EP0159913A1 - Lichtempfindliches photographisches Silberhalogenidmaterial - Google Patents

Lichtempfindliches photographisches Silberhalogenidmaterial Download PDF

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Publication number
EP0159913A1
EP0159913A1 EP85302680A EP85302680A EP0159913A1 EP 0159913 A1 EP0159913 A1 EP 0159913A1 EP 85302680 A EP85302680 A EP 85302680A EP 85302680 A EP85302680 A EP 85302680A EP 0159913 A1 EP0159913 A1 EP 0159913A1
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EP
European Patent Office
Prior art keywords
group
alkyl
silver halide
sensitive
light
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EP85302680A
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English (en)
French (fr)
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EP0159913B1 (de
Inventor
Takashi Kadowaki
Kaoru Onodera
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Konica Minolta Inc
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Konica Minolta Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39292—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
    • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
    • G03C7/3005—Combinations of couplers and photographic additives
    • G03C7/3006—Combinations of phenolic or naphtholic couplers and photographic additives

Definitions

  • the present invention relates to a silver halide photographic light-sensitive material and more particularly, to a silver halide color photographic light-sensitive material for a print.
  • a color light-sensitive material for a print is, usually, spectrographically sensitized using a silver halide and a sensitization coloring dye in accordance with a three-color separation process for a color reproducing purpose.
  • This material contains a yellow color coupler in a blue-sensitive silver halide emulsion layer, a magenta color coupler in a green-sensitive silver halide emulsion layer and a cyan color coupler in a red-sensitive silver halide emulsion layer.
  • the material After exposing imagewise, the material is subjected to a color development using a color developer containing a p-phenylene diamine derivative as a color developing agent to form a color dye image and a silver image.
  • cyan couplers include a light-resistance, spectroabsorptive characteristics of the color dye thereof, etc., and whereby a desirable cyan coupler is selected.
  • a sharpness will exert a great influence on the image quality.
  • the studies have been continued on anti-irradiation dyes, anti-halation dyes, supports and layer arrangements, and among these, dyes have presented a great effect on the sharpness, and have been zealously examined.
  • the characteristics, as such dyes will be selected, include 1) a spectroabsorptive characteristic and 2) an elusivity during treatment. Oxonol, azo and anthraquinone type dyes have been researched as those meeting these characteristics. Among these, particularly, oxonolpyrazolone dyes are excellent.
  • these oxonolpyrazolone dyes have the characteristics to affect a silver halide to increase fogs.
  • the examinations have been made of an anti-fogging agent, a mordant, a modification of an emulsion-added layer and the like, but in these examinations, no satisfactory effect is obtained.
  • a further object of the present invention is to provide a silver halide photographic light-sensitive material having an excellent stability in latent image and a good whiteness.
  • the constitution of the present invention resides in a silver halide photographic light-sensitive material which contains a compound represented by the following Formula [I] and a compound represented by the following Formula [II] on a support.
  • R 1 represents an alkyl, cycloalkyl, aryl, heterocyclic, alkoxy, aryloxy, alkylamino or arylamino group
  • R 2 represents hydrogen, a halogen, an alkyl or alkoxy group
  • R 3 represents an alkyl, cycloalkyl or aryl group, R 2 and R 3 may be bonded together to form a 5- or 6- membered ring condensed to the phenolic ring
  • Z represents hydrogen, or a group releasable by the coupling reaction with the oxidation product of an aromatic primary amine color developing agent.
  • R 4 and R 5 are respectively an alkyl or aryl group, -COOR', -OR', -NR', -NR'R", -CN, -NHCOR', -NHCONHR' or -CONHR' wherein R' and R" represents an alkyl or aryl group, respectively; and R 6 and R 7 are respectively an alkyl or aryl group containing at least one carboxy group or sulfonic acid group.
  • alkyl groups represented by R 1 in Formula [I] are preferably an straight or branched alkyl groups containing 1 to 20 carbon atoms, such as, for example, methyl, ethyl, i-propyl, t-butyl, dodecyl or pentadecyl group.
  • Cycloalkyl groups denoted by R 1 are cyclohexyl group, for example, and heterocyclic groups are preferably five- or six- membered.
  • the 5- membered heterocyclic groups are thienyl, pyrrolyl, furyl, thiazolyl, imidazolyl, pyrazolyl, succinimide, triazolyl and tetrazolyl groups.
  • the 6- membered heterocylic groups are pyridyl, pyrimidyl, triazinyl, thiazianyl and dithiazinyl groups. These heterocyclic groups may form, with benzene ring, condensed rings such as for example, brinyl indazolyl, benzoxazolyl, benzimidazolyl, quinolyl, indolyl or phthalimide group.
  • aryl groups denoted by R 1 are, for example, phenyl and naphthyl groups, and preferably, phenyl group.
  • alkoxy group denoted by R 1 is methoxy, ethoxy and t-butoxy groups, and examples of aryloxy groups are phenoxy and naphthoxy groups.
  • alkylamino group denoted by R 1 are N,N-di-t-butylamino, N-dodecylamino and N-pentadecylamino groups, and arylamino groups include amilino group. Each of these groups may be substituted.
  • R 1 is preferably phenyl group or an alkyl group, and when the alkyl group is substituted, the preferred substituents are halogen atoms such as fluorine, chlorine and bromine atoms, and particularly, the alkyl group is preferred to be a fluorine atom-substituted alkyl group.
  • substituents are a halogen atom (e.g., chlorine and fluorine atoms), hydroxyl, nitro, cyano, alkyl (e.g., methyl, ethyl, t-butyl and dodecyl), carboxylic acid (e.g., -COOH, -COONa), sulfonic acid (e.g., -SO 3 H and -SO 3 Na), alkylamino (e.g., N,N-dimethylamino, N,N-diethylamino and N-butylamino), arylamino (e.g., anilino) alkylsulfonyl (e.g., methyl- and ethyl-sulfonyl), arylsulfonyl (e.g., phenyl-sulfonyl), alkoxy (e
  • halogen atom e.g., chlorine and fluorine atom
  • Preferred sustituents introduce into the phenyl group include a halogen, an alkyl (particularly, halogen atom-substituted alkyl), cyano, alkylsulfonamide, arylsulfonamide, alkylsulfamoyl, arylsulfamoyl, alkylureido, arylureido, alkyloxycarbonyl, aryloxycarbonyl, alkylcarbonyloxy and arylcarbonyloxy groups.
  • a halogen denoted by R 2 in Formula [I] is chlorine, fluorine, etc., for example; and alkyl groups denoted by R 2 are linear or branched alkyl groups, including methyl, ethyl and t-butyl groups, for example. Alkoxy groups denoted by R 2 are methoxy, ethoxy and t-butoxy groups, for example. Each of these groups may be substituted.
  • R 2 is hydrogen or chlorine, or methyl group.
  • Alkyl groups denoted by R 3 in Formula [I] are straight or branched groups such as ethyl, butyl, iso-pentyl, hexyl, sec-octyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl and octadecyl groups, and preferably, alkyl groups containing 1 to 30 Carbon atoms.
  • alkyl groups may be substituted, and the representatives of these substituents include phenoxy [which may have further substituents including typically a halogen (e.g., fluorine and chlorine), and hydroxyl, nitro, cyano, alkyl (e.g., methyl, butyl and dodecyl), alkoxy (e.g., methoxy and ethoxy), aryl (e.g., phenyl and tolyl), aryloxy (e.g., phenoxy and naphthoxy, aralkyl (e.g., benzyl), alkylsulfamoyl (e.g., butylsulfamoyl), arylsulfamoyl (e.g., phenylsulfamoyl), alkyloxycarbonyl (e.g., n-octyloxycarbonyl), aryloxycarbonyl (e.g., plienoxycarbonyl
  • cycloalkyl groups denoted by R 3 are cyclobutyl, cyclopentyl, cyclohexyl, and cyclobutyl groups, and preferably, cyclohexyl group. These cycloalkyl groups may be substituted.
  • aryl groups denoted by R 3 are phenyl and naphthyl groups, and preferably, phenyl group. These aryl groups may be substituted, and the representatives of such substituents are a halogen (e.g., chlorine and fluorine), and hydroxyl, nitro, cyano, alkyl (e.g., methyl, butyl and dodecyl), alkoxy (e.g., methoxy and ethoxy), aryl (e.g., phenyl and tolyl), aryloxy (e.g., phenoxy), alkylsulfamoyl (e.g., butylsulfamoyl), arylsulfamoyl (e.g., phenylsulfamoyl), alkyloxycarbonyl (e.g., n-octyloxycarbonyl), aryloxycarbonyl (e.g., phenoxycarbonyl (
  • R 3 in Formula [I] are alkyl and aryl groups, and more preferred groups are those represented by the following Formula [III]:
  • n is an integer of 0 or 1
  • R 8 represents alkylene groups ⁇ for example, ⁇ -ethylmethylene, ⁇ -butylmethylene, ⁇ -dodecylmethylene, ⁇ -butylmethylene and ⁇ -dodecylmethylene groups, wherein the carbon atom in the ⁇ -position of the ethylene group indicates the carbon directly bonded to the carbon atom of the acylamino group in Formula [I] ⁇ ; or arylene groups such as phenylene group.
  • X represents divalent groups such as -0-, -COO-, -OCO-, -S0 2 -, -S-, -NHS0 2 -, -SO 2 NH-, -CONH-or -NHCO-, and preferably, -O- or -SO 2 -.
  • R 9 represents straight or branched alkyl groups (including those having 1 to 20 carbon atoms, such as n-butyl, n-pentyl, n-octyl, n-nonyl, n-dodecyl, n-hexadecyl, n-octadecyl, sec-pentadecyl, sec-tridecyl, t-octyl and t-nonyl groups), or aryl groups (such as phenyl group). These alkyl and aryl groups may be substituted.
  • the representatives of substituents of phenyl group are a halogen (such as fluorine, chlorine and bromine), and hydroxyl, cyano, nitro, alkyl (such as methyl, ethyl, butyl, pentyl, octyl, dodecyl, etc.), alkoxy (such as methoxy, ethoxy, butoxy, octyoxy, etc.), alkylsulfamoyl (such as butylsulfamoyl, octylsulfamoyl, etc.), arylsulfamoyl (such as phenylsulfamoyl, xylylsulfamoyl, tolylsulfamoyl, mesitylsulfamoyl, etc.), alkyloxycarbonyl (such as methyloxycarbonyl, butyloxycarbonyl, etc.), aryloxycarbonyl (such as
  • substituents on alkyl group include similarly those as described above.
  • Preferred groups designated by R 9 include unsubstituted phenyl groups or phenyl groups containing alkyl, alkylsulfonamide, alkoxy, alkylsulfamoyl, aminosulfonamide, alkyloxycarbonyl or aryloxycarbonyl group as the substituents thereof.
  • Groups designated by R 9 also include groups forming a 5-or 6- membered ring condensed to their phenclic rings by bonding R 2 with R 3 in Formula [I], such as a group forming carbostyryl or 3,4-dihydrocarboxtyryl.
  • Groups designated by Z in Formula [I], which is releasable through the coupling reaction with the oxidation product of an aromatic primary amine color developing agent are well known to those skilled in the art and which improve the reactivity of a coupler, or advantageously action to be released from the coupler so as to fulfill their functions of development inhibition, bleaching inhibition and color correction on a coated layer on the other layers of a silver halide color photographic light-sensitive material, containing the coupler.
  • Typical examples of such groups are a halogen (such as fluorine, chlorine and bromine), and alkoxy (such as methoxy, ethoxy and octoxy), aryloxy (such as phenyloxy), cyclohexyloxy, arylazo (such as phenylazo), and thioether (such as benzylthio) group as well as hetrocyclic groups (such as oxazolyl, diazolyl, triazolyl and tetrzolyl groups), and aralkylcarbonyloxy group.
  • Particularly suitable groups designated by Z are hydrogen, a halogen (preferably, chlorine), and alkoxy and aryloxy groups.
  • Particularly preferred cyan couplers represented by Formula [I] are compounds designated by the following
  • R 10 represents a halogen (such as chlorine and fluorine), alkylsulfonamide (such as methanesulfonamide and ethanesulfonamide), arylsulfonamide (such as benzenesulfonamide), alkylsulfamoyl (such as methylsulfamoyl and ethylsulfamoyl), arylsulfamoyl (such as phenylsulfamoyl), cyano, alkyloxycarbonyl (such as methoxycarbonyl and ethoxycarbonyl), aryloxycarbonyl (such as phenoxycarbonyl), and alkyl groups (such as methyl, ethyl, t-butyl, dodecyl, octadecyl, benzyl, phenethyl, trifluoromethyl and pentafluoroethyl).
  • alkylsulfonamide
  • R 11 represents straight or branched alkyl groups (such as methyl, ethyl, t-butyl, n-butyl and n-dodecyl groups), and preferably, straight or branched alkyl groups containing 1 to 20 carbon atoms.
  • R 12 designates straight or branched alkyl groups (such as methyl, ethyl, n-butyl, t-amyl, n-pentyl, n-octyl and n-dodecyl groups), alkylsulfonamide (such as methylsulfonamide, ethylsulfonamide, butylsulfonamide and benzylsulfonamide), alkylsulfamoyl (such as butylsulfamoyl and octylsulfamoyl), alkoxy (such as methoxy, ethoxy, butoxy and octoxy), alkylaminosulfonamide (such as N,N-dmethylaminosulfonamide and N-methylaminosulfonamide), alkyloxycarbonyl (such as ethoxycarbonyl and butoxycarbonyl) and aryloxycarbonyl (such as phenoxycarbonyl
  • Z" designates hydrogen and a halogen (such as chlorine and fluorine) atoms, and k and l are an integer of 0 to 5, respectively.
  • Typical specified examples of cyan couplers designated by Formula [I] according to the present invention are as follows and are intended not to be limited thereto.
  • a cyan coupler represented by Formula [I] given hereinbefore (hereinafter referred to as a cyan coupler according to the present invention) and hydrophobic additives such as an ultraviolet absorbent for a magenta coupler or a yellow coupler or the like are incorporated into a silver halide emulsion layer or a non-light-sensitive layer after being dispersed in an aqueous solution of a hydrophilic binder in a known process.
  • the processes for dispersing these hydrophobic compounds include a latex dispersion process or an oil drop-in-water type dispersion process, for example, as described in Japanese Patent O.P.I. Publication Nos. 74538/1974, 59943/1976 and 32552/1979, and Research Disclosure No.
  • the high boiling organic solvents which can be employed in the aforesaid process include one or more, alone or in combination, of organic acid amides, carbamates, esters, ketones and urea derivatives, and particularly, phthalate esters such as dimethyl phthalate, diethylphthalate, dipropyl phthalate, dibutyl phthalate, di-n-octyl phthalate, di-isooctyl phthalate, diamylphthalate, dinonyl phthalate and di-isodecyl phthalate; phosphoric esters such as tricresyl phosphate, triphenyl phosphate, tri-(2-ethylhexyl)phosphate, and tri-ison ⁇ nyl phosphate; sebacic esters such as dioctyl sebacate, di-(2-ethylhexyl)sebacate and di-isodecyl sebacate; esters of glycerol such
  • One or more cyan couplers according to the present invention may be employed alone or in combination, but may be combined with other cyan couplers if required.
  • the cyan coupler according to the present invention in a color light-sensitive material, it may be incorporated into any of blue, green and red-sensitive emulsion layers, but preferably, is usually incorporated into the red-sensitive emulsion layer in an amount within a range of 0.1 to 1 mole per mole of a silver halide.
  • Alkyl groups designated by R 4 and R 5 in Formula [II] in the present invention are straight or branched alkyl groups containing 1 to 10 carbon atoms, and may be substituted with sulfonic acid group or carboxy group, including methyl, ethyl, propyl, iso-propyl or butyl group, for example.
  • aryl groups denoted by R 4 and R 5 may be substituted with sulfonic acid group, carboxy group or the like, and include phenyl, sulfophenyl or other group, for example.
  • R' and R" in groups of -COOR' -OR', -NR'R", -NHCOR', -NHCONHR' and -CONHR' are straight or branched alkyl or aryl groups containing 1 to 10 carbon atoms.
  • alkyl groups may be substituted with sulfonic acid group or carboxy group and include methyl, ethyl, propyl or iso-propyl group, for example.
  • Such aryl groups may also be substituted with sulfonic acid group or carboxy group and include phenyl or sulfophenyl group, for example.
  • Alkyl groups designated by R 6 and R 7 and containing at least one carboxy group or sulfonic acid group are sulfomethyl, carboxymethyl, sulfoethyl, carboxyethyl, sulfopropyl, carboxypropyl, disulfobutyl or dicarboxybutyl group, for example, and aryl groups denoted by R 6 and R 7 and containing at least one carboxy group or sulfonic acid group are sulfophenyl, disulfophenyl, trisulfophenyl, sulfo-caroxyphenyl, carboxyphenyl or dicarboxyphenyl group.
  • R 4 and R 5 in Formula [II] in the present invention are preferably groups designated by -COOR' wherein R' is preferably hydrogen or a straight or branched alkyl group containing 1 to 10 carbon atoms.
  • R 6 and R 7 in Formula [II] in the present invention are preferably a phenyl group containing at least one sulfonic acid group, and more preferably a phenyl group containing two or more sulfonic acid groups.
  • R"' is hydrogen or an alkyl group (such as methyl, ethyl or propyl group), n is an integer of from 2 to 5, and M represents hydrogen or a monovalent metal atom (such as sodium or potassium atom).
  • a compound represented by Formula [II] is generally dissolved in water or an alcohol and then incorporated into a silver halide containing layer and/or a non-light-sensitive layer in an amount within a range of 0.01 to lmg per 100cm 2 .
  • the compounds represented by Formula [II] are normally added into a green light-sensitive silver halide emulsion layer, and the same effect may be obtained even when adding it into other layers.
  • magenta and yellow couplers are employed together with a coupler according to the present invention and particularly, 3-anilino-5--pyrazolone type magenta coupler and pivaloyl-acetoamide type yellow coupler are preferably used.
  • magenta and yellow couplers are usually contained in a silver halide emulsion layer in an amount within a range of 0.01 to 2 moles, preferably 0.1 to 1.0 mole per mole of the silver halide, respectively.
  • Silver halides used in a silver halide emulsion relating to the present invention include any of those used in a normal silver halide emulsion, such as silver bromide, silver chlorobromide, silver chloroiodobromide emulsions or the like.
  • the grains of these silver halides may be coarse or fine, and the grain sizes thereof may be distributed into a narrower or wider range.
  • the crystals of these silver halide grains may be normal or twin, and can have any of ratios of [1 0 0] plane to [1 1 1] plane.
  • the crystal structure of these silver halide grains may be uniform throughout from the inner portion to the outer portion or may be different in layer structure between the inner and outer portions.
  • These silver halides may be of a type forming a latent imge primarily on the surface or of a type forming a latent image in the interior of the grain. Further, these silver halides may be produced in any of neutral, ammonia and acidic processes and also in any of double-jet, normal, reverse processes or conversion processes.
  • a silver halide emulsion obtained by removing soluble salts therefrom in a silver halide color photographic light-sensitive material according to the present invention it is possible to use a silver halide emulsion containing unremoved soluble salts. Two or more silver halide emulsions separately prepared can be used in mixture.
  • a silver halide photographic emulsion obtained by dispersing silver halide grains in a binder solution can be sensitized with a chemical sensitizer.
  • chemical sensitizers which can be advantageously used in the present invention are classified broadly into four groups: a group of noble metal sensitizers, a group of sulfur sensitizers, a group of selenium sensitizers and a group of reduction sensitizers.
  • Noble metal sensitizers which can be employed include gold compounds as well as rutenium rhodium, palladium, iridium or platinum compounds or the like.
  • ammonium thiocyanate or sodium thiocyanate can be also used together.
  • Sulfur sensitizers which can be used include active gelatins and in addition, sulfur compounds.
  • Selenium sensitizers which can be used include active or inert selenium compounds.
  • reduction sensitizers include monovalent tin salts, polyamines, bis-alkylaminosulfides, silane compounds, iminoaminomethane sulfinic acid, hydrazinium salts and hydrazine derivatives.
  • a silver halide relating to the present invention is spectrally sensitized in accordance with the selection of a suitable sensitizing color dye in order to provide a sensitivity in a region of sensitive wavelength required for a red-sensitive emulsion.
  • a suitable sensitizing color dye in order to provide a sensitivity in a region of sensitive wavelength required for a red-sensitive emulsion.
  • Various spectrally sensitizing color dyes can be used and in practice, one or more such spectrally-sensitizing color dyes may be employed alone or in combination.
  • Binders used for component layers of a silver halide photographic light-sensitive material according to the present invention are most commonly gelatins such as alkali- or acid-treated gelatins, but along with a part of such a gelatin, the following compounds can also be used in combination: derivative gelatins such as phthalated gelatin, and phenylcarbamoyl gelatin; albumine, agar, gum arabic, alginic acid, partially-hydrolyzed cellulose derivatives, partially-hydrolyzed polyvinyl acetate, polyacrylamide, polyvinylalcohol, polyvinyl pyrrolidone and copolymers of these vinyl compounds.
  • derivative gelatins such as phthalated gelatin, and phenylcarbamoyl gelatin
  • albumine agar, gum arabic, alginic acid, partially-hydrolyzed cellulose derivatives, partially-hydrolyzed polyvinyl acetate, polyacrylamide, polyvinylalcohol, poly
  • additives can be incorporated in the emulsion layers and auxiliary layers of a light-sensitive material according to the present invention.
  • the following additives can be properly used: an anti-fogging agent, an anti-fading agent for color dye image, an anti-color-contamination agent, an optical brightening agent, antistatic agent, a hardener, a surfactant, a plasticizer, a wetting agent and an ultraviolet absorbent, as described in Research Disclosure No. 17,643.
  • a silver halide photographic light-sensitive material according to the present invention is made by applying individual component layers such as an emulsion layer and an auxiliary layer which, if required, contain various photographic additives incorporated thereinto as discussed above, onto a support directly or through a subbing layer and/or an inter layer, which support has been subjected to a corona discharge treatment, a flame treatment or an ultraviolet irradiation treatment.
  • individual component layers such as an emulsion layer and an auxiliary layer which, if required, contain various photographic additives incorporated thereinto as discussed above
  • supports which can be advantageously used are and barayta paper, polyethylene-coated paper, polyproylene synthetic paper and transparent or clear supports formed thereon with reflecting layer or reflector, including glass plates, films of polyesters such as cellulose acetate, cellulose nitrate and polyethylene terephthalate, and films of polyamides, polycarbonates and polystyrenes, for example. These supports are appropriately selected respectively according to the purposes of using light-sensitive materials.
  • the application of the emulsion layers and other component layers used in the present invention can be accomplished by various coating processes such as dipping, air-doctor, curtain, and hopper coating processes.
  • the simultaneous application of two or more layers can be conducted in the processes as described in U.S. Patent Nos. 2,761,791 and 2,941,898.
  • individual emulsion layers may be formed in any arrangement, and for example, an arrangement can be used of the blue, green and red-sensitive emulsion layers, or of the red, green and blue-sensitive emulsion layers, in the order from the support side.
  • the hydrophilic colloids capable of being employed in the emulsions as described above can be similarly used as a binder, and various photographic additives capable of being contained in the emulsion layers as discussed hereinbefore can be likewise incorporated into the component layers.
  • An ultraviolet absorbent layer can be formed on a layer adjacent to the emulsion layer farthest away from and on the side of the support, and an ultraviolet absorbent layer can be also formed as required on a layer on the opposite side of the support. Particularly, in the latter case, it is preferable to form a protective layer consisting substantially of only a gelatine on the uppermost layer.
  • the present invention When the present invention is applied to a color light-sensitive printing material, the light-sensitive material is exposed to light through a negative light-sensitive material bearing an image made of a coupling product, and then subjected to a color development.
  • the color development is conducted in a usual color development process.
  • the exposed light-sensitive material is first treated with a color developer solution containing a color developing agent.
  • the light-sensitive material which has contained a color developing agent or its precursor is treated with an activator.
  • the color development step using a color developer or an activator, bleaching step and fixing step may often conducted independently, but otherwise, can be carried out at a time (in a single bath) using a treating solution having those functions, instead.
  • the latter case include a method using a single bath comprising a color developer solution or activator solution containing a bleaching or fixing agent together as will be described hereinafter, a method using a bleach-fix bath containing bleaching and fixing agents for effecting the bleaching and fixing operaton after the color development, and the like.
  • the exposed light-sensitive material can be treated in a bleach-fix bath immediately after the treatment with a color developer solution or an activator solution, thereby to remove a silver, but an acidic stop bath can be provided between the color developing and bleach-fix steps.
  • An aqueous acetic or citric acid solution can be used in such an acidic stop bath. If necessary, it is possible to further provide a prehardening step and steps for the neutralization thereof, washing, and stabilization.
  • Color developing agents for the light-sensitive materials according to the present invention are representatively of aromatic primary amines.
  • color developing agents of aromatic primary amines are aminophenol or p-phenylenediamine derivatives which can be used in the free state or in the form of the hydrochloride or sulfate thereof, or the organic acid salts thereof such as p-toluene sulfonate, tetraphenyl borate and p-(t-octyl) benzene sulfonate.
  • a precursor of a color developing agent may be contained in the light-sensitive materials of the present invention.
  • the precursors of color developing agents are compounds capable of producing a color developing agent under an alkaline condition, and include those of aromatic aldehyde derivative-Schiff base type, polyvalent metal ion complex, phthalicimide derivative, amide phosphate derivative, sugar amine reactant and urethane type.
  • color developing agents of aromatic primary amines are usually contained in a color developer solution, in the amount of the order of 1 to 20g/l.
  • a color developer solution When such a developer is incorporated in the form of a precursor into the light-sensitive material, it is contained in the amount of the order of 0.5 to 3 moles per mole of a silver halide.
  • a water-soluble optical brightening agent may be added in the order of 0.1 to 10g/l into a color developer or activator solution used for the light-sensitive material of the present invention.
  • the color developer or activator solutions used for the light-sensitive material of the present invention are those containing alkaline materials such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate, potassium tertiary phosphate; sulfites such as sodium and potassium sulfites; and fluorides such as sodium, potassium and ammonium fluorides.
  • alkaline materials such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate, potassium tertiary phosphate
  • sulfites such as sodium and potassium sulfites
  • fluorides such as sodium, potassium and ammonium fluorides.
  • thiocynates such as sodium, potassium and ammonium thiocyanates
  • chlorides such as ammonium, potassium and sodium chlorides
  • organic solvents such as ethylene glycol, diethylene gl'ycol, methanol, ethanol, n-butanol, benzyl alcohol, acetone and dimethyl formamide
  • amines such as hydroxyamine, ethanolamine, ethylenediamine and diethanolamine
  • water softeners such as sodium hexamethaphosphate, tripolyphosphate, ethylenediamine tetraacetate and diethylenetriamine pentaacetate.
  • auxiliary developer may be incorporated into the color developer or activator solution used in the present invention.
  • auxiliary developers are 1-aryl-3-pyrazolidone derivatives and are used in an amount within a range of lmg to lg, preferably 10mg to 500mg per Jiter of the color developer or activator solution.
  • Representatives of auxiliary developers are 1-phenyl-3-pyrazolidone, 4-methyl-l-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-l-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-l--(p-tolyl)-3-pyrazolidone.
  • the color developer or activator solution used in the present invention is generally used at a temperature within a certain range and preferable within a range of 15°C to 70°C, and more preferably of 30°C to 50°C, depending upon the type, composition, application and purpose of a color light-sensitive printing material to be treated and according to the present invention.
  • Bleaching agents which can be employed in a bleaching bath or a bleaching-fix bath may be known compounds and include salts of aminopolycarboxylic ferric complexes such as sodium or ammonium salts of ethylenediamine tetraacetate ferric complex, and persulfates such as ammonium or sodium persulfates, for example.
  • Fixing agents which can be used in a fixing bath or a bleach-fix bath may also be known compounds and include thiosulfates such as sodium or ammonium thiosulfates, water-soluble sulfur-containing diols such as 3,6-dithia-l,8--octanediol and 3,6,9,12-tetrathia-1,14-tetradecanediol, and water-soluble sulfur-containing dibasic acids such ethylene--bis-thioglycolic acid and the sodium salts thereof.
  • thiosulfates such as sodium or ammonium thiosulfates
  • water-soluble sulfur-containing diols such as 3,6-dithia-l,8--octanediol and 3,6,9,12-tetrathia-1,14-tetradecanediol
  • water-soluble sulfur-containing dibasic acids such ethylene--bis-thioglycolic acid and the sodium salt
  • the application of the present invention to a color light-sensitive printing material enables a print having an excellent dark keeping property, sharpness and whiteness to be obtained and a print matched to needs of end users to be provided, and further enables a color light-sensitive printing material having an excellent latent image stability to be provided and a working efficiency in a laboratory to be substantially improved.
  • a color light-sensitive printing material was made in a manner as described in the following item (1). This sample was exposed imagewise and then treated with a color developer solution and a bleach-fix solution which will be described hereinbelow to determine the characteristics of the individual color dye images formed.
  • a paper support covered over with a polyethylene containing anatase-type titanium dioxide as a white pigment was pretreated by subbing a gelatin, and the following layers were coated on the pretreated support in turns to prepare a sample.
  • Layer 1 a blue-sensitive silver chlorobromide emulsion layer.
  • This layer was applied using an emulsified dispersion prepared by dissolving in dioctyl phthalate silver chlorobromide containing 5 mole% of silver chloride as well as a yellow coupler (Y-l) which will be described hereinbelow and 2,5-di-tert-octylhydroquinone.
  • Layer 2 a first interlayer.
  • This layer was formed using an emulsified dispersion produced by dissolving 2,5-di-tert-octylhydroquinone in dioctyl phthalate.
  • Layer 3 a green-sensitive silver chlorobromide emulsion layer.
  • This layer was formed by use of the mixture of an aqueous solution of a dye given in Table II with an emulsified dispersion made by dissolving in dioctyl phthalate silver chlorobromide containing 15 mole% of silver chloride, as well as a magenta coupler (M-1) to be described hereinafter and 2,5-di-tert-octylhydroquinone.
  • Layer 4 a second interlayer.
  • Layer 5 a red-sensitive silver chlorobromide emulsion layer.
  • This layer was formed using an emulsified dispersion resulting from the dissolving, in dioctyl phthalate, of silver chlorobromide emulsion containing 25 mole% of silver chloride, as well as a cyan coupler given in Table II and 2,5-di-tert-octylhydroquinone.
  • Layer 6 a protective layer.
  • This layer is formed by use of a mixture consisting essentially of a gelatin and a hardener.
  • the ten samples prepared in this manner were evaluated in fogginess and latent image stability.
  • the unexposed samples were subjected to the following treatments, and then determined in red density using Greterk D-122 type desitometer.
  • Composition of color developer solution Water is added to make one liter, and to adjust a pH to 10.0 with sodium hydroxide.
  • a whiteness desired for a color light-sensitive printing material is required to be 0.005 or less in fogginess and to be 0.95 or more in latent image stability (S 1 /S 2 ). It is apparent from Table III that only the samples 2, 3, 4, 9 and 10 according to the present invention satisfy both of the above two characteristics.
  • a paper support covered over with a polyethylene containing anatase-type titanium dioxide as a white pigment was pretreated by subbing a gelatin, and the following layers were coated on the pretreated support in turns to prepare a sample.
  • Layer 1 a blue-sensitive silver chlorobromide emulsion layer.
  • This layer was formed using an emulsified dispersion made by dissolving in dioctyl phthalate silver chlorobromide emulsion containing 5% of silver chloride, as well as the aforesaid yellow coupler (Y-l) and 2,5-di-tert-octylhydroquinone.
  • Layer 2 a first interlayer.
  • This layer was applied using an emulsified dispersion produced by dissolving 2,5-di-tert-octylhydroquinone in dioctyl phthalate.
  • Layer 3 a green-sensitive silver chlorobromide emulsion layer.
  • This layer was formed by use of the mixture of an aqueous solution of a dye given in Table V with an emulsified dispersion made by dissolving in dioctyl phthalate silver chlorobromide emulsion containing 15 mole% of silver chloride, as well as the above-described magenta coupler (M-l) and 2,5-di-tert-octylhydroquinone.
  • Layer 4 a second interlayer.
  • Layer 5 red-sensitive silver chlorobromide emulsion layer.
  • This layer was formed using an emulsified dispersion made by dissolving in dioctyl phthalate silver chlorobromide emulsion containing 25 mole % of silver chloride, a cyan coupler given in Table V and 2,5-di-tert-octylhydroquinone.
  • Layer 6 a third interlayer.
  • This layer was formed of an emulsified dispersion made by dissolving in dioctyl phthalate the aforesaid ultraviolet absorbent (UV-1) and 2,5-di-tert-octylhydroquinone.
  • This layer was formed using essentially a gelatin and a hardener.
  • Example 2 it is evident from Table VI that only the samples (Nos. 12, 13, 14, 19 and 20) according to the present invention satisfy both the characteristics of fogginess and latent image stability as in Example 1.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19850302680 1984-04-20 1985-04-17 Lichtempfindliches photographisches Silberhalogenidmaterial Expired EP0159913B1 (de)

Applications Claiming Priority (2)

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JP8058884A JPH0616167B2 (ja) 1984-04-20 1984-04-20 ハロゲン化銀写真感光材料
JP80588/84 1984-04-20

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EP0159913A1 true EP0159913A1 (de) 1985-10-30
EP0159913B1 EP0159913B1 (de) 1988-09-14

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DE (1) DE3565016D1 (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0185371A3 (en) * 1984-12-21 1988-06-08 Konishiroku Photo Industry Co. Ltd. Method of processing light-sensitive silver halide color photographic material
EP0199604A3 (en) * 1985-04-25 1988-07-06 Konishiroku Photo Industry Co. Ltd. Processing method of light-sensitive silver halide color photographic material
EP0186169A3 (en) * 1984-12-26 1988-07-06 Konishiroku Photo Industry Co. Ltd. Method for processing of light-sensitive silver halide color photographic material
EP0396900A1 (de) * 1989-04-07 1990-11-14 Eastman Kodak Company Photographisches Aufzeichnungsmaterial mit einem einen blaugrünen Farbstoff erzeugenden Kuppler
EP0399183A1 (de) * 1989-04-07 1990-11-28 Eastman Kodak Company Photographisches Aufzeichnungsmaterial mit einem blaugrünen Farbstoff erzeugenden Kuppler

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6396656A (ja) * 1986-10-13 1988-04-27 Konica Corp 色再現性にすぐれたハロゲン化銀写真感光材料
JP2557676B2 (ja) * 1988-01-13 1996-11-27 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
JP2860417B2 (ja) * 1989-11-14 1999-02-24 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2162481A1 (de) * 1971-12-06 1973-07-20 Fuji Photo Film Co Ltd
GB2066494A (en) * 1979-12-05 1981-07-08 Fuji Photo Film Co Ltd Colour photographic light-sensitive materials

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2162481A1 (de) * 1971-12-06 1973-07-20 Fuji Photo Film Co Ltd
GB2066494A (en) * 1979-12-05 1981-07-08 Fuji Photo Film Co Ltd Colour photographic light-sensitive materials

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0185371A3 (en) * 1984-12-21 1988-06-08 Konishiroku Photo Industry Co. Ltd. Method of processing light-sensitive silver halide color photographic material
EP0186169A3 (en) * 1984-12-26 1988-07-06 Konishiroku Photo Industry Co. Ltd. Method for processing of light-sensitive silver halide color photographic material
EP0199604A3 (en) * 1985-04-25 1988-07-06 Konishiroku Photo Industry Co. Ltd. Processing method of light-sensitive silver halide color photographic material
US4914008A (en) * 1985-04-25 1990-04-03 Konishiroku Photo Industry Co., Ltd. Processing method of light-sensitive silver halide color photographic material
EP0396900A1 (de) * 1989-04-07 1990-11-14 Eastman Kodak Company Photographisches Aufzeichnungsmaterial mit einem einen blaugrünen Farbstoff erzeugenden Kuppler
EP0399183A1 (de) * 1989-04-07 1990-11-28 Eastman Kodak Company Photographisches Aufzeichnungsmaterial mit einem blaugrünen Farbstoff erzeugenden Kuppler

Also Published As

Publication number Publication date
JPS60225155A (ja) 1985-11-09
JPH0616167B2 (ja) 1994-03-02
EP0159913B1 (de) 1988-09-14
DE3565016D1 (en) 1988-10-20

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