EP0316955A2 - Farbphotographische Silberhalogenidmaterialien - Google Patents

Farbphotographische Silberhalogenidmaterialien Download PDF

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Publication number
EP0316955A2
EP0316955A2 EP88119246A EP88119246A EP0316955A2 EP 0316955 A2 EP0316955 A2 EP 0316955A2 EP 88119246 A EP88119246 A EP 88119246A EP 88119246 A EP88119246 A EP 88119246A EP 0316955 A2 EP0316955 A2 EP 0316955A2
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Prior art keywords
group
groups
coupler
carbon atoms
represented
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English (en)
French (fr)
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EP0316955A3 (en
Inventor
Junichi C/O Fuji Photo Film Co. Ltd. Yamanouchi
Eiji C/O Fuji Photo Co. Ltd. Funatsu
Kei C/O Fuji Photo Co. Ltd. Sakanoue
Nobuo C/O Fuji Photo Co. Ltd. Sakai
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/327—Macromolecular coupling substances
    • G03C7/3275—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • This invention concerns silver halide color photographic materials which contain novel colored image forming couplers which can couple with the oxidized form of a primary aromatic amine developing agent.
  • Couplers obtained using this method do not mix with aqueous gelatin solutions and so they must be rendered soluble in alkali for addition to a gelatin solution, or alternatively they must be dissolved in an organic solvent of high boiling point for emulsification and dispersion in an aqueous gelatin solution.
  • Color couplers of this type may precipitate crystals in the emulsion or, in cases where an organic solvent of high boiling point is used, the emulsion layer may become soft and so large amounts of gelatin are required, and this is contrary to the requirements of thinner emulsion layers.
  • another method for introducing couplers into separate layers use is made of polymer latexes obtained by the polymerization of monomeric couplers.
  • Polymeric couplers in the form of a latex of this type for addition to gelatin/silver halide emulsions include four equivalent magenta polymeric couplers, the methods for their manufacture have been disclosed, for example, in U.S. Patent 4,080,211, British Patent 1,247,668 and U.S. Patent 3,451,820, the copolymer latexes with competitive couplers which have been disclosed in West German Patent 2,725,591 and U.S. Patent 3,926,436, and the cyan polymeric latexes which have been disclosed in U.S. Patent 3,767,412 and Research Disclosure 21728 (1982).
  • the main task of the invention is to provide high speed silver halide color photographic materials containing, novel polymeric couplers which have a high coupler unit content and which exhibit a high color forming ability.
  • a further task of the invention is to provide silver halide color photographic materials in which there is no color mixing because of the immobility of the couplers.
  • Another task of the invention is to provide a method of forming colored images having excellent quality, in particular light color density.
  • the task of the invention are achieved by means of a silver halide color photographic material containing in at least one silver halide emulsion layer and/or in at least one layer adjacent thereto at least one lipophilic polymeric coupler, characterized in that said lipophilic polymeric coupler is obtained by a polymerisation reaction using a chain transfer agent having at least 8 carbon atoms and a chain transfer constant with respect to the respective monomeric coupler in the range of from 0.1 to 20.
  • novel lipophilic polymeric couplers synthesized by means of a polymerization reaction using chain transfer agents having at least 8 carbon atoms and chain transfer constants for the monomeric couplers of at least 0.1 but not more than 20 are mixtures of polymers of various structures, but in the main they can be represented by the general formula [P] which is indicated below.
  • E represents a univalent group originating from the radical part which is formed by chain transfer to a chain transfer agent which has at least 8 carbon atoms and of which the chain transfer constant with respect to the monomeric coupler is at least 0.1 but not more than 20.
  • A represents a repeating unit which is derived from an ethylenically unsaturated monomer which has a coupler residual group which can couple with the oxidized form of a primary aromatic amine developing agent and form a dye.
  • B represents a repeating unit derived from a copolymerizable ethylenically unsaturated monomer.
  • X represents a univalent group.
  • x and y are the contents of each type of repeating units in the polymeric coupler, and the weight ratio of x and y (x:y) is from 10:90 to 100:0.
  • A is a repeating unit which has a coupler residual group which can couple with the oxidized form of a primary aromatic amine developing agent and form a dye, as mentioned above, and it is derived from a monomer which can be represented by the general formula [I] indicated below.
  • R 1 represents a hydrogen atom, an alkyl group which has from 1 to 4 carbon atoms or a chlorine atom
  • L 1 represents a
  • R 2 represents an alkyl group which has from 1 to 4 carbon atoms or a substituted alkyl group which has from 1 to 6 carbon atoms), a -COO- group, an -NHCO- group, an -OCO- group, an group (where R 3 and R 4 each independently represent a hydrogen atom, hydroxyl group, halogen atom or a substituted or unsubstituted alkyl, alkoxy, acyloxy or aryloxy group), an group (where R 2 , R 3 and R 4 have the same meaning as above), L 2 represents a linking group which links Q with L 1 , m represents 0 or 1, n represents 0 or 1, and Q represents a coupler residual group which can couple with an oxidized primary aromatic amine developing agent to form a dye.
  • the linking group represented by L 2 is typically represented by the formula: J 1 , J 2 and J 3 may be the same of different, each representing, for example, a -CO- group, -SO 2 group,
  • R 5 represents a hydrogen group, alkyl group (which has from 1 to 6 carbon atoms), substituted alkyl group (which has from 1 to 6 carbon atoms)), group (where R 5 has the same meaning as described above),
  • R 5 has the same meaning as described above and R 6 is an alkylene group which has from 1 to about 4 carbon atoms, an group (where R 5 and R 6 have the same meaning as described above and R 7 represents a hydrogen atom, an alkyl group (which has from 1 to 6 carbon atoms) or a substituted alkyl group (which has from 1 to 6 carbon atoms)), -0- group, -S- group, group (where R 5 and R 7 have the same meaning as described above, group (where R 5 and R 7 have the same meaning as described above), -COO- group, -OCO- group, (where R 5 has the same meaning as described above), (where R 5 has the same significance as described above).
  • X 1 , X 2 and X 3 may be the same Or different, each representing an alkylene group, substituted alkylene group, arylene group, substituted arylene group, aralkylene group or substituted aralkylene group.
  • p, q, r and s each represent 0 or 1.
  • X 1 , X 2 and X 3 may be the same or different, each representing a substituted or unsubstituted alkylene group which has from 1 to 10 carbon atoms, aralkylene having 7 to 20 carbon atoms, or a phenylene group having 6 to 20 carbon atoms, and the alkylene groups may be linear chain or branched groups.
  • alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene and decylmethylene groups
  • the benzylidene group is an example of an aralkylene group
  • examples of phenylene groups include p-phenylene, m-phenylene and methylphenylene groups.
  • substituent groups for the alkylene groups, aralkylene groups and arylene groups represented by X 1 , X 2 and X 3 include halogen atoms, nitro group, cyano group, alkyl groups, substituted aikyl groups, alkoxy groups, substituted alkoxy groups, groups which can be represented by -NHCOR 8 - (where R 8 represents an alkyl group, substituted alkyl group, phenyl group, substituted phenyl group, aralkyl group or a substituted aralkyl group), groups- which can be represented by -NHS0 2 R 8 (where R 8 has the same meaning as before), groups which can be represented by -SOR 8 (where R 8 has the same meaning as before), groups which can be represented by -SO 2 R 8 (where R 8 has the same meaning as before), groups which can be represented by -COR 8 (where R 8 has the same meaning as before), groups which can be represented by (where R 9 and R 10 may be the same or
  • substituent groups for the above mentioned substituted alkyl groups, substituted alkoxy groups, substituted phenyl groups and substituted aralkyl groups include hydroxyl group, nitro group, alkoxy groups which have from 1 to about 4 carbon atoms, groups which can be represented by -NHS0 2 R 8 (where R 8 has the same significance as before), groups which can be represented by -NHCOR 8 (where R 8 has the same meaning as before), groups which can be represented by (where R 9 and R 10 have the same meaning as before), amino group (thismay be substituted with alkyl groups), hydroxyl group and groups which forms a hydroxy group by hydrolysis. In cases where there are two or more substituent groups these groups may be the same or different.
  • substituent groups for the above mentioned substituted alkyl groups, substituted alkoxy groups, substituted phenyl groups and substituted aralkyl groups include hydroxyl group, nitro group, alkoxy groups which have from 1 to about 4 carbon atoms, groups which can be represented by -NHS0 2 R 8 (where R 8 has the same significance as before), groups which can be represented by -NHCOR 8 (where R 8 has the same meaning as before), groups which can be represented by (Where R 9 and R 10 have the same meaning as before), groups which can be represented by (where R 9 and R 10 have the same meaning as before), groups which can be represented by S0 2 R 8 (where R 8 has the same meaning as before), groups which can be represented by -COR 8 (where R 8 has the same meaning as before), halogen atoms, and amino group (this may be substituted with alkyl group).
  • the phenol type compounds which can be represented by the general formulae [II] and [V] and the naphthol type compounds which can be represented by the general formulae [III] and [IV] are preferred as cyan forming couplers (these compounds loose a hydrogen atom other than the hydroxyl hydrogen atom and link-up with the group).
  • R" represents a group which can be substituted on a phenol ring or a naphthol ring, and examples of such groups include halogen atoms, hydroxyl group, amino group, carboxyl group, sulfo group, cyano group, aliphatic groups, aromatic groups, heterocyclic groups, carbonamido groups, sulfonamido groups, carbamoyl groups, sulfamoyl groups, ureido groups, acyloxy groups, acyl groups, aliphatic oxy groups, aliphatic thio groups, aliphatic sulfonyl groups, aromatic oxy groups, aromatic thio groups, aromatic sulfonyl groups, sulfamoylamino groups, nitro group, imido groups etc.
  • R" has from 0 to 30 carbon atoms.
  • R 12 represents a -CONR 14 R 15 group, NHCOR 14 group, -NHCOOR 16 group, -NHSO 2 R 16 group, -NHCONR 14 R 15 group or -NHSO 2 R 14 R 15 group, where R' 4 and R 15 represent hydrogen atoms, aliphatic groups which have from 1 to 30 carbon atoms (for example a methyl group, ethyl group, butyl group, methoxyethyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, trifluoromethyl group, heptafluoropropyl group, dodecyloxypropyl group, 2,4-di-tert amylphenoxypropyl group, 2,4-di-tert-amylphenoxybutyl group), an aromatic group which has from 6 to 30 carbon atoms (for example a phenyl group,
  • R 14 and R 15 may be joined together to form a heterocyclic ring (for example morpholine ring, piperidine ring, pyrrolidine ring).
  • p is an integer of value 0 to 3
  • s is an integer of value 0 to 2
  • q and r are each integers of value 0 to 4.
  • X 4 represents an oxygen atom, a sulfur atom or an R 17 N ⁇ group, where R17 represents a hydrogen atom or a univalent group.
  • R 17 represents a hydrogen atom or a univalent group.
  • univalent groups which can be represented by R 17 include aliphatic groups which have from 1 to 30 carbon atoms (for example methyl group, ethyl group, butyl group, methoxyethyl group, benzyl group), aromatic groups which have from 6 to 30 carbon atoms (for example phenyl group, tolyl group), heterocyclic groups which have from 2 to 30 carbon atoms (for example 2-pyridyl group, 2- pyrimidyl group), carbonamido groups which have from 1 to 30 carbon atoms (for example formamido group, acetamido group, N-methylacetamido group, benzamido group), sulfonamido groups which have from 1 to 30 carbon atoms (for example methane
  • R 18 and R' 9 may be the same or different, each representing a hydrogen atom, an aliphatic group which has from 1 to 30 carbon atoms (for example methyl group, ethyl group, butyl group, dodecyl group, methoxyethyl group, trifluoromethyl group, pentafluoropropyl group), an aromatic group which has from 6 to 30 carbon atoms (for example phenyl group, tolyl group, 4-chlorophenyl group, pentafluorophenyl group, 4-cyanophenyl group, 4-hydroxyphenyl group) or a heterocyclic group which has from 2 to 30 carbon atoms (for example 4-pyridyl group, 3-pyridyl group, 2-furyl group).
  • R 18 and R' 9 may be joined together to form a heterocyclic group (for example a morpholino group, pyrrolidino group).
  • R 20 can represent any of the substituent groups indicated as examples of R 18 and R 19 except the hydrogen atom.
  • Z 1 represents a hydrogen atom or a group which can be eliminated by a coupling reaction with the oxidized form of a primary aromatic amine.
  • groups which can be eliminated include halogen atoms (for example fluorine atom, chlorine atom, bromine atom, iodine atom), aliphatic oxy groups which have from 1 to 30 carbon atoms (for example methoxy group, ethoxy group, 2-hydroxyethoxy group, carboxymethyloxy group, 3-carboxypropyloxy group, 2-methoxyethoxycarbamoylmethyloxy group, methanesulfonylethoxy group, 2-carboxymethylthioethoxy group, triazolylmethyloxy group), aromatic oxy groups which have from 6 to 30 carbon atoms (for example phenoxy group, 4-hydroxyphenoxy group, 2-acetamidophenoxy group, 2,4-dibenzenesulfonamidophenoxy group, 4-phenylazophenoxy group), heterocyclic oxy groups which have
  • Y Represents a group of atoms which is required to form, together with the carbon atoms to which it is bound, a five to seven membered ring. Actual example include -O-,
  • R and R'" each independently represent a hydrogen atom, alkyl group, aryl roup, halogen atom, alkoxy group, alkoxycarbonyl group, arylcarbonyl group, alkylcarbamoyl group, arylcarbamoyl group or a cyano group.
  • the preferred substituents represented by R 11 are Lalogen atoms (for example fluorine, chlorine, bromi e etc.), aliphatic groups (for example methyl group, ethyl group, isopropyl group), carbonamido groups (for example acetamido group, benzamido group), sulfonamido groups (for example methanesulfonamido group toluenesulfonamido group).
  • Lalogen atoms for example fluorine, chlorine, bromi e etc.
  • aliphatic groups for example methyl group, ethyl group, isopropyl group
  • carbonamido groups for example acetamido group, benzamido group
  • sulfonamido groups for example methanesulfonamido group toluenesulfonamido group.
  • the groups represented by -CONR 14 R 15 are preferred fo R 12 , and examples include carbamoyl group, ethyl carbamoyl group, morpholinocarbamoyl group, dodecylcarbamoyl group, hexadecylcarbamoyl group, decylcarbamoyl group, decyloxypropyl group, dodecyloxypropyl group, 2,4-di-tert-amylphenoxypropyl group and 2,4-ditert-amylphenoxybutyl group.
  • R 17 is preferred for X 4 , and even more desiiable for R 17 are the -COR' 8 group (for example formyl group, acetyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, pentafluorobenzoyl group, pchlorobenzoyl group), the -COOR 20 group (for example methoxycarbonyl group, ethoxycarbcnyl group, butoxycarbonyl group, dodecyloxycarbonyl group, methoxyethoxycarbonyl group, phenoxycarbonyl group), the -SO 2 R 20 group (for example methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, hexadecanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, p-chlorobenzenesulfon
  • the -COR 18 group, -COOR 20 group and the -S0 2 R 20 group are especially desirable for R 17 .
  • the preferred groups for Z 1 are the hydrogen atom, the halogen atoms, the aliphatic oxy groups, the aromatic oxy groups, the heterocyclic thio groups and the aromatic azo groups.
  • Couplers which can be represented by the general formulae [II]-[V] may consist of dimers or larger oligomers which are bonded together via linking groups which have a valency of two or more by means of the substituent groups R 11 , R 12 , X 4 or Z 1 .
  • the groups are not limited to the numbers of carbon atoms shown for each of the aforementioned substituent groups (linked by -(L 1 ) m -(L 2 ) n - in any of Ar, Z 2 ).
  • coupler residual groups which can be represented by the general formulae [VI], [VII], [VIII], [IX], [X], [XI] and [XII] are preferred as magenta color forming coupler residual groups (linked by -(L 1 ) m -(L 2 ) n - in any of Ar, Z 2 , R 21 to R 33 ).
  • Ar represents a substituent group of the known type in the 1-position of a 2-pyrazolin-5-one coupler, for example an alkyl group, substituted alkyl group (for example a haloalkyl group such as a fluoroalkyl group, acylalkyl group, benzylalkyl group), an aryl group or substituted aryl group with, as substituent groups, alkyl groups (for example methyl group, ethyl group), alkoxy groups (for example methoxy group, ethoxy group), aryloxy groups (for example phenyloxy group), alkoxycarbonyl groups (for example methoxycarbonyl group), acylamino groups (for example acetylamino group), carbamoyl groups, alkylcarbamoyl groups (for example methylcarbamoyl group, ethylcarbamoyl group), dialkylcarbamoyl groups (for example dimethylcarb
  • the preferred substituent groups are halogen atoms, alkyl groups, alkoxy groups, alkoxycarbonyl groups and cyano groups.], or a heterocyclic group (for example triazole, thiazole, benzthiazole, furan, pyridine, quinaldine, benzoxazole, pyrimidine, oxazole, imidazole).
  • R 21 represents an unsubstituted anilino group, an acylamino group (for example an alkylcarbonamido group, phenylcarbonamido group, alkoxycarbonamido group, phenyloxycarbonamido group), or a ureido group (for example an alkylureido group, phenylureido group), and these groups may have, as substituent groups, halogen atoms (for example fluorine atoms, chlorine atoms, bromine atoms), linear chain or branched alkyl groups (for example methyl group, t-butyl group, octyl group, tetradecyl- group), alkoxy groups (for example methoxy group, ethoxy group, 2-ethylhexyloxy group, tetradecyloxy group), acylamino groups (for example acetamido group, benzamido group, butanamido group, oct
  • alkylthio groups for example methylthio group, ethylthio group, hexylthio group, benzylthio group, tetradecylthio group, 2-(2,4-di-tert-amylphenoxy)ethylthio group), arylthio groups (for example phenylthio group, p-tolylthio group), alkyloxycarbonylamino groups (for example methoxycarbonylamino group, ethyloxycarbonylamino group, benzyloxycarbonylamino group, hex- adecyloxycarbonylamino group), alkylureido groups (for example N-methylureido group, N,N-dimethylureido group, N-methyl-N-dodecylureido group, N-hex- adecyloxycarbonylamino group), alkylureido groups (for example N-methylure
  • the number of carbon atoms in those of the above mentioned substituent groups designated as alkyl groups is from 1 to 36 and the number of carbon atoms in those groups designated as aryl groups is from 6 to 38.
  • R22 , R23 , R 24, R2 5, R 26, R 27, R 28, R29, R 3 0 , R3 1 , R 32 and R 33 each represents a hydrogen atom or a hydroxyl group, or they may each represent an unsubstituted or a substituted alkyl group (for example an alkyl group which has from 1 to 20 carbon atoms, such as a methyl group, propyl group, t-butyl group, trifluoromethyl group, tridecyl group etc.), an aryl group (for example an aryl group which has from 6 to 20 carbon atoms, such as a phenyl group, 4-t-butylphenyl group, 2,4-di-t-amylphenyl group, 4-methoxyphenyl group), a heterocyclic group (for example a 2 furyl group, 2-thienyl group, 2-pyrimidyl group, 2-benzothiazolyl group), an alkylamino group (for example an alkyla
  • Z 2 represents a hydrogen atom or a group which can be eliminated by a coupling reaction with the oxidized form of a primary aromatic amine developing agent.
  • the group which can be eliminated can be a halogen atom (for example a chlorine atom, bromine atom), a coupling elimination group which is linked with an oxygen atom (for example an acetoxy group, propanoyloxy group, benzoyloxy group, ethoxyox- aloyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group, 4- methanesulfonamidoohenoxy group, c-naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzoyloxy group, 2-phenethyloxy group, 2-phenoxyethoxy group, 5-phenyltetrazolyloxy group,
  • the group which can be eliminated is preferably a halogen atom, a coupling elimination group which is linked with an oxygen atom or a coupling elimination group which is linked with a nitrogen atom, and it is most desirably an alkyloxy group, a chlorine atom, a pyrazolyl group, an imidazolyl group or a triazolyl group.
  • coupler residual group is preferably of the acylacetamide type, and those of the pivaloylacetanilide type which can be represented by the general formulae [Xlll] and [XIII and those of the benzoylacetanilide type which can be represented by the general formulae [XIV], [XIV [XV] and [XV are especially preferred as yellow color forming coupler residual groups (the free bonds shown in the general formulae are linked to the -(L 1 ) m -(L 2 ) n - group.
  • R 34 , R 35 , R 36 and R 37 each represent a hydrogen atom or a known substituent group for a yellow color forming coupler residual group, for example an alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, halogen atom, alkoxycarbamoyl group, aliphatic amido group, alkylsulfamoyl group, alkylsulfonamido group, alkylureido group, alkyl substituted succinimido group, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamido group, arylsulfamoyl group, arylsulfonamido group, arylureido group, carboxyl group, sulfo group, nitro group, cyano group, thiocyano group, and these substituent groups may be the same or different.
  • Z 3 is a hydrogen atom or a group which can be represented by the general formulae [XVI], [XVII], [XVIII] or [XIX] as indicated below.
  • R 38 represents a heterocyclic group or an alkyl group which may be substituted.
  • R 39 and R 40 each represents a hydrogen atom, halogen atom, carboxylic acid ester group, amino group, alkyl group, alkylthio group, alkoxy group, alkylsulfonyl group, alkylsulfinyl group, carboxylic acid group, sulfonic acid group, unsubstituted or substituted phenyl group or a heterocyclic group, and these groups may be the same or different.
  • W is a group of non-metal atoms required to form a four, five or six membered ring together with the
  • R 41 and R 42 each represents a hydrogen atom, alkyl group, aryl group, alkoxy group, aryloxy group or a hydroxyl group
  • R 43 , R 44 and R 45 each represents a hydrogen atom, alkyl group, aryl group, aralkyl group or an acyl group
  • W 2 represents an oxygen atom or a sulfur atom.
  • Preferred examples of the ethylenic unsaturated monomers which provide the repeating units represented by B include acrylic acid, a-chloroacrylic acid, a-alkylacrylic acids (for example methacrylic acid), esters and amides derived from these acids (for example acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, 2-methoxyethylacrylamide, diacetoneacryl amide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-
  • B may be a repeating unit derived from an ethylenically unsaturated monomer which binds directly, or via a film hardening agent, with the binder of the layer in which the polymeric coupler is present.
  • Ethylenically unsaturated monomers of this type are indicated below:
  • Two or more types of ethylenically unsaturated monomer can be used conjointly.
  • ethyl acrylate and n-butyl acrylate For example, use can be made of ethyl acrylate and n-butyl acrylate, n-butylacrylate and styrene, n-butylacrylate and t-butylacrylamide, 2-methoxymethyl methacrylate and potassium styrenesulfinate, etc.
  • R' represents a hydrogen atom or a methyl group
  • LI represents -CONH, -COO-, -OCO-,
  • L 2 can be represented by:
  • J 1 , J 2 and J 3 may be the same or different, each representing -CO-, -SO 2 -, -CONH-, -S0 2 NH-, -NHCO-, -NHS0 2 , -O-, -NHCONH-, -S-, -COO-, -OCO-, -NHCOO- or -OCONH;
  • X 1 , X 2 and X 3 may be the same or different, each representing an alkylene group (which has from 1 to 4 carbon atoms), an arylene group, or a substituted arylene group, and p, q, r and s each represent 0 or 1.
  • the acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, maleic acid esters, styrenes, and ethylenic monomers which can bind directly or via a film hardening agent with the binder are the most desirable for B.
  • E represents a univalent group which has at least 8 carbon atoms and which originates from the radical part which is formed by chain transfer to a chain transfer agent of which the chain transfer constant for a monomeric coupler is at least 0.1 but not more than 20, and it can, for example, be represented by the general formula [XXII].
  • E' may be an alkyl group, substituted alkyl group, substituted aryl group, or substituted naphthyl group etc., which has at least 8 carbon atoms.
  • substituents group include halogen atoms, cyano group, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, -NHCOR 46 groups where R 46 represents an alkyl group, substituted alkyl group, phenyl group, substituted phenyl group or an aralkyl group), -NHSO 2 R 46 groups (where R 46 has the same significance as described above), -OCOR 46 groups (where R 46 has the same meaning as described above), -SOR 46 groups (where R 46 has the same meaning as described above),
  • R 47 and R 48 may be the same or different, each representing a hydrogen atom, alkyl group, substituted alkyl group, phenyl group, substituted phenyl group, aralkyl group, or a substituted aralkyl group),
  • substituent groups for the abovementioned alkyl groups, substituted alkoxy groups and substituted aralkyl groups include hydroxyl group, alkoxy groups which have from 1 to about 4 carbon atoms, -NHS0 2 R 46 groups (where R 46 has the same meaning as described above), NHCOR 46 groups (where R 46 has the same meaning as described above), -COOR4 6 groups (where R 46 has the same meaning as described above), -OCOR 46 6 groups (where R 46 has the same meaning as described above),
  • E 1 is not limited to these groups.
  • X preferably represents a hydrogen atom or a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom).
  • Typical examples of the monomeric couplers which provide coupler units which have a coupler residual group which can couple with a primary aromatic amine developing agent and form a dye, and which can be represented by the general formula [I] which is the color forming part, are indicated below, but the invention is not limited to these examples.
  • the monomeric couplers may be used individually or a plurality of monomeric couplers can be used.
  • polymeric couplers represented by the general formula [P] and as obtained by means of a polymerization reaction in which the chain transfer agents used in this invention are used about 0.1 to 20 wt% of compounds which can be represented by the general formulae [XXIII] and [XXIV] indicated below, may be present.
  • telomers Polymers represented by the general formula [P] which have been prepared using a chain transfer agent in accordance with this invention are known as telomers.
  • I, M and EX are respectively the initiator, the monomer and the chain transfer agent, EM * are propagating radicals, I* , and E * are respectively the primary radical, the grown polymer and the chain transfer agent radical, and k is the respective rate constant for each elementary reaction.
  • polymerization occurs with initiation via a radical which has been transferred to the chain transfer agent, after which reaction proceeds and then chain transfer onto the chain transfer agent occurs.
  • the chain transfer constant is defined as the ratio of the rate constants of the chain transfer reaction and the propagation reaction, ktr/kp.
  • the principal distinguishing feature of the method used to synthesize the telomeric couplers used in this invention is that a chain transfer agent which has at least 8 carbon atoms and which has a chain transfer constant of at least 0.1 but not more than 20 is used.
  • the chain transfer constant varies with the combination of chain transfer agent and monomeric coupler, but the use of mercaptans as chain transfer agents is preferred since they have a chain transfer constant in the range between 0.1 and 20 irrespective of the type of monomeric coupler.
  • chain transfer agents for use in the invention are indicated below, but the chain transfer agent is not limited to those listed here.
  • telomeric couplers of this invention can be achieved using the compounds disclosed in JP-A-56-5543, JP-A-57-94752, JP-A-57-176038, JP-A-57-204038, JP-A-58-28745, JP-A-58-10738, JP-A-58-42044, JP-A-58-145944 and JP-A-59-42543 as polymerization initiators and polymerization solvents.
  • Tlhe use of polymerization initiators which have at least 20 carbon atoms is preferred for the synthesis of the telomeric couplers of this invention. It is possible by using such initiators to increase the fastness to diffusion of the polymeric couplers of the aforementioned general formula [XXIV]
  • the polymerization initiator is used in an amount of from about 0.01 to about 10 mol%, and preferably in an amount of from 0.01 to 2.0 mol%, with respect to the monomer.
  • a polymerization solvent which as a low chain transfer constant is best, and those which have a chain transfer constant not exceeding 1 ⁇ 10 -3 are preferred.
  • the polymerization temperature must be set in accordance with the molecular weight of the telomer which is being formed and the type of initiating agent which is being used, and although temperatures below 0°C and above 100°C can be used, the polymerization is normally carried out at a temperature within the range from 0°C to 100° C. Higher temperatures are best for telomer synthesis and the preferred polymerization temperatures are within the range from about 70 C to 100 C.
  • the proportion of the color forming part as represented by the general formula [I] in a telomeric coupler is preferably from 10 to 95 wt% but, in respect of color reproduction, color forming ability and stability, the proportion is preferably from 20 to 90 wt%.
  • the equivalent molecular weight (the number of grams of polymer which contain 1 mol of monomeric coupler) is about 200 to 4,000, but no particular limit is imposed.
  • the number average molecular weight of a telomeric coupler of this invention is preferably from about 500 to about 10,000, and most desirably from about 500 to about 5,000, from the point of view of color forming ability and speed.
  • the mercaptan chain transfer agents which are preferably used in the invention are also present in amounts of about 0.01 to 0.3 wt% in the telomeric polymers after completion of the polymerization, and this causes undesirable effects such as fogging and loss of speed etc.
  • the following methods can be used to eliminate the mercaptans or to render them harmless from the point of view of photographic performance.
  • the second of these three possible methods is preferred from the point of view of the effectiveness of the reduction in the amount of mercaptan and from the point of view of characteristics such as color forming ability and speed.
  • a monomer which imparts water solubility such as acrylic acid, or acrylamide
  • a water re-precipitation process or extraction with a water/organic solvent system after completion of the subsequent polymerization it is possible to eliminate just the mercaptan very efficiently. That is to say, the mercaptans are expelled from the system as water scluble polymeric telomers of acrylic acid, or acrylamide without affecting the properties of the telomer (which is to say the coupler unit content or color forming performance).
  • the substances which are harmful in respect of the photographic performance can be removed without affecting the high color forming ability and the high speed properties of the telomer.
  • telomeric couplers of this invention are added to the silver halide emulsion layers or to layers which are adjacent thereto.
  • telomeric couplers of this invention are best added at a rate, based on the coupler monomer, of from 0.005 mol to 0.5 mol, and preferably of from 0.01 mol to 0.10 mol, per mol of silver when they are added to the same layer as the silver halide.
  • telomeric couplers of this invention when used in non-photosensitive layers, are coated at a rate of from 0.01 to 1.0 gram per square meter, and preferably at a rate of from 0.1 to 0.5 gram per square meter.
  • the number average molecular weight in this invention can be calculated on the basis of measurements made using gel permeation chromatography (GPC).
  • a calibration curve was prepared using TSK Standard Polystyrene (made by Toyo Soda).
  • the number average molecular weight was obtained using the method described on pages 204 to 208 of the Polymer Society publication entitled “Experimental Methods in Polymer Science” (published by Tokyo Kagaku Dojin, 1981), which is to say that it was calculated using a segment method.
  • the chromatogram obtained was divided into equally spaced counts (D), the peak height from the base line for the ith molecular weight fraction was taken as Hi and the number average molecular weight was obtained using the relationship shown in equation (1) below.
  • Ni represents the number of molecules of the ith type
  • Mi represents the molecular weight of the molecules of the ith type (Mi can be obtained from the aforementioned claibration curve).
  • the chain transfer constant in this invention can be calculated in various ways.
  • the method described on pages 126 to 127 of "Radical Polymerization (I)" by T. Ohtsu (published by Kagaku Dojin, 1971) can be used as a general method.
  • the residual monomeric coupler and the residual chain transfer agent in the reaction mixture in a polymerization reaction where x and y in general formula [P] are 100 and 0 respectively are determined and the chain transfer constant is obtained using equation (2) as shown below.
  • [S] represents the concentration of residual chain transfer agent and M represents the concentration of residual monomeric coupler.
  • selection of the monomer represented by the general formula [I] can be made in such a way as to have a good affect on the physical and/or chemical properties, which is to say the solubility, compatibility with the binders such as gelation which are used in photographic colloid compositions, flexibility, or thermal stability, of the copolymer.
  • the telomeric couplers of this invention may be prepared in the form of a latex by dissolving the coupler obtained by polymerization of the monomeric coupler in an organic solvent and emulsifying and dispersing this in an aqueous gelatin solution, or by using a direct emulsion polymerization method.
  • telomeric couplers of this invention Typical examples of the Synthesis of telomeric couplers of this invention are described below.
  • this telomeric coupler contained 49.8 wt% of the monomeric coupler (1) units.
  • the number average molecular weight by GPC was 2,800.
  • the chain transfer constant of the dodecylmercaptan used in this reaction was calculated on the basis of measurements made using gas chromatography and the GPC method indicated below.
  • telomeric couplers (II) to (XX) shown in table 1 were prepared in the same way as described in example of synthesis 1 (these reactions were carried out with adjustment of the amount of chain transfer agent in order to adjust the moledular weight).
  • this polymeric coupler had a monomeric coupler (14 ⁇ unit content of 50.2 wt%.
  • the number average molecular weight by GPC was 41,000.
  • Comparative polymeric coupler (B) was synthesized in using 30 grams of monomeric coupler (14) and 10 grams of butyl acrylate by following the same procedure as in comparative example of synthesis 1.
  • the monomeric coupler (14) unit content was found, by fluorine analysis, to be 74.6 wt%, and the number average molecular weight by GPC was 18,000.
  • Comparative polymeric coupler (C) was obtained under the same conditions as in comparative example of synthesis 1 except that ten times the amount of polymerization solvent and four times the amount of polymerization initiator were used.
  • Comparative polymeric coupler (D) was obtained under the same conditions as in comparative example of synthesis 2 except that eight times the amount of polymerization solvent and two times the amount of polymerization initiator were used.
  • this polymeric coupler had a monomeric coupler (26) unit. content of 50.8 wt%.
  • the number average molecular weight by GPC was 210,000.
  • Comparative polymeric coupler (F) was synthesized in using 30 grams of monomeric coupler (26) and 10 grams of butyl acrylate by following the same procedure as in comparative example of synthesis 3.
  • the monomeric coupler (14) unit content was found, by fluorine analysis (sic), to be 75.3 wt%, and the number average molecular weight by GPC was 3,000.
  • Comparative polymeric coupler (G) was obtained under the same conditions as in comparative example of synthesis 5 except that four times the amount of polymerization solvent and ten times the amount of polymerization initiator were used.
  • Comparative polymeric coupler (H) was obtained under the same conditions as in comparative example of synthesis 6 except that four times the amount of polymerization solvent and three times the amount of polymerization initiator were used.
  • Comparative polymeric couplers (I) to (L) were synthesized under the same conditions as used in comparative examples 1 to 4 respectively.
  • the comparative polymeric couplers (M) and (0) were synthesized under the same conditions as in comparative example of synthesis 5 and the comparative polymeric couplers (N) and (P) were synthesized under the same conditions as in comparative example of synthesis 6.
  • this polymeric coupler had a monomeric coupler (14) unit content of 49.5 wt%.
  • the number average molecular weight by GPC was 290,000.
  • this polymeric coupler had monomeric coupler (26) unit content of 51.4 wt%.
  • the number average molecular weight by GPC was 15,000.
  • Comparative polymeric coupler (S) (37.2 grams) was Synthesized under the same conditions as in comparative example of synthesis 17 using 20 grams of monomeric coupler (1), 17 grams of butyl acrylate and 3.0 grams of 2-hexadecanol.
  • this compound contained 49.7% of monomeric couDler. (1) units and the number average molecular weight by GPC was 29,000.
  • Comparative polymeric coupler (T) (35.2 grams) was synthesized under the same conditions as in comparative example of synthesis 18 using 20 grams of monomeric coupler (27), 17 grams of butyl acrylate and 3.0 grams of 2-hexadecanol.
  • this compound contained 50.9% of monomeric coupler (27) units, and the number average molecular weight by GPC was 20,000.
  • the silver halide which is contained in the photographic emulsion layer of a photographic material to which the invention is being applied is preferably a silver iodobromide, silver iodochloride or silver iodochlorobromide which contains not more than about 30 mol% of silver iodide.
  • the use of silver iodobromides which contain from about 2 mol% to about 25 mol% of silver iodide is most desirable.
  • the silver halide grains in the photographic emulsion may have a regular crystalline form, such as a cubic, octahedral or tetradecahedral form, an irregular crystalline form, such as a spherical or tabular form, they may have crystal defects such as twinned crystal planes, or they may have a composite form consisting of these forms.
  • the silver halide grains may be of a small size nQt more than about 0.2 microns, or of a large size such that the projected area diameter is up to about 10 microns, and they may take the form of a polydispersion or a mono-dispersion.
  • the silver halide photographic emulsions which can be used in the invention can be prepared, for example, using the methods disclosed for example in Research Disclosure (RD) No. 17643 (December 1978), pages 22 to 23, "I. Emulsion Preparation and Types", and in RD No. 18716 (November 1979), page 648; in Chemie et Phvsioue Photographique, by P. Glafkides, published by Paul Montel, 1967; in Photographic Emulsion Chemistry, by G.F. Duffin, published by Focal Press, 1966; and in . Making and Coating Photographic Emulsions, by V.L. Zelikman et al., published by Focal Press, 1964, etc.
  • tabular grains which have an aspect ratio of at least about 5 can be used in the invention.
  • Tabular grains can be prepared easily using the methods disclosed by Gutoff in Photographic Science and Enoineering, Volume 14, pages 248 to 257 (1970), in U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520, and in British Patent 2,112,157.
  • the crystal structure may be uniform, the interior and exterior parts may have a heterogeneous halogen composition, or the grains may have a layered structure and, moreover, the silver halides which have different compositions may be joined with an epitaxial junction or they may be joined with compounds other than silver halides such as silver thiocyanate or lead oxide etc.
  • Mixtures of grains of various crystalline forms may also be used.
  • the silver halide emulsions used have normally been subjected to physical ripening, chemical ripening and spectral sensitization.
  • Additives which can be used in these processes have been disclosed in Research Disclosure Nos. 17643 and 18716, and the locations of the said disclosures are summarized in the table below.
  • the 5-pyrazolone based, and pyrazoloazole based, compounds are preferred as magenta couplers, and those disclosed in U.S. Patents 4,310,619 and 4,351,897, in EP-B-73,636, in U.S. Patents 3,061,432 and 3,725,067, in Research Disclosure No. 24220 (June 1984), in JP-A-60-33552, in Research Disclosure No. 24230 (June 1984), in JP-A-60-43659, and in U.S. Patents 4,500,630 and 4,540,654 are most desirable.
  • Phenol based, and naphthol based, couplers are used as cyan couplers, and those disclosed in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, in West German Patent Laid Open No. 3,329,729, in EP-A-121,365, in U.S. Patents 3,446,622, 4,333,999, 4,451,559 and 4,427,767, and in EP-A-161,626 are preferred.
  • Couplers which release photographically useful residual groups on coupling can also be used preferentially in this invention.
  • the DIR couplers which release development inhibitors desclosed in the patents disclosed in the aforementioned Research Disclosure No. 17643, section VII-F, in JP-A-57-151944, 57 154234 and 60-184248, and in U.S. Patent 4,248,962 are preferred.
  • couplers disclosed in British Patents 2,097,140 and 2,131,188, and in JP-A-59 157638 and 59-170840 are preferred as couplers which release nucleating agents or development accelerators in the form of the image during development.
  • couplers which can be used in the light sensitive materials of this invention include the competitive couplers disclosed in U.S. Patent 4,130,427 etc., the multi-equivalent couplers disclosed in U.S. Patents 4,283,472, 4,338,393 and 4,310,618, the DIR and redox compound releasing couplers disclosed in JP-A-60-185950 and 62-24252, the couplers which release a dye to which color is restored after elimination as disclosed in EP-A-173,302, the bleaching accelerator releasing couplers disclosed in Research Disclosure Nos. 11449 and 24241, and in JP-A-61-201247, and the ligand releasing couplers disclosed in U.S. Patent 4,553,477.
  • color couplers which can be used in the invention in addition to the polymeric couplers described above are indicated below, but the invention is not limited to these color couplers.
  • the couplers which are used in the invention can be introduced into the light sensitive materials using various known methods of dispersion.
  • organic solvents etc. of boiling point at least about 30 C, and preferably of boiling point at least 50 C, but less. than about 160°C can also be used as auxiliary solvents.
  • auxiliary solvents include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.
  • the invention can be applied to various color photosensitive materials. Typical examples include color negative films for general purposes or for cinematographic purposes, color reversal films for slides or television purposes, color papers, color positive films and color reversal papers.
  • Suitable supports which can be used in the invention have been disclosed, for example, on page 28 of the aforementioned Research Disclosure, No. 17643 and in Research Disclosure, No. 18716 from the right hand column on page 647 to the left hand column on page 648.
  • Color photographic materials to which the invention has been applied can be developed and processed using the normal methods disclosed on pages 28 and 29 of the aforementioned Research Disclosure, No. 17643 and from the left hand column to the right hand column of page 651 of Research Disclosure, No. 18716.
  • the color development bath used for the development processing of photosensitive materials of this invention is preferably an aqueous alkaline solution which contains a primary aromatic amine based color developing agent as the principal component.
  • Aminophenol based compounds are also useful as color developing agents, but the use of p-phenylenediamine based compounds is preferred.
  • Typical examples of these compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino N-ethyl N-,8-hydroxyethylaniline, 3- methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline 3-methyl 4-amino-N-ethyl-N-p-methoxyethylaniline and the sulfate, hydrochloride and p-toluenesulfonate salts of these compounds. Two or more of these compounds can be used conjointly, depending on the intended purpose.
  • the color development baths generally contain pH buffers, such as the carbonates, borates or phosphates of the alkali metals, and development inhibitors or anti-fogging agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds etc.
  • pH buffers such as the carbonates, borates or phosphates of the alkali metals
  • development inhibitors or anti-fogging agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds etc.
  • They may also contain, as required, various preservatives, such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenylsemicar- apelides, triethanolamine, catechol sulfonic acids, triethylenediamine(1,4-diazabicyclo[2,2,2]octane) etc., organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, poly(ethylene glycol), quaternary ammonium salts and amines, color forming couplers, competitive couplers, fogging agents such as sodium borohydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents as typified by the aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids, typical examples of which include ethylenediamine tetra-acetic acid, ni
  • the known black and white developing agents for example the dihydroxybenzenes such as hydroquinone, the 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, and the amino phenols such as N-methyl-p-aminophenol, can be used individually or in combinations in the black and white development bath.
  • the pH of these color development baths and black and white development baths is generally within the range from 9 to 12.
  • the replenishment rate of the development bath depends on the color photographic material which is being processed, but it is generally not more than 3 liters per square meter of photosensitive material and it is possible, by reducing the bromide ion concentration in the replenisher, to use a replenishment rate of not more than 500 ml per square meter of photosensitive material.
  • the prevention of loss of liquid by evaporation, and aerial oxidation, by minimizing the contact area with the air in the processing tank is desirable in cases where the replenishment rate is low.
  • the replenishment rate can be reduced by using a means of suppressing the accumulation of bromide ion in the development bath.
  • the photographic emulsion layers are subjected to a normal bleaching process after color development.
  • the bleaching process may be carried out at the same time as the fixing process (in a bleach-fix process) or it may be carried out as a separate process.
  • a bleach-fix process can be carried out after a bleach process in order to speed-up processing.
  • processing can be carried out in two connected bleach-fix baths, a fixing process can be carried out before carrying out a bleach-fix process, or a bleaching process can be carried out after a bleach-fix process, according to the intended purpose of the processing.
  • bleaching agents include ferricyanides; dichromates; organic complex salts of iron(III) or cobalt(III), for example complex salts with aminopoly carbcxylic acids such as ethylenediamine tetra-acetic acid, diethylenetriamine penta-acetic acid, cyclohexanediamine tetra-acetic acid, methylimino diacetic acid, 1,3-diaminopropane tetra-acetic acid, glycol ether diamine tetra-acetic acid, or citric acid, tartaric acid, malic acid; persulfates; bromates; permanganates and nitrobenzenes.
  • aminopoly carbcxylic acids such as ethylenediamine tetra-acetic acid, diethylenetriamine penta-acetic acid, cyclohexanediamine tetra-acetic acid, methylimino diacetic acid, 1,3-diaminopropane tetra-acetic
  • aminopolycarboxylic acid iron(III) complex salts principally ethylenediamine tetra-acetic acid iron(III) complex salts, and persulfates is preferred from the points of view of both rapid processing and the prevention of environmental pollution.
  • the amino polycarboxylic acid iron(III) complex salts are especially useful in both bleach baths and bleach-fix baths.
  • the pH of a bleach or bleach-fix beth in which aminopolycarboxylic acid iron(IIII) complex salts are being used is normally from 5.5 to 8, but a lower pH can be used in order to speed-up processing.
  • Bleach accelerators can be used, as required, in the bleach baths, bleach-fix baths, or bleach or bleach-fix pre-baths. Actual examples of useful bleach accelerators have been disclosed in the following specifications: Thus there are the compounds which have a mercapto group or a disulfide group disclosed in U.S. Patent 3,893,858, West German Patent Nos.
  • Patent 3,706,561 the iodides disclosed in West German Patent 1,127,715 and in JP A-58-16235; the polyoxyethylene compounds disclosed in West German Patents 966,410 and 2,748,430; the polyamine compounds disclosed in JP-B-45-8836; the other compounds disclosed in JP-A-49-42434, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940; and bromide ions etc.
  • these compounds those which have a mercapto group or a disulfide group are preferred in view of their large accelerating effect, and the use of the compounds disclosed in U.S.
  • Patent 3,893,858, West German Patent 1,290,812, and in JP-A-53-95630 is especially desirable.
  • the use of the compounds disclosed in U.S. Patent 4,552.834 is also desirable.
  • These bleach accelerators may be added to the sensitive material. These bleach accelerators are especially effective when bleach-fixing color photosensitive materials for photographic purposes.
  • Thiosulfates, thiocyanates, thioether based compounds, thioureas and large quantities of iodide etc. can be used as fixing agents, but thiosulfates are generally used for this purpose, and ammonium thiosulfate in particular can be used in the widest range of applications. Sulfites, bisulfites, or carbonylbisulfite addition compounds, are preferred as preservatives for bleach-fix baths.
  • the silver halide color photographic materials of this invention are generally subjected to a water washing and/or stabilizing process after the desilvering process.
  • the amount of water used in the water washing process can be fixed within a wide range according to the nature of the photosensitive material (for example the materials, such as the couplers, which are being used), the wash water temperature, the number of washing tanks (the number of washing stages), the replenishment system, i.e. whether a counter-flow or a sequential-flow system is used, and various other conditions.
  • the relationship between the amount of water used and the number of water washing tanks in a multi-stage counter-flow system can be obtained using the method outlined on pages 248 to 253 of the Journal of the Society of Motion Picture and Television Engineers, Volume 64 ( May 1955).
  • the amount of wash water can be greatly reduced by using the multi-stage counter-flow system noted in the aforementioned literature, but bacteria proliferate due to the increased residence time of the water in the tanks and problems arise as a result of the sediments which are formed becoming attached to the photosensitive material.
  • the method in which the calcium ion and manganese ion concentrations are reduced as disclosed in Japanese Patent Application No. 61-131632 can be used very effectively to overcome problems of this sort in the processing of color photosensitive materials of this invention.
  • the pH value of the wash water used in the processing of the photosensitive materials of invention is within the range from 4 to 9, and preferably within the range from 5 to 8.
  • the wash water temperature and the washing time can be set variously according to the nature of the photosensitive material and the application etc. but, in general, washing conditions of from 20 seconds to 10 minutes at a temperature of from 15 to 45° C, and preferably of from 30 seconds to 5 minutes at a temperature of from 25 to 40° C, are selected.
  • the photosensitive materials of this invention can be processed directly in a stabilizing bath instead of being subjected to a water wash as described above.
  • the known methods disclosed in JP-A-57 8543, JP-A-58-14834 and JP-A-60-220345 can all be used for this purpose.
  • stabilizing baths which contain formalin and surfactant which are used as a final bath for color photosensitive materials used for photographic purposes are an example of such a process.
  • Various chelating agents and fungicides etc. can be added to these stabilizing baths.
  • the overflow which accompanies replenishment of the above mentioned wash water and/or stabilizer can be re-used in other processes such as the desilvering process etc.
  • a color developing agent may also be incorporated into the silver halide color photosensitive materials of this invention in order to simplify and speed-up processing.
  • the incorporation of various color developing agent precursors is preferred.
  • the indoaniline based compounds disclosed in U.S. Patent 3,342,597, the Schiff's base type compounds disclosed in U.S. Patent 3,342,599 and in Research Disclosure, Nos. 14850 and 15159, the aldol compounds disclosed in Research Disclosure, No. 13924, the metal salt complexes disclosed in U.S. Patent 3,719,492, and the urethane based compounds disclosed in JP-A-53-135628 can be used for this purpose.
  • the various processing baths are used at a temperature of from 10 to 50' C in this invention.
  • the standard temperature is normally from 33 to 38° C, but processing is accelerated and the processing time is shortened at higher temperatures and, conversely, increased picture quality and improved stability of the processing baths can be achieved at lower temperatures.
  • processes using hydrogen peroxide intensification or cobalt intensification as disclosed in West German Patent 2,226,770 or U.S. Patent 3,674,499 can be carried out in order to economize on silver in the photosensitive material.
  • silver halide photosensitive materials of this invention can also be used as the heat developable photosensitive materials disclosed in U.S. Patents 4,500,626, JP-A-60-133,449, JP-A-59-218443 and JP-A-61-238056, and in EP-A-210,660A2 etc.
  • a color photographic material was prepared by the lamination coating of the first to the fourteenth layers indicated below on a triacetate base.
  • Samples 102 to 110 were prepared by replacing the coupler (IV) of this invention added to the third, fourth and fifth layers of sample 101 with the same coated amounts (mol/square meter) of the couplers (V), (VI), (VII) and (III) of this invention and the comparative couplers (A), (B), (Q), (C) and (D).
  • the silver halide color photographic materials prepared in this way were processed in the way indicated below.
  • compositions of the processing baths were as indicated below.
  • the pH was adjusted with hydrochloric acid or potassium hydroxide.
  • the pH was adjusted with hydrochloric acid or sodium hydroxide.
  • the pH was adjusted with hydrochloric acid or potassium hydroxide.
  • the pH was adjusted using hydrochloric acid or potassium hydroxide.
  • the pH was adjusted using hydrochloric acid or potassium hydroxide.
  • the pH was adjusted using hydrochloric acid or potassium hydroxide.
  • the cyan densities of the cyan images and the relative speeds of the processed samples were measured.
  • Sample 201 a multi-layer color photosensitive material consisting of layers of which the compositions are indicated below was prepared on an undercoated cellulose triacetate film suppcrt.
  • the amounts coated are expressed in units of grams of silver per square meter in the case of the silver halides and colloidal silver, in units of grams per square meter in the case of couplers, additives and gelatin, and in units of mols per mol of silver halide in the same layer in the case of the sensitizing dyes.
  • the emulsion stabilizer Cpd-3 (0.04 gram per square meter) and the surfactant Cpd-4 (0.02 gram per square meter) as coating promoter were added to each layer as well as the components mentioned above.
  • Samples 202 to 207 were prepared in the same way as sample 201 except that the coupler (XI) of the invention added to the sixth and seventh layers of sample 201 was replaced with coupler (XII) of this invention and comparative couplers (E), (G), (R), (F) and (H) with equal coupler units, as shown in Table 3.
  • the silver halide color photographic materials prepared in this was were processed in the way indicated below after exposure through a continuous wedge.
  • compositions of the processing baths are indicated below.
  • telomeric couplers of this invention provide a harder gradation at high speed and a higher color density than the comparative couplers (conventional polymeric couplers and couplers obtained using a chain transfer agent of which the chain transfer constant is outside the range from 0.1 to 20).
  • a multi-layer color printing paper of which the structure is indicated below was prepared on a paper support which had been laminated on both sides with polyethylene.
  • Ethyl acetate (27.2 cc) and 7.7 cc of solvent (Soly-2) were added to 19.1 grams of yellow coupler EXY) and 4.40 grams of anti-color fading agent (Cpd-1) to form a solution, and this solution was emulsified and dispersed in 185 cc of 10% aqueous gelatin solution which contained 8 cc of 10% sodium dodecylbenzenesulfonate.
  • a silver chlorobromide emulsion (silver bromide content 80.8 mol%, containing 70 grams of silver per kilogram) to which the blue sensitizing dye indicated below hade been added at a rate of 5.0x10-4 per mol of silver was also prepared.
  • the above mentioned emulsified dispersion and the above mentioned emulsion were mixed together and dissolved to provide the first layer coating liquid of which the composition is indicated below.
  • the coating layers for the second to the seventh layers were prepared in the same way as the first layer coating liquid.
  • 1-Oxy-3,5-dichloro-s-triazine, sodium salt, was used as a gelatin hardening agent in each layer.
  • the compound indicated below was added at a rate of 2.6 ⁇ 10 -3 mol per mol of silver halide to the red sensitive emulsion layer.
  • 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue sensitive, green sensitive and red sensitive emulsion layers at the rates of 4.0 ⁇ 10 -6 mol, 3.0 ⁇ 10 -5 mol and 1.0 ⁇ 1 0 -5 mol, per mol of silver halide, respectively.
  • the dyes indicated below were added to the emulsion layers to prevent the occurrence of irradiation.
  • composition of each layer is indicated below.
  • the numerical values indicate the coated weights (grams per square meter) or, in the case of the silver halide emulsions, the coated weights calculated as silver.
  • the silver halide emulsion for the blue sensitive emulsion layer was preferred in the way indicated below.
  • Solution 1 was heated to 75 C and Solution 2 and 3 were added. Solutions 4 and 5 were then added simultaneously over a period of 9 minutes. Moreover, after a period of 10 minutes solutions 6 and 7 were added simultaneously over a period of 45 minutes. The temperature was reduced 5 minutes after the addition and the mixture was desalted. Gelatin dispersed in water was then added, the pH was adjusted to 6.2 and a mono-disperse cubic silver chlorobromide emulsion of average grain size 1.01 ⁇ m, variation coefficient (standard deviation divided by the average grain size, s/d) 0.08 which contained 80 mol% of silver bromide was obtained. Sodium thiosulfate was added to this emulsion and optimum chemical sensitization was carried out.
  • the silver halide emulsions for the green and red sensitive emulsion layers were prepared in the same way with different reagent quantities, temperatures and times.
  • Samples 302 to 308 were prepared in the same way as samples 301 except that the cyan coupler in the fifth layer of sample 301 was replaced by couplers (II) and (III) of this invention and comparative compounds (I), (J), (S), (K) and (L) at the same coated coupler weight (mol per square meter), as shown in Table 4.
  • Samples 401 to 409 were prepared in just the same way as in Example 3 except that the magenta coupler (EXM) in the third layer of the layer structure indicated in Example 3 was replaced with couplers (XIV), (XV), (XVI) and (XVII) of this invention and comparative couplers (M), (N), (T), (0) and (P), and the colored image stabilizers and anti staining agents were added as indicated in the table below.
  • the amount of each coupler coated (mol per square meter) was the same as in the case of coupler (EXM).

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP88119246A 1987-11-19 1988-11-18 Silver halide color photographic materials Withdrawn EP0316955A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP292599/87 1987-11-19
JP29259987A JPH01134358A (ja) 1987-11-19 1987-11-19 ハロゲン化銀カラー写真感光材料

Publications (2)

Publication Number Publication Date
EP0316955A2 true EP0316955A2 (de) 1989-05-24
EP0316955A3 EP0316955A3 (en) 1989-09-27

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ID=17783871

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88119246A Withdrawn EP0316955A3 (en) 1987-11-19 1988-11-18 Silver halide color photographic materials

Country Status (2)

Country Link
EP (1) EP0316955A3 (de)
JP (1) JPH01134358A (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5354642A (en) * 1992-08-10 1994-10-11 Eastman Kodak Company Polymeric couplers for heat image separation systems
US6074809A (en) * 1997-12-16 2000-06-13 Agfa-Gevaert N.V. Color photographic silver halide material

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4335197A (en) * 1980-11-25 1982-06-15 E. I. Du Pont De Nemours And Company Photoimaging process
JPS5942543A (ja) * 1982-09-03 1984-03-09 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
JP2540320B2 (ja) * 1987-03-25 1996-10-02 富士写真フイルム株式会社 ハロゲン化銀写真感光材料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5354642A (en) * 1992-08-10 1994-10-11 Eastman Kodak Company Polymeric couplers for heat image separation systems
US6074809A (en) * 1997-12-16 2000-06-13 Agfa-Gevaert N.V. Color photographic silver halide material

Also Published As

Publication number Publication date
EP0316955A3 (en) 1989-09-27
JPH01134358A (ja) 1989-05-26

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