EP0258662B1 - Farbaufnahmen und Verfahren zu deren Herstellung - Google Patents

Farbaufnahmen und Verfahren zu deren Herstellung Download PDF

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Publication number
EP0258662B1
EP0258662B1 EP19870111265 EP87111265A EP0258662B1 EP 0258662 B1 EP0258662 B1 EP 0258662B1 EP 19870111265 EP19870111265 EP 19870111265 EP 87111265 A EP87111265 A EP 87111265A EP 0258662 B1 EP0258662 B1 EP 0258662B1
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EP
European Patent Office
Prior art keywords
group
color
compound
mol
coupler
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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
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EP19870111265
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English (en)
French (fr)
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EP0258662A2 (de
EP0258662A3 (en
Inventor
Masakazu Fuji Photo Film Co. Ltd. Morigaki
Nobuo Fuji Photo Film Co. Ltd. Seto
Osamu Fuji Photo Film Co. Ltd. Takahashi
Hideaki Fuji Photo Film Co. Ltd. Naruse
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP62157031A external-priority patent/JPS63158545A/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0258662A2 publication Critical patent/EP0258662A2/de
Publication of EP0258662A3 publication Critical patent/EP0258662A3/en
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Publication of EP0258662B1 publication Critical patent/EP0258662B1/de
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/39296—Combination of additives
    • 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
    • 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
    • G03C7/39236—Organic compounds with a function having at least two elements among nitrogen, sulfur or oxygen
    • 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
    • G03C7/3924—Heterocyclic
    • 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
    • G03C7/3924—Heterocyclic
    • G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
    • G03C7/39248—Heterocyclic the nucleus containing only nitrogen as hetero atoms one nitrogen atom
    • 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
    • G03C7/3924—Heterocyclic
    • G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
    • G03C7/39252—Heterocyclic the nucleus containing only nitrogen as hetero atoms two nitrogen atoms
    • 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
    • G03C7/3924—Heterocyclic
    • G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
    • G03C7/39256—Heterocyclic the nucleus containing only nitrogen as hetero atoms three nitrogen atoms
    • 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
    • G03C7/3924—Heterocyclic
    • G03C7/39268—Heterocyclic the nucleus containing only oxygen as hetero atoms
    • 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
    • G03C7/3924—Heterocyclic
    • G03C7/39272—Heterocyclic the nucleus containing nitrogen and oxygen

Definitions

  • the present invention relates to color photographs and a method for preparation of the same, and more precisely, to color photographs and a method for preparation of color photographs having improved storability by chemically inactivating aromatic amine developing agents that exist in silver halide photographic materials after color development with storability improving agents.
  • Silver halide color photographic materials are imagewise exposed and developed with an aromatic amine series color developing agent, and the resulting oxidation product of the developing agent is reacted with a color image-forming coupler (hereinafter referred to as "coupler") in the material to give color images.
  • a color image-forming coupler hereinafter referred to as "coupler”
  • colors photographic materials in general, combinations of a yellow coupler, a cyan coupler and a magenta coupler are used.
  • a development processing solution comprises a color developer, a stop solution, a bleaching solution, a fixer or a blix and the procesing temperature is high, being 31 ° C to 43 C. Accordingly, the developing agent is decomposed when used for a long period of time or is oxidized by contact with air, or some components in the photographic materials as processed are dissolved out and precipitate in the processing solution during the processing of the materials, or the processing solution sticks to the materials as processed and is carried over into the next bath together with the materials, whereby the composition of the processing solution will often vary. A processing solution thus run for a long period of time becomes a so-called running solution.
  • the amount of the rinsing water to be used is desired to be reduced or the rinsing step is desired to be effected without water because of a shortage of water resources, rise in city water costs, and other economical and environmental reasons.
  • inorganic components such as thiosulfates, sulfites or meta-bisulfites present in the processing solution as well as organic components such as a developing agent present in the developer solution enter into or adhere onto the photographic materials processed.
  • couplers to be incorporated into photographic materials development of couplers capable of forming sharp cyan, magenta or yellow dyes with less side-absorption is being effected so as to attain a good color reproduction, and at the same time, development of highly active couplers capable of being color-developed in a short period of time is also being effected. Further, development of new additives capable of effectively inducing the excellent characteristics of these couplers is also being effected. Unfortunately, however, the newly induced characteristics often cause deterioration of the storability of the color photographs due to the reaction with the components of the processing solution that remain in the photographic materials after being processed.
  • the components of the processing solution that remain inn the photographic materials after development especially the developing agent which is an aromatic primary amine compound and compounds derived therefrom, cause the deterioration of the fastness of the image formed, for example, because of the influence of light, heat, moisture, oxygen, during storage for a long period of time, or the compounds themselves self-couple or convert into colored substances by the action of any co-existing materials to form so-called "stains". This is a fatal defect in color photographs.
  • an anti-fading agent for example, hydroquinones, hindered phenols, tocopherols, chromans, coumarans and compounds derived from these compounds by etherifying the phenolic hydroxyl group therein (U.S. Patent 3,935,016, 3,930,866, 3,700,455, 3,764,337, 3,432,300, 3,573,050 and 4,254,216, British Patents 2,066,975 and 1,326,889 and Japanese Patent Publication No. 30462/76), are known as anti-fading agents.
  • these compounds are still insufficient to provide images of high quality, although the compounds are accepted as having the effect of anti-fading agents for preventing the fading or discoloration of image dyes formed.
  • these compounds often cause variation in the hue of color images, generation of fog, occurrence of dispersion insufficiency or even formation of fine crystals in coated emulsions, and therefore, these compounds cannot be said to be able to display all-around effect for photographic use.
  • I-aryl-3-pyrazolidone derivative especially a precursor thereof
  • layers of photographic materials for example, in U.S. Patents 4,358,525, 4,465,762 and 4,552,917, Japanese Patent Application (OPI) Nos. 52055/80, 5330/80, 40245/82, 104641/82 and 121328/84,
  • OPI Japanese Patent Application
  • these compounds have, when added, the defect of deteriorating the light-fastness of the photographic materials, and especially, the color-faded degree of remarkable for 3-alkoxycarbonyloxy-2-pyrazolidone derivatives.
  • one object of the present invention is to provide a method for preparation of color phtotgraphs whose white background parts do not fade even when stored or placed on exhibition for along period of time.
  • Another object of the present invnetion is to provide color photographic materials capable of forming color images, after being color developed, bleached and fixed, which do not deteriorate or fade by the color developing agent that remains in the photographic material.
  • Still another object of the present invention is to provide a method for forming color images in color photographic materials, which are free from any harmful side-effects, such as image deterioration or stain generation, caused by aromatic amine color developing agents that remain in the photographic materials, even when the photographic materials are processed with processing solutions from which a noticeable amount of components of the processing solutions would enter into or adhere onto the phtographic materials processed, such as processing solutions under a running state, rinsing solutions containing a small amount of water or water-free solutions, substantially benzyl alcohol-free color developers, or other processing solutions which would be a burden on color development.
  • the present inventors repeatedly studied various matters and as a result have found that the above-mentioned objects can effectively be attained by incorporating a storability-improving compound into a color photograph to be obtained by imagewise exposure, color development and bleaching and fixation of a color photographic material which contains a color image-forming coupler capable of forming a dye by an oxidation-coupling reaction of the silver halide emulsion layer as coated on the support of the material and an aromatic amine series color developing agent, in any stage of during the production of the photographic material, or during or after the color development, the storability-improving compound being able to form a chemical bond with the aromatic amine series developing agent to give a chemically inactive and substantially colorless compound.
  • the present invention was achieved on the basis of the above-described discovery.
  • the subject matter of the present invention resides in a color photograph which contains a storability-improving compound capable of forming a chemical bond with an aromatic amine series color developing agent under the condition of a pH of 8 or less that remains in the photograph after the color development thereof, to give a chemically inactive and substantially colorless compound, in at least one photographic layer on the support of the photograph.
  • aromatic amine series color developing agents as referred to herein include aromatic primary, secondary and tertiary amine compounds, and more precisely, there may be mentioned phenylenediamine series compound and aminophenol series compounds. Typical examples of these compounds are 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, 4-methyl-2-amino-N,N-diethylaniline, 4-methyl-2-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 2-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-methyla
  • the compounds capable of forming a chemical bond with the aromatic amine series color developing agent after color development to give a chemically inactive and substantially colorless compound are those represented by the following general formulae (I) and (II):
  • R 1 and R 2 each represents an aliphatic group, an aromatic group or a heterocyclic group
  • X represents a group capable of reacting with an aromatic amine developing agent to be revoved
  • A represents a group capable of reacting with an aromatic amine developing agent to form a chemical bond
  • n represents 1 or 0
  • B represnts a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group
  • Y represents a group capable of accelerating the addition of an aromatic amine developing agent to the compound of the formula (II); and
  • R 1 and X, and Y and R 2 or B may be bonded together to form a cyclic structure (e.g., a cyclic acid anhydride, a succinimido ring).
  • those of the formula (I) are preferred, more preferably compounds capable of reacting at a secondary reaction rate constant k 2 (80 ° C) with p-anisidine of from 1.0 liter/mol.sec. to 1 x 10- 5 liter/mol.sec, most preferably compounds capable of reacting at a secondary reaction rate constant k 2 (80 ° C) with p-anisidine of from 1 ⁇ 10 -1 liter/mol.sec to 1 x 10- 4 liter/mol.sec.
  • the constant k 2 is larger than 1.0 liter/mol.sec., the compounds themselves are unstable and easy to react with gelatin or water to decompose.
  • the constant k 2 is smaller than 1 x 10- 5 liter/mol.sec., the reaction rate in the reaction with the remaining aromatic amine developing agent is low, and as a result, the prevention of the side-effect of the remaining aromatic amine developing agent, which is the object of the present invention, tends to be reduced.
  • the aliphatic group represented by R i , R 2 and B means a linear, branched or cyclic alkyl, alkenyl or alkynyl group, which may optionally be substituted by substituent(s).
  • the aromatic group represented by Ri, R 2 and B means either of a carbon-cyclic aromatic group (such as a phenyl group, a naphthyl group,) and a heterocyclic aromatic group (such as a furyl group, a thienyl group, a pyrazolyl group, a pyridyl group, an indolyl group,), which may be either a mono-cyclic system or a condensed cyclic system (such as a benzofuryl group, a phenanthridinyl group,). Fruther these aromatic rings can optionally have substituent(s).
  • the heterocyclic group represented by Ri, R 2 and B is preferably a group having a 3-membered to 10- membered cyclic structure which is composed of carbon, oxygen, nitrogen, sulfur and/or hydrogen atoms, and the hetero-ring itself may be a saturated ring or an unsaturated ring and may further by substitued by substituent(s) (for example, a coumarinyl group, a pyrrolidyl group, a pyrrolinyl group, a morpholinyl group,).
  • substituent(s) for example, a coumarinyl group, a pyrrolidyl group, a pyrrolinyl group, a morpholinyl group,).
  • X represents a group capable of reacting with an aromatic amine developer to be removed and is preferably a group linked with A via an oxygen atom, a sulfur atom or a nitrogen atom (such as a 3-pyrazolyloxy group, a 3H-1,2,4-oxadiazolin-5-oxygroup, an aryloxy group, an alkoxy group, an alkylthio group, an arylthio group, a substituted N-oxy group) or a halogen atom.
  • X is a halogen atom
  • n is 0.
  • A represents a group capable of reacting with an aromatic amine developing agent to form a chemical bond and is, for example, a group containing a low electron density atom. This includes, for example,
  • L represents a single bond, an alkylene group, or for example, a carbonyl group, a sulfonyl group, a sulfinyl group, a hydroxycarbonyl group, a phosphonyl group, a thiocarbonyl group, an aminocarbonyl group, a silyloxy group.
  • A is preferably a divalent group as represented by
  • the storability-improving compound used in the present invention is different from the 3-alkoxycarbonyloxy-2-pyrazolidone derivative such as a development accelerator.
  • More preferable examples of the compound represented by the general formula (I) are those represented by the following general formulae (I-a), (I-b), (I-c) and (I-d) and which react with p-anisidine at a secondary reaction rate constant k 2 (80 ° C) within the range of 1 x 10 -1 liter/ mol*sec to 1 x 10- 5 liter/mol* sec: where R 1 has the same meaning as R 1 in formula (I); Link is a single bond or -O-; Ar denotes an aromatic group having the same meaning as defined for Ri, R 2 and B, except that no group useful as a photographic reducing agent such as a hydroquinone derivative of a catechol derivative will be released as a result of reaction with an aromatic amine series developing agent; Ra, Rb and Rc which may be the same or different each represents a hydrogen atom, or an aliphatic group, an aromatic group or a heterocyclic group having the same meaning as defined for R 1 , R 2 and B; Ra, Rb
  • Compounds of formulae (I-a) to (I-d), in particular, compounds of formula (I-a), may be adjusted to have a secondary reaction rate k 2 (80 °C) with p-anisidine in the range of from 1 x 10 -1 liter/mol.sec to 1 x 10-5 liter/rnol•sec by selecting appropriate substituents if Ar is a carbon-ring based aromatic group.
  • the total of the Hammett's a value of the individual substituents is preferably at least 0.2, more preferably at least 0.4, most preferably at least 0.6.
  • the total number of carbon atoms in the compounds per se is preferably at least 13, and the more the carbon atoms that are present, the better.
  • the compound of formula (I) is preferably such that it will not decompose during development or subsequent processing.
  • R"' 4 , R and R each represents a hydrogen atom, an aliphatic group (such as a methyl group, an isopropyl group, a t-butyl group, a vinyl group, a benzyl group, an octadecyl group, a cyclohexyl group,), an aromatic group (such as a phenyl group, pyridyl group, a naphthyl group,), a heterocyclic group (such as a piperidyl group, a pyranyl group, a furanyl group, a chromanyl group,), an acyl group (such as an acetyl group, a benzoyl group,) or a sulfonyl group (such as a methanesulfonyl group, a benzenesulfonyl group,), and R"'5 and R"' 6 may be bonded together to form a cyclic group (such as
  • Acetonitrile 150 ml was added to 19.4 g of 3,3',5,5'-tetrachloro-4,4'-dihydroxybiphenylsulfone and 16.8 g of triethylamine with stirring.
  • 21.2 g of 2-ethylhexyl chloroformate was added dropwise at room temperature. After continued stirring for 3 hours, extraction was conducted with ethyl acetate and the ethyl acetate layer was washed with water and dried. The concentrated ethyl acetate layer was purified by chromatography on silica gel column to obtain a white crystal of Compound I-57. Yield: 20.5 g, 58.4%. Melting point: 65 - 66 ° C.
  • Acetonitrile 300 ml was added to 11.3 g of 3,3',5,5'-tetrabromobiphenylsulfone and 6.1 ml of triethylamine with stirring.
  • 12.3 g of palmitic acid chloride was added dropwise at room temperature. After continued stirring for 5 hours, the reaction mixture was poured into 500 ml of water. The resulting crystal was recovered by filtration, washed with water and dried. Recrystallization with a mixed solvent of chloroform and ethyl acetate produced a crystal of Compound 1-61. Yield: 17.5 g, 84.0%. Melting point: 125 - 126 C.
  • Acetonitrile 300 ml was added to 14.0 g of 3,3',5,5'-chloro-4,4'-dihydroxybiphenylsulfone and 11.2 ml of triethylamine with stirring.
  • 22.0 g of palmitic acid chloride was added dropwise at room temperature.
  • the internal temperature of the reaction system was elevated to 65 to 70 ° C and the mixture was stirred for 1 hour.
  • the reaction mixture was poured into 1,000 ml of water, and the resulting crystal was recovered by filtration, washed with water and dried. Recrystallization with a mixed solvent of chloroform and ethyl acetate produced a crystal of Compound 1-61. Yield: 19.7 g, 63.3%. Melting point: 125 - 126 C.
  • those having a low molecular weight or those which are easily soluble in water can be added to processing solutions so that the compounds can be introduced into photographic materials during the processing procedure.
  • the compounds used in the present invention are added to photographic materials during the manufacture procedure.
  • the compound in general, is dissolved in a single high boiling point solvent (oil) (b.p. 170°C or more under atmospheric pressure) or in a single low boiling poiint solvent or in a mixed solvent comprising the oil and a low boiling point solvent, and the resulting solution is emulsified and dispersed in an aqueous solution of a hydrophilic colloid such as gelatin to obtain the compound-containing emulsion.
  • the compounds of the present invention are preferably those which are soluble in high boiling point organic solvents.
  • the grain size of the grains in the emulsified dispersion is not specifically limitative but is preferably from 0.05 ⁇ m to 0.5 ⁇ m, especially preferred from 0.1 ⁇ m to 0.3 ⁇ m.
  • the compounds used in the present invention are preferably those capable of co-emulsifying with couplers.
  • the ratio of oil/coupler by weight is referably from 0.00 to 2.0.
  • the ratio of the compound used in the present invention in the emulsion is from 1 x 10- 3 to 10 mols, preferably from 3 x 10- 2 to 5 mols, per mol of coupler.
  • alkyl phthalates e.g., dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, dimethoxyethyl phthalate,
  • phosphates e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctylbutyl phosphate, monophenyl-p-t-butylphenyl phosphate, etc.
  • citrates e.g., tributyl acetylcitrate,
  • benzoates e.g., octyl benzoate,
  • alkylamides e.g, diethyllaurylamide, dibutyllaurylamide,
  • fatty acid esters e.g., dibutoxyethyl succinate, diethyl azelate,
  • trimesates e.
  • lower alkyl acetates such as ethyl acetate, isopropyl acetate and butyl acetate as well as ethyl propionate
  • methanol ethanol, secondary butyl alcohol, cyclohexanol
  • oily solvents of additives such as couplers (including substances which are solid at room temperature, such as wax,.) but also latex polymers can be used. Otherwise, additives themselves, such as couplers, color mixing preventing agents, ultraviolet absorbents, can be used as oily solvents.
  • the latex polymers those obtained from one or more monomers selected from acrylic acid, methacrylic acid and esters thereof (e.g., methyl acrylate, ethyl acrylate, butyl methacrylate,.), acrylamide, methacrylamide, vinyl esters (e.g., vinyl acetate, vinyl propionate,.), acrylonitrile, styrene, divinylbenzene, vinyl-alkylethers (e.g., vinyl-ethylether,), maleates (e.g., methyl maleate), N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinylpyridine,.
  • the monomers can be used singly or in mixtures thereof.
  • surfactants to be used for dispersing the solution containing the compound used in the present inventoin singly or in the form of a mixture with a coupler into an aqueous protective colloid solution, there may be mentioned saponin as well as sodium alkyl-sulfosuccinates, sodium alkylbenzenesulfonates,.
  • the compounds used in the present invention can be used in the form of a mixture with a yellow coupler, a magenta coupler or a cyan coupler.
  • the combined use of the compounds together with a magenta coupler is preferred for sufficiently attaining the effect of the present invention.
  • the couplers to be used in combination with the compound used in the present invention may be either 4-equivalent or 2-equivalent to silver ion and may also be in the form of a polymer or an oligomer.
  • the couplers for use in combination may be either single or in the form of a mixture of two or more of the couplers.
  • Couplers for use in the present invention are those represented by the following formulae:
  • R' 1 , R 4 and R 5 each represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group
  • R' 2 represents an aliphatic group
  • R 3 and R 6 each represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic-oxy group or an acylamino group
  • R s ' represents a hydrogen atom or has the same meaning as R s
  • R 7 and Rg each represents a substituted or unsubstituted phenyl group
  • R 8 represents a hydrogen atom, an aliphatic or aromatic acyl group or an aliphatic or aromatic sulfonyl group
  • Rio represents a hydrogen atom or a substituent
  • Q represents a substituted or unsubstituted N-phenylcarbamoyl group
  • R' 2 and R 3 , and R 5 and R 6 each may form a 5-, 6- or 7-membered ring as described in U.S. Patents 4,327,173, 4,564,586 and 4,430,423, and Japanese Patent Application (OPI) No. 390441/86.
  • OPI Japanese Patent Application
  • the typical examples of cyan couplers having an ureido group are those described in U.S. Patents 4,333,999, 4,451,559, 4,444,872, 4,427,767 and 4,579,813, and European Patent 067,689 Bl.
  • R' 1 , R' 2 , R 3 , or Y 1 ; R 4 , R s , R 6 or Y 2 ; R 7 , R 8 , R 9 or Y 3 ; R io , Za, Ab or Y 4 ; and Q or Y 5 may form a dimer orhigher polymer.
  • the aliphaitc group as referred to herein means a linear, branched or cyclic alkyl, alkenyl or alkynyl group.
  • the cyan couplers of the formulae (III) and (IV) can be synthesized by known methods.
  • the cyan couplers of the formual (III) can be synthesized by the methods descried in U.S. Patents 2,423,730 and 3,772,002,.
  • the cyan couplers of the formula (IV) can be synthesized by the methods described in U.S. Patents 2,895,826, 4,333,999 and 4,327,173,.
  • the magneta couplers of the formula (V) can be synthesized by the methods described in Japanese Patent Application (OPI) Nos. 74027/74, 74028/74, 27930/73 and 33846/78, U.S. Patent 3,519,429,.
  • the magenta couplers of the formula (VI) can be synthesized by the methods described in Japanese Patent Application (OPI) No. 162548/84, U.S. Patent 3,725,067, Japanese Patent Application (OPI) Nos. 171956/84 and 33552/85,.
  • the yellow couplers of the formula (VII) can be synthesized by the methods described in Japanese Patent Application (OPI) No. 48541/79, Japanese Patent Publication No. 10739/83, U.S. Patent 4,326,024, Research Disclosure, RD No. 18053,.
  • couplers are generally added to emulsions in an amount of from 2 x 10- 3 mol to 5 x 10 -1 mol, preferably from 1 x 10- 2 mol to 5 x 10- 2 mol, per mol of the silver in the emulsion layer.
  • the compounds used in the present invention can be used together with known anti-fading agents, and especially preferred anti-fading agents are (i) aromatic compounds represented by the following formula (VIII), (ii) amine compounds represented by the following formula (IX), or (iii) metal complexes comprising a center atom of copper, cobalt, nickel, palladium or platinum and at least one organic ligand having two or more conformations.
  • aromatic compounds represented by the following formula (VIII) (ii) amine compounds represented by the following formula (IX), or (iii) metal complexes comprising a center atom of copper, cobalt, nickel, palladium or platinum and at least one organic ligand having two or more conformations.
  • Ri represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group of a group of in which R 7 ", R ⁇ " and Rg" may be the same or different and each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group of an aryloxy group;
  • R 10 ' represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy-radical or a hydroxyl group
  • R 11 , R 12 , R 13 and R 14 may be the same or different and each represents a hydrogen atom or an alkyl group
  • A represents a non-metallic atomic group necessary for forming a 5-membered, 6-membered or 7-membered ring.
  • the amount of the compound of the formulae (VIII) and (IX) to be added is from 10 to 400 mol%, preferably from 30 to 300 mol%, to the coupler.
  • the amount of the metal complex to be added is from 1 to 100 mol%, preferably from 3 to 40 mol%, to the coupler.
  • the hydrophilic colloid layers contain a dye or an ultraviolet absorbent, these can be mordanted by a cationic polymer.
  • the photographic materials prepared can contain, as a color-fog inhibitor, a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative or a nascorbic acid derivative.
  • the photographic materials prepared can contain an ultraviolet absorbent in the hydrophilic colloid layer.
  • an ultraviolet absorbent in the hydrophilic colloid layer.
  • aryl group-substituted benzotriazole compounds for example, as described in U.S. Patent 3,533,794
  • 4-thiazolidone compounds for example, as described in U.S. Patents 3,314,794 and 3,352,681
  • benzophenone compounds for example, as described in Japanese Patent Application (OPI) No. 2784/71
  • cinnamic acid ester compounds for example, as described in U.S. Patents 3,705,805 and 3,707,375
  • butadiene compounds for example, as described in U.S. Patent 4,045,229
  • benzoxazole compounds for example, as described in U.S.
  • Patent 3,700,455 can be used.
  • Ultraviolet-absorbing couplers for example, a-naphthol series cyan dye-forming couplers and ultraviolet-absorbing polymers may also be used. These ultraviolet absorbents can be mordanted in speicifically determined layers.
  • the photographic materials can contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for the purpose of irradiation prevention or for any other various purposes.
  • a water-soluble dye in the hydrophilic colloid layer as a filter dye or for the purpose of irradiation prevention or for any other various purposes.
  • Such dyes include oxonole dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.
  • oxonol dyes, hemioxonol dyes and merocyanine dyes are especially useful.
  • gelatin is advantageously used, but other hydrophlic colloids can also be used singly or together with gelatin.
  • gelatin lime-processed gelatin as well as acid-processed gelatin can be used in the photographic materials.
  • the details of the method for the preparation of gelatins is described in Arthur Veis, The Macromolecular Chemistry of Gelatin (by Academic Press, 1964).
  • any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride can be used as a silver halide.
  • the mean grain size (the diameter of the grain when the grain has a spherical shape or resembles a spherical shape, or the mean value based on the projected area using the edge length as the grain size when the grain is a cubic shaped grain) of the silver halide grains in the phtographic emulsions is not specifically limitative but is preferably 2 /1 .m or less.
  • the grain size distribution of the silver halide emulsions may be narrow or broad, but a so-called monodispersed emulsion wherein the fluctuation value is 15% or less is preferably used in the present invention.
  • the silver halide grains in the photographic emulsions may have a regular crystal form such as cubic or octahedral or an irregular crystal form such as spherical or tabular, or further a composite form of these crystal forms.
  • the emulsions may be a mixture comprising grains of various crystal forms. In particular, the use of normal crystal grains is preferred.
  • a tabular grain silver halide emulsion wherein tabular silver halide grains having an aspect ratio (length/width) of 5 or more account for 50% or more of the total projected area of the silver halide grains may also be used.
  • the silver halide grains may have a different inner phase and surface layer phase.
  • these may be of a surface latent image type capable of forming latent images mainly on the surface thereof or of an interanl latent image type capable of forming latent images mainly in the inside thereof.
  • the silver halide grains may also be formed, or physically ripened, in the presence of a cadmium salt, a zinc salt, a thallium salt, a lead salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof.
  • the silver halide emulsions are generally subjected to chemical sensitization.
  • the photographic emulsions for use in the photographic materials of the present invention can contain various compounds so as to prevent the generation of fog in the manufacture step of the materials or during the storage or photographic processing of the materials or so as to stabilize the photographic characteristics of the materials.
  • various kinds of compounds which are known as an antifoggant or stabilizer can be added to the emulsions, and examples of such compounds are azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole,), mercaptopyrimidines, mercaptotriazines,; thioketo compounds such as
  • the present invention can be applied to multi-layer and multi-color photographic materials having at least two emulsion layers of different spectral sensitivities on a support.
  • Multi-layer natural color photographic materials generally have at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support.
  • the disposition order of these emulsion layers can be selected according to the intended use.
  • the red-sensitive emulsion layer contains a cyan-forming coupler
  • the green-sensitive emulsion layer contains a magenta-forming coupler
  • the blue-sensitive emulsion layer contains yellow-forming coupler, but as the case may be, different combinations can be used.
  • the supports for use in the present invention conventional ones which are generally used in photographic materials can be used, including cellulose nitrate film, cellulose acetate film, cellulose acetate- butyrate film, cellulose acetate-propionate film, polystyrene film, polyethylene terephthalate film, polycarbonate film, as well as laminates comprising the said films, thin glass film, paper,.
  • papers coated or laminated with baryta or an a-olefin polymer especially a polymer of an a-olefin having from 2 to 10 carbon atoms, such as polyethylene, polypropylene or ethylene-butene copolymer, as well as plastic film supports whose surface is roughened so as to improve the adhesiveness with other high molecular substances, as described in Japanese Patent Publication No. 19068/72, are usuable in the present invention, and these supports can yield a good result.
  • ultraviolet-setting resins can also be used.
  • the support transparent or opaque ones are selectively used in accordance with the intended object of thephotographic materials.
  • dyes or pigments can be added to the supports so as to make them transparently colored.
  • Opaque supports include, in addition to naturally opaque supports such as paper, those formed by adding a dye or a pigment such as titanium oxide to a transparent film; as well as surface-processed plastic films as described in Japanese Patent Publication No. 19068/72; and completely light-shielding papers or plastics to which a carbon black, or a dye is added.
  • the support generally has a subbing layer.
  • the surface of the support cn be pre-treated, for example, by corona discharge, ultraviolet irradiation or flame-treatment.
  • color photographic materials to be used for preparing the color photographs of the present invention conventional color photographic materials can be used, and in particular, color photographic materials for prints are especially preferred. Further, photographic materials to be processed by the color photographic process described in U.S. Patents 3,227,550, 3,227,551 and 3,227,552 and Temporarily Published U.S. Patent U.S. B. 351,673, etc.; in particular those to be processed by a color diffusion transfer photographic process, can also be used.
  • the color photographic materials are required to be subjected to color photographic development processing, after being exposed.
  • the color photographic development processing basically comprises a color development step, a bleaching step and a fixation step.
  • the two steps of bleaching and fixation ca be carried out in one operation.
  • a combination comprising color development, first fixation and then bleaching-fixation is also possible.
  • the development step is optionally combined with various steps of pre-hardening, neutralization, first development (black-and-white development), image stabilization, rinsing, if desired.
  • the processing temperature is generally 18°C or higher. Especially, the temperature is from 20 ° C to 60 ° C in most cases, and recently, the temperature is within the range of from 30 ° C to 60 ° C.
  • the color developer is an aqueous alkaline solution containing an aromaticprimary amine series color developing agent and having a pH value of 8 or more, preferably from 9 to 12.
  • the photographic materials are generally subjected to rinsing in water.
  • a simple step of only a so-called “stabilization” can also be effected with no substantial rinsing operation.
  • Preferred examples of aromatic primary amine series developing agents for use in the present invention are p-phenylenediamine derivatives, and specific examples thereof are set forth hereunder, which, however, are not limitative.
  • p-phenylenediamine derivatives may also be in the form of salts such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates,.
  • the above-mentioned compounds are described in U.S. Patents 2,193,015, 2,552,241, 2,566,271, 2,592,364, 3,656,950 and 3,698,525,
  • the concentration of the aromatic amine developing agent to be used in actual processing is from 0.1 g to 20 g, more preferably from 0.5 g to 10 g, per liter of the developer bath solution.
  • the color developer for use in the present invention can contain hydroxylamines, as are well known.
  • the processing temperature of the color developer in the practice of the present invention is preferably from 30 C to 50 C, more preferably from 33 C to 42 C.
  • the amount of the replenisher in the color development step is from 30 ml to 2000 ml, preferably from 30 ml to 1500 ml, per m 2 of the photographic materials being processed. In view of the necessity for reducing the amount of wastes, a small amount of the replenisher is better.
  • the amount of the benzyl alcohol is preferably 2.0 ml/liter or less, more preferably 0.5 ml/liter or less. No benzyl alcohol is most preferred.
  • the color development time is preferably within 2 minutes and 30 seconds or less, more preferably within the range of from 10 seconds to 2 minutes and 30 seconds. The most preferred range is from 45 seconds to 2 minutes.
  • sodium dodecylbenzenesulfonate was added to the emulsified dispersion as a coating auxiliary agent and then coated on a paper support both surfaces of which had been laminated with polyethylene.
  • the amount of the dye coated was so controlled that the color density as measured with Macbeth Densitometer RD-514 Type (Status AA Filter) was 1.0.
  • a gelatin protective layer (containing 1 g/m 2 of gelatin) was coated over the layer, to obtain Sample (A).
  • the samples thus obtained were stored in the dark at room temperature for 2 months.
  • the samples were subjected to a color fading test for 500 hours with a xenon tester (illuminance: 100,000 luxes) provided with an ultraviolet absorbing filter (by Fuji Photo Film) cutting a light of 400 nm or less, and the color retention (percentage) was obtained for each sample.
  • a xenon tester illuminatence: 100,000 luxes
  • an ultraviolet absorbing filter by Fuji Photo Film
  • the addition of the compound used in the present invention is effective for improving the fastness against the deterioration of the fastness caused by the developing agent remaining in the photographic material processed.
  • the degree of the effect could not be anticipated from any known anti-fading agents.
  • Example 2 These samples were stored for 2 months in the dark in the same manner as in Example 1. These were subjected to a color-fading test with a xenon tester for 200 hours, and the color retention (percentage) was obtained for each sample. The results are set forth in Table 2.
  • the compounds used in the present invention are extremely effective for preventing the deterioration of image quality caused by developing agents, although the fastness of images is deteriorated because of the existence of the developing agents remaining in the photographic materials. The effect could not be anticipated from any know compounds.
  • Example 3 These samples were stored for 2 months in the dark in the same manner as in Example 1. In order to test the light-fastness of each samle, these samples were subjected to a color-fading test in the same manner as in Example 1 with a xenon tester for 800 hours. In addition, in order to test the heat-resistance of each sample, the samples were stored in the dark for 500 hours at 100 C. The results of the color retention (percentage) of each sample are shown in Table 3.
  • P-anisidine and the compound of the formula (I) of the present invention were dissolved in trinonyl phosphate each in a concentration of 0.03 mol/liter. 10 ml of the mixture was heated in a thermostatic bath at 80 ° C, whereupon the reaction was followed by high performance liquid chromatography to obtain the secondary reaction rate constant.
  • Plural layers comprising the first layer (undermost layer) to the second layer (uppermost layer) as described below were coated in order on a paper support both surfaces of which had been laminated with polyethylene, to obtain a color photographic material sample.
  • the polethylene-laminated paper support contained a white pigment (such as Ti0 2 ) and a bluish dye (such as ultramarine) in the polyethylene in the side of the first layer.
  • a white pigment such as Ti0 2
  • a bluish dye such as ultramarine
  • the following dyes were used.
  • the anti-irradiation dye for the respective layers the following dyes were used.
  • Sample (D) was obtained.
  • Sample (D-1) through Sample (D-25) were also prepared in the same manner as the preparation of Sample (D), except that the combination of the yellow coupler and the compound of the invention as shown in the following Table 5 was used.
  • the samples thus prepared were exposed to light through an optical wedge and then processed in accordance with the following process (A) or (B) to form color images in the respective samples.
  • the samples exposed were subjected to running development with Fuji Color Roll Processor FMPP 1000 (partly modified) (by Fuji Photo Film Co.) under the conditions described below.
  • the rinsing step was carried out by means of a three tank-countercurrent system, where a replenisher was replenished into the rinsing tank (3), the solution overflown from the rinsing tank (3) was introduced into the bottom of the rinsing tank (2), the solution overflown from the rinsing tank (2) was introduced into the bottom of the rinsing tank (1), and the solution overflown from the rinsing tank (1) was drained out therefrom.
  • the amount of the processing solution as taken out from the previous bath into the next bath together with the photographic paper being processed in this system was 25 ml per m 2 of the paper.
  • the yellow reflection density in the non-image part of each of the samples as processed by the above-mentioned process was measured after one hour from the processing.
  • the yellow reflection density in the non-image part of each sample was also measured. The results are shown in the following Table 5.
  • Table 5 indicates that in the process B where the rinsing and bleach-fixing time was long and the amount of the replenisher in the respective processing steps was sufficient, there occurred no problem of yellow stain in the samples processed, while in the process A where the processing time was short and the amount of replenisher was small, the samples processed had noticeable yellow stain. Even under such circumstances, the yellow stain was sufficiently prevented by the addition of the compound used in the present invention.
  • Example 5 In the same manner as Example 5, the plural layers as mentioned in Example 5 were coated in order on a paper support both surfaces of which had been laminated with polyethylene to prepare color photographic material samples.
  • Sample (E) was removed from the first layer and the fifth layer, respectively, and the above-mentioned Compound (M-28) was used as the magenta coupler in the third layer, to obtain Sample (E). Further, Sample (E-1) through Sample (E-28) were also prepared in the same manner as the preparation of Sample (E), except that the combination of the magenta coupler and the compound used in the invention as shown in the following Table 6 was used.
  • the samples thus prepared were exposed to light through an optical wedge and then processed for color development in accordance with the following process where the developing agent and other processing solutions used were so constituted that they would easily remain in the photographic samples processed to form stains thereon, especially for the purpose of clearly demonstrating the effect of the present invention.
  • magenta reflection density (stain) in the non-image part of each sample was measured with a green light by a Fuji-type Auto-densitometer, after one hour from the development. Further, the magenta reflection density (stain) in the non-image part of each sample was also measured, after the samples were left at 80 ° C (70% RH) for 3 days or were left at room temperature for 50 days. The results are set forth in Table 6, where the increment of the stain from that measured one hour after the color development is shown.
  • Table 6 clearly indicates that the effect of preventing the generation of stains after storage by the use of the compounds used in the invention is remarkable as compared with the use of the conventional known comparative compounds.
  • Example 5 In the same manner as Example 5, the plural layers as mentioned in Example 5 were coated in order on a paper support both surfaces of which had been laminated with polyethylene to prepare color photographic material samples.
  • Sample (F) Speicifically, the yellow coupler and the magenta coupler were removed from the first layer and the third layer, respectively, and the above-mentioned Compound (C-2) was used as the cyan coupler in the fifth layer, to obtain Sample (F). Further, Sample (F-1) through Sample (F-21) were also prepared in the same manner as the preparation of Sample (F), except that the combination of the cyan coupler and the compound used in the invention as shown in the following Table 7 was used.
  • the samples thus prepared were exposed to light and processed for color development in the same manner as Example 6. After being processed, the cyan relfection density in the non-image part of each sample was measured with a red light by a Fuji-Type Auto-Densitometer. Further, th cyan reflection density in the non-image part of each sample was also measured, after the samples were left at 80 ° C (70% RH) for 3 days or were left at 80 ° C (dry, 10 to 15% RH) for 5 days. The results are set forth in Table 7.
  • Table 7 clearly indicates that the effect of preventing the generation of stains after storage by the use of the compounds used in the invention is remarkable, and the level of the effect is high which could not be attained by any conventional technical arts.
  • Example 5 In the same manner as Example 5, the first to seventh layers were coated on a paper support both surfaces of which has been laminated with polyethylene to prepare color photographic material samples.
  • Sample (G) was used as the yellow coupler in the first layer
  • the above mentioned Compound (M-23) was used as the magenta coupler in the third layer
  • a mixture (1/1 by mol) of the above mentioned Compounds (C-2) and (C-14) was used as the cyan coupler in the fifth layer, to obtain Sample (G).
  • Samples (G-1) through (G-12) were also prepared in the same manner as the preparation of Sample (G), except that the combination of the magenta coupler and the compound used in the invention as shown in the following Table 8 was used.
  • the color development was carried out in a conventional roller-transport type developing machine whereupon the replenishment of the replenishers was effected normally and the processing solutions used had almost equilibrated compositions.
  • magenta reflection density (stain) in the non-image part of each sample was measured after one hour from the development. Further, the magenta reflection density (stain) in the non-image part of each sample was also measured, after the samples were left at 80°C (70% RH) for 3 days or were left at room temperature for 50 days. The results are set forth in Table 8, where the increment of the stain from that measured in one hour after the color development is shown.
  • a color photographic material (Sample H) was prepared as follows:
  • the light-sensitive layers had the following compositions. All the amounts coated were designated by the unit of g/m 2 , whereas the amount of the silver halide coated was designated by the unit of g/m 2 as Ag.
  • the processing solutions used had the following compositions.
  • magenta reflection density (stain) in the non-image part of each sample was measured after the development. Further, the magenta reflection density (stain) in the non-image part of each sample was also measured, after the samples were left at 80 ° C (70% RH) for 3 days or were left at room temperature for 80 days. The results are set forth in Table 9, where in increment of the stain from that measured at one hour after the color development is shown.
  • a color photographic material ws prepared by multiple-coating the first to the fourteenth layers (see below) on a paper support laminated with polyethylene on both sides.
  • the polyethylene on the side to be coated with the first layer contained titanium white as a white pigment and a slight amount of ultramarine as a bluish dye.
  • compositions of the light-sensitive layers employed are indicated below in terms of components and the amounts coated, the latter being designated by the unit of g/m 2.
  • the amount of silver halide coated is designated in terms of silver deposit. All of the emulsions except the one incorporated in the 14th layer were prepared by the following method.
  • Aqueous solutions of potassium bromide and silver nitrate were added simultaneously under vigorous agitation at 75 ° C over a period of about 20 minutes to an aqueous solution of gelatin containing 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione per mole of Ag.
  • a monodispersed silver bromide emulsion comprising octahedral grains with mean size of 0.40 ⁇ m was obtained.
  • the emulsion was chemically sensitized by heating at 75 ° C for 80 minutes in the presence of 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mole of Ag.
  • the emulsion was chemically sensitized by heating at 60°C for 60 minutes in the presence of 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mole of Ag, so as to prepare a silver halide emulsion for internal latent image type.
  • Each of the light-sensitive layers contained 10- 3 wt% of N-I-9 (as a nucleating agent) and 10- 2 wt% of ExZS-1 (as a nucleation accelerator) on the basis of the silver halide deposit in each layer.
  • Each of the 1 st to 14th layers contained Alkanol XC (product of Dupont) and a sodium alkylbenzenesul- fonate as emulsification and dispersion aids, and a succinic acid ester and Magefac F-120 (product of Dainippon Ink & Chemicals, Inc.) as coating aids.
  • Stabilizers Cpd-19, 20 and 21 were incorporated in the silver halide or colloidal silver containing layers.
  • the sample prepared using the above-mentioned layers was designated (I). The compounds employed in this example are identified below.
  • magenta reflection density (stain) in the non-image area of each sample was measured after the development. Further, the magenta reflection density (stain) in the non-image area of each sample was also measured, after the samples were left at 80 ° C (70% RH) for 3 days or were left at room temperature and 80 days. The results are set forth in Table 11, where the increment of the stain from that measured at one hour after the color development is shown.
  • Rinsing water was replenished by the "countercurrent replenishing system" in which the rinse bath (2) was replenished, with the overflow from the rinse bath (2) being introduced into the rinse bath (1).
  • pH adjustment was achieved by addition of potassium hydroxide or hydrochloric acid.
  • pH adjustment was achieved by addition of aqueous ammonia or hydrochloric acid.
  • Pure water was obtained from tap water that had been subjected to an ion-exchange treatment so that all cations other than hydrogen ions and all anions except hydroxyl ions were reduced to concentration of no more than 1 ppm.
  • a multi-layered color photographic paper J was prepared by coating a plurality of layers as shown below on a paper support laminated with polyethylene on both sides.
  • the necessary coating solutions were prepared in the following manner.
  • the concentration of gelatin in the solution was so adjusted as to provide the composition indicated below.
  • the so prepared solution was used as a coating solution for the first layer.
  • Coating solutions for the second to seventh layers were prepared in a similar manner.
  • a sodium salt of 1-oxy-3,5-dichloro-s-triazine was used as a gelatin hardener in each of the layers.
  • compositions of the individual layers are shown below, in whch the numerals denote the amounts of individual components added (g/m 2 ) except that the amounts of silver halide emulsions are expressed in terms of silver deposit.
  • the sample prepared in this example contained CPd-15 and Cpd-22 as anti-irradiation dyes.
  • Each of the 1 st to 7th layers contains Alkanol XC (product of Dupont) and a sodium alkylbenzenesul- fonate as emulsification and dispersion aids, and a succinic acid ester and Magefacx F-120 (product of Dainippon Ink & Chemicals, Inc.) as coating aids.
  • Silver halides were stabilized by incorporation of Cpd-19 and 21.
  • the silver halide emulsions employed in this example are characterized below.
  • the samples thus prepared were exposed to light through an optical wedge, then processed by the following process (I) to form color images.
  • the samples exposed were subjected to running development with a Fuji Color Paper Processor FPRP 115 (Fuji Photo Film Co., Ltd.) under the conditions described below.
  • magenta reflection density (stain) in the non-image area of each of the light-sensitive materials was measured after the development. Further, the magenta reflection density (stain) in the non-image area of each sample was also measured, after the samples were left at 80 ° C (70% RH) for 3 days or were left at room temperature for 50 days. The results are set forth in Table 11, where the increment of the stain from that measured at one hour after the color development is shown.
  • the compounds used in the present invention are highly effective against magenta staining.
  • Example 12 A sample prepared as in Example 12 was exposed to light through an optical wedge and subsequently processed by one of the following processes (II) to (V). Evaluation of resistance to magenta staining that was conducted as in Example 12 showed that the comparative samples experienced increased magenta staining whereas the samples incorporating the compounds used in the present invention were substantially free from detectable stain.
  • the processing solutions had the following compositions.
  • the samples exposed were subjected to running development with Fuji Color Roll Processor FMPP 1000 (partly modified) (by Fuji Photo Film Co.) under the conditions described below.
  • the rinsing step was carried out by means of a three tank-countercurrent system, where a replenisher was replenished into the rinsing tank (3), the solution overflown from the rinsing tank (3) was introduced into the bottom of the rinsing tank (2), the solution overflown from the rinsing tank (2) was introduced into the bottom of the rinsing tank (1), and the solution overflown from the rinsing tank (1) was drained out therefrom.
  • the amount of the processing solution as taken out from the previous bath into the next bath together with the photographic paper being processed in this system was 25 ml pr m 2 of the paper.
  • Example 12 Additional samples were prepared as in Example 12 except that the silver halide emulsions (EM-1 to EM-6) employed in the light-sensitive materials prepared in Example 12 were respectively replaced by silver halide emulsions (EM-7 to EM-12) characterized below, or that couplers ExC-1 to ExC-6 were used as cyan couplers.
  • EM-1 to EM-6 silver halide emulsions
  • EM-7 to EM-12 silver halide emulsions
  • couplers ExC-1 to ExC-6 were used as cyan couplers.
  • Example 12 The performance of the samples was evaluated as in Example 12 and the compounds used in the present invention proved to be equally effective in preventing the occurence of stains in magenta image irrespective of variations in emulsions or couplers in layers other than magenta-forming layers.
  • This effect can sufficiently be attained even when the photographic materials are processed with processing solutions from which a noticeable amount of components of the processing solutions would enter into or adhere onto the photographic materials processed, such as processing solutions under running state, rinsing solutions containing a small amount of water or water-free rinsing solutions, substantially benzyl alcohol-free color developers or when the photographic materials are processed with other processing solutions which would be a burden on color development.

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Claims (26)

1. Farbphotographie, enthaltend eine die Lagerfähigkeit verbessernde Verbindung, die fähig ist, mit einem Farbentwicklungsmittel der aromatischen Amin-Reihe, das in einem photographischen Material nach dessen Farbentwicklungsbehandlung zurückbleibt, unter der Bedingung eines pH von 8 oder weniger eine chemische Bindung zu bilden, um in mindestens einer photographischen Schicht auf einem Träger eine chemisch inaktive und im wesentlichen farblose Verbindung zu ergeben, dadurch gekennzeichnet, daß die die Lagerfähigkeit verbessernde Verbindung aus Verbindungen der allgemeinen Formel (I) und (II) gewählt ist:
Figure imgb0528
Figure imgb0529
worin bedeuten:
R1 und R2 jeweils eine aliphatische Gruppe, aromatische Gruppe oder heterocyclische Gruppe;
X eine Gruppe, die fähig ist, mit einem zu entfernenden aromatischen Amin-Entwicklungsmittel zu reagieren;
A eine Gruppe, die fähig ist, mit einem aromatischen Amin-Entwicklungsmittel zur Bildung einer chemischen Bindung zu reagieren; n 1 oder 0;
B ein Wasserstoffatom, eine aliphatische Gruppe, aromatische Gruppe, heterocyclische Gruppe, Acylgruppe oder Sulfonylgruppe;
Y eine Gruppe, die fähig ist, die Addition eines aromatischen Amin-Entwicklungsmittels an die Verbindung der Formel (II) zu beschleunigen;
wobei R1 und X, und Y und R2 oder B zur Bildung einer cyclischen Struktur miteinander verbunden sein können.
2. Farbphotographie nach Anspruch 1, wobei die die Lagerfähigkeit verbessernde Verbindung eine sekundäre Reaktionsgeschwindigkeitskonstante k2 (80 C) mit p-Anisidin im Bereich von 1,0 Liter/Mol . sec bis 1 x 10-5 Liter/Mol . sec besitzt.
3. Farbphotographie nach Anspruch 2, wobei die die Lagerfähigkeit verbessernde Verbindung eine sekundäre Reaktionsgeschwindigkeitskonstante k2 (80 C) mit p-Anisidin von 1 x 10-1 Liter/Mol . sec bis 1 x 10-4 Liter/Mol . sec besitzt.
4. Farbphotographie nach Anspruch 1, wobei die Verbindung der Formel (I) aus Verbindungen der allgemeinen Formeln (I-a), (I-b), (I-c) und (I-d) gewählt ist und eine sekundäre Reaktionsgeschwindigkeitskonstante k2 (80 C) mit p-Anisidin im Bereich von 1 x 10-1 Liter/Mol . sec bis 1 x 10-5 Liter/Mol . sec besitzt.
Figure imgb0530
Figure imgb0531
Figure imgb0532
Figure imgb0533
worin R1 die gleiche Bedeutung wie R1 in Formel (I) hat; Link eine einfache Bindung oder -O- ist; Ar eine aroamtische Gruppe bezeichnet mit der gleichen Bedeutung, wie für Ri, R2 und B definiert, mit der Ausnahme, daß keine als photographisches Reduktionsmittel, wie ein Hydrochinon-Derivat oder ein Catechol-Derivat, geeignete Gruppe als Ergebnis der Reaktion mit einem Entwicklungsmittel der aromatischen Amin-Reihe freigesetzt wird; Ra, Rb und Rc, die gleich oder verschieden sein können, jeweils ein Wasserstoffatom oder eine aliphatische Gruppe, aromatische Gruppe oder heterocyclische Gruppe mit der gleichen Bedeutung, wie für Ri, R2 und B definiert, darstellen; Ra, Rb und Rc können weiterhin eine Alkoxygruppe, Aryloxygruppe, heterocyclische Oxygruppe, Alkylthiogruppe, Arylthiogruppe, heterocyclische Thiogruppe, Aminogruppe, Alkylaminogruppe, Acylgruppe, Aminogruppe, Sulfonamidogruppe, Sulfonylgruppe, Alkoxycarbonylgruppe, Sulfogruppe, Carboxylgruppe, Hydroxylgruppe, Acyloxygruppe, Ureidogruppe, Urethangruppe, Carbamoylgruppe oder Sulfamoylgruppe bedeuten, mit der Maßgabe, daß Ra und Rb oder Rb und Rc zur Bildung eines 5- bis 7-gliedrigen Heterorings kombiniert sein können, wobei der Heteroring weiterhin durch einen Substituenten substituiert sein kann, oder einen Spiroring, einen Bicycloring bilden können oder mit einem aromatischen Ring kondensiert sein können; Z1 und Z2, die zur Bildung eines 5- bis 7-gliedrigen Heterorings erforderliche nichtmetallische Atomgruppe bedeuten, wobei der Heteroring weiterhin durch einen Substituenten substituiert sein kann, oder einen Spiroring, einen Bicycloring bilden oder mit einem aromatischen Ring kondensiert sein können, mit der Ausnahme, daß Z1 nicht eine solche Gruppe ist, daß sie einen Kuppler, ein 1-Phenyl-3-pyrazolid als Ergebnis der Reaktion mit einem Entwicklungsmittel der aromatischen Aminreihe freisetzt.
5. Farbphotographie nach Anspruch 4, wobei die in dem photographischen Material enthaltene Verbindung der Formel (I) eine Verbindung der allgemeinen Formel (I-a) oder (I-b) mit einer Gesamtzahl von mindestens 13 Kohlenstoffatomen enthält.
6. Farbphotographie nach Anspruch 1, wobei die photographische Schicht die die Lagerfähigkeit verbessernde Verbindung zusammen mit einem Gelbkuppler, einem Magenta-Kuppler oder einem Cyankuppler enthält.
7. Farbphotographie nach Anspruch 6, wobei der Kuppler aus Verbindungen der allgemeinen Formeln (III), (IV), (V), (VI) und (VII) gewählt ist:
Figure imgb0534
Figure imgb0535
Figure imgb0536
Figure imgb0537
Figure imgb0538
worin bedeuten:
R'1 , R4 und R5 jeweils eine aliphatische Gruppe, aromatische Gruppe, heterocyclische Gruppe, aromatische Aminogruppe oder heterocyclische Aminogruppe;
R'2 eine aliphatische Gruppe;
R3 und R6 jeweils ein Wasserstoffatom, Halogenatom, eine aliphatische Gruppe, aliphatische Oxygrup-
pe oder Acylaminogruppe;
R'5 ein Wasserstoffatom oder die gleiche Bedeutung wie Rs;
R7 und Rg jeweils eine substituierte oder unsubstituierte Phenylgruppe;
R8 ein Wasserstoffatom, eine aliphatische oder aromatische Acylgruppe oder eine aliphatische oder aromatische Sulfonylgruppe;
R10 ein Wasserstoffatom oder einen Substituenten;
Q eine substituierte oder unsubstituierte N-Phenylcarbamoylgruppe;
Za und Zb jeweils eine Methingruppe, substituierte Methingruppe oder = N-;
Y1, Y2, Y3, Y4 und Y5 jeweils ein Wasserstoffatom oder eine Gruppe, die bei der Kupplungsreaktion mit einem oxidierten Produkt eines Entwicklungsmittels entfernt werden kann;
wobei R'2, R3 und R5 und R6 jeweils einen 5-, 6- oder 7-gliedrigen Ring bilden können;
R'1, R'2, R3 oder Y1; R4, Rs, R6 oder Y2; R7, R8, R9 oder Y3; R10, Za, Zb oder Y4; und Q oder Y5 jeweils ein Dimer oder ein höheres Polymer bilden können.
8. Farbphotographie nach Anspruch 1, wobei die photographische Schicht weiterhin ein die Verblassung verhinderndes Mittel zusammen mit dem die Lagerfähigkeit verbessernden Mittel enthält.
9. Farbphotographie nach Anspruch 8, wobei das die Verblassung verhindernde Mittel eine aromatische Verbindung der allgemeinen Formel (VIII) ist:
Figure imgb0539
worin bedeuten:
R1" ein Wasserstoffatom, eine Alkylgruppe, Alkenylgruppe, Arylgruppe, heterocyclische Gruppe oder eine Gruppe
Figure imgb0540
worin R7", Rε" und Rg" gleich oder verschieden sein können und jeweils eine Alkylgruppe, Alkenylgruppe, Arylgruppe, Alkoxygruppe, Alkenoxygruppe oder Aryloxygruppe bedeuten;
R2 ", R3 ", R4 ", R5" und R6 ", die gleich oder verschieden sein können, jeweils ein Wasserstoffatom, eine Alkylgruppe, Alkenylgruppe, Arylgruppe, Acylaminogruppe, Alkylaminogruppe, Alkylthiogruppe, Arylthiogruppe, Alkoxycarbonylgruppe, Aryloxycarbonylgruppe, ein Halogenatom oder -O-R1 "', worin R1 '" die gleiche Bedeutung wie R1 " hat;
oder R1" und R2" können zur Bildung eines 5-gliedrigen, 6-gliedrigen oder eines Spirorings miteinander verbunden sein;
oder R2" und R3", oder R3" und R4" können zur Bildung eines 5-gliedrigen Rings, eines 6-gliedrigen Rings oder eines Spirorings miteinander verbunden sein.
10. Farbphotographie nach Anspruch 9, wobei die Menge der zuzugebenden Verbindung der Formel (VIII) 10 bis 400 Mol-% bezüglich des Kupplers beträgt.
11. Farbphotographie nach Anspruch 9, wobei die Menge der zuzugebenden Verbindung der Formel (VIII) 30 bis 300 Mol-% bezüglich des Kupplers beträgt.
12. Farbphotographie nach Anspruch 8, wobei das die Verblassung verhindernde Mittel eine Aminverbindung der allgemeinen Formel (IX) ist:
Figure imgb0541
worin bedeuten:
R'10 ein Wasserstoffatom, eine Alkylglruppe, Alkenylgruppe, Alkinylgruppe, Acylgruppe, Sulfonylgruppe, Sulfinylgruppe, einen Oxyrest oder eine Hydroxylgruppe;
R11, R12, R13 und R14, die gleich oder verschieden sein können, jeweils ein Wasserstoffatom oder eine Alkylgruppe;
A eine zur Bildung eines 5-gliedrigen, 6-gliedrigen oder 7-gliedrigen Rings erforderliche nichtmetallische Atomgruppe.
13. Farbphotographie nach Anspruch 12, wobei die Menge der zuzugebenden Verbindung der Formel (IX) 10 bis 400 Mol-% bezüglich des Kupplers beträgt.
14. Farbphotographie nach Anspruch 12, wobei die Menge der zuzugebenden Verbindung der Formel (IX) 30 bis 300 Mol-% bezüglich des Kupplers beträgt.
15. Farbphotographie nach Anspruch 8, wobei das die Verblassung verhindernde Mittel ein Metallkomplex ist, umfassend ein Zentrumsatom aus Kupfer, Kobalt, Nickel, Palladium oder Platin und mindestens einen organischen Liganden mit zwei oder mehreren Konformationen.
16. Farbphotographie nach Anspruch 15, wobei die Menge des zuzugebenden Metallkomplexes 1 bis 100 Mol-% bezüglich des Kupplers beträgt.
17. Farbphotographie nach Anspruch 15, wobei die Menge des Zuzugebenden Metallkomplexes 3 bis 40 Mol-% bezüglich des Kupplers beträgt.
18. Verfahren zur Herstellung von Farbphotographien, wobei ein photographisches Material, enthaltend eine Silberhalogenidemulsionsschicht und einen farbbildbildenden Kuppler, der fähig ist, durch eine Oxidations-Kupplungsreaktion mit einem Farbentwicklungsmittel der aromatischen Amin-Reihe einen Farbstoff zu bilden, beschichtet auf einem Träger, bildmäßig belichtet und dann einer photographischen Verarbeitung unterzogen wird, umfassend das Ausführen der photographischen Verarbeitung in Gegenwart einer die Lagerfähigkeit verbessernden Verbindung, die fähig ist, mit dem Farbentwicklungsmittel der aromatischen Amin-Reihe eine chemische Bindung zu bilden, um eine chemisch inaktive und im wesentlichen farblose Verbindung zu ergeben, dadurch gekennzeichnet, daß eine die Lagerfähigkeit verbessernde Verbindung, wie in mindestens einem der Ansprüche 1 bis 5 definiert, verwendet wird.
19. Verfahren zur Herstellung von Farbphotographien nach Anspruch 18, wobei das photographische Material die die Lagerfähigkeit verbessernde Verbindung in mindestens einer photographischen Schicht enthält.
20. Verfahren zur Herstellung von Farbphotographien nach Anspruch 19, wobei Gehalt der die Lagerfähigkeit verbessernden Verbindung in dem photographischen Material innerhalb des Bereichs von 1 x 10-2 bis 10 Mol pro Mol des farbbildbildenden Kupplers liegt.
21. Verfahren zur Herstellung von Farbphotographien nach Anspruch 18, wobei der Farbentwickler Benzylalkohol in einer Menge von 2,0 ml/1 oder weniger enthält.
22. Verfahren zur Herstellung von Farbphotographien nach Anspruch 18, wobei der Farbentwickler Benzylalkohol in einer Menge von 0,5 ml/1 oder weniger enthält.
23. Verfahren zur Herstellung von Farbphotographien nach Anspruch 18, wobei der Farbentwickler keinen Benzylalkohol enthält.
24. Verfahren zur Herstellung von Farbphotographien nach Anspruch 18, wobei die Farbentwicklungszeit innerhalb 2 Minuten und 30 Sekunden oder weniger liegt.
25. Verfahren zur Herstellung von Farbphotographien nach Anspruch 18, wobei die Farbentwicklungszeit innerhalb des Bereichs von 10 Sekunden bis 2 Minuten und 30 Sekunden oder weniger liegt.
26. Verfahren zur Herstellung von Farbphotographien nach Anspruch 18, wobei die Farbentwicklungszeit innerhalb des Bereichs von 45 Sekunden bis 2 Minuten liegt.
EP19870111265 1986-08-05 1987-08-04 Farbaufnahmen und Verfahren zu deren Herstellung Expired EP0258662B1 (de)

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JPH07122747B2 (ja) * 1987-09-11 1995-12-25 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
JPH07122746B2 (ja) * 1987-09-11 1995-12-25 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
JPH02860A (ja) * 1988-02-10 1990-01-05 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料の処理方法
JPH0227346A (ja) * 1988-07-16 1990-01-30 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JPH07117732B2 (ja) * 1988-07-25 1995-12-18 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
DE68915916T2 (de) * 1988-09-27 1994-09-29 Fuji Photo Film Co Ltd Farbphotographisches Material.
JPH0820718B2 (ja) * 1988-10-03 1996-03-04 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の処理方法
JPH02217845A (ja) * 1989-02-20 1990-08-30 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JP2005003791A (ja) * 2003-06-10 2005-01-06 Konica Minolta Photo Imaging Inc ハロゲン化銀カラー写真感光材料及び画像形成方法
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