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

Definitions

• the present invention relates to a novel photographic cou­pler which is used as a color photographic component material, and more particularly to a photographic coupler for the forma­tion of a dye image having an excellent fastness against heat, moisture and light.
• an oxidation product of a color developing agent reacts with a dye-forming coupler to produce a dye, whereby a color image is formed.
• color reproduction is general strictlyly carried out by a subtractive color process to form a color image composed of yellow, magenta and cyan dyes.
• a photographic coupler used for the formation of a yellow dye image includes acylacetanilide couplers; a magenta color image-forming coupler includes pyrazolone, pyrazolobenzimid­azole, pyrazolotriazole and indazolone couplers; and cyan color image-forming coupler includes phenol and naphthol cou­plers.
• Dye images formed by these couplers are requested to cause no fading and discoloration even when exposed to light over a long period of time and stored under high temperature/­moisture conditions.
• the other object is to provide a photographic coupler used for the formation of a cyan dye image that undergoes no discoloration attributable to heat, moisture and light.
• R represents a substitutent: 1 is an integer of zero to 4; m is an integer of zero to 5; n is an integer of zero to 3, provided that when 1, m or n is 2 or more, R's may be the same or different; Y is a substituent whose Hammett's substi­tuent constant ⁇ p is not less than 0.3 and not more than 1.5; Z is a group of atoms necessary to form a 5- to 7-member nitro­gen-containing heterocyclic ring: and X is a hydrogen atom or a substituent which splits off upon reaction with an oxidation product of a color developing agent.
• Formulas I to V wherein R represents a substitutent: 1 is an integer of zero to 4; m is an integer of zero to 5; n is an integer of zero to 3, provided that when 1, m or n is 2 or more, R's may be the same or different; Y is a substituent whose Hammett's substi­tuent constant ⁇ p is
• the substituent represented by R includes an alkyl group, an aryl group, an anilino group, an acylamino group, a sulfonamido group, an alkylthio group, an arylthio group, an alkenyl group, a cycloalkyl group, a halo­gen atom, a cycloalkenyl group, an alkynyl group, a heterocycl­ic group, a sulfonyl group, a sulfinyl group, a phosphonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a cyano group, an alkoxy group, a sulfonyloxy group, an aryloxy group, a heterocyclic-oxy group, a siloxy group, an acyloxy group, a carbamoyloxy group, an amino group, an alkylamin
• the alkyl group has preferably 1 to 32 carbon atoms.
• the aryl group is preferably phenyl.
• the acylamino group is preferably an alkylcarbonyl amino or arylcarbonylamino group.
• the sulfonamido group is preferably an alkylsulfonylamino or arylsulfonylamino group.
• alkyl and aryl components of the alkylthio and aryl­thio groups are the above alkyl and aryl groups.
• the alkenyl group has preferably 2 to 32 carbon atoms, and the cycloalkyl group has preferably 3 to 12 carbon atoms, more preferably 5 to 7 carbon atoms.
• the cycloalkenyl group has preferably 3 to 12 carbon atoms, more preferably 5 to 7 carbon atoms.
• the sulfonyl group is an alkylsulfonyl or arylsulfonyl group.
• the sulfinyl group is an alkylsulfinyl or arylsulfinyl group.
• the phosphonyl group is an alkylphosphonyl, arylphosphon­yl, alkoxyphosphonyl or aryloxyphosphonyl group.
• the acyl group is an alkylcarbonyl or arylcarbonyl group.
• the carbamoyl group is an alkylcarbamoyl or arylcarbamoyl group.
• the sulfamoyl group is an alkylsulfamoyl or arylsulfamoyl group.
• the acyloxy group is an alkylcarbonyloxy or arylcarbonyl­oxy group.
• the carbamoyloxy group is an alkylcarbamoyloxy or arylcar­bamoyloxy group.
• the ureido group is an alkylureido or arylureido group.
• the sulfamoylamino group is an alkylsulfamoylamino or aryl­sulfamoylamino group.
• the heterocyclic group is preferably 5- to 7-member ring such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 1-pyrrolyl and 1-tetrazolyl.
• the heterocyclic-oxy group is preferably a 5- to 7-member ring, such as 3,4,5,6-tetrahydropyranyl-2-oxy and 1-phenyltetr­azole-5-oxy.
• the heterocyclic-thio group is preferably a 5- to 7-member ring such as 2-pyridylthio, 2-benzothiazolylthio and 2,4-diphen­oxy-1,3,5-triazole-6-thio.
• the siloxy group is trimethylsiloxy, triethylsiloxy or dimethylbutylsiloxy.
• the imido group is succinic acid imido, 3-heptadecylsuc­cinic acid imido, phthalimido or glutarimido.
• the spiro compound residue is preferably spiro[3.3]hept­ane-1-yl.
• the bridged hydrocarbon compound residue is bicyclo[2.2.1]­heptane-1-yl, tricyclo[3.3.1.1 3′7 ]decane-1-yl, or 7,7-dimethyl­ bicyclo[2.2.1]heptane-1-yl.
• R Preferred among the above substituents represented by R are the alkyl, aryl, carboxyl, oxycarboxyl, cyano, hydroxy, alkoxy, aryloxy, amino, amido and sulfonamido groups and halo­gen atom.
• R's may combine with each other to form a ring, and the formed ring is preferably a 5- to 8-member ring such as a pyri­dine ring and a quinoline ring.
• the above groups may have further a substituent of a non-­diffusible group such as a long-chain hydrocarbon group and a polymer residue.
• the groups represented by X are a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic-oxy group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, an aryl­oxycarbonyl group, an alkyloxalyloxy group, an alkoxyoxalyloxy group, an alkylthio group, an arylthio group, a heterocyclic­thio group, an alkyloxythiocarbonylthio group, an acylamino group, a sulfonamido group, a nitrogen-containing heterocyclic group which has a reactive site at the N atom, an alkyloxycar­bonylamino group, an aryloxycarbonylamino group, and a carbox­yl group.
• the substituent represented by Y have the Hammett's substituent constant ′p of not less than 0.3 and not more than 1.5, of which examples are a cyano group, a nitro group: a sulfonyl group such as octylsulfonyl, phenyl­sulfonyl, trifluoromethylsulfonyl and pentafluorophenylsulfon­yl; a ⁇ -carboxyvinyl group; a sulfinyl group such as t-butyl­sulfinyl, tolylsulfinyl, trifluoromethylsulfinyl and pentafluo­rophenylsulfinyl; a ⁇ , ⁇ -dicyanovinyl group; a halogenated alkyl group such as trifluoromethyl, perfluorooctyl and ⁇ -hydro­perfluorodo
• Preferred among these groups are the cyano, sulfonyl and sulfamoyl groups.
• the coupler does not sub­stantially develop color, while the ⁇ p value more than 1.5 makes it substantially impossible to synthesize the coupler.
• Z is preferably a group of non-metal­lic atoms, and more preferably a group of non-metallic atoms containing the following units: wherein R′ and R ⁇ each represent the same substituents as those represented by the foregoing R. The above units may be contained in combination.
• the precipitated solid was filter­ed, dried, and recrystallized in a toluene-ethanol mixture sol­vent, whereby 23.7g of a white crystalline intermediate 2 were obtained, which was identified by 1HNMR, FD mass spectrum and IR.
• the coupler of the invention is used normally in an amount of 1x10 ⁇ 3 mole to 1 mole, and preferably 1x10 ⁇ 2 mole to 8x10 ⁇ 1 mole per mole of silver halide.
• the coupler of the invention may be used in combination with different other cyan couplers.
• the coupler of the invention may be used as a color photo­graphic component material in any color-forming processes - a coupler-in-developer process and a coupler-in-emulsion process.
• the coupler of the inven­tion dissolved in an alkaline aqueous solution or an organic solvent such as an alcohol is added to a developer.
• the coupler of the invention is incorporated into a photographic light-sensitive material.
• the coupler of the invention is incor­porated into a silver halide emulsion, and the emulsion is coated on a support to form a color light-sensitive material.
• the coupler of the invention may be applied to any photograph­ ic light-sensitive materials such as color negative and posi­tive films and a color photographic paper.
• the light-sensitive materials in which the coupler of the invention is used may be of either monochrome or multicolor.
• the coupler of the invention is normally incorporated into a red-sensitive silver halide emulsion layer.
• the multicolor light-sensitive mate­rial comprises the dye image forming component layers spectral­ly sensitive to three primary color regions of the spectrum.
• each light-sensitive layer comprises a single emul­sion layer or a plurality of emulsion layers sensitive to the prescribed regions of the spectrum.
• the overall photographic component layers including the image-forming layers may be arranged in various orders.
• a typical multicolor light-sensi­tive material comprises a support having thereon a red-sensi­tive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler and a blue-sensitive silver halide emulsion layer containing a yellow coupler.
• the light-sensitive material may also have other layers such as a filter layer, an intermediate layer, a protective layer and a subbing layer.
• the coupler of the invention is incorporated in accordance with known methods. For example, the couplers of the invention dissolved in high or low-­boiling organic solvents are mixed with a gelatin aqueous solu­ tion containing a surface active agent, and after emulsifying by a high-speed rotary mixer or a colloid mill, silver halide was added, whereby the silver halide emulsion used in the invention is prepared.
• the silver halides suitably usable for the light-sensi­tive material containing the coupler of the invention are sil­ver chloride, silver chlorobromide and silver chloroiodo­bromide.
• a mixture of silver halides such as silver chlo­ride plus silver bromide is also preferable.
• a silver halide emulsion used for a color photographic paper for which a par­ticularly high-speed developability is required comprises pre­ferably silver chloride, and more preferably silver chloro­bromide or silver chloroiodobromide each containing at least 1% silver chloride.
• the silver halide emulsion is chemically sensitized in usual manner, and also spectrally sensitized to a desired wave­length region.
• the light-sensitive material containing the coupler of the invention may contain conventional additives such as an antistain agent, an antifoggant, a dye image stabilizer, a UV absorber, an antistatic agent, a matting agent and a surface active agent.
• the photographic light-sensitive material comprising the coupler of the invention is subjected to color developing, bleaching and fixing.
• the bleaching and fixing may be per­ formed simultaneously in a single bath.
• the light-sensitive material is normally subjected to washing.
• the washing may be replaced by stabili­zation or performed in combination therewith.
• Samples 2 to 15 of the invention and 16 for compari­son were prepared in the same manner as in Sample 1 except that the comparative coupler A was replaced by the couplers given in Table 1 without changing the addition amount.
• Each of Samples 1 to 16 was exposed through a wedge in the usual manner, and then processed in the following steps: Processing steps Color developing 38°C 3 min. 30 sec. Bleach-fixing 38°C 1 min. 30 sec. Stabilizing 25°C to 30°C 3 min. Drying 75°C to 80°C 2 min.
• compositions of the processing solutions used in the above steps are as follows: Developer Benzyl alcohol 15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 0.7 g Sodium chloride 0.2 g Potassium carbonate 30.0 g Hydroxylamine sulfate 3.0 g Polyphosphoric acid (TPPS) 2.5 g 3-Methyl-4-amino-N-ethyl-N-( ⁇ -methanesulfonamidoethyl)-aniline sulfate 5.5 g Brightening agent, 4,4′-diaminostilbenedisulfonic acid derivative 1.0 g Potassium hydroxide 2.0 g Water to make 1 liter.
• Each of the processed Samples 1 to 16 was subjected to measurement of an initial density with a densitometer, and then allowed to stand over a period of 14 days under a high temperature/humidity condition (60°C/80%RH) for examination of the dye image's resistance to heat and moisture.
• a high temperature/humidity condition 60°C/80%RH
• the samples of the invention which contain the couplers of the invention have higher dye residual rates and more excellent resistance to heat, moisture and light than the sample containing the comparative coupler.
• Sample 16 containing comparative coupler B in which -CH2Br cor­responding Y in formula II has the ⁇ p value of 0.12 developed no color.
• Samples 18 to 31 of the invention were prepared in the Same manner as Sample 17 except that the comparative coupler C was replaced by the couplers given in Table 2 without chang­ing the addition amount.
• compositions of the processing solutions used in the above steps are as follows: Color developer : 4-Amino-3-methyl-N-ethyl-N-( ⁇ -hydroxyethyl)-aniline sulfate 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Trisodium nitrilotriacetate monohydrate 2.5 g Potassium hydroxide 1.0 g Water to make 1 liter. Adjust pH to 10.6 with sodium hydroxide.
• Bleacher Ferric-ammonium ethylenediaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water to make 1 liter. Adjust pH to 6.0 with ammonia water. Fixer : Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Water to make 1 liter. Adjust pH to 6.0 with acetic acid. Stabilizer : Formalin (37% by weight) 1.5 ml Koniducks (product of KONICA Corporation) 7.5 ml Water to make 1 liter.
• the samples of the invention which contain the couplers of the invention have higher dye residual rates and more excellent resistance to heat, moisture and light than the sample containing the comparative coupler.
• compositions of the processing solutions used are as follows: First developer Sodium tetrapolyphosphate 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate monohydrate 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water to make 1000 ml Reversal Solution Hexasodium nitrilotrimethylenephosphonate 3 g Stannous chloride dihydrate 1 g p-Aminophenol 0.1 g Sodium hydroxide 5 g Glacial acetic acid 15 ml Water to make 1000 ml Color developer Sodium tetrapolyphosphate 2 g Sodium sulfite 7 g Sodium tertiary phosphate dodecahydrate 36 g Potassium bromide 1 g Potassium iodide (0.1%
• the samples of the invention which contain the couplers of the invention have higher dye residual rates and more excellent resistance to heat, moisture and light than the sample containing the comparative coupler.
• a multicolor film Sample 43 was prepared by coating the following component layers on a support having an antihalation layer. Component layers.... Pro layer, BH layer, BL layer, YF layer, GH layer, GL layer, IL layer, RH layer, RL layer, and support.
• RL layer Low-speed red-sensitive silver halide emulsion layer containing 1.0g of a red-sensitive AgBrI emulsion comprising Emulsion I having an average grain size ( r ) of 0.47 ⁇ m, varia­tion coefficient (s/ r ) of 0.12 and an average AgI content of 8 mole%; 1.0g of an AgBrI emulsion (Emulsion II) having an aver­age grain size of 0.31 ⁇ m, a variation coefficient of 0.10 and an average AgI content of 8 mole%; and a dispersion prepared by dispersing in an aqueous solution of 2.4g gelatin a solu­tion of 0.07g of disodium 1-hydroxy-4-[4-(1-hydroxy-8-acet­amido-3,6-disulfo-2-naphthylazo)-phenoxy]-N-[ ⁇ -(2,4-di-t-amyl­phenoxy)butyl]-2
• C-A 1-hydroxy-2-[ ⁇ -­(2,4-di-t-a mylphenoxy)-n-butyl]napthoamide
• TCP tricresyl phosphate
• RH layer High-speed red-sensitive silver halide emulsion layer containing 2.0g of a red-sensitive AgBrI emulsion com­prising Emulsion III having an average grain size of 0.7 ⁇ m, a variation coefficient of 0.12 and an average AgI content of 6 mole%; and a dispersion prepared by dispersing in an aqueous solution of 1.2g gelatin a solution of 0.20g of a cyan coupler (C-A) and 0.03g of a colored cyan coupler (CC-A) each dissolv­ed in 0.23g of TCP.
• C-A cyan coupler
• CC-A colored cyan coupler
• GL layer Low-speed green-sensitive silver halide emulsion layer containing 1.5g of green-sensitive Emulsion I; 1.5g of green-sensitive Emulsion II; and a dispersion prepared by dis­persing in an aqueous solution of 2.4g gelatin a solution of 0.35g of 1-(2,4,6-trichlorophenyl)-3-[3-(p-dodecyloxybenzene­sulfonamido)benzamido)-5-pyrazolone (M-A), 0.10g of 1-(2,4,6-­trichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenyl­succinimidoanilino)-5-pyrazolone (CM-A) and 0.04g of DIR com­pound D-1 each dissolved in 0.68g of TCP.
• M-A 1-(2,4,6-trichlorophenyl)-3-[3-
• GH layer High-speed green-sensitive silver halide emulsion layer containing 2.0g of green-sensitive Emulsion III; and a dispersion prepared by dispersing in an aqueous solution of 2.4g gelain a solution of 0.14g of magenta coupler M-A and 0.045g of colored magenta coupler CM-A each dissolved in 0.27g of TCP.
• BL layer Low-speed blue-sensitive silver halide emulsion layer containing 0.5g of blue-sensitive Emulsion I; 0.5g of blue-sensitive Emulsion II; and a dispersion prepared by dis­persing in an aqueous solution of 1.8g gelatin a solution of 0.7g of ⁇ -pivaloyl- ⁇ -(1-benzyl-2-phenyl-3,5-dioxyimidazolidine-­4-yl)-2-chloro-5-[ ⁇ -dodecyloxycarbonyl)-ethoxycarbonyl]acetani­lide (Y-A) and 0.02g of DIR compound D-1 each dissolved in 0.68g of TCP.
• BH layer High-speed blue-sensitive silver halide emulsion containing 0.9g of a blue-sensitive AgBrI emulsion hav­ing an average grain size of 0.80 ⁇ m, a variation coefficient of 0.14 and an average AgI content of 6 mole%, and a disper­sion prepared by dispersing in an aqueous solution of 2.0g gelatin a solution of 0.25g of yellow coupler Y-A dissolved in 0.25g of TCP.
• IL layer Intermediate layer containing a solution of 0.07g of 2,5-di-t-octylhydroquinone (HQ-1) dissolved in 0.07g of dibut­yl phthalate (DBP).
• YF layer Yellow filter layer containing 0.15g of yellow col­loidal silver; 0.2g of HQ-1 (antistain agent) dissolved into 0.11g of DBP; and 1.0g of gelatin.
• Pro layer Protective layer containing 2.3g of gelatin.
• Samples 44 to 63 were prepared in the same manner as in Sample 43 except that C-A contained in the low-speed and high-­speed red-sensitive silver halide emulsion layers of Sample 43 was replaced by the same molar amount of the couplers of the invention as shown in Table 4.

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• 1990
  • 1990-02-28 EP EP90302133A patent/EP0386931A1/de not_active Withdrawn

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