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
  • G03C7/32—Colour coupling substances
  • G03C7/36—Couplers containing compounds with active methylene groups
  • G03C7/38—Couplers containing compounds with active methylene groups in rings
  • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings

Definitions

• Such color mixing is caused by development fog.
• This phenomenon occurs in that at the color forming development of an emulsion layer, the silver halide grains in the unexposed portions of the emulsion layer are developed to produce an undesirable dye.
• the green-sensitive emulsion layer to be developed by a magenta color developing solution is subjected to cyan color development before it is subjected to the magenta color development.
• cyan fog development tends to occur resulting in cyan color mixing.
• yellow fog development tends to occur to cause yellow color mixing.
• an object of this invention is to provide a coupler-in-developer type reversal color photographic light-sensitive material capable of providing a magenta color image having a high color purity unaccompanied with the occurrence of cyan color mixing and yellow color mixing after development in the coupler-in-developer type reversal color photographic processing.
• Another object of this invention is to provide a multiple layer type color photographic light-sensitive material having high color density after development in the coupler-in-developer type color photographic processing.
• the oxidation product of the primary eveloping agent predominantly reacts with the diffusion resistant magenta coupler present in the green-sensitive emulsion layer rather than with the yellow coupler supplied from the developing solution to give a magenta image. This results in also reducing markedly the occurrence of yellow color mixing.
• the diffusion resistant magenta coupler used in this invention can be selected from the generally known magenta couplers (see: W. Pelz, Mitanderen ans de Anlagens- Laboratorien der Agfa Leverkusen-Munchen, III, 126-156 1961)
• magenta couplers see: W. Pelz, Mitanderen ans de Anlagens- Laboratorien der Agfa Leverkusen-Munchen, III, 126-156 1961
• the compounds represented by the following general Formulae I and II are preferred:
• R represents an aryl group, a heterocyclic ring group, a carbamyl group, or a thiocarbamyl group
• R represents a hydrogen atom, an alkyl group, an aryl group, an amino group, an ureido group, a carbonamide group, a sulfonamide group, or a sulfamyl group
• R represents a lower alkyl group or an aryl group
• X represents a hydrogen atom or a group capable of being displaced on coupling; at least one of the R and R groups having at least one hydrophobic residual group having from 8 to 30 carbon atoms necessary to provide diffusion resistance to the coupler.
• R in the general Formulae I and II above can be an aryl group or an aryl group, substituted by an alkyl group having from 1 to 18 carbon atoms, an alkoxy group, an aryloxyl group, an alkoxycarbonyl group, an amino group, a carbonamide group, a sulfonamide group, a carbamyl group, a sulfamyl group, a sulfone group, a sulfonyl group, a hydroxyl group, a carboxyl group, or a halogen atom.
• R as an aryl or substituted aryl group are a phenyl group, a 4-methoxyphenyl group, a Z-octadecoxyphenyl group, a 4-phenoxyphenyl group, a 2-chlorophenyl group, a 2,4- dichlorophenyl group, a 2,4,6-trichlorophenyl group, a 2-chloro-4,fi-dimethylphenyl gr0up, a 4 bromophenyl group, a 4 methoxy-2,6-dichlorophenyl group, a 4-fiuorophenyl group, a 2-chloro-5tetra-decoxycarbonylphenyl group, a Z-ChlOI'O-S-[a (2,4 ditert-amylphenoxy)acetamido] phenyl group, a 2-chloro-5-(4-methylphenylsulfonamido) phenyl group,
• R can also be a 5- or 6-membered heterocyclic ring group or a 5- or 6-membered heterocyclic ring group substituted with substituents such as those described above for the substituted aryl group.
• Suitable heterocyclic ring groups are a furanyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group, a quinolinyl group, and the like.
• R can also be a group in the carbamyl series, such as carbamyl group, and the like; a group in the thiocarbamyl series, such as a thiocarbamyl group, an ethylthiocarbamyl group, a phenylthiocar'bamyl group.
• R is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms and which may optionally contain a substituent or be unsaturated (for example, an alkoxyl group, an aryl group, an aryloxyl group, a halogen atom, a hydroxyl group, and the like), such as a methyl group, a 2-propenyl group, a pentadecyl group, a Z-methoxyethyl group, a benzyl group, a 2-phenoxyethyl group, a hydroxyethyl group, and the like; an aryl group or an aryl group substituted by substituents as described above for R R can" also be a group in the amino series such as a primary amino group, a benzylamino group, a 3,5-dicarboxyanilino group, a 4-nitroanilino group, a 2,4-dichloroanilino group, a 2-chloro-4-[
• R can also be a group of the ureido series, such as an N (0a,,B dicarboxyethyl)ureido group, an octylureido group, a 3-[a-(2,4-di-tert-amylphenoxy) acetamido]-phenyluredio group, and the like.
• R can also be a group in the carbonamide series such as an octadecylamido group, an octadecylsuccinmonoamido group, a 3-(octadecylsuccinmonoamido) benzamido group, a 3-[a-(2,4-di-tert-amylphenoxy)acetamido] benzamido group, an a-(4-tert-butylphenoxy) propionamido group, a 3-[a-(3pentadecyl-4-sulfophenoxy) acetamido]benzamido group, a 'y-(4-N-butyl-N-pentadecoxycarbonylamino)propionamido group, and the like; a group in the sulfonamido series, such as a 4-methylphenylsulfonamido group, and the like: or a sul
• R is an alkyl group having from 1 to 4 carbon atoms, such as a methyl group, an ethyl group, and the like; or an aryl group such as a phenyl group, and the like.
• X is a hydrogen atom; or a group capable of being liberated or displaced on coupling, such as a halogen atom, a SCN group, an OR group, a 4R, group, an OCOR, group, or an 0SO R group (in which R represents an alkyl group, an aryl group or a heterocyclic group), for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a SCN group, a phenoxy group, a 4-nitrophenoxy group, an acetyloxy group, a 4-nitrophenylthio group, a benzthiazolethio group, a methyl sulfonyloxy group, a 3-nitro-phenylsulfonyloxy group, and the like.
• R represents an alkyl group, an aryl group or a heterocyclic group
• diffusion resistant magenta couplers used in this invention are shown below. Other magenta couplers can also be used.
• the diffusion resisting magenta couplers illustrated above can be prepared using well known methods. For example, they can be produced by the methods described in Fiat Final Report 943 and in U.S. Pat. Nos. 2,369,489 and 2,600,788; Japanese patent publication No. 32/ 7,039; UK. Pat. Nos. 1,018,810 and 1,142,553; and U.S. Pat. No. 2,618,641.
• magenta coupler described above can be incorporated in the photographic emulsion using conventional methods.
• one method comprises adding directly thereto as an alkaline solution thereof, in a second method, the magenta coupler is dissolved in an organic solvent, such as dibutyl phthalate or tricresyl phthalate, the solution is dispersed in an aqueous medium such as an aqueous gelatin solution, and then the dispersion is added to the photographic emulsion (see, for example, C. E. K. Mees and T. H.
• the magenta coupler can be added to the photographic emulsion at any step before coating the photographic emulsion but it is preferable to add the coupler in a step after ripening and before coating.
• the amount of the magenta coupler to be added to the photographic emulsion depends upon the nature of the silver halide photographic emulsion to be used but suitably ranges from 0.0005 to 0.25 mol per mol of the silver halide in the green-sensitive emulsion layer.
• a hardening treatment using a prehardening bath containing formaldehyde is generally practiced.
• a compound having an active methine group such as magenta coupler tends to form yellow stains by reacting with the formaldehyde.
• the amount of the magenta coupler is limited in such cases.
• the density of the yellow stain depends upon the type of magenta coupler used, the manner of incorporating the magenta coupler in the photographic emulsion, the composition of the hardening bath, and the like, but the amount of the magenta coupler defined above gives rise to no dilficulties with yellow staining. Of course, the amount can be increased further under the conditions that such yellow stain is less formed.
• magenta couplers shown above can be used alone or as a combination of two or more couplers.
• silver halide emulsion to be used is the greensensitive emulsion layer
• a silver halide iodobromide emulsion is most preferred but other silver halide emulsions, such as a silver chloride emulsion, a silver chlorobromide emulsion or a silver bromide emulsion, can be used.
• the silver halide photographic emulsion used in this invention can be chemically sensitized using methods well known in the art, for example, with a compound containing an unstable sulfur, such as ammonium thiosulfate or allylthiocarbamide; a gold compound, such as a complex salt of monovalent gold and thiocyanic acid; a reducing agent, such as stannous chloride; a polyalkylene derivative or a combination of them.
• an unstable sulfur such as ammonium thiosulfate or allylthiocarbamide
• a gold compound such as a complex salt of monovalent gold and thiocyanic acid
• a reducing agent such as stannous chloride
• a polyalkylene derivative or a combination of them such as stannous chloride
• the photographic emulsion can contain also a stabilizer, such as 4-hydroxy-6- methyl-l,3,3a,7-tetrazaindene, benzimidazole, or l-phenyl- S-mercaptotetrazole, and a hardening agent, such as formaldehyde or mucobrornic acid.
• a stabilizer such as 4-hydroxy-6- methyl-l,3,3a,7-tetrazaindene, benzimidazole, or l-phenyl- S-mercaptotetrazole
• a hardening agent such as formaldehyde or mucobrornic acid.
• the emulsion can contain a wetting agent, such as saponin or sodium alkylbenzene sulfonate.
• Sensitizing dyes giving green sensitivity to the photographic emulsion are cyanine dyes capable of sensitizing the wave length region ranging from 500 to 600 my, such as 1,1'-diethyl-2,2'-cyanine iodide, anhydro-5,5'-diphenyl- 9-ethyl-3,3'-di(2-sulfoethyl) benzoxazolocarbocyanine hydroxide, anhydro-S,5',6,6-tetrachloro-1,l'-diethyl-3,3'- di(3-sulfobutyl)benzimidazolocarbocyanine hydroxide, and the like. These dyes can be used alone or in combination.
• the green-sensitive emulsion layer containing the above-described magenta coupler be between a red-sensitive layer and a blue-sensitive layer. That is, it is preferred that the order of the emulsion layers coated on the support be a red-sensitive emulsion layer, the green-sensitive emulsion layer containing the magenta coupler, a yellow filter layer, and a blue-sensitive emulsion layer.
• the red-sensitive emulsion layer and the blue-sensitive emulsion layer generally contain no couplers.
• the red-sensitive emulsion layer can contain a diffusion resistant cyan coupler and the blue-sensitive emulsion layer can contain a difiusion resistant yellow coupler.
• the multiple layer type color photographic light-sensitive material of this invention having the green-sensitive. emulsion layer containing the magenta coupler is desirably processed by the coupler-in-developer type color photographic processing.
• the cyan, magenta and yellow color developing solutions contain at least a color forming primary develop ing agent and doiffusing couplers to be coupled into cyan, magenta and yellow dyes respectively.
• Suitable color forming primary developing agents are the well-known p-phenylenediamine derivatives, such as 4-amino-N,N diethylaniline, 4-amino-N,N diethyl-3- methylaniline, 4-amino-3-methyl-N ethyl-N-(B-methylsulfonamidoethyl)aniline, 4-amino-3-methyl-N-ethyl-N- (B-hydroxyethyUaniline (see, e.g., C. E. K. Mees & T. H. James, The Theory of the Photographic Process, 3rd edition, 387, Macmillan Co. (1966)).
• the diffusing cyan couplers which can be added to the cyan-forming developing solution are the well-known phenolic couplers, such as 2-chloro-l-naphthol, 2,4-dichloro-l-naphthol, 1-hydroxy-N butyl-2-naphthamide, 1- hydroxy-N-(Z-acetamidophenethyl) Z-naphthamide and the like (Mees et al., supra, page 387).
• the diffusing magenta coupler which can be added to the magenta-forming developing solution are the ringclosed methylenic couplers, such as acylacetonitrile, 2- cyanoethyl-benzofuran, benzyl-acetonitrile or the cyclic methylene couplers such as l-phenyl-3-methyl-5-pyrazolone, 1-phenyl-3-(4-chlorobenzamido) 5-pyrazolone, 1-phenyl-3-(3-nitrobenzoylamino) S-pyrazolone, 1-(2,4, 6-trichlorophenyl)-3 (4-nitroanilino)-5-pyrazolone, and the like.
• methylenic couplers such as acylacetonitrile, 2- cyanoethyl-benzofuran, benzyl-acetonitrile or the cyclic methylene couplers such as l-phenyl-3-methyl-5-pyrazolone, 1-phenyl
• the diffusing yellow coupler which can be added to the yellow forming developing solution are the wellknown acylacetamide type open chain methylenic couplers, such as 2-acetoanilide, 2-aceto-2',4'-dichloroacetoanilide, 2-benzoylacetoanilide, 2-benzoyl-2-methoxyacetoanilide, 2-benzoyl(4'-p-toluenesulfonamido)acetoanilide, and the like (see, for example, Mees, supra, page 389 and G. H. Broun et al., Journal of American Chemical Society, 79, 2919-2927 (1957)).
• acylacetamide type open chain methylenic couplers such as 2-acetoanilide, 2-aceto-2',4'-dichloroacetoanilide, 2-benzoylacetoanilide, 2-benzoyl-2-methoxyacetoanilide, 2-benzoyl(4'-p-tol
• EXAMPLE 1 After melting by heating a gelatino silver iodobromide emulsion for a high speed reversal color photographic light-sensitive material, which had been sulfur-sensitized and gold-sensitized, the emulsion was green-sensitized using anhydro-5,5-diphenyl-9-ethyl-3,3'-di(2-sulfoethyl)- benzoxazolocarbocyanine hydroxide and anhydro-5,5',6,
• the green-sensitive emulsion thus prepared, was divided into several parts. To each of the green-sensitive emulsions were added an aqueous alkaline solution of the magenta coupler shown in Table 1 below and citric acid, and, then the pH of the emulsion was adjusted to 7.0.
• the green-sensitive emulsion was applied to a red-sensitive silver halide emulsion layer containing no coupler for reversal color photograpic material formed on a cellulose triacetate film base so that the proportion of silver in the green-sensitive layer was 15 mg./ cm.*.
• the yelow filter layer and a bluesensitive emulsion containing no yellow coupler, for reversal color photographic material were further applied to the green-sensitive layer in this order and they were dried.
• the green-sensitive emulsion containing the magenta coupler was applied to a red-sensitive emulsion layer containing no coupler for reversal color photographic material and formed on a cellulose triacetate film so that the amount of the silver in the green-sensitive layer was 15 mg./ cm.
• a yellow filter layer and a blue-sensitive emulsion layer containing no yellow coupler for reversal color photographic material were dried.
• Example 3 The same procedure as used in Example 1 was followed except that the couplers shown in Table 3 were used. The sample was subjected uniformly to a magenta exposure as in Example 1 and then processed in the same manner as in Example 1, except that the pre-hardening treatment was conducted for 3 minutes at 27 C. using a pre-hardening bath having the following composition:
• the green-sensitive emulsion layer containing the magenta coupler was applied on a red-sensitive emulsion layer containing no coupler for reversal color photographic material and formed on a polyethylene terephthalate film so that the content of silver in the greensensitive layer was 15 mg./100 cm. and on the emulsion layer were applied a yellow filter layer and a blue-sensitive emulsion containing no yellow coupler for reversal color photographic material and they were dried.
• the sample thus obtained was exposed, developed and the density measured in the same manner as in Example 1 except that the diffusing couplers for the cyan, yellow and magenta color developing solutions as shown in Table 4 were employed.
• the numerical values in Table 4 show the dilferences in yellow density, cyan densities and magenta between the results obtained by adding the dilfusion resisting magenta coupler to the green-sensitive emulsion layer and by adding no such magenta coupler.
• magenta density was high After melting by heating the green-sensitive gelatino silver iodobromide emulsion for high speed reversal color photographic materials as in Example 1, the silver halide
• other diffusion resistant magenta couplers than those shown in Examples 1, 2, 3 and 4 were used, similar improved results were obtained.
• the procedure similar to the above was repeated using developing solutions for coupler-in-developer type color photo graphic processing having difierent compositions than those used in the above examples, similar improved results were obtained.
• a method for the prevention of color mixing for a multi-layer-type reversal photographic light-sensitive silver halide material forming developer which comprises: developing said multi-layer-type reversal photographic light-sensitive silver halide material having on a support thereof (a) a red-sensitive emulsion layer containing no couplers,
• R is a member selected from the group consisting of an aryl group, a heterocyclic ring, a carbamyl group, and a thiocarbamyl group
• R is a member selected from the group consisting of a hydrogen atom, an alkyl group, and aryl group and amino group, a ureido group, a carbonamide group, a sulfonamide group, and a sulfamyl group
• R is a member selected from the group consisting of an alkyl group having from 1 to 4 carbon atoms and an aryl group
• X is a member selected from the group consisting of a hydrogen atom and a group capable of being displaced during coupling; at least one of R and R containing at least one hydrophobic
• R is selected from the group consisting of (1) an aryl group
• substituents being selected from the group consisting of an alkyl group having from 1 to 18 carbon atoms, an alkoxyl group, an aryloxyl group, an alkoxycarbonyl group, an amino group, a carbonamide group, a sulfonamide group, a carbamyl group, a sulfamyl group, a sulfone group, a sulfonyl group, a hydroxyl group, a carboxyl group and a halogen atom;
• R is selected from the group consisting of a hydrogen atom; an alkyl group having from 1 to 30 carbon atoms; a substituted alkyl group having from 1 to 30 carbon atoms, said substituent being selected from the group consisting of an alkoxyl group, an aryl group, an aryloxyl group, a halogen atom and a hydroxyl group; an aryl group; a substituted aryl group, said substituents being selected from the group consisting of an alkyl group having from 1 to 18 carbon atoms, an alkoxyl group, an aryloxyl group, an alkoxycarbonyl group, an amino group, a carbonamide group, a sulfonamide group, a carbamyl group, a sulfarnyl group, a sulfone group, a sulfonyl group, a hydroxyl group, a carboxyl group and a halogen atom; a primary amino group
• X is selected from the group consisting of a hydrogen atom, a halogen atom, a SON group, an -OR., group, a -SR group, an -OC0R group, and an --0S0 R group, in which R, is selected from the group consisting of an alkyl group, an aryl group and a hetero cyclic group.
• the difl'usion resistant magenta coupler is a compound selected from the group consisting of compounds having the structural formulae:
• Coupler 13 /N CNHC ONHCmHar in C-CH:
• Coupler 14 C1 N CNHC ONH Coupler 15 6 (U J n OCHzCONH 6H1

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• 1969
  • 1969-07-17 JP JP44056670A patent/JPS4838416B1/ja active Pending
• 1970
  • 1970-07-15 BE BE753496D patent/BE753496A/xx unknown
  • 1970-07-16 FR FR7026146A patent/FR2055179A5/fr not_active Expired
  • 1970-07-16 GB GB3461570A patent/GB1314893A/en not_active Expired
  • 1970-07-16 DE DE19702035382 patent/DE2035382A1/de active Pending
  • 1970-07-17 US US56006A patent/US3706556A/en not_active Expired - Lifetime

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