffraction pattern is made as above. It is the same when the third region exists in the core portion.
• a layer structure grain the so-called three fold grain having a core of high silver halide content, a shell of low silver halide content and an intermediate layer therebetween, as proposed in, for example, JP-A-61-275741, JP-A-61-250643, JP-A-61-250645, JP-A-61-246747, JP-A-61-246739, etc.
• the photographic emulsion of silver halide usable in the present invention can be prepared by the use of methods as described in, for example, Research Disclosure , No. 17643, pages 22-23 (Dec., 1978), I. Emulsion preparation and types", ibid No. 18716, page 648 (Nov., 1979) P. Glafkides, Chemie et Phisique published by Focal Press (1967), V.L. Zelikman et al, Making and Coating Photographic Emulsion published by Focal Press (1964), etc.
• a tabular grain having an aspect ratio of about 5 or more can be used in the present invention.
• the tabular grain can be simply prepared according to the methods as described in Gutoff, Photographic Science and Engineering , Vol. 14, pages 248-257 (1970), U.S. Patents 4,434,226, 4,414,310, 4,433,048, and 4,439,520, British Patent 2,112,157, etc.
• the crystal structure can be uniform ones or those having inner and outer halogen compositions different from each other, those having layer structures or those wherein silver halides of different compositions are joined with one another by an epitaxial junction or with the compounds such as silver rhodanide, lead oxide, etc. other than the silver halide. Further, mixtures of various crystal system grains can also be used.
• the silver halide emulsions are usually used after physical ripening, chemical ripening and spectral sensitization.
• Additives used in such steps are described in Research Disclosure Nos. 17643 and 18716 and the relevant places are summarized in the following table.
• Well known additives for photography usable in the present invention are also described in the above mentioned two Research Diusclosure literatures and the relevant places are shown in the following table.
• Kind of Additive RD 17643 RD 18716 1. Chemical sensitizer Pages 23 Page 648, right column 2. Sensitivity improver ditto 3. Spectral sensitizer, Color sensitizer Pages 23-24 Page 648, right column to page 649, right column 4. Whitening agent Page 24 5.
• Dye image stabilizer Page 25 9.
• JP-B-58-10739 As a yellow coupler, those described in, for example, U.S. Patents 3,933,501, 4,022,620, 4,326,024, and 4,401,752, JP-B-58-10739 (the term "JP-B” as used herein means an "examined Japanese patent publication"), British Patents 1,425,020 and 1,476,760, etc. are preferble.
• magenta coupler 5-pyrazolone type or pyrazoloazol type compounds are preferable, and those described in U.S. Patents 4,310,619, 4,351,897, European Patent 73,636, U.S. Patents 3,061,432, 3,725,067, Research Disclosure , No. 24220 (June, 1984), JP-A-60-33552, Research Disclosure No. 24230 (June, 1984), JP-A-60-43659, U.S. Patents 4,500,630, 4,540,654, etc. are particularly preferable.
• cyan coupler As a cyan coupler, phenol type or naphthol type couplers are given, and those described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, and 4,327,173, West German Patent Application (OLS) No. 3,329,729, European Patent 121,365A, U.S. Patents 3,446,622, 4,333,999, 4,451,559, and 4,427,767 are preferable.
• OLS West German Patent Application
• a coupler which releases a photographically useful residue with coupling is also used preferably in the present invention.
• a DIR coupler which releases a development inhibitor those described in patents described in the above Research Disclosure , No. 17643, VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248 and U.S. Patent 4,248,962 are preferable.
• couplers usable as a photosensitive material other than the above ones are competing couplers described in U.S. Patent 4,130,427, etc., multiequivalent couplers described in U.S. Patents 4,238,472, 4,338,393, 4,310,618, etc., DIR redox compound releasing couplers described in JP-A-60-185950, etc., couplers which release dyes for recoloration after being released as described in European Patent 173,302A, and the like.
• benzoylacetanilide type 2-equivalent coupler is preferable, and as a magenta coupler, 1-phenyl-5-pyrazolone type 2-equivalent coupler is preferable.
• the couplers used in the present invention can be introduced into the photosensitive materials by various known dispersion methods.
• phthalic acid esters e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate
• phosphoric or phosphonic acid esters e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ehylhexylphenyl phosphonate), benzoic acid esters (e.g., 2-ethylhexyl benzoate, dodecyl esters (e.g., 2-ethylhexyl benzoate, dodecyl esters (e.g., 2-ethy
• organic solvents having a boiling point of about 30°C or higher, preferably 50°C or higher and not higher than about 160°C can be used, and typical examples thereof are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide).
• the present invention can be applied to various types of color photographic materials.
• Color negative film for general or movie purpose, color reversal film for slide or television, color paper, color positive film, color reversal paper and the like can be given as typical examples.
• the color photographic materials according to the present invention can be subjected to a development treatment by a usual methods as described in the above described Research Disclosure , No. 17643, pages 28-29 and ibid . No. 18716, page 651, left column to right column.
• the color developer employed in development treatment of photosensitive material in the present invention is preferably an alkaline aqueous solution mainly composed of aromatic primary amine type color developing agent.
• aromatic primary amine type color developing agent aminophenol type compounds are useful, but p-phenylenediamine type compounds are preferably used and typical examples thereof are 3-methyl-4-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesuylfonamidoethylaniline, 3-methyl-4-amino-N-ethyl- ⁇ -methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. Two or more kinds of these compounds can be jointly used depending upon the purposes.
• the color developers in general, contain a pH buffer agent such as carbonate, borate or phosphate of an alkali metal and also contain a development inhibitor or an antifoggant such as bromide salt, iodide salt, benzimidazoles, benzothiazoles or mercapto compounds.
• a pH buffer agent such as carbonate, borate or phosphate of an alkali metal
• a development inhibitor or an antifoggant such as bromide salt, iodide salt, benzimidazoles, benzothiazoles or mercapto compounds.
• ком ⁇ онентs such as hydroxylamine, diethylhydroxylamine, hydrazine sulfites, phenylsemicarbazides, triethanolamine, catecholsulfonic acids and triethylenediamine-(1,4-diaza-bicyclo[2,2,2]octane), organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salt and amines, fogging agents such as dye forming coupler, competing coupler and sodiumboron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity imparting agent, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylsulfonic acid and phosphonocarboxylic acid, e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid,
• black and white developing agents e.g., dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyirazolidone or amino phenols such as N-methyl-p-aminophenol
• dihydroxybenzenes such as hydroquinone
• 3-pyrazolidones such as 1-phenyl-3-pyirazolidone
• amino phenols such as N-methyl-p-aminophenol
• the pH values of the color developer and black and white developer are generally 9 to 12.
• Replenishing amount of these developers depends on the color photosensitive material but in general, it is 3 liters or less per 1 m2 of the photosensitive material, and it can be decreased to 500 ml or less by lowering the ion concentration of bromide in the replenish solution.
• the replenishing amount is decreased, it is preferable that an area contacting with air in the processing tank is reduced to prevent an evaporation of the replenish solution and also avoid an air oxidation. It is also possible to reduce the replenishing amount by means of controlling an accumulation of bromide ion concentration in the developers.
• the phototographic emulsion layer after color development is usually treated with bleaching agent.
• the bleaching treatment can be made simultaneously with fixing treatment (bleach-fix treatment) or can also be made individually.
• the bleach-fix treatment after bleaching treatment can also be employed.
• a treatment in continuous two bleach-fix baths, a fix treatment before bleach-fix treatment or a bleaching treatment after bleach-fix treatment can also be carried out optionally according to the purposes.
• bleaching agent to be used are, for example, multivalent metal compounds of iron (III), cobalt (III), chrome (VI), copper (II), peracids, quinones, and nitro compounds.
• Typical bleaching agents to be used are ferricyanide compounds; dichromates; organic complex salts of iron (III) or cobalt (III) (e.g., aminocarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycoletherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid.; persulfates; bromates; permanganates; nitrobenzenes and the like.
• iron (III) or cobalt (III) e.g., aminocarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diamin
• iron (III) complex salts of aminopolycarboxylic acid including the iron (III) complex salt of ethylenediaminetetraacetic acid, and peracid salts are preferable from viewpoints of quick treatment and prevention of environmental pollution.
• the ion (III) complex salt of aminopolycarboxylic acid is especially useful as both the bleaching solution and bleach-fix solution.
• the pH value of bleaching solution or bleach-fix solution using such iron (III) complex salt of aminopolycarboxylic acid is usually 5.5 to 8, and the lower pH value can be employed for quickening the treatment.
• a bleach accelerator can be used, if necessary.
• the compounds having mercapto group or disulfide group are preferable because of those having much accelerating effect, and particularly, compounds as described in U.S.
• Patent 3,893,858 West German Patent 1,290,812 and JP-A-53-95630 and also compounds as described in U.S. Patent 4,552,834 are preferable.
• These bleach accelerators can be added to the photosensitive material. These bleach accelerators are especially effective when the color photosensitive material for photographic use is bleach-fixed.
• thiosulfates As a fixing agent, thiosulfates, thiocyanates, thioether type compounds, thioureas, iodide salts, etc. can be given, and generally the thiosulfates are used and particularly, ammonium thiosulfate is used most widely.
• sulfites, bisulfites or carbonyl bisulfite addition compounds are preferable.
• the silver halide color photosensitive material in the present invention is subjected to washing and/or stabilizing step after desilvering treatment.
• the amount of washing water in the washing step can be determined in the wide range according to photosensitive material (characteristic of, for example, used material such as coupler, etc.), use, temperature of washing water, number of washing tank (number of steps), replenishing systems such as counter current, forward current, etc. and the other various conditions.
• photosensitive material characteristic of, for example, used material such as coupler, etc.
• number of washing tank number of steps
• replenishing systems such as counter current, forward current, etc. and the other various conditions.
• a relation between washing tank number and water amount in multistage counter current system can be obtained by the method described in Journal of the Society of Motion Picture and Television Engineers , Vol. 64, pages 248-253 (May 1955).
• chlorine type sterilizers such as isothiazolone compounds as described in JP-A-57-8542, thiabendazoles and chlorinated isocyanuric acid sodium salt
• the other sterilizers such as benzotriazole as described in Hiroshi Horiguchi, Bokin Bobai no Kagaku ("Chemistry of Bactericides and Fungicides"), Eisei Gijutukai ("Sanitary Technology Society”) ed., : Biseibutsu no Mekkin, Sakkin, Bobai Gijutsu ("Techniques of Sterilization, Pasteurization, and Fungicides of Microoganisms") and Nippon Bokinbobaigakkai (“Japan Bactericide and Fungicide Society”) ed., Bokin Bobaizai Jiten (“Dictionary of Bactericides and Fungicides”) can be used.
• the pH value of washing water in the photosensitive material treatment of the present invention is 4 to 9, preferably 5 to 8.
• Washing water temperature and washing time can be determined variously according to characteristics, uses, etc. and generally ranges of 20 seconds to 10 minutes at 15°C to 45°C, preferably 30 seconds to 5 minutes at 25°C to 40°C are chosen.
• the photosensitive material of the present invention can be treated directly with a stabilizing solution in place of the above water washing. In such a stabilizing treatment, all the well known methods as described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used.
• a stabilizing bath containing formalin and a surface active agent which is used as a last bath for the color photosensitive material for photographic use can be given.
• Various chelating agent and fungicides can also be added to this stabilizing bath.
• a color developing agent can be included for the purpose of simplification and speed up of the treatment.
• the preferable inclusion is to use various precursors of the color developing agent.
• the precursors indoaniline type compounds described in U.S. Patent 3,342,597, Schiff base type compounds described in U.S. Patent 3,342,599 and Research Disclosure No. 14850, ibid. No. 15159, aldol compounds described in Research Disclosure , No. 13924, metal salt complexes described in U.S. Patent 3,719,492 and urethane type compounds described in JP-A-53-135628.
• various 1-phenyl-3-pyrazolidones can be included, if necessary, for the purpose of accelerating the color development. Typical examples thereof are described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.
• the various processing solutions in the present invention are used at 10°C to 50°C.
• the temperature at 33°C to 38°C is standard, but it is possible that the processing can be accelerated at higher temperature to shorten the processing time, while an image quality improvement and an improvement of processing solution stability can be attained at lower temperature.
• a treatment using a cobalt intensification or hydrogen peroxide intensification as described in West German Patent 2,267,770 or U.S. Patent 3,674,499 can be carried out.
• the silver halide photosensitive material of the present invention can also be applied to heat developable photosensitive materials as described in U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056, and EP-A-0, 210, 660.
• Emulsions A to K used in the following Examples were prepared as follows:
• Emulsion A Emulsion A
• Emulsion A After desalting the emulsion in a usual manner, 18 mg of sodium thiosulfate and 14 mg of chloroauric acid were added to the emulsion which was ripened at 60°C for 50 minutes and chemically sensitized to obtain an Emulsion A having a mean grain diameter r of 0.7 »m and a fluctuation coefficient S/ r of 0.40.
• octahedron emulsions having 10 mol % of silver iodide contents, a mean grain diameter of 0.55 »m and respective fluctuation coefficients of 0.26, 0.23 and 0.19 were prepared as a core emulsion. After washing these core emulsions with water, a shell attaching with pure silver bromide was caried out in such a manner that silver content of the core portion became equal to that of the shell portion.
• Emulsions E, F Emulsions E, F
• Emulsion E having 2 mol % of silver iodide content, mean grain diameter ( r ) of 0.7 »m and fluctuation coefficient (S/ r ) of 0.39, and Emulsion F having 6 mol % of silver iodide content, r of 1.4 »m and S/ r of 0.45 were prepared.
• Emulsion G and Emulsion H as a chemical sensitizer respectively having 2 mol % of silver iodide content, r of 0.7 »m, S/ r of 0.17 and 6 mol % of silver iodide content, r of 0.7 »m, S/ r of 0.20 were prepared.
• Emulsion B the shell attaching was carried out with pure silver bromide.
• Emulsion I having core/shell ratio of 1/1, 4 mol % silver iodide in core, r of 0.7 »m, S/ r of 0.16
• Emulsion J having core/shell ratio of 1/1, 12 mol % of silver iodide in core, r of 0.7 »m, S/ r of 0.19
• Emulsion K having core/shell ratio of 1/2, 18 mol % of silver iodide in core, r of 0.7 »m, S/ r of 0.19 were prepared.
• Emulsion L having core/intermediate/shell ratio of 1/1/1, respective silver iodide content ratio of 15/5/1, r of 0.7 »m, S/ r of 0.16 was prepared.
• the figures corresponding to respective ingredients show coating amounts represented by unit of g/m2, the silver halide and colloidal silver are shown by coating amount of silver as converted, and the sensitizing dye is shown by coating amount of mol unit per 1 mol of silver halide in the same layer.
• the first layer (Antihalation layer) Black colloidal silver 0.2 Gelatin 1.0 Ultraviolet absorber UV-1 0.05 Ultraviolet absorber UV-2 0.1 Ultraviolet absorber UV-3 0.1 Dispersion oil OIL-1 0.02
• the second layer (Intermediate layer) Fine grain silver halide (Mean grain diameter 0.07 »m) 0.15 Gelatin 1.0
• the third layer (The first red-sensitive emulsion layer) Emulsion A 1.42 Gelatin 0.9 Sensitizing dye A 2.0 x 10 ⁇ 4 Sensitizing dye B 1.0 x 10 ⁇ 4 Sensitizing dye C 0.3 x 10 ⁇ 4 Cp-b 0.35 Cp-c 0.052 Cp-d 0.047 D-1 0.023 D-2 0.035 HBS-1 0.10 HBS-2 0.10
• the fourth layer (Intermediate layer) Gelatin 0.8 Cp-b 0.10 HBS-1 0.05
• the fifth layer (The second red-sensitive emulsion layer) Emulsion A 1.38 Gelatin 1.0 Sensitizing
• the other surface active agent K-1, gelatin hardener H-1 were added.
• Samples 102, 103 and 105 were prepared similarly to the Sample 101 except that the couplers Cp-b in the third, fourth and fifth layers of the Sample 101 were replaced by the couplers Cp-c, Cp-n and the coupler (A-17) of the present invention respectively in an equimolar amount.
• Samples 106-108, 110-113, 115-118 and 120 were prepared by replacing the Emulsion A in the third, and fifth layers of the Samples 101 to 103 and 105 with the Emulsions B, C and D, respectively.
• Samples 121 to 123 and 125 were prepared similarly to the samples 111 to 113 and 115 except that in the third layer the HBS-1 was decreased to 0.02, the HBS-2 to 0.02, the gelatin to 0.6; in the fourth layer the HBS-1 was decreased to 0.01, the gelatin to 0.5; and in the fifth layer the HBS-1 was decreased to 0.01, the HBS-2 to 0.02, the gelatin to 0.7.
• Sample 126 was prepared similarly to the Sample 125 except that the Cp-h in the eighth layer and ninth layer were replaced with 1.5 time mol of Cp-e; and the coating amount of the gelatin in the eighth layer and ninth layer were replaced with 1.2 and 1.8, respectively.
• Sample 127 was prepared by replacing the Cp-i in the eleventh and twelfth layers of the Sample 125 with 1.6 time mol of Cp-o; and the coating amount of the gelatin with 2.4 and 0.8, respectively.
• cyan color image MTF value was measured by exposing with white light and developing a MTF measuring pattern.
• the MTF measurement was carried out according to the method as described in Mees, The Theory of the Photographic Process , 3rd ed., published by Macmillan Publishing Co., Inc.
• Table 1 shows a color turbidity which was obtained by subtracting a fog density from a magenta density in the exposure wherein cyan density became (photographic fog + 1.5).
• Processing compositions used in respective steps are as follows: Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Patassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfuric acid salt 2.4 g 4-(N-ethyl-N- ⁇ -hydroxyethylamino) -2-methylaniline sulfuric acid salt 4.5 g Water to make 1.0 l pH 10.0 Bleaching-A solution Ammonium ethylenediamine- tetraacetato ferrate 100.0 g Disodium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water to make 1.0 l pH 6.6 Fixing solution Disodium ethylenediaminetetraacetate 1.0g Sodium sulfite 4.0
• Bleaching-A solution was changed to Bleaching-B solution as prescribed below.
• This Bleaching-B solution was prepared as a forced deterioration solution to model a state which is fatigued by the processing of a large amount of photosensitive materials.
• the Bleaching-B solution is a mixture of 900 ml (B-1) solution and 100 ml (B-2) solution.
• the Samples of the present invention are fast in cyan color image, little in density lowering caused by forced Bleaching-B, and excellent in color reproducibility and also in sharpness expressed by MTF valuex.

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