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
  • G03C7/407—Development processes or agents therefor
  • G03C7/413—Developers

Definitions

• This invention relates to a method for processing a silver halide color photographic material. More particularly, it relates to a method for processing a silver halide color photographic material at a markedly reduced replenishment rate of a color developer while preventing, even on continuous processing, a variation of photographic characteristics.
• JP-A a photographic emulsion having a high silver chloride content to thereby considerably decrease the amount of an overflow of a color developer as disclosed in JP-A-61-70552 (the term "JP-A” as used herein means an "unexamined published Japanese patent application"), a method of using a specific coupler and processing the photographic material with a color developer having a high bromide content as disclosed in JP-A-53-146625 and JP-A-59-198454, and a method of using a silver iodobromide emulsion and a specific coupler as disclosed in JP-A-61-243453, JP-A-61-251851, JP-A-61-251852, and JP-A-61-261741.
• magenta couplers of formula (III) cause an increase of stains when color development is carried out at a low replenishment rate of a color developer.
• One object of this invention is to provide a method of processing at a considerably reduced rate of replenishment of a color developer.
• Another object of this invention is to provide a method of processing which is less causative of a variation of photographic characteristics and of fog even when processing is carried out continuously.
• the method according to the present invention is preferably applied to processing of a silver halide color photographic material containing at least one of the above-described magenta couplers represented by formula (III).
• the color developer contains substantially no bromine or iodine ion.
• a sulfite ion usually added as a preservative for various developing agents, reacts with an oxidation product of a color developing agent, thus becoming a competitor to couplers.
• the sulfite ion also serves as a solvent for a silver halide emulsion to give influences to the development rate or developability of maximum density and, as a result, causes a variation of photographic characteristics. Since the change of sulfite ion concentration thus results in significant variation of photographic characteristics, it is preferable in the present invention that the color developer contains substantially no sulfite ion.
• the color developer contains substantially no hydroxylamine not only because hydroxylamine becomes a competitor to couplers similarly to sulfite ion but also decomposition products of the hydroxylamine frequently influence silver developability.
• R 1 , R 2 , and R 3 each represents a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having from 1 to 20 carbon atoms, e.g., methyl, ethyl, sulfopropyl, carboxybutyl, hydroxyethyl, cyclohexyl, benzyl, phenethyl), a substituted or unsubstituted aryl group (preferably having from 6 to 20 carbon atoms, e.g., phenyl, 2,5-dimethoxyphenyl, 4-hydroxyphenyl, 2-carboxypfienyl), or a substituted or unsubstituted heterocyclic group [preferably a 5- or 6-membered ring containing from 1 to 20 carbon atoms and at least one hetero atom, e.g., oxygen, nitrogen, and sulfur (e.g., pyridin-4-yl, N-acetylpiperidin-4-yl
• R 4 represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrazino group (e.g., hydrazino, methylhydrazino, phenylhydrazino),, a substituted or unsubstituted alkyl group (preferably containing from 1 to 20 carbon atoms, e.g., methyl, ethyl, sulfopropyl, carboxybutyl, hydroxyethyl, cyclohexyl, benzyl, t-butyl, n-octyl), a substituted or unsubstituted aryl group (preferably having from 6 to 20 carbon atoms, e.g., phenyl, 2,5-dimethoxyphenyl, 4-hydroxyphenyl, 2-carboxyphenyl, 4-sulfophenyl), a substituted or unsubstituted heterocyclic group [preferably a 5- or 6-membered
• Substituents for R 1 , R 2 , R 3 , and R4 preferably include a halogen atom (chlorine, bromine) and hydroxyl, carboxyl, sulfo, amino, alkoxy, amido, sulfonamido, carbamoyl, sulfamoyl, alkyl, aryl, aryloxy, alkythio, arylthio, nitro, cyano, sulfonyl, and sulfinyl groups, each of which may be further substituted.
• halogen atom chlorine, bromine
• X 1 preferably represents a divalent organic group, such as -CO-, -S0 2 -, and .
• n is 0 or 1.
• R 4 is selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocylic group.
• R' and R 2 , or R 3 and R 4 may be taken together to form a heterocylic group.
• R 1 , R 2 , R 3 , and R 4 is a substituted or unsubstituted alkyl group, more preferably R 1 , R 2 , R 3 , and R4 each represents a hydrogen atom or a substituted or unsubstituted alkyl group, provided that all of them do not simultaneously represent a hydrogen atom, and most preferably R', R 2 , and R 3 each represents a hydrogen atom, and R 4 represents a substituted or unsubstituted alkyl group; R' and R 3 each represents a hydrogen atom and R 2 and R 4 each represents a substituted or unsubstituted alkyl group; or R' and R 2 each represents a hydrogen atom, and R 3 and R 4 each represents a substituted or unsubstituted alkyl group, or R 3 and R 4 are taken together to form a heterocyclic group.
• n 1
• X 1 represents -CO-
• R 4 represents a substituted or unsubstituted amino group
• R 1 , R 2 , and R 3 each represents a hydrogen atom or a substituted or unsubstituted alkyl group.
• n is preferably 0.
• the alkyl group as represented by R 1 , R 2 , R 3 , or R 4 preferably contains from 1 to 10 carbon atoms, and more preferably from 1 to 7 carbon atoms.
• Preferred substituents for the alkyl group include a hydroxyl group, a carboxyl group, a sulfo group, and a phosphono group. When the alkyl group has two or more substituents, they may be the same or different.
• Included in the compounds of formula (I) are dimers, trimers and polymers formed at R 1 , R 2 , R 3 , or R 4 .
• the compound of formula (I) is usually used in an amount of from 0.01 to 50 g, preferably from 0.1 to 30 g, more preferably 0.5 to 10 g, per liter of a color developer.
• the above-recited content of the compound of formula (I) is in the working developing solution.
• the replenisher for the color developer may have the same content of the compound of formula (I), or the compound of formula (I) may be stocked as a separate part and mixed on use.
• R 5 represents a straight chain or branched alkylene group having at least one of and at least one kind of substituents selected from a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, a sulfo group, a phosphono group, a sulfonyl group, a ureido group, an acyl group, an alkylthio group, an arylthio arouo. a carbamovl arouo. a sulfamovl arouo. an acvlamino group. a sulfonamido arouo. a haloaen atom.
• R 6 , R 7 , R 8 , and R 9 which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
• Substituents for the alkyl or aryl group for R 6 , R 7 , R 8 , and R 9 preferably include a hydroxyl group, an alkoxy group, an aryloxy group, a carboxyl group, an amino group, a sulfo group, a phosphono group, a suifonyl group, a ureido group, an acyl group, an alkylthio group, an arylthio group, a carbamoyl group, a sulfamoyl group, an acylamino group, a sulfonamido group, a halogen atom, a cyano group, and a nitro group.
• substituents may further have two or more of and two or more kinds of substituents per alkyl or aryl moiety.
• a carboxyl group, a phosphono group, and a sulfo group may be in the form of a salt with an alkali metal (e.g., sodium, potassium) or a cationic atom or group (e.g., NH 4 ⁇ , Ca 2 ⁇ , and an amino group may be in the form of a salt with various acids (e.g., hydrochloric acid, nitric acid, phosphoric acid, oxalic acid, acetic acid).
• R 5 preferably represents a hydroxyl-substituted alkylene group, an alkoxy-substituted alkylene group, an amino-substituted alkylene group, a sulfo-substituted alkylene group, and a ureido- substituted alkylene group.
• R 6 , R 7 , R 8 , and R 9 each preferably represent a hydrogen atom, an unsubstituted alkyl group (e.g., methyl, ethyl, isopropyl), a hydroxyl-substituted alkyl group, an alkoxy-substituted alkyl group, a carboxyl-substituted alkyl group, and a sulfo-substituted alkyl group.
• an unsubstituted alkyl group e.g., methyl, ethyl, isopropyl
• a hydroxyl-substituted alkyl group e.g., methyl, ethyl, isopropyl
• a hydroxyl-substituted alkyl group e.g., methyl, ethyl, isopropyl
• a hydroxyl-substituted alkyl group e.g.,
• the total number of the carbon atoms contained in R 5 , R 6 , R 7 R 8 , and R 9 is preferably 30 or less, and more preferably 20 or less.
• the compound of formula (II) is preferably added to a color developer in an amount of from 0.1 to 20 g, more preferably from 0.5 to 10 g, per liter.
• the compounds of formula (II) are easily available as commercial products, or can be easily synthesized according to the processes described in Organic Synthesis I, 102, ibid, II, 154, 328 and 558, and ibid, III, 370 and 800.
• the terminology "dimer or higher polymer” as used in the definition of formula (III) means a bis-compound or polymer coupler comprising two or more of the moiety represented by formula (III).
• the polymer coupler includes a homopolymer solely comprising a monomer unit represented by formula (III), preferably a monomer unit having a vinyl group (hereinafter referred to as a vinyl monomer) and a copolymer of such a monomer and a non-color-forming ethylenically unsaturated monomer which does not undergo coupling with an oxidation product of an aromatic primary amine developing agent.
• the compound of formula (III) is a 5-membered ring-5-membered ring condensed nitrogen-containing heterocyclic ring coupler whose chromophoric nucleus exhibits aromaticity isoelectric to a naphthalene ring, and has a chemical structure generally referred to as "azapentalene".
• Preferred of the couplers of formula (III) are 1H-imidazo[1,2-b]pyrazoles, 1H-pyrazolo[1,5-b]pyrazoles, 1H- pyrazolo[5,1-c][1,2,4]triazoles, 1H-pyrazolo[1,5-b]-[1,2,4]triazoles, 1H-pyrazolo[1,5-d]tetrazoles, and 1H-pyrazolo[1,5-a]benzimidazoles, represented by the following formulae (Illa), (IIIb), (Illc), (IIId), (Ille), and (Illf), respectively. Particularly preferred of them are those of formulae (Illa), (IIIc), and (IIId):
• R 12 , R 13 , and R 14 each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, a ureido group, an imido group, a sulfamoylamino group, a carbamoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycar- bonyiamino group, an aryloxycarbonylamino group, a sulfonamido group, a carbamoy
• R 12 , R 13 , and R 14 represent a mere bond or a linking group, via which the moiety and a vinyl group are linked.
• R 12 , R13, and Ri4 each represents a hydrogen atom, a halogen atom (e.g., chlorine, bromine), an alkyl group (e.g., methyl, propyl, isopropyl, t-butyl, trifluoromethyl, tridecyl, 3-(2,4-di-t-amylphenoxy)propyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexylsulfonylethyl, cyclopentyl, benzyl), an aryl group (e.g., phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl), a heterocyclic group (e.g., 2-furyl, 2-thienyl, 2-pyrimidinyl, 2 benzothiazolyi), a cyano group, an alkoxy group (e.
• X represents a hydrogen atom, a halogen atom (e.g., chlorine, bromine, iodine), a carboxyl group, or a group containing an oxygen atom at which it is bonded (e.g., acetoxy, propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxy, 4- methanesulfonamidophenoxy, 4-methanesulfonylphenoxy, a-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, 2-phenethyloxy, 2-phenoxyethoxy, 5-phenyltetrazolyloxy, 2-benzothiazolyloxy), a group containing a nitrogen atom
• the divalent group as represented by R 12 ,, Ri 3 , R 14 , or X, at which a bis-compound is formed includes a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, 1,10-decylene, -CH 2 CH 2 -0-CH 2 CH 2 -), a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene, 1,3-phenylene, and -NHCO-Ris-CONH- (wherein Ris represents a substituted or unsubstituted alkylene or phenylene group).
• a substituted or unsubstituted alkylene group e.g., methylene, ethylene, 1,10-decylene, -CH 2 CH 2 -0-CH 2 CH 2 -
• a substituted or unsubstituted phenylene group e.g., 1,4-phenylene, 1,3-phenylene, and
• the linking group as represented by R 12 , R 13 , or R 14 includes a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, 1,10-decylene, -CH 2 CH 2 OCH 2 CH 2 -), a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene, 1,3-phenylene, ), -NHCO-, -CONH-, -0-, -OCO-, and an aralkylene group (e.g., and a combination of these linking groups.
• a substituted or unsubstituted alkylene group e.g., methylene, ethylene, 1,10-decylene, -CH 2 CH 2 OCH 2 CH 2 -
• a substituted or unsubstituted phenylene group e.g., 1,4-phenylene, 1,3-phenylene,
• -NHCO- e.g., 1,
• the vinyl group in the vinyl monomer may have a substituent other than the moiety represented by formulae Illa) to (Illf).
• a substituent are a hydrogen atom, a chlorine atom, and a lower alkyl group having from 1 to 4 carbon atoms.
• the non-color-forming ethylenically unsaturated monomer which does not undergo coupling with an oxidation product of an aromatic primary amine developing agent includes acrylic acid, a-chloroacrylic acid, a-alacrylic acid (e.g., methacrylic acid), and esters or amides of these acrylic acids (e.g., acrylamide, n-butylacrylamide, t-butylacrylamide, diacetonacrylamide, methacrylamide, 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, ⁇ -hydroxymethacrylate), methylenebisacrylamide, vinyl
• JP-A-59-162548 for the compounds of formula ilia JP-A-60-43659 for the compounds of formula (Illb); JP-B-47-27411 for the compounds of formula (Illc); JP-A-59-171956 and JP-A-60-172982 for the compounds of formula (IIId); JP-A-60-33552 for the compounds of formula (IIIe); and U.S. Patent 3,061,432 for the compounds of formula (Illf).
• ballast group having high color forming properties disclosed in JP-A-58-42045, JP-A-59-214854, JP-A-59-177553, JP-A-59-177544, and JP-A-59-177557.
• the coupler of formula (III) is used in an amount of from 2 x 10- 3 to 5 x 10-' mol, preferably from 1 x 10- 2 to 5 x 10-' mol, per mol of silver in a silver halide emulsion layer.
• two or more different kinds of the coupler of formula (III) may be incorporated into the same layer, or the coupler of the same kind may be incorporated into two or more layers.
• a color developer which can be used in the present invention contains a known aromatic primary amine color developing agent, preferably a p-phenylenediamine derivative. Typical examples of the p-phenylenediamine developing agent are shown below.
• the p-phenylenediamine derivative recited above may be in the form of a salt with sulfuric acid, hydrochloric acid, sulfurous acid, p-toluenesulfonic acid, etc.
• the aromatic primary amine developing agent is used in a concentration of from about 0.1 g to about 20 g, preferably from about 0.5 g to about 10 g, per liter of the color developer.
• the color developer may contain a sulfite type preservative, such as sulfites (e.g., sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite) and a carbonylsulfite adduct.
• a sulfite type preservative such as sulfites (e.g., sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite) and a carbonylsulfite adduct.
• sulfite type preservative such as sulfites (e.g., sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite) and a carbonylsulfite adduct.
• the color developer may contain other various preservatives in addition to the compound of formula (I), but, it is preferable that the color developer contains substantially no hydroxylamine preservative for reasons stated above.
• substantially no hydroxylamine as used herein means that the hydroxylamine concentration in the color developer is no more than 0.01 mol, preferably of from zero up to 0.005 mol, per liter.
• the color developer may further contain various additives.
• various additives for example, it is preferable to add hydroxamic acids disclosed in JP-A-63-43138, phenols disclosed in JP-A-63-44657, and JP-A-63-58443,a-hydroxyketones or a-aminoketones disclosed in JP-A-63-44656, and various sugars disclosed in JP-A-63-36244.
• the color developer may also contain monoamines disclosed in JP-A-63-4235, JP-A-63-24254, JP-A-63-21647, JP-A-63-146040, JP-A-63-27841, and JP-A-63-25654, polyamines disclosed in Japanese Patent Application Nos.
• preservatives which may be added to the color developer if desired are various metals as described in JP-A-57-44148 and JP-A-57-53749, salicylic acid derivatives as described in JP-A-59-180588, alkanolamines as described in JP-A-54-3532, polyethyleneimines as disclosed in JP-A-56-94349, and aromatic polyhydroxy compounds as described in U.S. Patent 3,746,544.
• addition of the aromatic polyhydroxy compounds, trimethanolamine or the compounds disclosed in Japanese Patent Application No. 265149/86 is advantageous.
• the color developer according to the present invention preferably has a pH of from 9 to 12, more preferably from 9 to 11.0.
• the color developer can contain conventionally known developer components.
• the buffering agent to be used includes carbonates, phosphates, borates, tetraborates, hydroxybenzoates, glycine salts, N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrates, 2 amino-2-methyl-1,3-propanediol salts, valine salts, proline salts, tris- hydroxyaminomethane salts, and lysine salts.
• Particularly preferred among them are carbonates, phosphates, tetraborates, and hydroxybenzoates because they exhibit good dissolution property and superior buffering activity in a high pH region of 9.0 or more, give no adverse influences on photographic performance properties, such as fog, when added to a color developer, and are cheap.
• these preferred buffering agents are sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium tertiary phosphate, potassium tertiary phosphate, sodium secondary phosphate, potassium secondary phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).
• the amount of the buffering agent to be added to the color developer is preferably not less than 0.1 molit, more preferably from 0.1 to 0.4 mol/t.
• the color developer can also contain various chelating agents as a suspension agent for calcium or magnesium or for improving stability of the color developer.
• the chelating agent to be used preferably include organic acid compounds, such as aminopolycarboxylic acids disclosed in JP-B-48-30496 and JP-B-44-30232; organic phosphonic acids disclosed in JP-A-56-97347, JP-B-56-39359, and West German Patent 2.227,639; phosphonocarboxylic acids disclosed in JP-A-52-102726, JP-A-53-42730, JP-A-54-121127, JP-A-55-126241, and JP-A-55-659506; and the compounds disclosed in JP-A-58-195845, JP-A-58-203440 and JP-B-53-40900.
• these chelating agents are nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydrox- yphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and N,N -(bis2-hydroxybenzyi)ethyfenediamine-N.N -diacetic acid.
• chelating agents may be used in combination of two or more thereof, if desired.
• the amount of the chelating agent to be added is determined so as to be enough to sequester or deactivate metallic ions in the color developer and usually ranges from about 0.1 to about 10 g per liter.
• the color developer may contain an arbitrary development accelerator.
• the color developer contains substantially no benzyl alcohol as development accelerator.
• substantially no benzyl alcohol means that the content of benzyl alcohol in the color developer is no more that 2 ml per liter, and preferably nil.
• development accelerators which may be used in the present invention include thioether compounds as described in JP-B-37-16088, JP-B-37-5987, JP-B-38-7826, JP-B-44-12380, JP-B-45-9019 and U.S. Patent 3,813,247; p-phenylenediamine compounds as described in JP-A-52-49829 and JP-A-50-15554; quaternary ammonium salts as described in JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429; amine compounds as described in U.S.
• an arbitrary antifoggant can be added to the color developer.
• the antifoggant to be used includes alkali metal halides (e.g., potassium bromide, potassium iodide) and organic antifoggants, such as nitrogen-containing heterocyclic compounds (e.g., benzotriazole, 6-nitrobenzimidazole, 5-nitrosoindazole , 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethyl- benzimidazole, indazole, hydroxyazaindolizine, adenine).
• alkali metal halides e.g., potassium bromide, potassium iodide
• organic antifoggants such as nitrogen-containing heterocyclic compounds (e.g., benzotriazole, 6-nitrobenzimidazole, 5-nitrosoindazole , 5-methylbenzotriazole, 5-nitrobenz
• the amount of these antifoggants, if added, is preferably minimized for reasons stated above. It is particularly desirable that the color developer contains substantially no bromine or iodine ion that gives great influences on photographic characteristics.
• substantially no bromine or iodine ion means that the concentration of a bromine ion or iodine ion is up to 2.5 x 10- 3 mol/t, preferably up to 1 x 10- 3 mol/t, or up to 3 x 10 -4 mol/t, preferably up to 1 x 10- 4. mol/t, respectively.
• the color developer to be used in the present invention preferably contains a brightening agent, preferably 4,4'-diamino-2,2'-disulfostilbene compounds, in an amount of up to 5 g/t, preferably from 0.1 to 4 g/t.
• a brightening agent preferably 4,4'-diamino-2,2'-disulfostilbene compounds
• various surface active agents such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids, may also be added to the color developer.
• the color development processing according to the present invention is carried out at a processing solution temperature of from 20 to 50 C, preferably from 30 to 40 C, for a period of from 20 seconds to 5 minutes, preferably from 0.5 to 2 minutes.
• the color developer is replenished at a rate of from 20 to 120 mt, preferably 30 to 100 ml, per m 2 of the photographic material.
• the quantity of the replenisher is 50 ml/m 2 or less, the overflow of the color developer can be substantially eliminated since the color developer is carried away together with the processed photographic materials or evaporated during processing.
• Desilvering generally comprises a combination of bleach and fixation, a combination of fixation and blix, a combination of bleach and blix, or blix, and any of these systems may be used in this invention.
• the effects of the present invention can be taken full advantage of by reducing the time of desilvering, e.g., to 2 minutes or less, preferably between 15 and 60 seconds.
• any conventional bleaching agent may be used.
• Particularly recommended bleaching agents are organic complex salts of iron (III), for example, complex salts with aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid), aminopolyphosphonic acids, phosphonocarboxylic acids, or organic phosphonic acids; organic acids (e.g., citric acid, tartaric acid, malic acid); persulfates; and hydrogen peroxide.
• aminopolycarboxylic acids e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid
• aminopolyphosphonic acids e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid
• aminopolyphosphonic acids e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid
• aminopolyphosphonic acids e.g., ethylened
• organic complex salts of iron (III) are particularly preferred from the viewpoint of rapidness of processing and prevention of environmental pollution.
• Specific examples of the aminopolycarboxylic acids, aminopolyphosphonic acids or organic phosphonic acids or salts thereof which are useful for preparing the organic complex salts of iron (III) are ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, and glycol ether diaminetetraacetic acid, as well as their salts with sodium, potassium, lithium or ammonium.
• iron (III) complex salts are iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid because of their high bleaching capacity.
• ferric ion complex salts may be used in the form of a complex salt from the first; or the ferric ion complex may be formed in situ from a ferric salt (e.g., ferric sulfate, ferric chloride, ferric nitrate, ammonium ferric sulfate, ferric phosphate) and a chelating agent (e.g., aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid). In the latter case, the chelating agent may be used in excess.
• a ferric salt e.g., ferric sulfate, ferric chloride, ferric nitrate, ammonium ferric sulfate, ferric phosphate
• a chelating agent e.g., aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid
• the chelating agent may be used in excess.
• aminopolycarboxylic acid-iron complexes
• the bleach bath, blix bath and/or their prebathes may contain various bleaching accelerators, such as compounds having a mercapto group or a disulfide bond as described in U.S. Patent 3,893,858, German Patent 1,290,812, JP-A-53-95630, and Research Disclosures, No. 17129 (Jul., 1978); thiourea compounds as described in JP B-45-8506, JP-A-52-20832, JP-A-53-32735, and U.S. Patent 3,706,561; and halides of an iodine or bromine ion.
• the above-enumerated compounds are advantageous because of their excellent bleaching capacity.
• the bleach or blix bath may further contain a rehalogenating agent, such as bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride) and iodides (e.g., ammonium iodide).
• a rehalogenating agent such as bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride) and iodides (e.g., ammonium iodide).
• they may furthermore contain one or more of organic or inorganic acids or alkali metal or ammonium salt thereof which have buffering activity (e.g., boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid) or a corrosion inhibitor (e.g., ammonium nitrate, guanidine,.
• buffering activity e.g., boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid
• a corrosion inhibitor e.g., ammonium nitrate, guanidine,.
• the blix bath or fixer contains one or more of conventional fixing agents, i.e., water-soluble silver halide solvents, such as thiosulfates (e.g., sodium thiosulfate, ammonium thiosulfate); thiocyanates (e.g., sodium thiocyanate, ammonium thiocyanate); thioether compounds (e.g., ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol); and thiourea.
• thiosulfates e.g., sodium thiosulfate, ammonium thiosulfate
• thiocyanates e.g., sodium thiocyanate, ammonium thiocyanate
• thioether compounds e.g., ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol
• a special blix bath containing the fixing agent in combination with a large quantity of a halide e.g., potassium iodide
• a halide e.g., potassium iodide
• a recommended amount of the fixing agent in the fixer is from 0.3 to 2 mol/t, preferably from 0.5 to 1.0 mol! t.
• the blix bath or fixer preferably has a pH of from 3 to 10, more preferably from 5 to 9.
• the blix bath may further contain other various additives, such as brightening agents, defoaming agents, surface active agents, and organic solvents (e.g., polyvinylpyrrolidone, methanol).
• additives such as brightening agents, defoaming agents, surface active agents, and organic solvents (e.g., polyvinylpyrrolidone, methanol).
• the blix bath or fixer contains, as a preservative, a sulfite ion-releasing compound such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite), and metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite).
• a sulfite ion-releasing compound such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite), and metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite).
• sulfite it is usual to use the sulfite as a preservative, but other preservatives, e.g., ascorbic acid, a carbonyl-bisulfurous acid adduct, and a carbonyl compound, may also be added.
• preservatives e.g., ascorbic acid, a carbonyl-bisulfurous acid adduct, and a carbonyl compound
• the blix bath or fixer may further contain other additives, such as a buffering agent, a brightening agent, a chelating agent, a defoaming agent, and an antifungal agent.
• a buffering agent such as a buffering agent, a brightening agent, a chelating agent, a defoaming agent, and an antifungal agent.
• the desilvering by fixation or blix is generally followed by washing and/or stabilization.
• the quantity of water for washing is selected from a broad range depending on the characteristics of the photographic material (for example, the kind of components used, e.g., couplers),, the end use of the photographic material, the temperature of water, the number of washing tanks (the number of stages), the washing system (a counter current system or a direct current system), and other various factors.
• the relationship between the number of washing tanks and the quantity of water in a multi-stage counter current system can be decided according to the method described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pp. 248-253 (May, 1955).
• the number of stages in a multi-stage counter current system is usually 2 to 6, and preferably 2 to 4.
• the multi-stage counter current system since the requisite quantity of water can be greatly decreased, for example, to 0.5 ti M 2 to 1 Um2 or even less, the effects of the present invention are remarkably produced.
• this system tends to allow bacteria to grow in the tank due to the increased retension time of water, resulting in deposition of the scum onto the photographic material.
• the method of reducing calcium and magnesium in water as disclosed in JP-A-62-288838 can be effectively applied to the present invention.
• the washing water can further contain a surface active agent as a wetting agent or a chelating agent (e.g., EDTA) as a water softener.
• a surface active agent as a wetting agent or a chelating agent (e.g., EDTA) as a water softener.
• the above-described washing step may be followed by or substituted by treatment with a stabilizing bath.
• the stabilizing bath to be used contains compounds having functions to stabilize the photographic image, for example, aldehyde compounds (e.g., formalin), buffering agents for adjusting the film to a pH suitable for dye stabilization, or ammonium compounds.
• aldehyde compounds e.g., formalin
• buffering agents for adjusting the film to a pH suitable for dye stabilization
• ammonium compounds ammonium compounds.
• the above-enumerated various bactericides or antifungal agents can also be used for preventing growth of bacteria in the bath or imparting antifungal properties to the processed photographic material.
• the stabilizing bath may further contain a surface active agent, a brightening agent, and a hardening agent.
• a chelating agent e.g., 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.
• so-called rinsing solution may be used as washing water or stabilizing bath after desilvering.
• the pH of the processing solution is kept between 4 and 10, preferably between 5 and 8.
• the temperature usually ranges from 15 to 45 C, preferably from 20 to 40 C.
• the processing time is arbitrary, but the effects of the present invention become significant with the time being shorter.
• a preferred time is from 0.5 to 4 minutes, more preferably from 0.5 to 2 minutes. The smaller the quantity of a replenisher, the better the results obtained in terms of running cost, reduction of a waste liquid, ease on handling, and manifestation of the effects of the present invention.
• a recommended quantity of the replenisher is set at 0.5 to 50 times, preferably 3 to 40 times, the amount per unit area which has been carried over from the prebath.
• a recommended quantity of the replenisher is 1 t or less, preferably 500 m or less, per m 2 of the photographic material.
• the replenishment may be effected either continuously or intermittantiy.
• the processing solution which has been used for washing and/or stabilization may be recycled to the prebath.
• the overflow of washing water which is reduced by a multi-stage counter current system, is made to flow into the blix bath (i.e., the prebath), while replenishing the blix bath with a concentrated solution, to thereby reduce the amount of waste liquid.
• the method of the present invention can be applied to any type of photographic processing.
• the method is applicable to processing of color papers, color reversal papers, color direct positive light-sensitive materials, color positive films, color negative films, color reversal films, and so on.
• application to color papers and color reversal papers is suitable.
• color couplers as used herein means compounds capable of coupling with an oxidation product of an aromatic primary amine developing agent to form a color.
• Useful color couplers typically include naphthol or phenol compounds as cyan couplers; pyrazolone or pyrazoloazole compounds as magenta couplers; and open- chain or heterocyclic ketomethylene compounds as yellow couplers. Specific examples of these cyan, magenta, and yellow couplers are described in patents cited in Research Disclosure (RD), 17643, VII-D (Dec., 1978) and ibid, 18717 (Nov., 1979).
• the color couplers to be incorporated into the photographic material have a ballast group or are polymerized and are thereby non-diffusing.
• Two-equivalent color couplers in which the coupling site is substituted with a releasable group are preferred to four-equivalent color couplers in which the coupling site is substituted with a hydrogen atom because the requisite silver coverage can be reduced, thereby producing greater effects of the present invention accordingly.
• Couplers which produce a dye showing moderate diffusion, colorless compound forming couplers, so-called DIR couplers capable of releasing a developing inhibitor on coupling reaction, or couplers capable of releasing a development accelerator on coupling reaction may also be used.
• the yellow couplers which can be used in the present invention typically include oil-protected type acylacetamide couplers. Specific examples thereof are described in U.S. Patents 2,407,210, 2,875,057, and 3,265,506. As stated above, 2-equivalent yellow couplers are preferred.
• the 2-equivalent yellow couplers typically include those having oxygen atom linked releasing groups as described in U.S. Patents 3,408,194, 3,447,928, 3,933,501, and 4,022,620 and those having nitrogen atom linked releasing groups as described in JP-B-58-10739, U.S.
• Patents 4,401,752 and 4,326,024, RD 18053 (Apr., 1979), British Patent 1,425,020, West German Patent Application (OLS) Nos. 2,219,917, 2,261,361, 2,329,587, and 2,433,812.
• a-Pyvaloylacetanilide couplers are excellent in dye fastness, particularly to light.
• a-Benzoylacetanilide couplers are excellent in color density.
• magenta couplers which can be used in this invention include oil-protected type indazolone or cyanoacetyl couplers, and preferably pyrazoloazole couplers, such as 5-pyrazolone couplers and pyrazolotriazole couplers.
• pyrazoloazole couplers such as 5-pyrazolone couplers and pyrazolotriazole couplers.
• those in which the 3-position is substituted with an arylamino group or an acylamino group are preferred in view of hue and density of the color developed.
• Typical examples of such 5-pyrazolone couplers are described in U.S. Patents 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896, and 3,936,015.
• Preferred releasable groups for the 2-equivalent 5-pyrazolone couplers include nitrogen atom linked releasing groups as disclosed in U.S. Patent 4,310,619 and arylthio groups as disclosed in U.S. Patent 4,351,897.
• 5-Pyrazolone couplers having the ballast group disclosed in European Patent 73,636 provide high densities.
• Pyrazoloazole couplers which are particularly preferred in the present invention include pyrazoloben- zimidazoles as described in U.S. Patent 3,369,879, and more preferably pyrazoio[5,1-d][1,2,4]triazoies as described in U.S. Patent 3,725,067; pyrazolotetrazoles as described in RD 24220 (Jun., 1984); and pyrazolopyrazoles as described in RD 24230 (Jun., 1984).
• the imidazolo[1,2-d]pyrazoles disclosed in European Patent 119,741 are preferred.
• the pyrazolo[1,5-b][1,2,4]triazoles disclosed in European Patent 119,860 are particularly preferred.
• the cyan couplers which can be used in the present invention include oil-protected type naphthol and phenol couplers. Typical and preferred examples thereof are naphthol couplers as disclosed in U.S. Patent 2.474,293, and 2-equivalent naphthol couplers having oxygen atom linked releasing groups as disclosed in U.S. Patents 4,052,212, 4,146,396, 4,228,233, and 4,296,200. Specific examples of the phenol couplers are given in U.S. Patents 2.369,929, 2,801,171, 2,772,162, and 2,895,826. Cyan couplers providing a dye resistant to moisture and heat are preferably used in this invention.
• cyan couplers include phenol cyan couplers having an alkyl group containing 2 or more carbon atoms at the m-position of the phenol nucleus as disclosed in U.S. Patent 3,772,002, 2,5-diacylamino-substituted phenol couplers as disclosed in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011, and 4,327,173, West German Patent Application (OLS) No. 3,329,729, and Japanese Patent Application No. 42671 / 83, and phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position as disclosed in U.S. Patents 3,446,622, 4,333,999, 4,451,559, and 4,427,767.
• the 2-equivalent cyan, magenta, or yellow couplers which are preferred for use in the present invention particularly from the standpoint of minimizing changes of photographic characteristics, such as gradation, can be represented by the following formulae (IV) or (V); (VI); or (VII); respectively.
• R 21 , R 24 , and R 25 each represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aromatic amino group, or a substituted or unsubstituted heterocyclic amino group;
• R 22 represents a substituted or unsubstituted aliphatic group;
• R 23 and R 26 each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aliphatic oxy group, or a substituted or unsubstituted acylamino group; or R 22 and R 23 , or R 2 s and R 26 are taken together to form a 5- to 7-membered ring; and Y, and Y 2 each represents a halogen
• R 27 represents a group capable of substituting a benzene ring
• R 28 represents a halogen atom, an alkoxy group, or an alkyl group
• R 29 represents a substituted or unsubstituted phenyl group
• Y 3 has the same meaning as Y 1 or Y 2 in formulae (IV) or (V); and n is 1 or 2; or R 27 , R 28 , R 29 , or Y 3 represents a mere bond or a divalent linking group to form a dimer or higher polymer.
• Q represents a substituted or unsubstituted N-phenylcarbamoyl group
• Y s has the same meaning as Y 1 or Y 2 in formulae (IV) or (V); or Q or Y s represents a mere bond or a divalent linking group to form a dimer or a higher polymer.
• aliphatic group as used herein means a straight chain or branched or cyclic alkyl, alkenyl or alkynyl group.
• the releasable group as represented by Yi, Y 2 , Y 3 , or Ys includes a group connecting the coupling active carbon atom and an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic, aromatic or heterocyclic sulfonyl group, or an aliphatic, aromatic or heterocyclic carbonyl group via an oxygen atom, a nitrogen atom, a sulfur atom, or a carbon atom; a halogen atom; an aromatic azo group; etc.
• the aliphatic, aromatic or heterocyclic groups contained in these releasable groups may be substituted with one or more substituents, which may be the same or different, selected from those acceptable for R 21 (hereinafter described).
• the substituent(s) may further be substituted with the substituent acceptable for R 21 .
• these coupling releasable groups are a halogen atom (e.g., fluorine, chlorine, bromine), an alkoxy group (e.g., ethoxy dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), an aryloxy group (e.g., 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), an acyloxy group (e.g., acetoxy, tetradecanoyloxy, benzoyloxy), an aliphatic or aromatic sulfonyloxy group (e.g., methanesulfonyloxy, toluenesulfonyloxy), an acylamino group (e.g., dichloroacetylamino, hep- tafluorobutyrylamino), an aliphatic or aromatic sulful
• the releasable groups may contain a photographically useful group acting as a development inhibitor, a development accelerator, or the like.
• the cyan couplers of formula (IV) and (V) can be synthesized by known processes.
• the cyan couplers of formula (IV) are synthesized by the processes described in U.S. Patents 2,423,730 and 3,772,002, and the cyan couplers of formula (V) are synthesized by the processes of U.S. Patents 2.895,826, 4,333,999, and 4,327,173.
• R 21 , R24, and R 2s each preferably represents an aliphatic group having from 1 to 36 carbon atoms, or an aromatic, heterocyclic, aromatic amino or heterocyclic amino group having from 6 to 36 carbon atoms, each of which may be substituted with a substituent(s) preferably having up to 24 carbon atoms, more preferably up to 12 carbon atoms, e.g., an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkenyloxy group, an acyl group, an ester group, an amido group, a sulfamido group, an imido group, a ureido group, an aliphatic or aromatic sulfonyl group, an aliphatic or aromatic thio group, a hydroxyl group, a cyano group, a carboxyl group, a nitro group, a sulfo go
• aliphatic group means a saturated or unsaturated, and straight chain, branched, or cyclic aliphatic hydrocarbon group and includes an alkyl group, an alkenyl group, and an alkynyl group. Typically included therein are methyl, ethyl, butyl, dodecyl, octadecyl, eicosyl, isopropyl, t-butyl, t-octyl, t-dodecyl, cyclohexyl, cyclopentyl, allyl, vinyl, 2-hexadecenyl, and propargyl.
• R 22 preferably represents an aliphatic group having from 1 to 20 carbon atoms, which may be substituted with a substituent(s) selected from those enumerated above for R 21 .
• R 23 and R 26 preferably represents a hydrogen atom, a halogen atom, an aliphatic group having from 1 to 20 carbon atoms, an aliphatic oxy group having from 1 to 20 carbon atoms, or an acylamino group having from 1 to 20 carbon atoms.
• the aliphatic, aliphatic oxy, or acylamino group may be substituted with a substitutent(s) selected from those enumerated above for R 21 .
• R 22 and R 23 in formula (IV) and R 25 and R 26 in formula (V) may be taken together to form a 5- to 7- membered ring.
• the compounds of formulae (IV) and (V) include dimerized or polymerized couplers formed at one or more of R 21 , R 22 , R 23 , and Y, in formula (IV) or at one or more of R 23 , R 25 , R 26 , and Y 2 in formula (V) independently or in cooperation.
• the group at which it is formed represents a mere bond or a divalent linking group (e.g., an alkylene group, an arylene group, an ether group, an ester group, an amido group, etc., or a combination of these divalent groups).
• the groups at which it is formed are preferably in the polymer main chain or bonded to the polymer main chain vra a divalent group, such as those described above.
• the polymer coupler may be either a homopolymer of the coupler derivative or a copolymer comprising such a coupler derivative and other non-color-forming ethylenically unsaturated monomer(s) (e.g., acrylic acid, methacrylic acid, methyl acrylate, n-butylacrylamide, ⁇ -hydroxymethacrylate, vinyl acetate, acrylonitrile, styrene, crotonic acid, maleic anhydride, N-vinylpyrrolidone).
• ethylenically unsaturated monomer(s) e.g., acrylic acid, methacrylic acid, methyl acrylate, n-butylacrylamide, ⁇ -hydroxymethacrylate, vinyl acetate, acrylonitrile, styrene, crot
• R 21 in formula (IV) and R 2s in formula (V) each more preferably represents a substituted or unsubstituted alkyl or aryl group.
• the substituent for the alkyl group preferably includes a substituted or unsubstituted phenoxy group (the substituent therefore preferably includes an alkyl group, an alkoxy group, a halogen atom, a sulfonamido group, and a sulfamido group) and a halogen atom.
• the aryl group preferably includes a phenyl group substituted with at least one of a halogen atom, an alkyl group, a sulfonamido group, and an acylamino group.
• R24 in formula (V) more preferably represents a substituted alkyl group or a substituted or unsubstituted aryl group.
• the substituent for the alkyl group preferably includes a halogen atom.
• the aryl group preferably includes a halogen atom.
• the aryl group preferably includes a phenyl group susbtituted with at least one of a halogen atom and a sulfonamido group.
• R 22 in formula (IV) more preferably represents a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, and most preferably an alkyl group having from 2 to 4 carbon atoms.
• the substituent for the alkyl group preferably includes an alkyl or aryloxy group, an acylamino group, an alkyl or arylthio group, an imido group, a ureido group, and an alkyl or arylsulfonyl group.
• R 23 in formula (IV) more preferably represents a hydrogen atom, a halogen atom (fluorine or chlorine being particularly preferred), or an acylamino group, with a halogen atom being the most preferred.
• R 26 in formula (V) more preferably represents a hydrogen atom, an alkyl or alkenyl group having up to 20 carbon atoms, and most preferably a hydrogen atom.
• R 2 sand R 26 are taken together to form a 5- or 6-membered nitrogen-containing heterocyclic ring.
• Y 1 and Y 2 each preferably represents a halogen atom, more preferably a chlorine atom.
• the cyan couplers of formula (IV) and (V) may be used either individually or in combinations of two or more thereof.
• magenta couplers represented by formula (VI) are disclosed in JP-A-60-262161 and JP-A-60-238832.
• R 29 represents a phenyl group, preferably a substituted phenyl group having one or more substituents selected from a halogen atom, an alkyl group (preferably having from 1 to 5 carbon atoms), an alkoxy group (preferably having from 1 to 5 carbon atoms), an aryloxy group, an alkoxycarbonyl group, a cyano group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfonamido group, and an acylamino group.
• a preferred substituent is a halogen atom, and particularly a chlorine atom.
• the coupling releasable group as represented by Y 3 specifically includes a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, and a group represented by formula: wherein Z represents an atomic group comprising atoms selected from carbon, oxygen, nitrogen and sulfer atoms, which is necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring in cooperation with the nitrogen atom.
• R 23 represents a halogen atom, an alkoxy group (preferably having from 1 to 5 carbon atoms), or an alkyl group (preferably having from 1 to 5 carbon atoms), preferably a halogen atom. and more preferably a chlorine atom.
• R 27 is a group capable of substituting the benzene ring, and n is 1 or 2. When n is 2, the two R 27 groups may be the same or different.
• the group as represented by R 27 includes a halogen atom, and wherein R , R", and R , which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.
• Preferred of these groups are R CONH-, R'SO 2 NH-, and
• magenta couplers of formula (VI) include those disclosed in JP-A-60-262161 with compound Nos. of M-1 through M-37 and those disclosed in JP A-60-238832 with compound Nos. of M-1 through M-34, as well as mixtures of two or more of these compounds. Preferred among them are the compounds listed below and the compounds used in the working examples hereinafter given.
• a preferred N-phenylcarbamoyl group for Q includes those represented by formula (VII-A): wherein G 1 represents a halogen atom or an alkoxy group; G 2 represents a hydrogen atom, a halogen atom, or a substituted or unsubstitutued alkoxy group; and R 34 represents a substituted or unsubstituted alkyl group.
• substituents for the alkoxy group (G 2 ) or the alkyl group (R 34 ) typically include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a dialkylamino group, a heterocyclic group (e.g., N-morpholino, N-piperidino, 2-furyl), a halogen atom, a nitro group, a hydroxyl group, a carboxyl group, a sulfo group, and an alkoxycarbonyl group.
• a heterocyclic group e.g., N-morpholino, N-piperidino, 2-furyl
• a halogen atom e.g., a nitro group, a hydroxyl group, a carboxyl group, a sulfo group, and an alkoxycarbonyl group.
• the releasable group as represented by Y s preferably include those represented by formulae (X) to (XVI) wherein R 40 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. wherein R 4 .
• R 42 which may be the same or different, each represents a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsufinyl group, a carboxyl group, a sulfo group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted heterocyclic group.
• W 1 represents a non-metallic atom group necessary for forming a 4- to 6-membered ring together with the moiety
• R 43 and R 44 each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a hydroxyl group
• R 4 . s , R 46 , and R 47 each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an acyl group
• W 2 represents an oxygen atom or a sulfur atom.
• the yellow couplers of formula (VII) can be synthesized in accordance with the processes described, e.g., in JP A-54-48541, JP-B-58-10739, U.S. Patent 4,326,024, and Research Disclosure No. 18053.
• 4-equivalent couplers may also be used in combination, if desired.
• couplers which produce a dye having moderate diffusibility may be used in combination to improve graininess. Examples of such diffusible dye forming couplers are described in U.S. Patent 4,366,237 and British Patent 2,125,570 as for magenta couplers; and in European Patent 96,570 and West German Patent Application (OLS) No. 3,234,533 as for yellow, magenta, and cyan couplers.
• the above-described dye forming couplers and other special couplers may be in the form of a polymer inclusive of a dimer.
• Typical examples of polymerized dye forming couplers are described in U.S. Patents 3,451.820 and 4,080,211.
• Specific examples of polymerized magenta couplers are described in British Patent 2,102,173 and U.S. Patent 4,367,282.
• two or more different kinds of the couplers described above may be incorporated into one layer, or the coupler of one kind may be incorporated into two or more layers.
• a standard amount of the color coupler to be used ranges from 0.001 to 1 mol per mol of light-sensitive silver halide.
• a preferred amount is from 0.01 to 0.5 mol as to yellow couplers; from 0.003 to 0.3 mol as to magenta couplers; and from 0.002 to 0.3 mol as to cyan couplers, each per mol of silver halide.
• the couplers can be incorporated into the light-sensitive material by various known dispersion methods. Examples of high-boiling organic solvents to be used in an oil-in-water dispersion method are described, e.g., in U.S. Patent 2,322,027. A latex dispersion method, its effects, and specific examples of latices to be used for impregnation are described in U.S. Patent 4,199,363 and West German Patent Publication Nos. 2,541,174 and 2,541,230.
• the silver halide emulsion to be used in the light-sensitive material may have any halogen composition, such as silver iodobromide, silver bromide, silver chlorobromide, and silver chloride.
• any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide, and silver chloride.
• the individual silver halide grains may have either a homogeneous phase or a heterogeneous phase, such as a core-shell structure or a layered structure having a fused structure, or a combination of these phases.
• a mean grain size distribution of the silver halide grains may be either narrow or broad, but it is preferable to use a so-called monodisperse emulsion whose grain size distribution curve has a coefficient of variation (a quotient obtained by dividing a standard deviation by a mean size, expressed by per cent) within 20%, and particularly within 15%.
• two or more monodisperse silver halide emulsions (preferably having the above-recited coefficient of variation) differing in mean grain size can be incorporated into one layer or into separate layers having substantially the same color sensitivity.
• two or more polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be incorporated into one layer or separately incorporated into two or more layers.
• the silver halide grains may have a regular crystal form, e.g., a cubic form, an octahedral form, a rhombic dodecahedral form, a tetradecahedral form, and a combination thereof; an irregular crystal form, e.g., a spherical form; or a composite form thereof.
• An emulsion comprising tabular grains particularly an emulsion comprising tabular grains having an aspect ratio of from 5 to 8 or even more in a proportion of at least 50% based on the projected area of the total grains, can also be used.
• An emulsion comprising a mixture of grains having various crystal forms as described above may be used.
• the emulsions may be either surface latent image type emulsion wherein a latent image is formed mainly on the surface of grains therein or internal latent image type emulsion wherein a latent image is formed mainly in the interior of grains therein.
• the silver halide emulsions to be used can be prepared by known processes as disclosed, e.g.,' in Research Disclosure, Vol. 176, No. 17643, I, II, and III (Dec., 1978).
• the emulsion to be used in the present invention is usually subjected to physical ripening, chemical ripening, and spectral sensitization.
• Additives which can be used in these steps and other photographically useful additives which can be used in the present invention are described in Research Disclosure, Vol. 176, No. 17643 (Dec., 1979) and ibid, Vol. 187, No. 18716 (Nov., 1979) as tabulated below.
• the photographic materials comprise the abovedescribed emulsion layers provided on a commonly employed flexible support, such as a plastic film (e.g., cellulose nitrate, cellulose acetate, polyethylene terephthalate) and paper, or a rigid support, such as glass.
• a plastic film e.g., cellulose nitrate, cellulose acetate, polyethylene terephthalate
• a rigid support such as glass.
• Research Disclosure, Vol. 176, No. 17643, XV (p.27) and XVII (p.28) (Dec., 1978) can be referred to.
• a reflective support is used advantageously.
• the reflective support functions to enhance reflecting properties to thereby make a dye image formed on the silver halide emulsion layer clearer.
• a reflective support includes a support coated with a hydrophobic resin having dispersed therein a reflecting substance (e.g., titanium oxide, zinc oxide, calcium carbonate, calcium sulfate) and a support made of a hydrophobic resin having dispersed therein such a reflecting substance.
• a multi-layer color paper having the following layer structure was prepared by coating these layers in the order listed on a paper support having a polyethylene laminate on both sides thereof.
• the polyethylene layer on the side to be coated with a 1st layer contained a white pigment (Ti0 2 ) and a bluing dye.
• the resulting sample was designated as Sample A.
• the method of preparing the coating compositions was as follows, taking the composition for the first layer for instance.
• Each of the 1st to 7th layers further contained a sodium salt of 1-oxy-3,5-dichloro-s-triazine as a gelatin hardening agent and Cpd-1 as a thickener.
• Cpd-12 and Cpd-13 were used as anti-irradiation dyes.
• Each layer furthermore contained Alkanol XC (a trade name of Du Pont), a sodium alkylbenzenesulfonate, a succinic ester, and Magefacx F-120 (a trade name of Dai-Nippon Ink & Chemicals, Inc.) as dispersing agent or coating aid, and Cpd-14 and Cpd-15 as stabilizer for silver halide.
• Alkanol XC a trade name of Du Pont
• Magefacx F-120 a trade name of Dai-Nippon Ink & Chemicals, Inc.
• the compounds used in sample A are as follows.
• Sample A was exposed to light through an optical wedge and then processed under conditions shown in Table 2 using processing solutions having the following formulations.
• the processing was carried on for 75 days at a rate of 2 m 2 /day (hereinafter referred to as Running Test I) or for 10 days at a rate of 15 m 2 /day (hereinafter referred to as Running Test II).
• Deionized water having a calcium or magnesium content of not more than 3 ppm was used.
• Samples B to G were prepared in the same manner as for Sample A of Example 1, except for altering the kind of couplers used as indicated in Table 4.
• Sample C of Example 2 was imagewise exposed to light and then subjected to continuous processing under conditions shown in Table 6 using processing solutions whose formulations are described below.
• Stabilizing Bath (The tank soltuion and the replenisher had the same formulation)
• a multi-layer color paper having the following layer structure was prepared by coating these layers in the order listed on a paper support having a polyethylene laminate on both sides thereof.
• the polyethylene layer on the side to be coated with a 1 st layer contained a white pigment (Ti0 2 ) and a bluing dye.
• the method of preparing the coating compositions was as follows, taking the composition for the first layer for instance.
• Each of the 1st to 7th layers further contained a sodium salt of 1-oxy-3,5-dichloro-s-triazine as a gelatin hardening agent and Cpd-2 as a thickener.
• 3rd Layer Green-Sensitive Laver
• Cpd-13 and Cpd-14 were used as anti-irradiation dyes.
• Each layer furthermore contained Alkanol XC (a trade name of Du Pont), a sodium alkylbenzenesulfonate, a succinic ester, and Magefacx F-120 (a trade name of Dai-Nippon Ink & Chemicals, Inc.) as dispersing agent or coating aid, and Cpd-15 and Cpd-16 as stabilizer for silver halide.
• Alkanol XC a trade name of Du Pont
• Magefacx F-120 a trade name of Dai-Nippon Ink & Chemicals, Inc.
• the compounds used in the sample preparation are as follows.
• Washing Water (The tank solution and the replenisher had the same formulation)
• Deionized water having a calcium or magnesium content of not more than 3 ppm was used.
• Example 2 The same color paper as prepared in Example 1 was continuously processed under conditions shown in Table 11 using processing solutions whose formulation are described below until the total quantity of the color developer replenisher reached three times the developer tank.
• Rinsing Solution (The tank solution and the replenisher had the same formulation)
• the sample was exposed to light through an optical wedge and processed either before and after the abovedescribed continuous processing.
• the changes of minimum density and gradation (gamma) with the progress of running were obtained, and the results are shown in Table 12.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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• 1989
  • 1989-01-17 CA CA 588471 patent/CA1332029C/fr not_active Expired - Fee Related
  • 1989-01-20 EP EP89100966A patent/EP0325277A3/en not_active Withdrawn

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