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
  • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material

Definitions

• the present invention is directed toward silver halide color photographic materials and, more precisely, it is directed toward silver halide color photographic materials which contain naphthol based cyan couplers which have a substituent group in the 5-position and pyrazoloazole based magenta couplers which have an alkoxy group or an aryloxy group in the 6-position.
• JP-A-62-180365 the term "JP-A” as used herein signifies "unexamined published Japanese patent application”
• JP-A Japanese Patent Application
• problems affecting photographic performance have arisen. These problems include instability of the silver halide photosensitive materials during storage.
• the object of the present invention is to provide photosensitive materials which simultaneously satisfy all of the various properties required of a color sensitive material. More precisely, the first objective of the present invention is to provide color sensitive materials which have excellent color reproduction. The second objective is to provide stable color sensitive materials exhibiting little variation in performance due to the passage of time during the storage of the coating liquids, during the manufacture of the sensitive material, during the storage of the photosensitive material, or during the storage of a latent image. The third objective of the present invention is to provide color sensitive materials whose images have excellent storage properties. The fourth objective of the present invention is to provide color sensitive materials in which the fluctuation in density after processing is slight even when deteriorated or low pH bleach or bleach-fix baths are used. The fifth objective of the present invention is to provide color sensitive materials which exhibit excellent sharpness at high speed.
• silver halide color photographic materials having at least one red sensitive silver halide emulsion layer which contains cyan couplers, at least one green sensitive silver halide emulsion layer which contains magenta couplers, and at least one blue sensitive silver halide emulsion layer which contains yellow couplers. These layers are established on a support. At least one of the aforementioned cyan couplers is a coupler which can be represented by the general formula [A], and at least one of the aforementioned magenta couplers is a coupler which can be represented by the general formula [I] or the general formula [II].
• R1 represents a halogen atom, aliphatic group, aromatic group, heterocyclic group, amidino group, guanidino group or a group which can be represented by -COR4, -SO2R4, -SOR4, -NHCOR4, -NHSO2R4, -HNSOR4, or R2 represents a halogen atom, hydroxyl group, carboxyl group, sulfo group, amino group, cyano group, nitro group, aliphatic group, aromatic group, carbonamido group, sulfonamido group, carbamoyl group, sulfamoyl group, ureido group, aryl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic sulfonyl group, aromatic sulfonyl group, aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic oxycarbonyl
• R3 represents a hydrogen atom or an R6U group.
• T represents a hydrogen atom or a group which can be eliminated by a coupling reaction with the oxidized form of a primary aromatic amine developing agent.
• R4 and R5 each independently represent an aliphatic group, aromatic group, heterocyclic group, amino group, aliphatic oxy group or an aromatic oxy group
• R6 represents a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, -OR7 group, -SR7 group, -COR8 group, -PO(R7)2 group, -PO(-OR7)2 group, -CO2R7 group, -SO2R7 group, -SO2OR7 group or an imino group
• U represents a -CO- group, an -SO2- group, an -SO- group or a single bond
• R7 represents an aliphatic group, aromatic group or a heterocyclic group.
• R8 represents a hydrogen atom, aliphatic group, aromatic group or a heterocyclic group.
• R9 and R10 each independently represent a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, aliphatic sulfonyl group or an aromatic sulfonyl group.
• the R2 groups may be the same or different, or they may be joined together to form a ring. Further, R2 and R3, or R3 and T, may be joined to each other to form rings respectively. Also, dimers or larger units (oligomers or polymers) can be formed by linking together via divalent groups or groups of higher valence in any of R1, R2, R3 or T.
• aliphatic group signifies a linear chain, branched or cyclic alkyl group, alkenyl group or alkynyl group, and these may be substituted or unsubstituted groups.
• aromatic group signifies a substituted or unsubstituted aryl group and these may have condensed rings.
• heterocyclic group signifies a substituted or unsubstituted, simple ring or condensed ring, heterocyclic group.
• aliphatic groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, cyclopentyl group, t-pentyl group, cyclohexyl group, n-­octyl group, 2-ethylhexyl group, n-decyl group, n-­dodecyl group, n-tetradecyl group, n-hexadecyl group, n-­octadecyl group, 2-hexyldecyl group, adamantyl group, trifluoromethyl group, carboxymethyl group, methoxyethyl group, vinyl group, allyl group, hydroxyethyl group, heptafluoropropyl group, benzyl group, phenethyl group, phenoxyethyl
• aromatic groups include phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 4-chlorophenyl group, 4-nitrophenyl group, 4-­cyanophenyl group, 4-hydroxyphenyl group, 3-hydroxy­phenyl group, 1-naphthyl group, 2-naphthyl group, o-­biphenylyl group, p-biphenylyl group, pentafluorophenyl group, 2-methoxyphenyl group, 2-ethoxyphenyl group, 4-­methoxyphenyl group, 4-t-butylphenyl group, 4-t-octyl­phenyl group, 4-carboxyphenyl group, 4-methylsulfon­amidophenyl group, 4-(4-hydroxyphenylsulfonyl)phenyl group, 2-n-tetradecyloxyphenyl group, 4-n-tetradecyl­oxyphenyl group
• heterocyclic groups include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-­ furyl group, 2-thienyl group, 3-thienyl group, 4-­quinolyl group, 2-imidazolyl group, 2-benzimidazolyl group, 4-pyrazolyl group, 2-benzo-oxazolyl group, 2-­benzthiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, 5-tetrazolyl group, 1,3,4-thiadiazol-2-yl group, 2-pyrrolyl group, 3-triazolyl group, 4-oxazolyl group, 4-thiazolyl group, 2-pyrimidyl group, 1,3,5-triazin-2-yl group, 1,3,4-oxadiazol-2-yl group, 5-pyrazolyl group, 4-­pyrimidyl group, 2-pyrazyl group, succinimido group, phthalimido group, morpholino group, pyrrolidino group, pipe
• R1 in general formula [A] represents a halogen atom, aliphatic group, aromatic group, heterocyclic group, amidino group, guanidino group or a group which can be represented by -COR4, -SO2R4, -SOR4, -NHCOR4, -NHSO2R4, -NHSOR4 or R4 and R5 each independently represent an aliphatic group which has from 1 to 30 carbon atoms, an aromatic group which has from 6 to 30 carbon atoms, a heterocyclic group which has from 1 to 30 carbon atoms, an amino group which has from 0 to 30 carbon atoms [for example an amino group, methylamino group, dimethylamino group, n-butylamino group, anilino group, N-(2-n-tetradecyloxyphenyl)amino group, pyrrolidino group, morpholino group, piperidino group, 2-ethylhexylamino group, n-do
• R4 and R5 may also be joined together to form a ring.
• this halogen atom can be a fluorine atom, chlorine atom, bromine atom or iodine atom.
• R1 is an amidino group or guanidino group the group has from 1 to 30 carbon atoms and may be substituted with aliphatic groups, aromatic groups, hydroxyl groups, aliphatic oxy groups, acyl groups, aliphatic sulfonyl groups, aromatic sulfonyl groups, acyloxy groups, aliphatic sulfonyloxy groups or aromatic sulfonyloxy groups.
• two nitrogen atoms may be joined together to form a heterocycle such as an imidazole or a benzimidazole.
• R2 in general formula [A] represents a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, an amino group which has from 0 to 30 carbon atoms (for example an amino group, methylamino group, dimethylamino group, pyrro­lidino group, anilino group), an aliphatic group which has from 1 to 30 carbon atoms, an aromatic group which has from 6 to 30 carbon atoms, a carbonamido group which has from 1 to 30 carbon atoms (for example formamido group, acetamido group, trifluoroacetamido group, benzamido group), a sulfonamido group which has from 1 to 30 carbon atoms (for example methylsulfonamido group, trifluoromethylsulfonamido group, n-butyl
• R3 in general formula [A] represents a hydrogen atom or R6U.
• R6 represents a hydrogen atom, an aliphatic group which has from 1 to 30 carbon atoms, an aromatic group which has from 6 to 30 carbon atoms, a heterocyclic group which has from 1 to 30 carbon atoms, an -OR7 group, an SR7 group, a -COR8 group, an group, a -PO(R7)2 group, a -PO(-OR7)2 group, a a -CO2R7 group, an -SO2R7 group, an -SO2OR7 group, or an imido group which has from 4 to 30 carbon atoms (for example succinimido group, maleimido group, phthalimido group, diaceylamino group).
• U represents -CO- group, -SO2- group, -SO- group or a single bond.
• R7 represents an aliphatic group which has from 1 to 30 carbon atoms, an aromatic group which has from 6 to 30 carbon atoms or a heterocyclic group which has from 1 to 30 carbon atoms.
• R8 represents a hydrogen atom, an aliphatic group which has from 1 to 30 carbon atoms, an aromatic group which has from 6 to 30 carbon atoms or a heterocyclic group which has from 1 to 30 carbon atoms.
• R9 and R10 each independently represents a hydrogen atom, an aliphatic group which has from 1 to 30 carbon atoms, an aromatic group which has from 6 to 30 carbon atoms, a heterocyclic group which has from 1 to 30 carbon atoms, an acyl group which has from 1 to 30 carbon atoms (for example acetyl group, trifluoroacetyl group, benzoyl group, p-chlorobenzoyl group) or a sulfonyl group which has from 1 to 30 carbon atoms (for example methylsulfonyl group, n-butylsulfonyl group, phenylsulfonyl group, p-nitrophenylsulfonyl group).
• R9 and R10 may be joined together to form a ring.
• T in general formula [A] represents a hydrogen atom or a group which can be eliminated by a coupling reaction with the oxidized form of a primary aromatic amine developing agent.
• groups of the latter type of group include halogen atoms (fluorine atom, chlorine atom, bromine atom and iodine atom), sulfo group, thiocyanato group, isothiocyanato group, selenocyanato group, aliphatic oxy groups which have from 1 to 30 carbon atoms, aromatic oxy groups which have from 6 to 30 carbon atoms, aliphatic thio groups which have from 1 to 30 carbon atoms, aromatic thio groups which have from 6 to 30 carbon atoms, heterocyclic thio groups which have from 1 to 30 carbon atoms, heterocyclic oxy groups which have from 1 to 30 carbon atoms, aromatic azo groups which have from 6 to 30 carbon atoms, heterocyclic groups which have from 1 to 30 carbon atoms, acyloxy groups which
• R2 and R3, R3 and T, or a plurality of R2 groups in general formula [A] may be joined together to form rings respectively.
• Examples of cases in which R3 and T are joined together include the -CH2C- group and the -COO- group.
• R1 in general formula [A] is preferably a halogen atom, a -COR4 group or an -SO2R4 group, and cases in which R4 is an amino group are especially desirable.
• the -COR4 group include carbamoyl group, N-­ethylcarbamoyl group, N-n-butylcarbamoyl group, N-cyclo­hexylcarbamoyl group, N-(2-ethylhexyl)carbamoyl group, N-dodecylcarbamoyl group, N-hexadecylcarbamoyl group, N-­(3-decyloxypropyl)carbamoyl group, N-(3-dodecyloxy­propyl)carbamoyl group, N-[3-(2,4-di-t-pentylphenoxy)­propyl]carbamoyl group, N-[
• Examples of the -­ SO2R4 group include the sulfamoyl group, N-­methylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-­diisopropylsulfamoyl group, N-(3-dodecyloxy­propyl)sulfamoyl group, N-[3-(2,4-di-t-pentylphenoxy)­propyl]sulfamoyl group, N-[4-(2,4-di-t-pentylphenoxy)­butyl]sulfamoyl group, pyrrolidinosulfamoyl group, N-­phenylsulfamoyl group, N-(2-butoxyphenyl)sulfamoyl group, N-(2-tetradecyloxyphenyl)sulfamoyl group.
• R1 is most desirably
• (R2)l′ in general formula [A] is preferably such that l′ is zero, followed by the case in which l′ is equal to 1.
• the R2 group is preferably a halogen atom, aliphatic group, aromatic oxy group, carbonamido group, sulfonamido group, or cyan group. Of these groups the most desirable are the fluorine atom, chlorine atom, trifluoromethyl group, methoxy group and the cyano group.
• the R2 group is preferably substituted in the 2-position or the 4-position with respect to the R3NH- group.
• R6 is preferably an aliphatic group, aromatic group, -OR7 group or an -SR7 group, and U is preferably -CO- or -SO2-.
• aliphatic groups include methyl group, trifluoromethyl group, trichloromethyl group, ethyl group, heptafluoroethyl group, t-butyl group, 1-ethylpentyl group, cyclohexyl group, benzyl group, undecenyl group, tridecenyl group, and 1-(2,4-di-t-pentylphenoxy)propyl group.
• aromatic groups include phenyl group, 1-naphthyl group, 2-naphtyl group, 2-chlorophenyl group, 4-methoxyphenyl group, 4-nitrophenyl group, and pentafluorophenyl group.
• Examples of -OR7 groups include methoxy group, isopropoxy group, n-butoxy group, iso-butoxy group, t-butoxy group, n-pentyloxy group, n-­hexyloxy group, n-octyloxy group, 2-ethylhexyl group, n-­decyloxy group, n-dodecyloxy group, 2-methoxyethoxy group, benzyloxy group, trichloroethoxy group, trifluoroethoxy group, phenoxy group, and p-­methylphenoxy group.
• Examples of -SR7 groups include methylthio group, ethylthio group, allylthio group, n-­butylthio group, benzylthio group, n-dodecylthio group, phenylthio group, p-t-octylphenylthio group, p-­dodecylphenylthio group, and a p-octyloxyphenylthio group.
• R3 is an aliphatic oxycarbonyl group (R6 is R7O- and U is -CO-) or an aliphatic or aromatic sulfonyl group (R6 is an aliphatic group or an aromatic group and U is -SO2) and, most desirably, R3 is an aliphatic oxycarbonyl group.
• T in general formula [A] is preferably a hydrogen atom, halogen atom, aliphatic oxy group, aromatic oxy group, aliphatic thio group or a heterocyclic thio group.
• the aliphatic oxy groups include methoxy group, ethoxy group, 2-­hydroxyethoxy group, 2-chloroethoxy group, carboxy­methoxy group, 1-carboxyethoxy group, methoxyethoxy group, 2-(2-hydroxyethoxy)ethoxy group, 2-methyl­sulfonylethoxy group, 2-methylsulfonyloxyethoxy group, 2-methylsulfonylamidoethyl group, 2-carboxyethoxy group, 3-carboxypropoxy group, 2-(carboxymethylthio)ethoxy group, 2-(1-carboxytridecylthio)ethoxy group, 1-carboxy­tridecyl group, N-(2-methoxyethyl)carbamoy
• aromatic oxy groups include 4-nitrophenoxy group, 4-­acetamidophenoxy group, 2-acetamidophenoxy group, 4-­methylsulfonylphenoxy group, and a 4-(3-carboxypropan­amido)phenoxy group.
• aliphatic thio group include methylthio group, 2-hydroxyethylthio group, carboxymethylthio group, 2-carboxyethylthio group, 1-carboxyethylthio group, 3-carboxypropylthio group, 2-dimethylaminoethylthio group, benzylthio group, n-dodecylthio group, and a 1-carboxytridecylthio group.
• heterocyclic thio groups include 1-phenyl-­1,2,3,4-tetrazol-5-ylthio group, 1-ethyl-1,2,3,4-­tetrazol-5-ylthio group, 1-(4-hydroxyphenyl)-1,2,3,4-­tetrazol-5-ylthio group, 4-phenyl-1,2,4-triazol-3-ylthio group, 5-methyl-1,3,4-oxadiazol-2-ylthio group, 1-(2-­carboxyethyl)-1,2,3,4-tetrazol-5-ylthio group, 5-­methylthio-1,3,4-thiadiazol-2-ylthio group, 5-methyl-­1,3,4-thiadiazol-2-ylthio group, 5-phenyl-1,3,4-oxadi­azol-2-ylthio group, 5-amino-1,3,4-thiadiazol-2-ylthio group, benzoxazol-2-ylthio group, 1-methylbenzy
• Couplers which can be represented by the general formula [A] may take the form of dimers or larger units which are bonded together via divalent groups or groups of higher valency in the substituent groups R1, R2, R3 or T. In such cases the number of carbon atoms may be outside the specified range for each of the aforementioned types of substituent groups.
• Typical examples of cases in which the couplers represented by the general formula [A] are in an oligomeric form include homopolymers or copolymers of addition polymerizable ethylenic unsaturated compounds which have cyan dye forming coupler residual groups (cyan color forming monomers).
• the oligomer has repeating units of general formula [B], and, one or more types of the cyan color forming repeating units represented by the general formula [B] can be included in the oligomer, or the oligomer may take the form of a copolymer which contains one or more non-color forming ethylenic monomers as a copolymerized component.
• R represents a hydrogen atom, an alkyl group which has from 1 to 4 carbon atoms or a chlorine atom.
• G represents a -CONH- group, a -COO- group or a substituted or unsubstituted phenylene group.
• J represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group.
• L represents a -CONH- group, -NHCONH- group, -NHCOO- group, -NHCO- group, -OCONH- group, -NH- group, -COO- group, -OCO- group, -CO- group, -O- group, -SO2- group, -NHSO2- group or an -SO2NH- group.
• a′, b′ and c′ each represent 0 or 1.
• Q represents a cyan coupler residual group in which a hydrogen atom other than that of the hydroxyl group in the 1-position has been removed from a compound which can be represented by the general formula [A].
• Copolymers of cyan color forming monomers which provide a coupler unit of general formula [B] and the non-color forming ethylenic monomers indicated below are preferred as oligomers.
• Non-color forming ethylenic monomers which do not couple with the oxidation products of primary aromatic amine developing agents include acrylic acid, ⁇ -chloroacrylic acid, ⁇ -alkylacrylic acids (for example methacrylic acid), esters and amides derived from these acrylic acids (for example acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacryl­amide, N-methylolacrylamide, N-(1,1-dimethyl-2-sulfon­atoethyl)acrylamide, N-(3-sulfonatopropyl)acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-­butyl acrylate, t-butyl acrylate, isobutyl acrylate, acetoacetoxyethyl acrylate, n-hexyl acrylate, 2-­ ethylhexyl
• the acrylic acid esters, methacrylic acid esters and maleic acid esters are especially desirable.
• Two or more types of the non-color forming ethylenic monomers can be used together.
• the ethylenic unsaturated monomer for copolymerization with a vinyl based monomer corres­ponding to the aforementioned general formula [B] is selected so as to improve the physical and/or chemical properties of the copolymer which is formed, as is well known in the polymeric coupler field.
• these properties include solubility, compatibility with binding agents such as gelatin used in photographic colloid compositions, flexibility and heat resistance.
• a lipophilic non-color forming ethylenic monomer for example an acrylic acid ester, methacrylic acid ester, maleic acid ester, vinyl benzene
• a lipophilic non-color forming ethylenic monomer for example an acrylic acid ester, methacrylic acid ester, maleic acid ester, vinyl benzene
• the lipophilic polymeric couplers obtained by the polymerization of a vinyl monomer provide a coupler unit which can be represented by the aforementioned general formula [B].
• [B] can be made by emulsification and dispersion in the form of a latex in aqueous gelatin solution, or by direct emulsion polymerization.
• hydrophilic non-color forming ethylenic monomers such as N-(1,1-diethyl-2-sulfonato­ethyl)acrylamide, 3-sulfonatopropyl acrylate, sodium styrenesulfonate, potassium 2-styrenesulfinate, acryl­amide, methacrylamide, acrylic acid, methacrylic acid, N-vinylpyrrolidone, N-vinyl pyridine for the copolymer component is preferred for obtaining hydrophilic polymeric couplers which can be dissolved in neutral or alkaline water.
• hydrophilic non-color forming ethylenic monomers such as N-(1,1-diethyl-2-sulfonato­ethyl)acrylamide, 3-sulfonatopropyl acrylate, sodium styrenesulfonate, potassium 2-styrenesulfinate, acryl­amide, methacrylamide, acrylic acid, methacrylic
• Hydrophilic polymeric couplers can be added to coating liquids as aqueous solutions, and they can also be added as solutions in solvent mixtures obtained by mixing water with a lower alcohol, tetrahydrofuran, acetone, ethyl acetate, cyclohexane, ethyl lactate, dimethylformamide, or dimethylacetamide. Moreover, they can be added after being dissolved in aqueous alkaline solutions and alkali containing organic solvents. A small quantity of surfactant can also be added.
• R31 represents an alkyl group, aryl group or a heterocyclic group
• R32 represents a hydrogen atom or a substituent group
• X represents a hydrogen atom or a coupling elimination group.
• R31 represents the same groups as mentioned above.
• R32′ represents an alkyl group, alkylthio group, arylthio group, heterocyclic thio group or an aryl group.
• X represents a hydrogen atom or a coupling elimination group.
• R31 represents an alkyl group such as a methyl group, ethyl group, isopropyl group, t-­butyl group, trifluoromethyl group, phenylmethyl group, methoxyethyl group, 2-phenoxyethyl group, 2-methyl­sulfonylethyl group, 2-hydroxyethyl group, 3,3,3-tri­fluoropropyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 3-­oxobutyl group or an aryl group such as a phenyl group, 4-methylphenyl group, 4-t-butylphenyl group, 4-­acylaminophenyl group, 4-halogenophenyl group, 4-­alkoxyphenyl group, or a heterocyclic group such as a 2-­furyl group, 2-thienyl group, 2-pyrimidyl group,
• R32 is a hydrogen atom, a halogen atom (for example a chlorine atom, bromine atom), an alkyl group [for example a substituted alkyl group such as a sulfon­amido substituted alkyl group (e.g., sulfonamidomethyl group, 1-sulfonamidoethyl group, 2-sulfonamidoethyl group, 1-methyl-2-sulfonamidoethyl group, 3-sulfonamido­propyl group), acylamino substituted alkyl group (e.g., acylaminomethyl group, 1-acylaminoethyl group, 2-acyl­aminoethyl group, 1-methyl-2-acylaminoethyl group, 3-­acylaminopropyl group), sulfonamido substituted phenylalkyl group (e.g., p-sulfonamidophenylmethyl group
• R32′ represents a substituted alkyl group, such as a sulfonamido substituted alkyl group (for example a sulfonamidomethyl group, 1-sulfonamidoethyl group, 2-­sulfonamidoethyl group, 1-methyl-2-sulfonamidoethyl group, 3-sulfonamidopropyl group), an acylamino substi­tuted alkyl group (for example an acylaminomethyl group, 1-acylaminoethyl group, 2-acylaminoethyl group, 1-­methyl-2-acylaminoethyl group, 3-acylaminopropyl group), a sulfonamido substituted phenylalkyl group (for example a p-sulfonamidophenylmethyl group, p-­sulfonamidophenylethyl group, 1-(p-sulfonamidopheny
• substituted alkyl groups and substituted aryl groups are preferred, and the substituted alkyl groups are the more desirable.
• X represents a hydrogen atom, halogen atom (for example chlorine atom, bromine atom, or iodine atom), carboxyl group or a group which is linked via an oxygen atom (for example acetoxy group, propanoyloxy group, benzoyloxy group, 2,4-dichlorobenzoyloxy group, ethoxyoxaloyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group, 4-­methanesulfonamidophenoxy group, 4-­methanesulfonylphenoxy group, ⁇ -naphthoxy group, 3-­pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-­phenethyloxy group, 2-phenoxyethoxy group, 5-­phenyltetrazolyloxy group, 2-benz
• X preferred examples include chlorine atom, an aryloxy group (e.g., phenoxy group, 4-cyanophenoxy group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group), and an arylthio group (e.g., phenylthio group, 2-methoxy-5-t-­octylphenylthio group, 2-butoxy-5 t-octylphenylthio group).
• an aryloxy group e.g., phenoxy group, 4-cyanophenoxy group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group
• an arylthio group e.g., phenylthio group, 2-methoxy-5-t-­octylphenylthio group, 2-butoxy-5 t-octylphenylthio group.
• R31, R32, R32′ or X is a divalent linking group and dimers are formed
• R31, R32 or R32′ represents a substituted or unsubstituted alkylene group (for example methylene group, ethylene group, 1,10-­ decylene group, -CH2CH2-O-CH2-CH2- group), a substituted or unsubstituted phenylene group (for example 1,4-­phenylene group, 1,3-phenylene group, and X represents a divalent group corresponding appropriately with the above mentioned univalent groups.
• the linking groups represented by any of R31, R32 or R32′ when the compounds represented by the general formulae [I] and [II] are included in a vinyl monomer are groups established by combining groups selected from among the alkylene groups (substituted or unsubstituted alkylene groups, for example methylene group, ethylene group, 1,10-decylene group, -CH2CH2OCH2CH2- group), phenylene groups (substituted and unsubstituted phenylene groups, for example 1,4-phenylene group, 1,3-­phenylene group, -NHCO- group, -CONH- group, -O- group, -OCO- group and the aralkylene groups (for example group,
• the vinyl group may have substituent groups other than that represented by the general formula [I] and the preferred substituent groups are hydrogen atoms, chlorine atoms and lower alkyl groups which have from 1 to 4 carbon atoms (for example methyl group, ethyl group).
• Monomers which contain a part which can be represented by general formula [I] or general formula [II] can be formed into copolymers with non-color forming ethylenic monomers which do not couple with the oxidation products of primary aromatic amine developing agents.
• non-color forming ethylenic monomers which do not couple with the oxidation products of primary aromatic amine developing agents include acrylic acid, ⁇ -chloroacrylic acid, ⁇ -alkylacrylic acids (for example methacrylic acid), esters and amides derived from these acrylic acids (for example acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-­butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and ⁇ -hydroxyethylmethacrylate), methylenebisacrylamide, vinyl esters and
• Two or more types of non-color forming ethylenic monomer used here can be used together.
• the non-color forming ethylenic unsaturated monomer for copolymerization with a solid water insoluble monomeric coupler is selected so as to improve the physical and/or chemical properties of the copolymer which is formed, as is well known in he polymeric field.
• these properties include solubility, compatibility with binding agents such as gelatin used in photographic colloid compositions, flexibility and heat resistance.
• the polymeric couplers used in the present invention may be water soluble or water insoluble.
• the use of the polymeric coupler latexes from among these materials is preferred.
• the cyan couplers which can be represented by the general formula [A] can be prepared easily using the method disclosed in European Patent No. 161,626A. Furthermore, the magenta couplers represented by the general formulae [I] and [II] can be prepared easily using the methods disclosed in European Patent No. 226,849A and U.S. Patent 4,540,654.
• the cyan couplers represented by the general formula [A] of the present invention are added to a red sensitive emulsion layer and/or adjacent layers, and the total amount added is from 0.01 to 1.5 grams per square meter, preferably from 1.0 to 1.2 grams per square meter, and more desirably from 0.2 to 1.0 gram per square meter.
• the red sensitive emulsion layer preferably consists of two or more layers which have different speeds.
• the use of four equivalent cyan couplers in which T is a hydrogen atom is preferred in the low speed layer and the use of two equivalent couplers in which T is a group other than a hydrogen atom is preferred in the high speed layer.
• the method used to add the cyan couplers of the present invention to the photosensitive material is based on the method used for the other couplers described hereinafter.
• the amount of high boiling point organic solvent which is used as a dispersing medium with respect to the couplers is preferably from 0 to 1.0, more desirably from 0 to 0.5, and most desirably from 0 to 0.3, in terms of the ratio by weight.
• magenta couplers represented by general formula [I] or [II] of the present invention are added to the green sensitive emulsion layer and/or adjacent layers, and the total amount added is from 0.01 to 1.0 gram per square meter, preferably from 0.05 to 0.8 grams per square meter, and more desirably from 0.1 to 0.5 gram per square meter.
• the method used to add the magenta couplers of this invention to the photosensitive material is based on the method used for the other couplers described hereinafter.
• the amount of high boiling point organic solvent which is used as a dispersing medium with respect to the couplers is from 0 to 4.0, preferably from 0.1 to 2.0, and more desirably from 0.3 to 1.0, in terms of the ratio by weight.
• At least one silver halide emulsion layer (e.g., blue-­sensitive layer, green-sensitive layer, red-sensitive layer) is coated on a support.
• a silver halide photographic material comprising a light-­ sensitive layer consisting of a plural silver halide emulsion layer which has a substantially same color sensitivity but has a different light sensitivity, wherein a unit light-sensitive layer has a sensitivity with respect to any one of blue light, green light, or red light.
• the order of a unit light-­sensitive layer is generally a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer from a support. According to a purpose, this coating order may be in reverse order, or a layer having a different light sensitivity may be inserted into a layer having the same color sensitivity.
• non light-sensitive layer such as an intermediate layer may be coated between the silver halide light-sensitive layers, and it may be used as an uppermost layer, a lowermost layer, etc.
• the intermediate layer may contain the coupler described in JP-A-61-43748, JP-A-59-113438, JP-A-59-­113440, JP-A-61-20037, and JP-A-20038, DIR coupler and so on or a color-mixing preventing agent as in a conventional photographic material.
• the plural silver halide layers which constitutes unit light-sensitive layer is preferably comprised of two layers having a high sensitive emulsion layer and a low sensitive emulsion layer as disclosed in West German Patent 1,121,470 and British Patent 923,045
• the preferred order is such that the light sensitivity of the silver halide layers decreases orderly toward a support, and a non light-sensitive may be coated between each silver halide emulsion layers.
• a low-­sensitive layer may be coated on the farther side from a support and a high-sensitive emulsion layer may be coated in the nearer side from a support.
• JP-B-55-34932 the term "JP-B” as used herein means an "examined Japanese patent publication”
• the order of a blue-sensitive layer/GH/RH/GL/RL from the farthest side from a support may be used.
• the order of a blue-sensitive layer/GL/RL/GH/RH from the farthest side from a support may be used.
• the arrangement having the constitution of three layers differing in light sensitivity in which a silver halide emulsion layer having the highest light sensitivity is used as an upper layer, a silver halide emulsion layer having a lower light sensitivity than that of the upper layer is used as a middle layer, and a silver halide emulsion layer having a lower light sensitivity than that of the middle layer is used as a lower layer and the light sensitivity of the silver halide emulsion layers decreases orderly toward a support may be used.
• the order of a middle-­sensitive emulsion layer/a high-sensitive emulsion layer/a low-sensitive emulsion layer from the farthest side from a support may be used in a same color sensitivity layer as described in JP-A-59-202464.
• various types of a layer structure and a layer order can be selected according to the purpose of a photographic materials.
• the silver halide contained in the photographic emulsions of the photographic materials of the present invention is preferably a silver iodobromide, silver iodochloride or silver iodochlorobromide which contains not more than about 30 mol% of silver iodide.
• the most desirable silver halides are silver iodobromides which contain from about 2 mol% to about 25 mol% of silver iodide.
• the silver halide grains in the photographic emulsion may have a regular crystalline form, such as a cubic form, octahedral form or tetradecahedral form, an irregular crystalline form such as a spherical form or tabular from, a form in which there are crystal defects such as twinned crystal planes, or forms in which these various forms are combined.
• the grain size of the silver halide may be fine with a grain diameter of less than about 0.2 microns or large with a projected area diameter up to about 10 microns. Further, the grains may take the form of a poly-disperse emulsion or a mono-disperse emulsion.
• the silver halide photographic emulsion used in the present invention can be prepared utilizing known methods including those disclosed on pages 22 to 23 of Research Disclosure (RD) No. 17643 (February 1978), "I, Emulsion Preparation and Types", in RD No. 18716 (November 1979), page 648; in Chemie et Physique Photographique , by P. Glafkides, published by Paul Montel, 1967; in Photographic Emulsion Chemistry , by G.F. Duffin, published by Focal Press, 1966; and in Making and Coating Photographic Emulsions , by V.L. Zelikman et al., published by Focal Press, 1964.
• tabular grains which have an aspect ratio of at least about 5 can be used in the present invention.
• Tabular grains can be prepared easily utilizing known methods including those disclosed by Gutoff in Photographic Science and Engineering , Volume 14, pp. 248 - 257 (1970), in U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520, and in British Patent 2,112,157.
• the crystal structure of the grains may be uniform, the interior and exterior parts may have a heterogeneous halogen composition or the grains may have a layered structure. Further, silver halides of different compositions may be joined with an epitaxial junction or they may be joined to compounds other than silver halides such as silver thiocyanate or lead oxide.
• Mixtures of grains of various crystalline forms may also be used.
• the silver halide emulsions used are normally subjected to physical ripening, chemical ripening and spectral sensitization.
• Additives which can be used in these processes have been disclosed in Research Disclosure Nos. 17643 and 18716 and the locations of these items are summarized in the table below.
• Dye image stabilizers Page 25 9. Film hardening agents Page 26 Page 651, left column 10. Binders Page 26 as above 11. Plasticizers and lubricants Page 27 Page 650, right column 12. Coating promoters, surfactants Pages 26 to 27 as above 13. Anti-static agents Page 27 as above
• the 5-pyrazolone based and pyrazoloazole based compounds are preferred as magenta couplers.
• the magenta couplers disclosed in U.S. Patents 4,310,619 and 4,351,897, European Patent 73,636, U.S. Patents 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, and in U.S. Patents 4,500,630 and 4,540,654 are most desirable.
• Phenol based and naphthol based couplers are used as cyan couplers, and those disclosed in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, West German Patent Application (OLS) No. 3,329,729, European Patent 121,365A, and in U.S. Patents 3,446,622, 4,333,999, 4,451,559 and 4,427,767 are preferred.
• OLS West German Patent Application
• the colored couplers for correcting the unwanted absorptions of the colored dyes disclosed in Research Disclosure No. 17643, section VII-G, U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patents 4,004,929 and 4,138,258, and in British Patent 1,146,368 are preferred.
• Couplers whose colored dyes have a suitable degree of diffusibility such as those disclosed in U.S. Patent 4,366,237, British Patent 2,125,570, European Patent 96,570, and in West German Patent Application (OLS) No. 3,234,533 are preferred.
• Couplers that release residual groups and are useful photographically in coupling are also desirable for use in the present invention.
• the use of the DIR couplers which release development inhibitors disclosed in the patents indicated in the aforementioned Research Disclosure No. 17643, section VII-F, in JP-A-57-151944, JP-A-57-254234 and JP-A-60-184248, and in U.S. Patent 4,248,962 is desirable.
• couplers which release nucleating agents or development accelerators in the form of the image during development, disclosed in British Patents 2,097,140 and 2,131,188, and in JP-A-59-157638 and JP-A-­59-170840 is desirable.
• couplers which can be used in the photosensitive materials of the present invention include the competitive couplers disclosed in U.S. Patent 4,130,427, the multi-equivalent couplers disclosed in U.S. Patents 4,283,472, 4,338,393 and 4,310,618, the DIR redox compound releasing couplers disclosed in JP-A-60-185950, the couplers which release a dye which restores coloration after elimination disclosed in European Patent 173,302A, the bleach accelerator releasing couplers disclosed in Research Disclosure No. 11449 and 24241, and in JP-A-61-201247, and the ligand releasing couplers disclosed in U.S. Patent 4,553,477.
• the couplers which are used in the present invention can be introduced into the light sensitive materials by various known methods of dispersion.
• Suitable supports which can be used in the present invention have been disclosed on page 28 of the aforementioned Research Disclosure No. 17643, and in the section from the right hand column of page 647 to the left hand column of page 648 of Research Disclosure No. 18716.
• a total film thickness of the hydrophilic colloid layer is 28 ⁇ m or less in the side of the emulsion layers and a film sevelling speed (T 1/2 ) is 30 sec. or less.
• the film thickness means a film thickness which is determined under moisture conditioning at 25°C for 55% RH (2 days).
• the film swelling speed (T 1/2 ) is determined according to a known method in the art, for example, using a swelling meter whose type is described in A. Green et al, Photoraphic Science and Engineering , vol. 19, No. 2, pages 124 to 129.
• the film swelling speed (T 1/2 ) is defined as a time that the film thickness reaches a saturated film thickness which is 90% of the maximum swell thickness when treated with a color developer at 30°C for 3 min. 15 sec.
• the film swelling speed (T 1/2 ) can be adjusted be adding a hardner to gelatin as a binder or changing conditions with time after coating. Furthermore, the swell (%) is preferably 150 to 400%. The swell (%) is calculated from the following equation using a maximum swell film thickness in the above condition:
• the color development bath used is preferably an aqueous alkaline solution which contains a primary aromatic amine based color developing agent as the principal component.
• Aminophenol based compounds are useful as color developing agents.
• the use of p-phenyl­enediamine based compounds is preferred.
• Typical examples of these compounds include 3-methyl-4-amino-­N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -­hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -­methanesulfonamidoethylaniline, 3-methyl-4-amino-N-­ethyl-N- ⁇ -methoxyethylaniline, and the sulfate, hydro­chloride and p-toluenesulfonate salts of these compounds. Two or more of these compounds can be used conjointly, depending on the intended purpose.
• the color development baths generally contain pH buffers such as the carbonates, borates or phosphates of alkali metals, and development inhibitors or anti-­fogging agents such as bromides, iodides, benzimid­azoles, benzothiazoles or mercapto compounds.
• pH buffers such as the carbonates, borates or phosphates of alkali metals
• development inhibitors or anti-­fogging agents such as bromides, iodides, benzimid­azoles, benzothiazoles or mercapto compounds.
• They may also contain, as required, various preservatives, such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines, phenylsemicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine(1,4-diazabi­cyclo[2,2,2]octane), organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, poly(ethylene glycol), quaternary ammonium salts and amines, color forming couplers, competitive couplers, fogging agents such as sodium borohydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents as typified by the aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids, typical examples of which include ethylenediamine tetra­acetic acid, nitril
• Color development is carried out after a normal black and white development in the case of reversal processing.
• the known black and white developing agents for example the dihydroxybenzenes such as hydro­ quinone, the 3-pyrazolidones such as 1-phenyl-3-­pyrazolidone, and the amino phenols such as N-methyl-p-­aminophenol, can be used individually or in combinations in the black and white development bath.
• the pH of the color and black and white developing baths is generally within the range of from 9 to 12.
• the replenishment rate of the development bath depends on the color photographic material which is being processed, but it is generally less than 3 liters per square meter of photosensitive material and it is possible, by reducing the bromide ion concentration in the replenisher, to use a replenishment rate of less than 500 ml per square meter of photo­sensitive material.
• the prevention of evaporation, and aerial oxidation, by minimizing the contact area with the air in the processing tank is desirable in cases where the replenishment rate is low.
• the replenishment rate can be reduced by suppressing the accumulation of bromide ion in the developer.
• the photographic emulsion layers are subjected to a normal bleaching process after color development.
• the bleaching process may be carried out at the same time as the fixing process (in a bleach-fix process) or it may be carried out as a separate process.
• a bleach-fix process can be carried out after a bleach process in order to speed-up processing.
• processing can be carried out in two connected bleach-­fix baths, a fixing process can be carried out before carrying out a bleach-fix process, or a bleaching process can be carried out after a bleach-fix process, according to the intended purpose of the processing.
• bleaching agents Compounds of a multivalent metal such as iron(III), cobalt(III), chromium(VI), copper(II), peracids, quinones, nitro compounds can be used as bleaching agents.
• Typical bleaching agents include ferricyanides; dichromates; organic complex salts of iron(III) or cobalt(III).
• Examples of complex salts with aminopolycarboxylic acids include ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, cyclohexanediamine tertraacetic acid, methylimino diacetic acid, 1,3-diaminopropane tetraacetic acid, glycol ether diamine tetraacetic acid or citric acid, tartaric acid, malic acid etc.; persulfates; bromates; permanganates and nitrobenzenes.
• aminopolycarboxylic acid iron(III) complex salts principally ethylenediamine tetraacetic acid iron(III) complex salts, and persulfates
• amino polycarboxylic acid iron(III) complex salts are especially useful in both bleach baths and bleach-fix baths.
• the pH of the bleach or bleach-fix baths in which aminopolycarboxylic acid iron(III) complex salts are being used is normally from 5.5 to 8, but processing can be carried out at lower pH values to speed-up processing.
• Bleach accelerators can be used, as required, in the bleach baths, bleach-fix baths, or bleach or bleach-­fix pre-baths. Actual examples of useful bleach accelerators have been disclosed in the following specifications: compounds having a mercapto group or a disulfide gorup are disclosed in U.S.
• Patent 3893,858 West German Patents 1,290,812 and 2,059,988, JP-A-53-­32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-­A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-­124424, JP-A-53-141623 and JP-A-53-28426, and in Research Disclosure No.
• Patent 3,706,561 the iodides disclosed in West German Patent 1,127,715 and in JP-A-58-16235; the polyoxyethylene compounds disclosed in West German Patents 966,410 and 2,748,430; the polyamine compounds disclosed in JP-B-55-8836; the other compounds disclosed in JP-A-49-42434, JP-A-49-­ 59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506, and JP-A-58-163940; and bromide ions.
• these compounds those which have a mercapto group or a disulfide group are preferred in view of their large acceleration effect, and the use of the compounds disclosed in U.S.
• Patent 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 is especially desirable.
• the use of the compounds disclosed in U.S. Patent 4,552,834 is also desirable.
• These bleach accelerators may be added to the sensitive material. These bleach accelerators are especially effective when bleach-fixing color photosensitive materials for photographic purposes.
• Thiosulfates, thiocyanates, thioether based compounds, thioureas and large quantities of iodides can be used as fixing agents, but thiosulfates are generally used for this purpose, and ammonium thiosulfate in particular can be used in the widest range of applica­tions. Sulfites or bisulfites, or carbonyl-bisulfite addition compounds, are the preferred preservatives for bleach-fix baths.
• the silver halide color photographic materials of this invention are generally subjected to a water washing and/or stabilizing process after the desilvering process.
• the amount of water used in the water washing process can be fixed within a wide range according to the nature of the photosensitive material (for example the materials, such as the couplers, which are being used), the porpose for use, the wash water temperature, the number of washing tanks (the number of washing stages), the replenishment system, i.e., whether a counter-flow or a sequential-flow system is used, and various other conditions.
• the relationship between the amount of water used and the number of water washing tanks in a multi-stage counter-flow system can be obtained using the method outlined on pages 248 to 253 of Journal of the Society of Motion Picture and Television Engineers , Volume 64 ( May 1955).
• the amount of wash water can be greatly reduced by using the multi-stage counter-flow system noted in the aforementioned literature, but bacteria proliferate due to the increased residence time of the water in the tanks, thus causing sediments to form on the photosensitive material.
• a method to reduce calcium ion and manganese ion concentrations is disclosed in JP-A-­62-288838. This method can be used very effectively to overcome problems of sedimentation in the processing of color photosensitive materials of the present invention.
• the isothiazolone compounds and thiabendazoles disclosed in JP-A-57-8542 and the chlorine based disinfectants such as chlorinated sodium isocyanurate, and benzotriazoles, and the disinfectants disclosed in Chemistry of Biocides and Fungicides by Horiguchi, Reduction of Microorganisms, Biocidal and Fungicidal Techniques , published by the Health and Hygiene Technical Society and in A Dictionary of Biocides and Fungicides , published by the Japanese Biocide and Fungicide Society, can be used for this purpose.
• the pH of the wash water used in the processing of the photosensitive materials of invention is within the range of from 4 to 9, and preferably within the range of from 5 to 8.
• the wash water temperature and washing time can be set variously according to the nature of the photosensitive material and the application. In general, washing conditions of from 20 seconds to 10 minutes at a temperature of from 15 to 45°C, and preferably of from 30 seconds to 5 minutes at a temperature of from 25 to 40°C, are selected.
• the photosensitive materials of the present invention can be processed directly in a stabilizing bath instead of being subjected to a water wash as described above.
• the known methods disclosed in JP-A-­57-8543, JP-A-58-14834 and JP-A-60-220345 can all be used for this purpose.
• a stabilization process may be carried out following the aforementioned water washing process.
• the stabilizing baths contain formalin and surfactant and are used as a final bath for color photosensitive materials.
• Various chelating agents and fungicides can be added to these stabilizing baths.
• the overflow which accompanies replenishment of the above mentioned wash water and/or stabilizer can be re-used in other processes such as a desilvering process.
• a color developing agent may also be incorporated into the silver halide color photosensitive materials of the present invention in order to simplify and speed-up processing.
• the use of various color developing agent precursors is preferred for incorporat­ion.
• the indoaniline based compounds disclosed in U.S. Patent 3,342,597, the Schiff's base type compounds disclosed in U.S. Patent 3,342,599 and in Research Disclosure Nos. 14850 and 15159, the aldol compounds disclosed in Research Disclosure No. 13924, the metal salt complexes disclosed in U.S. Patent 3,719,492, and the urethane based compounds disclosed in JP-A-53-135628 can be used for this purpose.
• the various processing baths are used at a temperature of from 10 to 50°C in the present invention.
• the standard temperature is normally from 33 to 38°C, but processing is accelerated and the processing time is shortened at higher temperatures and, conversely, higher picture quality and improved stability of the processing baths can be achieved at lower temperatures.
• processes using hydrogen peroxide intensification or cobalt intensification as disclosed in West German Patent 2,226,770 or U.S. Patent 3,674,499 can be carried out in order to economize on silver in the photosensitive material.
• silver halide photosensitive materials of this invention can also be used as heat developable photosensitive materials as disclosed in U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218443 and JP-A-61-238056, and in European Patent 210,660A2, etc.
• Sample 101 a multi-layer color photosensitive material, was prepared by the lamination coating of each of the layers on an undercoated cellulose triacetate film support.
• the composition of the layers is indicated below.
• the numbers corresponding to each component indicate the amount coated onto the support, in units of grams per square meter, the amount after calculation as silver being shown in the case of the silver halides and colloidal silver. In the case of the sensitizing dyes, the amount coated is indicated in units of mols per mol of silver halide in the same layer.
• gelatin hardening agent H-1 and surfactant were added to each layer as well as the components indicated above.
• Samples 102 to 117 were prepared by replacing the couplers in the fifth and ninth layers of Sample 101 with other couplers as shown in Table 1. Here EX-11 was replaced with 0.5 times molar of the other coupler.
• the color development process was carried out in accordance with the scheme indicated below at a temperature of 38°C. Color Development 3 minutes 15 seconds Bleach-A 6 minutes 30 seconds Water Wash 2 minutes 10 seconds Fix 4 minutes 20 seconds Water Wash 3 minutes 15 seconds Stabilization 1 minute 05 seconds
• composition of the processing bath used in each process was as indicated below.
• Diethylenetriamine pentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Sodium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4-(N-Ethyl-N- ⁇ -hydroxyethylamino)-2-methylaniline sulfate 4.5 g Water to make up to 1.0 l pH 10.0
• Ethylenediamine tetraacetic acid, disodium salt 1.0 g Sodium sulfite 4.0 g
• Aqueous ammonium sulfate solution (70%) 175.0 ml Sodium bisulfite 4.6 g Water to make up to 1.0 l pH 6.6
• Formalin (40%) 2.0 ml Polyoxyethylene p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Water to make up to 1.0 l
• the bleach-A bath was replaced by the processing bath indicated below.
• the bleach-B bath was prepared so as to simultate forcedly deteriorated bath, i.e., as if the bath had been used to process a large amount of photosensitive material.
• the bleach-B bath was prepared by mixing 900 ml of solution (B-1) with 100 ml of solution (B-2).
• the (B-2) bath was prepared by introducing steel wool into (B-2′), closing the container and leaving the mixture to stand so as to provide a solution in which the Fe(III)-EDTA had been turned into Fe(II)-EDTA.
• Samples 107 to 117 of the present invention exhibit little loss of density on processing in the tired bleach-B bath as compared with Samples 101 and 102 for comparison, high sensitivity in a green-sensitive layer as compared with Sample 103, and little loss of relative sensitivity in a green-sensitive layer on processing in a forced condition.
• Samples 201 to 214 were prepared by replacing the various couplers in the third, fourth, fifth, seventh, eighth and ninth layers of sample 101 as shown in Table 2.
• Equimolar amounts of the couplers 5, 6, 18 and 19 of the present invention were used to replace EX-­6 in the seventh and eighth layers, and the amounts of HBS-1 and gelatin in the seventh layer were changed to 0.10 and 1.00 respectively while the amount of HBS-1 and gelatin in the eighth layer were changed to 0.08 and 0.80 respectively.
• coupler 18 of the present invention was used at a rate of 1/2 molar to replace EX-11 in the ninth layer.
• samples 215 to 218 the HBS-1 in the third and fourth layers of sample 214 was added at a rate of 0.2, 0.4, 0.8 and 1.1 times by weight respectively with respect to A-18, and the amount of gelatin was changed to 1.40, 1.50, 1.65 and 1.80.
• compositions of the processing baths were as follows:
• Town water was treated by passing through a mixed bed type column which had been packed with an H-­type strongly acidic cation exchange resin ("Amberlite IR-120B”, made by the Rhom and Haas Co.) and an OH-type anion exchange resin ("Amberlite IR-400", made by the same company) so as to reduce the calcium and magnesium ion concentrations to less than 3 mg/liter, after which 20 mg/liter of sodium dichlroisocyanurate and 1.5 g/liter of sodium sulfate were added.
• H-­type strongly acidic cation exchange resin (“Amberlite IR-120B”, made by the Rhom and Haas Co.)
• Amberlite IR-400 made by the same company
• the pH of this bath was within the range of from 6.5 to 7.5.
• the relative speeds of the red sensitive layers and green sensitive layers were obtained from processed strips in the same way as in Example 1. Furthermore, the value obtained by subtracting the yellow fog density from the yellow density at the point at which the magenta density was equal to fog + 1.0 with processed samples which had been exposed to green light are shown as the color turbidity in Table 2.
• the samples were exposed to white light with a pattern intended for MTF value measurement purposes, and the MTF value for 25 cycles/mm was obtained with the cyan image.
• Samples 205 to 214 of the present invention exhibit excellent sharpness as represented by MTF value and excellent color reproducibility represented by color turbidity as compared with Samples 101, 201, and 202 for comparison, and little loss of density on processing in the tired bleach-B bath as compared with Samples 101, 203, and 204. From the results of Samples 214 to 218, it can be said that the smaller amount of a high boiling point organic solvent for dispersing the cyan coupler of the present invention is preferred in view of sharpness.

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• 1987
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