EP0423693B1 - Farbfotografisches Silberhalogenidmaterial - Google Patents

Farbfotografisches Silberhalogenidmaterial Download PDF

Info

Publication number
EP0423693B1
EP0423693B1 EP19900119763 EP90119763A EP0423693B1 EP 0423693 B1 EP0423693 B1 EP 0423693B1 EP 19900119763 EP19900119763 EP 19900119763 EP 90119763 A EP90119763 A EP 90119763A EP 0423693 B1 EP0423693 B1 EP 0423693B1
Authority
EP
European Patent Office
Prior art keywords
group
silver halide
light
sensitive
emulsion layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19900119763
Other languages
English (en)
French (fr)
Other versions
EP0423693A2 (de
EP0423693A3 (en
Inventor
Munehisa C/O Fuji Photo Film Co. Ltd. Fujita
Katsuro C/O Fuji Photo Film Co. Ltd. Nagaoka
Shinsuke C/O Fuji Photo Film Co. Ltd. Bando
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP26857989A external-priority patent/JPH03130761A/ja
Priority claimed from JP26955889A external-priority patent/JPH03131845A/ja
Priority claimed from JP26955989A external-priority patent/JPH03131846A/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0423693A2 publication Critical patent/EP0423693A2/de
Publication of EP0423693A3 publication Critical patent/EP0423693A3/en
Application granted granted Critical
Publication of EP0423693B1 publication Critical patent/EP0423693B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83—Organic dyestuffs therefor
    • G03C1/832—Methine or polymethine dyes
    • 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
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • G03C2007/3025—Silver content

Definitions

  • the present invention relates to a silver halide color photographic material which exhibits improved sharpness and preservability.
  • One approach is to inhibit light scattering. Another is to improve the edge effect.
  • colloidal silver has been previously used to absorb yellow light and inhibit halation.
  • colloidal silver does not provide a maximum increase in sharpness because incorporating it causes an increase in fogging of a light-sensitive silver halide emulsion layer adjacent to the colloidal silver layer.
  • Another known approach is to drastically reduce the coated amount of silver.
  • the number of active points is reduced which causes a deterioration in graininess.
  • Examples of approaches for improving the edge effect include the use of an unsharp mask and the use of DIR couplers for color negative films.
  • the use of an unsharp mask is limited in its practicality because it is a complicated process.
  • DIR couplers are known in many ways.
  • DIR couplers examples include the compounds described in JP-B-55-34933 (the term “JP-B” as used herein refers to an "examined Japanese patent publication”), JP-A-57-93344 (the term “JP-A” as used herein refers to a "published unexamined Japanese patent application”), and U.S. Patents 3,227,554, 3,615,506, 3,617,291 and 3,701,793.
  • MTF Modulation Transfer Function
  • DIR couplers cause an undesirable side effect such as a sensitivity or density drop.
  • the edge effect can be dramatically enhanced by increasing the silver density of the light-sensitive silver halide emulsion layer.
  • this increases fogging as well as causes a deterioration in the preservability of the light-sensitive material.
  • the silver density of the light-sensitive silver halide emulsion layer is predetermined to a high range not only to enhance the activity of solution physical development which results in an increase in the edge effect and also to reduce the film thickness per unit of silver, providing an unexpected increase in sharpness. That is, sharpness is increased beyond the expected increase attained using each of the above approaches.
  • the present process does not suffer from any deterioration in preservability, which has been heretofore unavoidable when the silver density is raised.
  • An object of the present invention is to provide a silver halide color photographic material which exhibits excellent sharpness and color reproducibility and has improved preservability and desilverability.
  • a silver halide color photographic material comprising a support; at least a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer on said support, and comprising one or more hydrophilic colloidal layers containing a dispersion of microcrystals of at least one compound represented by general formulae (I), (II), (III), (IV), (V) and (VI):
  • a and A' may be the same or different and each represents an acidic nucleus
  • B represents a basic nucleus
  • X and Y may be the same or different and each represents an electrophilic group;
  • R represents a hydrogen atom or an alkyl group;
  • R 1 and R 2 each represents an alkyl group, an aryl group, an acyl group or a sulf
  • Said photographic sensitizing dye may be added to said at least one light-sensitive silver halide emulsion layer before the completion of the formation of grains or between the completion of the formation of grains and the completion of chemical sensitization.
  • the object of the present invention is still further satisfied by a silver halide color photographic material as defined above, wherein said at least one light-sensitive silver halide emulsion layer contains silver halide grains containing silver iodide wherein the average silver iodide content in said at least one light-sensitive silver halide emulsion layer is 8 mol% or less.
  • a silver halide color photographic material as defined above, that further comprises an emulsion layer containing at least one compound represented by general formula (VII): wherein M 1 represents a hydrogen atom, a cation, or a protective group for a mercapto group which undergoes cleavage by an alkali; X' represents an atomic group required for the formation of a 5- or 6-membered heterocyclic group containing sulfur, selenium, nitrogen, or oxygen as hetero atoms and which may be substituted or part of a condensed ring; R' represents a straight or branched chain alkylene group, a straight or branched chain alkenylene group, a straight or branched chain aralkylene group, or an arylene group; R" represents a hydrogen atom or a group which can substitute for the hydrogen atom; Z represents a polar substituent; Y represents in which R' 1 , R' 2 , R' 3 ,
  • the acidic nucleus represented by A or A' preferably represents 2-pyrazoline-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isooxazolidinone, barbituric acid, thiobarbituric acid, indandione, pyrazolopyridine, or hydroxypyridone.
  • the basic nucleus represented by B preferably represents pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole, or pyrrole.
  • Examples of the heterocyclic group represented by B include a pyrrole group, an indole group, a thiophene group, a furan group, an imidazole group, a pyrazole group, an indolizine group, a quinoline group, a carbazole group, a phenothiazine group, a phenoxazine group, an indoline group, a thiazole group, a pyridine group, a pyridazine group, a thiadiazine group, a pyran group, a thiopyran group, an oxadiazole group, a benzoquinolizine group, a thiadiazole group, a pyrrolothiazole group, a pyrrolopyridazine group, and a tetrazole group.
  • the group containing a dissociative proton having a pKa (acid dissociation constant) value of 4 to 11 in a 1/1 by volume mixture of water and ethanol is not specifically limited in kind and position of substitution in a dye molecule so long as it makes a dye molecule substantially water-insoluble at pH 6 or less and substantially water-soluble at pH 8 or more.
  • a dissociative group is a carboxyl group, a sulfamoyl group, a sulfonamide group, or a hydroxyl group; more preferably a carboxyl group.
  • the dissociative group may substitute a dye molecule either directly or via a divalent connecting group such as an alkylene group and a phenylene group.
  • dissociative groups which substitute a dye molecule via a divalent connecting group include a 4-carboxyphenyl group, a 2-methyl-3-carboxyphenyl group, a 2,4-dicarboxyphenyl group, a 3,5-dicarboxyphenyl group, a 3-carboxyphenyl group, a 2,5-dicarboxyphenyl group, a 3-ethylsulfamoylphenyl group, a 4-phenylsulfamoylphenyl group, a 2-carboxyphenyl group, a 2,4,6-trihydroxyphenyl group, a 3-benzenesulfonamidophenyl group, a 4-(p-diaminobenzenesulfonamido)phenyl group, a 3-hydroxyphenyl group, a 2-hydroxyphenyl group, a 4-hydroxyphenyl group, a 2-hydroxy-4-carboxyphenyl group, a 3-methoxy-4-carbox
  • the alkyl group represented by R, R 3 , or R 6 is preferably a C 1-10 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isoamyl group, and an n-octyl group.
  • the alkyl group represented by R 1 or R 2 is preferably a C 1-20 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isobutyl, and an isopropyl group.
  • Such an alkyl group may contain substituents such as a halogen atom (e.g., chlorine, bromine); a nitro group; a cyano group; a hydroxyl group; a carboxyl group; an alkoxy group (e.g., methoxy, ethoxy); an alkoxycarbonyl group (e.g., methoxycarbonyl, i-propoxycarbonyl); an aryloxy group (e.g., phenoxy); a phenyl group; an amide group (e.g., acetylamino, methanesulfonamide); a carbamoyl group (e.g., methylcarbamoyl, ethylcarbamoyl); and a sulfamoyl group (e.g., methylsulfamoyl, phenylsulfamoyl).
  • a halogen atom e.g., chlorine, bromine
  • the aryl group represented by R 1 or R 2 is preferably a phenyl group or a naphthyl group which may contain substituents.
  • substituents include those described with reference to the alkyl group represented by R 1 and R 2 (e.g., methyl, ethyl).
  • the acyl group represented by R 1 or R 2 is preferably a C 2-10 acyl group such as an acetyl group, a propionyl group, an n-octanoyl group, an n-decanoyl group, an isobutanoyl and a benzoyl group.
  • Examples of the alkylsulfonyl or arylsulfonyl group represented by R 1 or R 2 include a methanesulfonyl group, an ethanesulfonyl group, a n-butanesulfonyl group, a n-octanesulfonyl group, a benzenesulfonyl group, a p-toluenesulfonyl group and an o-carboxybenzenesulfonyl group.
  • the alkoxy group represented by R 3 or R 6 is preferably a C 1-10 alkoxy group such as a methoxy group, an ethoxy group, a n-butoxy group, a n-octoxy group, a 2-ethylhexyloxy group, an isobutoxy group, and an isopropoxy group.
  • Examples of the halogen atom represented by R 3 or R 6 include chlorine, bromine, and fluorine.
  • An example of the ring formed by the connection of R 1 to R 4 or R 2 to R 5 is a julolidine ring.
  • Examples of the 5- or 6-membered ring formed by the connection of R 1 to R 2 include a piperidine ring, a morpholine ring, and a pyrrolidine ring.
  • the methine ring represented by L 1 , L 2 , or L 3 may contain substituents such as a methyl group, an ethyl group, a cyano group, a phenyl group, a chlorine atom, and a hydroxypropyl group.
  • the electrophilic groups represented by X or Y may be the same or different and each represents a cyano group; a carboxyl group; an alkylcarbonyl group, which may be substituted, for example, an acetyl group, a propionyl group, a heptanoyl group, a dodecanoyl group, a hexadecanoyl group, a 1-oxo-7-chloroheptyl group; an arylcarbonyl group, which may be substituted, for example, a benzoyl group, a 4-ethoxycarbonylbenzoyl group, a 3-chlorobenzoyl group; an alkoxycarbonyl group, which may be substituted, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a t-amyloxycarbonyl group, a hexyloxycarbonyl group, a 2-ethyl
  • the synthesis of dyes that can be used in the present invention can be accomplished using any suitable method. Examples of suitable methods are described in International Patent WO 88/04794, European Patents 0,274,723A1, 276,566 and 299,435, JP-A-52-92716, JP-A-55-155350, JP-A-55-155351, JP-A-61-205934, JP-A-48-68623, and U.S. Patents 2,527,583, 3,486,897, 3,746,539, 3,933,798, 4,130,429 and 4,040,841.
  • the dyes used in the present invention are incorporated as a dispersion of finely divided solid into a layer of the emulsion such as a hydrophilic colloidal layer to be coated on a photographic element.
  • a dispersion can be prepared by precipitating a dye in the form of dispersion and/or by subjecting a dye to fine grinding by a known grinding means such as ball mill (e.g., a ball mill, a vibrating ball mill, or a planetary ball mill), a sand mill, a colloid mill, a jet mill, or a roller mill in the presence of a dispersant.
  • a solvent e.g., water or alcohol
  • such a dispersion can be prepared by dissolving a dye in a proper solvent, and then adding a nonsolvent of the dye to the solution to cause precipitation of the dye in the form of powder of microcrystal.
  • a surface active agent for dispersion may be used.
  • Yet another method for preparing such a dispersion is to dissolve a dye in a proper solvent while properly adjusting the pH value of the solvent and then changing the pH to crystallize the dye.
  • Dye grains of the dispersion should have a mean diameter of 10 ⁇ m or less, preferably 2 ⁇ m or less, particularly 0.5 ⁇ m or less. More preferably, the dye grain is in the form of finely divided powder having a diameter of 0.1 ⁇ m or less.
  • the content of the dye used in the present invention is in the range of 1 to 1,000 mg/m 2 , preferably 5 to 800 mg/m 2 .
  • the present dye dispersion can be incorporated in any layer regardless of whether it is an emulsion layer or interlayer.
  • Colloidal silver which are normally incorporated in the yellow filter layer and antihalation layer can be partly or entirely replaced by the present dye dispersion to attain the effects of the present invention more remarkably.
  • the volume of an emulsion layer is the product of coated area and dried film thickness.
  • the silver density is in the range of 0.4 g/cm 3 or more to accomplish the objects of the present invention.
  • the silver density should be in the range of 2 g/cm 3 or less, more preferably 0.6 to 1.5 g/cm 3 , particularly 0.8 to 1 g/cm 3 .
  • a silver halide emulsion layer having the above silver density may be present in any layer in the light-sensitive material.
  • the silver halide emulsion layer having the above silver density is located as close as possible to the layer containing the solid dye dispersion of the present invention, to better accomplish the objects of the present invention. More preferably, the silver halide emulsion layer having the above silver density is located adjacent to the layer containing the solid dye dispersion of the present invention.
  • At least one layer having the above described silver density needs to be present in the light-sensitive material. More preferably, two or more such layers are present in the light-sensitive material.
  • a multicolor light-sensitive material comprising a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer
  • the silver density of at least one of the light-sensitive emulsion layer having the lowest sensitivity in these respective color-sensitive layers is preferably within the above described range. More preferably, all the light-sensitive emulsion layers constituting these color-sensitive layers have the above described silver density.
  • the temperature at which the sensitizing dye is incorporated is in the range of 50°C or higher, more preferably 60°C or higher to reduce fog.
  • the sensitizing dye can be incorporated at any time between before the beginning of the formation of grains and the actual coating, e.g., between after the chemical ripening and before the coating; during the chemical ripening; during the desalting step; or during the grain formation step.
  • the reaction vessel can be previously charged with sensitizing dye before the formation of grains.
  • sensitizing dye be incorporated before or during the chemical ripening, or before or during the formation of grains in order to intensify the adsorption of the sensitizing dye and attain a higher sensitization.
  • sensitizing dye is incorporated into the system at an elevated temperature, the adsorption of the dye is intensified which often causes the desilvering speed to be lowered when the photographic material is developed. In the present invention, however, the desilvering speed is not reduced.
  • the sensitizing dye in the present invention can be incorporated in the system either batchwise or continuously during a specified period of time.
  • the sensitizing dye can be incorporated in the silver halide emulsion in the form of solution in water or an organic solvent.
  • a substantially water-insoluble sensitizing dye can be used in the form of dispersion in an aqueous solvent.
  • any known sensitizing dye can be used in the present invention.
  • a sensitizing dye include a methine dye such as a cyanine dye, a merocyanine dye, a hemicyanine dye, a rhodacyanine dye, an oxonol dye, a hemioxonol dye, and a styryl dye.
  • a methine dye such as a cyanine dye, a merocyanine dye, a hemicyanine dye, a rhodacyanine dye, an oxonol dye, a hemioxonol dye, and a styryl dye.
  • Useful among these dyes are monomethine and trimethine cyanine dyes containing one or two sulfone or sulfoalkyl groups as substituents.
  • Particularly useful among these dyes are oxacarbocyanine, thiocarbocyanine,
  • Spectral sensitizing dyes that can be used are described in West German Patent 929,080, U.S. Patents 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,959, 3,672,897, 3,694,217,4,025,349, 4,046,572, 2,688,545, 2,977,229, 3,397,060, 3,522,062, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,814,609, 3,837,862, and 4,026,707, British Patents 1,242,588, 1,344,281, and 1,507,803, JP-B-44-14030, JP-B-52-24844, JP-B-43-4936, JP-B-53-12375, JP-A-52-110618, JP-A-52-109925, and JP-A-50-80827.
  • cyanine dyes include those represented by general formula (VIII): wherein Z" 1 and Z" 2 each represents an atomic group required for the formation of a heterocyclic nucleus commonly incorporated in a cyanine dye, particularly a thiazole nucleus, a thiazoline nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, an oxazole nucleus, an oxazoline nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a tetrazole nucleus, a pyridine nucleus, a quinoline nucleus, an imidazoline nucleus, an imidazole nucleus, a benzimidazole nucleus, a naphthoimidazole nucleus, a selenazo
  • nuclei may be substituted by a lower alkyl group such as a methyl group, a halogen atom, a phenyl group, a hydroxyl group, a C 1-4 alkoxy group, a carboxyl group, an alkoxycarbonyl group, an alkylsulfamoyl group, an alkylcarbamoyl group, an acetyl group, an acetoxy group, a cyano group, a trichloromethyl group, a trifluoromethyl group, or a nitro group, for example.
  • a lower alkyl group such as a methyl group, a halogen atom, a phenyl group, a hydroxyl group, a C 1-4 alkoxy group, a carboxyl group, an alkoxycarbonyl group, an alkylsulfamoyl group, an alkylcarbamoyl group, an acetyl group, an acetoxy group,
  • L" 1 , L" 2 or L" 3 each represents a methine group or a substituted methine group.
  • a substituted methine group include a methine group having a lower alkyl group such as a methyl group or an ethyl group, and an aralkyl group such as a phenyl group, a substituted phenyl group, a methoxy group, an ethoxy group, or an aralkyl group such as a phenethyl group as a substituent.
  • L" 1 and R" 1 , L" 3 and R" 2 , and, if m 1 is 3, L" 2 and L" 2 may be crosslinked to each other with alkylene to form a 5- or 6-membered ring.
  • R" 1 and R" 2 each represents a lower alkyl group (preferably a C 1-6 alkyl group), or a substituted alkyl group having a carboxyl group, a sulfo group, a hydroxyl group, a halogen atom, a C 1-4 alkoxy group, a phenyl group, or a substituted phenyl group as a substituent (preferably containing C 1-5 alkylene portion) (e.g., ⁇ -sulfoethyl, ⁇ -sulfopropyl, ⁇ -sulfobutyl, ⁇ -sulfobutyl, 2-[2-(3-sulfopropoxy)ethoxy]ethyl, 2-hydroxysulfopropyl, 2-chlorosulfopropyl, 2-methoxyethyl, 2-hydroxyethyl, carboxymethyl, 2-carboxyethyl, 2,2,3,3-tetrafluoropropyl, 3,
  • n 1 represents an integer 1, 2 or 3.
  • X" 1 ⁇ represents an acid anion group commonly incorporated in a cyanine dye such as an iodine ion, a bromine ion, a p-toluenesulfonic acid ion, or a perchloric acid ion.
  • the suffix nl represents an integer 1 or 2. If the cyanine dye has a betaine structure, n 1 is 1.
  • cyanine dyes include:
  • the amount of sensitizing dye to be incorporated during the preparation of the silver halide emulsion depends on the kind of the sensitizing dyes or the silver halide content and cannot be unequivocally specified. In general, however, the sensitizing dye can be used in substantially the same amount as that used in the conventional process.
  • M 1 represents a hydrogen atom, a cation, or a protective group for a mercapto group which undergoes cleavage with an alkali. More particularly, M 1 represents a hydrogen atom; a cation (e.g., a sodium ion, a potassium ion, an ammonium ion); or a protective group of a mercapto group which undergoes cleavage with an alkali (e.g., -COR', -COOR', -CH 2 CH 2 COR' in which R' represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group).
  • a cation e.g., a sodium ion, a potassium ion, an ammonium ion
  • a protective group of a mercapto group which undergoes cleavage with an alkali e.g., -COR', -COOR', -CH 2
  • X' represents an atomic group required for the formation of a 5- or 6-membered heterocyclic group which contains as a hetero atom sulfur, selenium, nitrogen, or oxygen. X' may be substituted or condensed.
  • Examples of such a 5- or 6-membered heterocyclic group include tetrazole, triazole, imidazole, oxazole, thiadiazole, pyridine, pyrimidine, triazine, azabenzimidazole, purine, tetraazaindene, triazaindene, pentaazaindene, benzotriazole, benzimidazole, benzoxazole, benzothiazole, benzoselenazole, and naphthoimidazole.
  • R' represents a straight or branched chain alkylene group, a straight or branched chain alkenylene group, a straight or branched chain aralkylene group or arylene group.
  • Z represents a polar substituent.
  • Y represents in which R' 1 , R' 2 , R' 3 , R' 4 , R' 5 , R' 6 , R' 7 , R' 8 , R' 9 , and R' 10 each represents a hydrogen atom, or a substituted or unsubstituted alkyl, aryl, alkenyl, or aralkyl group.
  • R" represents a hydrogen atom or a group which can substitute for a hydrogen atom.
  • the suffix n represents the integer 0 or 1.
  • the suffix m represents the integer 0, 1, or 2.
  • Examples of the polar substituent represented by Z include a substituted or unsubstituted amino group (which may or may not be in the form of salt); a quaternary ammonium group; an alkoxy group; an aryloxy group; an alkylthio group; an arylthio group; a heterocyclic oxy group; a heterocyclic thio group; a sulfonyl group; a carbamoyl group; a sulfamoyl group; a carbonamide group; a sulfonamide group; an acyloxy group; a ureido group; an acyl group; an aryloxycarbonyl group; a thioureido group; a sulfonyloxy group; a heterocyclic group; a hydroxyl group; and a carboxyl group.
  • R' 1 , R' 2 , R' 3 , R' 4 , R' 5 , R' 6 , R' 7 , R' 8 , R' 9 , and R' 10 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aralkyl group.
  • R" represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a C 1-6 substituted or unsubstituted alkyl group, a C 6-12 substituted or unsubstituted aryl group, a C 1-6 substituted or unsubstituted alkoxy group, a C 6-12 substituted or unsubstituted aryloxy group, a C 1-12 sulfonyl group, a C 1-12 sulfonamide group, a C 1-12 sulfamoyl group, a C 1-12 carbamoyl group, a C 2-12 amide group, a C 1-12 ureido group, a C 2-12 aryloxy or alkoxycarbonyl group, a C 2-12 aryloxy or alkoxycarbonylamino group, and a cyano group.
  • R be a substituted or unsubstituted alkylene group. It is preferred that Y be It is preferred that R' 2 , R' 3 , R' 6 and R' 7 ve a hydrogen atom. It is preferred that Z be a substituted or unsubstituted amino group, a salt of an amino group, or a heterocyclic group.
  • Particularly preferred among these compounds are Compounds VII-1, VII-4, VII-10, and VII-13.
  • the compound represented by general formula (VII) is used in an amount of from 10 -7 to 10 -2 mol, preferably 10 -6 to 10 -3 mol, more preferably 10 -5 to 10 -3 mol, per mol of silver halide in the emulsion in which it is to be incorporated.
  • the compound of general formula (VII) can be incorporated into the emulsion at any time between before the beginning of the formation of grains and the actual coating, more precisely after chemical ripening and before coating, during chemical ripening, during the desilvering step, or during the grain formation step.
  • the sensitizing dye can be charged into the reaction vessel prior to the formation of grains.
  • the color photographic light-sensitive material of the present invention can comprise at least one blue-sensitive layer, at least one green-sensitive layer, and at least one red-sensitive layer on a support.
  • the number of silver halide emulsion layers and light-insensitive layers and the order of arrangement of these layers are not specifically limited.
  • the silver halide photographic material of the present invention comprises light-sensitive layers consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity and different light sensitivities on a support.
  • the light-sensitive layers are unit light-sensitive layers having a color sensitivity to any of blue light, green light and red light.
  • these unit light-sensitive layers are normally arranged in the following order: red-sensitive layer, green-sensitive layer, blue-sensitive layer, support.
  • red-sensitive layer green-sensitive layer
  • blue-sensitive layer support.
  • the order of arrangement can be reversed depending on the purpose of the application.
  • two unit light-sensitive layers having the same color sensitivity can be arranged with a unit light-sensitive layer having a different color sensitivity interposed between them.
  • Light-insensitive layers such as various interlayers can be provided between the silver halide light-sensitive layers, on the uppermost layer, and on the lowermost layer.
  • interlayers can comprise couplers such as DIR as described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037, and JP-A-61-20038. These interlayers can further comprise a color stain inhibitor as commonly used.
  • the plurality of silver halide emulsion layers constituting each unit light-sensitive layer are preferably a two-layer structure, i.e., a high sensitivity emulsion layer and a low sensitivity emulsion layer as disclosed in West German Patent 1,121,470 and British Patent 923,045.
  • these layers are preferably arranged in such an order that the light sensitivity decreases towards the support.
  • a light-insensitive layer can be provided between these silver halide emulsion layers.
  • a low sensitivity emulsion layer can be provided in a position relatively far away from the support while a high sensitivity emulsion layer can be provided nearer to the support.
  • the layers have the following arrangement in a position relatively far away from the support: a low sensitivity blue-sensitive layer (BL), a high sensitivity blue-sensitive layer (BH), a high sensitivity green-sensitive layer (GH), a low sensitivity green-sensitive layer (GL), a high sensitivity red-sensitive layer (RH), and a low sensitivity red-sensitive layer (RL).
  • the layers have the following arrangement: BH, BL, GL, GH, RH, and RL.
  • the layers have the following arrangement: BH, BL, GH, GL, RL, and RH.
  • the layers can be arranged as follows: a blue-sensitive layer, GH, RH, GL, and RL in a position relatively far away from the support.
  • the arrangement can be a blue-sensitive layer, GL, RL, GH, and RH.
  • a layer arrangement can be used such that the uppermost layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lowermost layer is a silver halide emulsion layer having a lower sensitivity than that of the middle layer.
  • the light sensitivity decreases towards the support.
  • the layer structure comprises three layers having different light sensitivities, a middle sensitivity emulsion layer, a high sensitivity emulsion layer and a low sensitivity emulsion layer can be so arranged relatively far away from the support in a color-sensitive layer as described in JP-A-59-202464.
  • a high sensitivity emulsion layer, a low sensitivity emulsion layer and a middle sensitivity emulsion layer or a low sensitivity emulsion layer, a middle sensitivity emulsion layer, and a high sensitivity emulsion layer can be so arranged.
  • the layer structure comprises four or more layers, too, the order and arrangement of layers can be altered as described above.
  • a donor layer (CL) having an interimage effect and a different spectral sensitivity distribution from a main light-sensitive layer such as BL, GL, and RL is preferably provided adjacent, or close to, the main light-sensitive layer.
  • a suitable silver halide to be incorporated in the photographic emulsion layer of the color light-sensitive photographic material of the present invention is silver bromoiodide, silver chloroiodide, or silver bromochloroiodide containing silver iodide in an amount of about 30 mol% or less.
  • Preferred are silver bromoiodide and silver bromochloroiodide containing silver iodide in an amount of 8 mol% or less, more preferably 6 mol% or less, most preferably 4 mol% or less.
  • the silver iodide content in the emulsion layer is reduced, fog occurs during storage of the lightsensitive material.
  • Material of the present invention shows no increase in the occurrence of fog and thus exhibits improved preservability.
  • Silver halide grains in the photographic emulsions may be regular grains having a regular crystal form (such as a cubic, octahedral and tetradecahedral form); those having an irregular crystal form (such as a spherical or tabular form); those having a crystal defect such as a twinning plane; or those having a combination of these crystal forms.
  • regular crystal form such as a cubic, octahedral and tetradecahedral form
  • those having an irregular crystal form such as a spherical or tabular form
  • those having a crystal defect such as a twinning plane
  • the silver halide grains may be either fine grains of about 0.2 ⁇ m or smaller in diameter or giant grains having a projected area diameter of up to about 10 ⁇ m. Preferred are fine grains having a diameter of 0.1 to 0.2 ⁇ m.
  • the emulsion may be either a monodisperse emulsion or a polydisperse emulsion.
  • the preparation of the silver halide photographic emulsion which can be used in the present invention can be accomplished by any suitable method.
  • suitable methods are described in Research Disclosure , No. 17643 (December, 1978), pages 22-23, "I. Emulsion Preparation and Types"; Research Disclosure , No. 18716 (November, 1979), page 648; P. Glafkides, Chimie et Physique Photographique , Paul Montel (1967); G.F. Duffin, Photographic Emulsion Chemistry , Focal Press, 1966; and V.L. Zelikman et al., Making and Coating Photographic Emulsions , Focal Press, 1964.
  • monodisperse emulsions as described in U.S. Patents 3,574,628 and 3,655,394 are preferably used in the present invention.
  • Tabular grains having an aspect ratio of about 5 or more can be used in the present invention.
  • the preparation of such tabular grains is easily accomplished by any suitable method such 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, and British Patent 2,112,157.
  • the individual silver halide crystals may have either a homogeneous structure or heterogeneous structure composed of a core and an outer shell that differ in halogen composition, or the crystals may have a layered structure. Furthermore, the grains may have fused to them a silver halide having a different halogen composition or a compound other than a silver halide, e.g., silver thiocyanate or lead oxide, by an epitaxial junction.
  • the silver halide emulsion to be used in the present invention is normally subjected to physical ripening, chemical ripening, and spectral sensitization. Additives to be used in these steps are described in Research Disclosure , Nos. 17643 and 18716 a summary of which is presented in Table A below.
  • color couplers can be used in the present invention. Specific examples of these are described in Research Disclosure , No. 17643, Section VII-C ⁇ G.
  • Preferred yellow couplers are those described in U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752, 4,248,961, 3,973,968, 4,314,023 and 4,511,649, JP-B-58-10739, British Patents 1,425,020 and 1,476,760, and European Patent 249,473A.
  • Preferred magenta couplers are 5-pyrazolone compounds and pyrazoloazole compounds. Particularly preferred are the compounds described in U.S. Patents 4,310,619, 4,351,897, 3,061,432, 3,725,064, 4,500,630, 4,540,654 and 4,556,630, European Patent 73,636, JP-A-60-33552, JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, Research Disclosure , No. 24220 (June, 1984), Research Disclosure , No. 24230 (June, 1984), and WO 88/04795.
  • Cyan couplers include naphthol and phenol couplers. Preferred are 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, 4,327,173, 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212 and 4,296,199, West German Patent Publication No. 3,329,729, European Patents 121,365A and 249,453A, and JP-A-61-42658.
  • Colored couplers for correction of unnecessary absorption of developed color preferably include those described in Research Disclosure , No. 17643, Section VII-G, U.S. Patents 4,163,670, 4,004,929 and 4,138,258, JP-B-57-39413, and British Patent 1,146,368. Furthermore, couplers for correction of unnecessary absorption of developed color by a fluorescent dye released upon coupling as described in U.S. Patent 4,774,181 and couplers containing as a separable group a dye precursor group capable of reacting with a developing agent to form a dye as described in U.S. Patent 4,777,120 are preferably used.
  • Couplers which form a dye having moderate diffusibility preferably include those described in U.S. Patent 4,366,237, British Patent 2,125,570, European Patent 96,570, and West German Patent Publication No. 3,234,533.
  • Couplers capable of releasing a photographically useful residue upon coupling can also be used in the present invention.
  • DIR couplers which release a developing inhibitor are described in the patents cited in Research Disclosure , No. 17643, Section VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, and JP-A-63-37346, and U.S. Patents 4,248,962 and 4,782,012.
  • Couplers capable of imagewise releasing a nucleating agent or a developing accelerator at the time of development preferably include those described in British Patents 2,097,140 and 2,131,188, and JP-A-59-157638 and JP-A-59-170840.
  • the photographic material according to the present invention can further comprise competing couplers as described in U.S. Patent 4,130,427; polyequivalent couplers as described in U.S. Patents 4,283,472, 4,338,393 and 4,310,618; DIR redox compounds, DIR couplers, or DIR coupler releasing couplers as described in JP-A-60-185950 and JP-A-62-24252; couplers capable of releasing a dye which returns to its original color after release as described in European Patent 173,302A; couplers capable of releasing a bleach accelerator as described in Research Disclosure , No. 11449, Research Disclosure , No.
  • couplers capable of releasing a ligand as described in U.S. Patent 4,553,477 couplers capable of releasing a leuco dye as described in JP-A-63-75747; and couplers capable of releasing a fluorescent dye as described in U.S. Patent 4,774,181.
  • high boiling point organic solvents having a boiling point of 175°C or higher at normal pressure which can be used in the oil-in-water dispersion process
  • phthalic acid esters e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl)phthalate, bis(2,4-di-t-amylphenyl)isophthalate, bis(1,1-diethylpropyl)phthalate); phosphate or phosphonate esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate, trichloro
  • an organic solvent having a boiling point of about 30°C or higher, preferably 50°C to about 160°C can be used.
  • Typical examples of such an organic solvent include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.
  • Various preservatives or antifungal agents such as 1,2-benzisothiazoline-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2-(4-thiazolyl)benzimidazole as described in JP-A-63-257747, JP-A-62-272248, and JP-A-1-80941 are preferably incorporated in the color photographic light-sensitive material of the present invention.
  • the present invention is applicable to various types of color photographic light-sensitive materials, most particularly preferably to color negative films for common use or motion pictures, color reversal films for slides or television, color papers, color positive films, and color reversal papers.
  • Suitable supports which can be used in the present invention are described in Research Disclosure , No. 17643 (page 28); and Research Disclosure , No. 18716 (right column on page 647 to left column on page 648).
  • the total thickness of all hydrophilic colloidal layers on the emulsion side is preferably in the range of 28 ⁇ m or less, more preferably 23 ⁇ m or less, most preferably 20 ⁇ m or less.
  • the film swelling rate (T 1 ⁇ 2 ) is preferably in the range of 30 seconds or less, more preferably 20 seconds or less.
  • the film thickness is determined after the film has been stored at 25°C and a relative humidity of 55% over 2 days.
  • the film swelling rate (T 1 ⁇ 2 ) can be determined by a method known in the art, e.g., by means of a swellometer of the type as described in A. Green, et al., Photographic Science & Engineering , Vol.
  • T 1 ⁇ 2 is defined as the time necessary for one half of the film thickness to be saturated, where a film is considered saturated when its thickness is 90% of the maximum swollen film thickness reached when it is processed with a color developer at a temperature of 30°C over 195 seconds.
  • the film swelling rate (T 1 ⁇ 2 ) can be adjusted by adding a film hardener to a binder gelatin or altering the aging condition after coating.
  • the percentage swelling of the light-sensitive material is preferably in the range of 150% to 400%.
  • the percentage swelling can be calculated from the maximum swollen film thickness determined as described above in accordance with the equation: (maximum swollen film thickness - film thickness)/film thickness.
  • the color photographic light-sensitive material of the present invention can be developed in accordance with known methods such as those described in Research Disclosure , No. 17643 (pages 28-29) and Research Disclosure , No. 18716 (left column to right column on page 615).
  • the color developer used to develop the material of the present invention is preferably an alkaline aqueous solution containing as a main component an aromatic primary amine color developing agent.
  • a color developing agent that can be effectively used is an aminophenolic compound.
  • p-phenylenediamine compounds are preferably used.
  • Typical examples of such p-phenylenediamine compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline, and sulfates, hydrochlorides and p-toluenesulfonates of these compounds. Particularly preferred among these is 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate. These compounds can be used in a combination of two or more depending on the purpose of the application.
  • the color developer used normally contains a pH buffer (such as a carbonate, a borate, or a phosphate of alkali metal); or a development inhibitor or fog inhibitor (such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles, and mercapto compounds).
  • a pH buffer such as a carbonate, a borate, or a phosphate of alkali metal
  • a development inhibitor or fog inhibitor such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles, and mercapto compounds.
  • the color developer used may also contain various preservatives (such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines like N,N-biscarboxymethyl hydrazine, phenylsemicarbazides, triethanolamine, and catecholsulfonic acids); organic solvents (such as ethylene glycol and diethylene glycol); development accelerators (such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines); color forming couplers; competing couplers; auxiliary developing agents (such as 1-phenyl-3-pyrazolidone); viscosity imparting agents; various chelating agents (such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids).
  • preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines like N,N-biscarboxymethyl hydrazine,
  • Examples of useful phosphonocarboxylic acids are ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, and ethylenediaminedi(o-hydroxyphenylacetic acid) and salts of these acids.
  • Black-and-white developers that can be used contain one or more of known black-and-white developing agents, such as dihydroxybenzenes (e.g., hydroquinone, 3-pyrazolidones and 1-phenyl-3-pyrazolidone) and aminophenols (e.g., N-methyl-p-aminophenol).
  • dihydroxybenzenes e.g., hydroquinone, 3-pyrazolidones and 1-phenyl-3-pyrazolidone
  • aminophenols e.g., N-methyl-p-aminophenol
  • the color developer or black and-white developer usually has a pH of from 9 to 12.
  • the replenishment rate of the developer is usually 3 liters or less per square meter of the light-sensitive material, depending on the type of the color photographic material to be processed.
  • the replenishment rate may be reduced to 500 ml/m 2 or less by decreasing the bromide ion concentration in the replenisher.
  • Opening Value Area of Liquid Surface in Contact With Air (cm 3 ) Volume of Liquid (cm 3 )
  • the opening value is preferably in the range of 0.1 or less, more preferably 0.001 to 0.05.
  • the reduction of the opening value can be accomplished by providing a cover such as floating cover on the surface of the photographic processing solution in the processing tank; by a process which comprises the use of a mobile cover (as described in JP-A-1-82033); or a slit development process (as described in JP-A-63-216050).
  • the reduction of the opening value can be applied to both the color development and black-and-white development as well as to the subsequent steps such as bleach, blix, fixing, rinse, and stabilization.
  • the replenishment rate can also be reduced by using a means to suppress accumulation of the bromide ion in the developing solution.
  • the color development time normally selected is between 2 and 5 minutes.
  • the color development time can be further reduced by carrying out color development at an elevated temperature and a high pH with color developing solution containing a high concentration of color developing agent.
  • the photographic emulsion layer that has been color developed is normally subjected to bleaching.
  • Bleaching may be done at the same time as the emulsion layer is fixed (i.e., blix), or these two steps may be carried out separately.
  • bleaching may be followed by blix.
  • any embodiment where two blix baths are connected in series; blix is preceded by fixation; or blix is followed by bleaching may also be used to speed up processing.
  • Bleaching agents that can be used are compounds of polyvalent metals (e.g., iron(III), peroxides, quinones, and nitro compounds).
  • bleaching agents are organic complex salts of iron(III) with aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid); citric acid; tartaric acid; or malic acid.
  • aminopolycarboxylic acids e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid
  • citric acid tartaric acid
  • malic acid e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
  • aminopolycarboxylic acid-iron(III) complex salts such as (ethylenediaminetetraacetato)iron(III) complex salts and (1,3-diaminopropanetetraacetato)iron-(III) complex salts are preferred in order to speed up processing and conserve the environment.
  • aminopolycarboxylic acid-iron(III) complex salts are useful in both bleaching and blix solutions.
  • Bleaching or blix solution containing an aminopolycarboxylic acid-iron(III) complex salt normally has a pH value of 4.0 to 8.0. For speeding up processing, it is possible to use solutions having a lower pH.
  • the bleaching bath, blix bath, or a prebath of either can contain, if desired, a bleaching accelerator.
  • a bleaching accelerator examples include compounds containing a mercapto group or a disulfide group (as described in U.S. Patent 3,893,858, West German Patent 1,290,812, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, and JP-A-53-28426, and Research Disclosure , No.
  • Preferred among these compounds are compounds that contain a mercapto group or a disulfide group because they have great accelerating effects.
  • the compounds disclosed in U.S. Patent 3,893,858, West German Patent 1,290,812, JP-A-53-95630 and U.S. Patent 4,552,834 are preferred.
  • These bleach accelerators may be incorporated into the light-sensitive material. These bleaching accelerators are particularly effective for blix of color photographic light-sensitive materials.
  • the bleaching or blix solution used in the present invention preferably also contains an organic acid in addition to the above mentioned compounds in order to inhibit bleach stain.
  • organic acids are ones having pKa of 2 to 5.
  • Specific examples of such an organic acid are acetic acid and propionic acid.
  • Fixing agents that can be used are the thiosulfates, thiocyanates, thioethers, thioureas, and a number of iodides.
  • the thiosulfates are normally used; ammonium thiosulfate has the most broad applicability.
  • the thiosulfates are preferably used in combination with thiocyanates, thioether compounds, and thiourea.
  • As a preservative of the fixing or blix bath it is preferable to use sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds as described in European Patent 294,769A.
  • the total desilvering time is preferably short so long as no misdesilvering takes place.
  • the total desilvering time is preferably in the range of 1 to 3 minutes, more preferably 1 to 2 minutes.
  • the desilvering temperature is in the range of 25 to 50°C, preferably 35 to 45°C. In this preferred temperature range, the desilvering rate can be improved, and the occurrence of stain after processing can be effectively inhibited.
  • agitation is preferably intensified as much as possible.
  • the agitation can be intensified by jetting the processing solution to the surface of the emulsion layer in the light-sensitive material (as described in JP-A-62-183460 and JP-A-62-183461); by using a rotary means (as described in JP-A-62-183461); by moving the light-sensitive material with the emulsion surface in contact with a wiper blade provided in the bath so that a turbulence occurs on the emulsion surface; by increasing the total circulated amount of processing solution (this method can be effectively applied to the bleaching bath, blix bath, or fixing bath).
  • the improved agitation increases the supplying rate of a bleaching agent, fixing agent or the like into the emulsion film, which improves the desilvering rate.
  • the agitation improving method is more effective when a bleach accelerator is used. Agitation improving not only enhances the bleach accelerating effect but also eliminates the inhibition of fixation by the bleach accelerator.
  • An automatic developing machine to be used in the present invention is preferably equipped with a light-sensitive material conveying means as described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259.
  • a conveying means will remarkably reduce the amount of the processing solution carried over from a bath to its succeeding bath; which greatly inhibits the deterioration of properties of the processing solution. This reduces the processing time at each step as well as the replenishment rate of the processing solution.
  • desilvered silver halide color photographic materials of the present invention are subjected to washing and/or stabilization.
  • the quantity of water used in the washing can be selected from a broad range depending on the characteristics of the light-sensitive material (for example, the kind of couplers, etc.), the end use of the light-sensitive material, the temperature of washing water, the number of washing tanks (number of stages), the replenishment system (e.g., counterflow system or direct flow system), and various other factors.
  • the relationship between the number of washing tanks and the quantity of water in a multistage counterflow system can be obtained according to the method described in Journal of the Society of Motion Picture and Television Engineers , Vol. 64, pages 248 to 253 (May, 1955).
  • isothiazolone compounds or thiabendazoles as disclosed in JP-A-57-8542
  • chlorine type bactericides e.g., chlorinated sodium isocyanurate, benzotriazole
  • bactericides as described in Hiroshi Horiguchi, Bokin Bobaizai no Kagaku (Chemistry of Bactericidal and Fungicidal Agents) , Sankyo Shuppan (1986); Association of Sanitary Technique (ed.), Biseibutsu no Mekkin, Sakkin, Bobaigijutsu (Bactericidal and Fungicidal Techniques to Microorganisms) , published by Association of Engineering Technology (1982); and Nippon Bactericidal and Fungicidal Association (ed.), Bokin Bobaizai Jiten (Encyclopedia of Bactericidal and Fungicidal Agents) (1986).
  • the washing water has a pH value of from 4 to 9, preferably from 5 to 8.
  • the temperature of the water and the washing time can be selected from broad ranges depending on the characteristics and end use of the light-sensitive material, but usually ranges from 15 to 45°C in temperature and from 20 seconds to 10 minutes in time, preferably from 25 to 40°C in temperature and from 30 seconds to 5 minutes in time.
  • the light-sensitive material of the present invention may be directly processed with a stabilizer in place of the washing step.
  • any of the known techniques described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used.
  • the washing step may be followed by stabilization.
  • a stabilizing bath containing a dye stabilizer and a surface active agent can be used as a final bath for color light-sensitive photographic materials.
  • a dye stabilizer include aldehydes (such as formalin and glutaraldehyde), N-methylol compounds, hexamethylenetetramine, and aldehyde-sulfurous acid adducts.
  • the stabilizing bath may also contain various chelating agents or bactericides.
  • the overflow accompanying replenishment of the washing bath and/or stabilizing bath can be reused in other steps such as desilvering.
  • water is preferably supplied to the system to maintain the proper concentration.
  • Silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and expediting processing.
  • a color developing agent is preferably used in the form of a precursor.
  • precursors include indoaniline compounds (as disclosed in U.S. Patent 3,342,597); Shiff's base type compounds (as disclosed in U.S. Patent 3,342,599, and Research Disclosure , Nos. 14850 and 15159); aldol compounds (as disclosed in Research Disclosure , No. 13924); metal complexes (as disclosed in U.S. Patent 3,719,492); and urethane compounds (as disclosed in JP-A-53-135628).
  • the silver halide color light-sensitive material of the present invention may optionally comprise various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical examples of such compounds are disclosed in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.
  • the various processing solutions are used at a temperature of from 10°C to 50°C.
  • the standard temperature range is normally from 33°C to 38°C.
  • a higher temperature range can be used to accelerate processing, thus reducing the processing time.
  • a lower temperature range can be used to improve the picture quality or the stability of the processing solutions.
  • processing using cobalt intensification or hydrogen peroxide intensification as disclosed in West German Patent 2,226,770 and U.S. Patent 3,674,499 can be used.
  • the present silver halide photographic material can also be applied to a heat developable light-sensitive material as disclosed in U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056, and European Patent 210,660A2.
  • a multilayer color light-sensitive material was prepared as Sample 201 by coating on an undercoated cellulose triacetate film support various layers having the compositions described below.
  • the figures indicate the amount (unit: g) of each component added per m 2 of light-sensitive material.
  • the coated amount of silver halide is represented as calculated in terms of silver.
  • the coated amount of sensitizing dye is represented in molar amount per mol of silver halide contained in the same layer.
  • Second Layer Antihalation Layer Black Colloidal Silver 0.18 (as Ag) Gelatin 1.40
  • Second Layer Interlayer
  • Third Layer First Red-Sensitive Emulsion Layer Emulsion A 0.25 (as Ag) Emulsion B 0.25 (as Ag) Sensitizing Dye 20 6.9 ⁇ 10 -5 Sensitizing Dye 21 1.8 ⁇ 10 -5 Sensitizing dye 6 3.1 ⁇ 10 -4 EX-2 0.335 EX-10 0.020 V-1 0.07 V-2 0.05 V-3 0.07 HBS-1 0.060 Gelatin 0.87
  • Fourth Layer Second Red-Sensitive Emulsion Layer
  • Fifth Layer Third Red-Sensitive Emulsion Layer Emulsion D 1.60 (as Ag) Sensitizing Dye 20 5.4 ⁇ 10 -5 Sensitizing Dye 21 1.4 ⁇ 10 -5 Sensitizing Dye 6 2.4 ⁇ 10 -4 EX-3 0.010 EX-4 0.080 EX-2 0.097 HBS-1 0.22 HBS-2 0.10 Ge
  • a silver bromide shell (second coating layer) was then formed on the above mentioned emulsion as a core emulsion.
  • the molar proportion of the first coating layer to the second coating layer was 1/4.
  • a monodisperse emulsion of core/shell octahedral grains having an average diameter of 0.7 ⁇ m (fluctuation coefficient: 14%, calculated in terms of sphere) and an internal silver iodide content of 25 mol% was obtained.
  • K 3 IrCl 6 was added to the emulsion in an amount of 4 ⁇ 10 -4 mol per mol of silver halide.
  • the emulsion was then subjected to optimum gold-sulfur sensitization with sodium thiosulfate, chloroauric acid and potassium thiocyanate at a temperature of 60°C.
  • silver bromoiodide grains having a diameter of 0.3 ⁇ m calculated in terms of projected area and a silver iodide content of 25 mol% were obtained to form nuclei.
  • 800 ml of a 1.5 M silver nitrate solution and 800 ml of a halide solution containing 0.375 M potassium iodide and 1.13 M potassium bromide were simultaneously added to the system at a temperature of 75°C in a double jet process in 100 minutes.
  • the emulsion was then cooled to 35°C, and washed with water in the ordinary flocculation process.
  • 70 g of gelatin was added to the emulsion so that the pH value and pAg value thereof were adjusted to 6.2 and 8.8, respectively.
  • a first coating layer was formed.
  • an emulsion of octahedral silver bromoiodide grains having a diameter of 0.7 ⁇ m calculated in terms of projected area was obtained (silver iodide content: 25 mol%).
  • a silver bromide shell (second coating layer) was then formed on the above mentioned emulsion as core emulsion.
  • the molar proportion of the first coating layer to the second coating layer was 1/2.
  • a monodisperse emulsion of core/shell octahedral grains having an average diameter of 1.0 ⁇ m (fluctuation coefficient: 10%) calculated in terms of sphere and an internal silver iodide content of 25 mol% was obtained.
  • K 3 IrCl 6 was added to the emulsion in an amount of 7 ⁇ 10 -4 mol per mol of silver halide.
  • the emulsion was then subjected to optimum gold-sulfur sensitization with sodium thiosulfate, chloroauric acid, and potassium thiocyanate at a temperature of 60°C.
  • a potassium bromide solution containing 75 g of silver nitrate and 25 mol% of potassium iodide was added to the system in an amount equimolecular with silver nitrate at an accelerated flow rate (the final flow rate was 10 times the initial value) over 40 minutes.
  • 75 g of silver nitrate and an equimolecular amount of potassium bromide to the above silver nitrate were then added to the system at an accelerated flow rate (the final flow rate was twice the initial value) over 20 minutes (formation of shell).
  • the emulsion was cooled to a temperature of 35°C, and washed with water in the ordinary flocculation process. 60 g of gelatin was added to and dissolved in the emulsion at a temperature of 40°C.
  • the pH value and pAg value of the emulsion were adjusted to 6.5 and 8.6, respectively.
  • the resulting tabular grains had a core/shell structure (core/shell ratio: 1) comprising a core made of silver bromoiodide having a silver iodide content of 25 mol% and a shell made of pure silver bromide.
  • the tabular grains thus obtained also had average diameter of 2.3 ⁇ m calculated in terms of sphere, a diameter fluctuation coefficient of 15%, and a thickness of 0.33 ⁇ m.
  • Emulsion L thus obtained was subjected to optimum gold-sulfur sensitization with sodium thiosulfate, chloroauric acid and potassium thiocyanate at a temperature of 60°C.
  • Emulsions J, K and L were subjected to spectral sensitization with sensitizing dyes as set forth in Tables 1, 2 and 3 to prepare Emulsions J-1 to J-15, K-1 to K-15, and L-1 to L-15.
  • Multilayer color light-sensitive material Samples 301 to 305 were prepared in the same manner as Sample 201 of Example 1 except that silver halide emulsions as set forth in Table 4 were used.
  • Samples 306 to 310 were prepared in the same manner as Samples 301 to 305, respectively, except that the first layer was formed by coating a dye dispersion which had been prepared as follows from a 1/1 (by weight) mixture of Compound III-34 and Compound I-4 free of black colloidal silver in such an amount that the sum of the content of the dyes reached 0.26 g/m 2 and the tenth layer was formed by coating a dye dispersion of Compound I-1 free of colloidal silver in such an amount that the coated amount of Compound I-1 reached 0.23 g/m 2 .
  • the dye was subjected to dispersion in a vibration mill in the following manner:
  • the content was withdrawn and then added to 8 g of a 12.5% aqueous solution of gelatin.
  • the material was then filtered to remove the beads to obtain the gelatin dispersion of dye.
  • the mixing ratio of these dyes was equimolar to each other.
  • Samples 302 to 305 prepared by incorporating sensitizing dyes in silver halide emulsions at an elevated temperature exhibit an improved sensitivity but poor desilverability as compared to Sample 301 prepared by incorporating a sensitizing dye in a silver halide emulsion at a low temperature.
  • Samples 307 to 310 prepared by replacing black silver in the antihalation layer or colloidal silver in the yellow filter layer by a dye dispersion, exhibit remarkably improved desilverability compared to Sample 301.
  • Samples 307 to 310 exhibit substantially the same desilverability as Sample 306, prepared simply by replacing the colloidal silver in the antihalation layer and the yellow filter layer by a dye dispersion.
  • the fixing tank in the automatic developing machine used was equipped with a jet agitator as described in JP-A-62-183460 (Page 3). In this arrangement, the fixing solution was jetted to the surface of the light-sensitive material to be processed.
  • Color Developer Running Solution Replenisher Hydroxyethyliminodiacetic Acid 5.0 g 6.0 g Sodium Sulfite 4.0 g 5.0 g Potassium Carbonate 30.0 g 37.0 g Potassium Bromide 1.3 g 0.5 g Potassium Iodide 1.2 mg - Hydroxylamine Sulfate 2.0 g 3.6 g 4-[N-Lithyl-N- ⁇ -hydroxyethylamino]-2-methylaniline Sulfate 1.0 ⁇ 10 -2 mol 1.3 ⁇ 10 -2 mol Water to make 1.0 liter 1.0 liter pH 10.00 10.15 Bleaching Solution: Running Solution Replenisher Ferric 1,3-Diaminopropanetetraacetic Acid Complex Salt 130 g 190 g 1,

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (5)

  1. Farbphotographisches Silberhalogenidmaterial, umfassend:
    einen Träger,
    mindestens eine blauempfindliche Emulsionsschicht, eine grünempfindliche Emulsionsschicht und eine rotempfindliche Emulsionsschicht auf dem Träger, und umfassend:
    eine oder mehrere hydrophile Kolloidschichten, die eine Dispersion von Mikrokristallen mindestens einer Verbindung der allgemeinen Formel (I), (II), (III), (IV), (V) und (VI) enthalten:
    Figure imgb0203
    Figure imgb0204

            A=L1-(L2=L3)n-A'     (III)



            A=(L1-L2)2-q=B     (IV)

    Figure imgb0205
    Figure imgb0206
    wobei A und A' gleich oder verschieden sein können und jeweils einen sauren Ring bedeuten, B einen basischen Ring bedeutet, X und Y gleich oder verschieden sein können und jeweils eine elektrophile Gruppe bedeuten, R ein Wasserstoffatom oder einen Alkylrest darstellt, R1 und R2 jeweils einen Alkylrest, einen Arylrest, einen Acylrest oder einen Sulfonylrest bedeuten und R1 und R2 miteinander verbunden sein können, um einen 5- oder 6-gliedrigen Ring zu bilden, R3 und R6 jeweils ein Wasserstoffatom, einen C1-10 Alkylrest, eine Hydroxylgruppe, eine Carboxylgruppe, einen Alkoxyrest oder ein Halogenatom bedeuten, R4 und R5 jeweils ein Wasserstoffatom oder eine nichtmetallische Atomgruppe bedeuten, die erforderlich ist, um R1 und R4 oder R2 und R5 miteinander zu verbinden, um einen 5- oder 6-gliedrigen Ring zu bilden, L1, L2 und L3 jeweils eine Methingruppe bedeuten, m 0 oder 1 bedeutet, n und q jeweils 0, 1 oder 2 bedeuten, p 0 oder 1 bedeutet und B' eine Carboxylgruppe, eine Sulfamoylgruppe oder eine heterocyclische Gruppe, die eine Sulfonamidgruppe enthält, bedeutet, mit der Maßgabe, daß wenn p 0 ist,
    (i) R3 eine Hydroxylgruppe oder eine Carboxylgruppe bedeutet und R4 und R5 jeweils ein Wasserstoffatom bedeuten und
    (ii) die Verbindung der allgemeinen Formel (I), (II), (III), (IV), (V) oder (VI) pro Molekül mindestens eine Dissoziationsgruppe enthält, die einen pKa-Wert von 4 bis 11 in einem 1/1-Gemisch (Volumen) von Wasser und Ethanol aufweist,
    und mindestens eine lichtempfindliche Silberhalogenidemulsionsschicht mit einer Silberdichte (d) von 0,4 g/cm3 oder mehr,
    wobei d N/V bedeutet, wobei N die Gesamtzahl der Grammenge Silber in der einen oder den mehreren Silberhalogenidemulsionsschichten bedeutet und V das Volumen in cm3 der lichtempfindlichen Silberhalogenidemulsionsschicht bedeutet, wobei die mindestens eine lichtempfindliche Silberhalogenidemulsionsschicht mindestens eine lichtempfindliche Silberhalogenidemulsion enthält, die durch Zugabe eines photographischen Sensibilisierungsfarbstoffes bei einer Temperatur von 50 °C oder höher spektral sensibilisiert ist.
  2. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, wobei der photographische Sensibilisierungsfarbstoff zu der mindestens einen lichtempfindlichen Silberhalogenidemulsionsschicht zwischen der Vollendung der Bildung der Silberhalogenidkörner und der Vollendung der chemischen Sensibilisierung zugegeben wird.
  3. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, wobei der photographische Sensibilierungsfarbstoff zu der mindestens einen lichtempfindlichen Silberhalogenidemulsionsschicht vor der Vollendung der Bildung des Silberhalogenidkörner zugegeben wird.
  4. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, wobei die mindestens eine lichtempfindliche Silberhalogenidemulsionsschicht Silberhalogenidkörner enthält, die Silberjodid enthalten, wobei der durchschnittliche Silberjodidgehalt in mindestens einer lichtempfindlichen Silberhalogenidemulsionsschicht 8 mol% oder weniger beträgt.
  5. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, weiterhin umfassend:
    eine Emulsionsschicht, die mindestens eine Verbindung der allgemeinen Formel (VII):
    Figure imgb0207
     enthält, in der M1 ein Wasserstoffatom, ein Kation oder eine Schutzgruppe für eine Mercaptogruppe bedeutet, die der Spaltung durch Alkali unterliegt,
    X' eine Atomgruppe bedeutet, die zur Bildung eines 5- oder 6-gliedrigen heterocyclischen Restes, der Schwefel, Selen, Stickstoff oder Sauerstoff als Heteroatome enthält, notwendig ist und der substituiert oder Teil eines kondensierten Ringes sein kann,
    R' einen gerad- oder verzweigtkettigen Alkylenrest, einen gerad- oder verzweigtkettigen Alkenylenrest, einen gerad- oder verzweigtkettigen Aralkylenrest oder einen Arylenrest bedeutet, R" ein Wasserstoffatom oder eine Gruppe bedeutet, die das Wasserstoffatom ersetzen kann,
    Z einen polaren Substituenten bedeutet,
    Y eine Gruppe
    Figure imgb0208
     bedeutet, in denen R1', R'2, R'3, R'4, R'5, R'6, R'7, R'8, R'9 und R'10 jeweils ein Wasserstoffatom, einen substituierten oder unsubstituierten Alkylrest, einen Arylrest, einen Alkenylrest oder einen Aralkylrest bedeuten, n 0 oder 1 bedeutet, und M 0, 1 oder 2 bedeutet.
EP19900119763 1989-10-16 1990-10-15 Farbfotografisches Silberhalogenidmaterial Expired - Lifetime EP0423693B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP26857989A JPH03130761A (ja) 1989-10-16 1989-10-16 ハロゲン化銀カラー写真感光材料
JP268579/89 1989-10-16
JP269558/89 1989-10-17
JP26955889A JPH03131845A (ja) 1989-10-17 1989-10-17 ハロゲン化銀カラー写真感光材料
JP26955989A JPH03131846A (ja) 1989-10-17 1989-10-17 ハロゲン化銀カラー写真感光材料
JP269559/89 1989-10-17

Publications (3)

Publication Number Publication Date
EP0423693A2 EP0423693A2 (de) 1991-04-24
EP0423693A3 EP0423693A3 (en) 1991-07-31
EP0423693B1 true EP0423693B1 (de) 1997-04-09

Family

ID=27335645

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900119763 Expired - Lifetime EP0423693B1 (de) 1989-10-16 1990-10-15 Farbfotografisches Silberhalogenidmaterial

Country Status (2)

Country Link
EP (1) EP0423693B1 (de)
DE (1) DE69030416T2 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0437841A (ja) * 1990-06-04 1992-02-07 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
US5288600A (en) * 1991-08-21 1994-02-22 Fuji Photo Film Co., Ltd. Silver halide photographic material containing an oil-soluble dye dispersion
JP2767335B2 (ja) * 1992-01-20 1998-06-18 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JP2717475B2 (ja) * 1992-02-26 1998-02-18 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JPH0619091A (ja) * 1992-04-16 1994-01-28 Eastman Kodak Co 改良された多層性カラー写真要素
EP0582000A1 (de) * 1992-08-03 1994-02-09 Agfa-Gevaert N.V. Photographischer Farbnegativ- oder Intermediärfarbfilm
JPH06250353A (ja) * 1993-02-26 1994-09-09 Konica Corp ハロゲン化銀カラー感光材料および撮影ユニット包装体
JPH06337493A (ja) * 1993-05-31 1994-12-06 Konica Corp ハロゲン化銀カラー写真感光材料
JPH07168299A (ja) * 1993-12-16 1995-07-04 Konica Corp ハロゲン化銀写真乳剤、ハロゲン化銀写真感光材料及びその処理方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0209118B1 (de) * 1985-07-17 1991-10-23 Konica Corporation Photographisches Silberhalogenidmaterial
JPH0713729B2 (ja) * 1986-10-03 1995-02-15 富士写真フイルム株式会社 ハロゲン化銀カラ−写真感光材料
US4855221A (en) * 1987-07-13 1989-08-08 Eastman Kodak Company Photographic elements having oxonol dyes
DE3774121D1 (de) * 1986-12-23 1991-11-28 Eastman Kodak Co Filterfarbstoffe in einer festpartikeldispersion fuer photographische zusammensetzungen.
US4908303A (en) * 1987-02-12 1990-03-13 Fuji Photo Film Co., Ltd. Silver halide photographic materials spectrally sensitized with luminous dye

Also Published As

Publication number Publication date
DE69030416D1 (de) 1997-05-15
EP0423693A2 (de) 1991-04-24
DE69030416T2 (de) 1997-07-17
EP0423693A3 (en) 1991-07-31

Similar Documents

Publication Publication Date Title
EP0423693B1 (de) Farbfotografisches Silberhalogenidmaterial
US5296344A (en) Silver halide photographic light-sensitive material
EP0501306B1 (de) Farbphotographisches Silberhalogenidmaterial
EP0362870A2 (de) Farbphotographisches Silberhalogenidmaterial
EP0438129B1 (de) Farbphotographisches Silberhalogenidmaterial
US5192651A (en) Silver halide color photographic photosensitive materials containing at least two types of cyan dye forming couplers
EP0442323B1 (de) Photographisches Silberhalogenidfarbumkehrmaterial mit Zwischenbildeffekt
EP0451859B1 (de) Farbphotographisches lichtempfindliches Silberhalogenidmaterial
EP0514896B1 (de) Farbphotographisches lichtempfindliches Silberhalogenidmaterial
US5273866A (en) Silver halide color photographic material
EP0456181B1 (de) Farbphotographisches Silberhalogenidmaterial und Verfahren zu dessen Verarbeitung
US5360709A (en) Silver halide photographic material containing a DIR compound
US5432051A (en) Silver halide color photographic material
EP0435295A1 (de) Farbphotographisches lichtempfindliches Silberhalogenidmaterial
EP0610921A2 (de) Farbphotographisches Silberhalogenidmaterial
US5447833A (en) Silver halide photographic material and imidazole derivatives
US5024924A (en) Method for processing silver halide color photographic materials
US5266456A (en) Silver halide color photographic material having a high silver iodide content and containing a yellow colored cyan coupler
US5380631A (en) Silver halide color photographic light-sensitive material
US5284740A (en) Silver halide color photographic material
US5538835A (en) Silver halide color photographic material
EP0428902B1 (de) Farbfotografische Silberhalogenidmaterialien
US5338654A (en) Silver halide color photographic material
JP2579220B2 (ja) ハロゲン化銀カラー写真感光材料
US5449598A (en) Silver halide color photographic material

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE FR GB NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB NL

17P Request for examination filed

Effective date: 19911121

17Q First examination report despatched

Effective date: 19950119

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19970409

Ref country code: FR

Effective date: 19970409

REF Corresponds to:

Ref document number: 69030416

Country of ref document: DE

Date of ref document: 19970515

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
EN Fr: translation not filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20041013

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20051015

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20051015

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20081014

Year of fee payment: 19

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100501