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
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
  • G03C7/30576—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the linking group between the releasing and the released groups, e.g. time-groups
• • 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
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
  • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
  • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
  • G03C7/30529—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site in rings of cyclic compounds

Definitions

• This invention relates to a silver halide color photographic material containing a compound capable of utilizing a development inhibiting group during the development processing.
• a development inhibitor releasing coupler (DIR coupler) is used for improving the photographic performance such as the sharpness, the graininess, the color reproducing property, etc.
• the photographic action of the DIR couplers is described in T.H. James, The Theory of the Photographic Process, 4th ed., pages 610 to 611, and page 344 (published by Macmillan Publishing Co., New York, 1977).
• a DIR coupler which releases a development inhibitor by the coupling reaction with the oxidation product of a color developing agent and forms at the same time a magenta dye at development is preferred in the view point of the color reproducing property and the sharpness of the color photographic material.
• the reason is as follows. That is, since when a DIR coupler forming a magenta dye is used for a green-sensitive emulsion layer, the dye formed from the DIR coupler can be utilized as a part of the magenta density, the total amount of organic compounds such as couplers being added to the green-sensitive emulsion layer can be reduced as compared to the case of using a DIR coupler which does not form a magenta dye, whereby an effect of improving the sharpness of images by reducing the thickness of the emulsion layer is obtained. Furthermore, the use of a DIR coupler coloring other color than a magenta color for a green-sensitive emulsion layer is undesirable since a color turbidity follows.
• a coupler-having a 5-pyrazolone nucleus As a DIR coupler coloring in magenta color, a coupler-having a 5-pyrazolone nucleus is well known but a DIR coupler having a 5-pyrazolone nucleus has a fault that the heat stability is low.
• a DIR coupler is so designed that the coupler exists in an inactive state until a development occurs by bonding a development inhibitor having a property of largely changing the performance of a color photographic material by strongly acting to a silver halide emulsion to the coupling active position of the coupler directly or via a linkage group such that the active point is protected.
• the DIR coupler is decomposed to form a material giving had influences on the photographic performance to fatally reduce the photographic performance.
• This danger is increased as the amount of the DIR coupler is increased and hence in the case of using the DIR coupler of a 5-pyrazolone nucleus having a low heat resistance, there is a restriction that the amount thereof can not be increased too much.
• JP-B-63-22571 the term "JP-B" as used herein means an "examined published Japanese patent application”
• JP-A-60-185950 JP-A-61-177455
• JP-A-61-177456 JP-A-61-28947
• JP-A-61-231553, JP-A-61-233741 JP-A-61-240240
• JP-A-61-236551 JP-A-61-238057
• JP-A-61-249052 JP-A-61-251847, JP-A-61-251848
• JP-A-61-267046 JP-A-61-267047
• JP-61-267048 JP-A-61-272741, JP-A-62-24252, JP-A-62-26962
• JP-A-62-26962 JP-A-62-26962
• the object of this invention is to solve the problem on the heat stability of a conventional magenta coloring DIR coupler and to provide a silver halide color photographic material excellent in sharpness, graininess, and storage stability by developing a magenta coloring DIR coupler having large improving effects of the sharpness and the graininess.
• a silver halide color photographic material containing a development inhibitor releasing coupler (DIR coupler) represented by following formula (I); wherein R, represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclic
• R represents a hydrogen atom,
• R represents a hydrogen atom, a halogen atom (e.g., chlorine and bromine), an alkyl group, e.g., a straight chain or branched alkyl group having from 1 to 32 carbon atoms, a C 7 - 32 aralkyl group, a C 2 - 32 alkenyl group, a C 2-32 alkinyl group, a C 3-32 cycloalkyl group, and a C 3 - 32 cyclo-alkenyl group; and practically, for example, methyl, ethyl, propyl, isppropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 3- 4- 2-[4-(4-hydroeyphenylsulfonyl)phenoxy]dodecaneamido phenyl propyl, 2-ethoxytridecy
• a C 6--30 aryloxy group e.g., phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycar- bamoylphenoxy and 2-methoxyphenoxy
• a C 1-32 acylamino group e.g., acetamido, benzamido, tetradecaneamido, 2-(2,4-di-t-amyiphenoxy)-butaneamido, 4-(3-t-butyl-4-hydroxyphenoxy)-butaneamido, and 2- ⁇ 4-(4-hydroxyphenylsulfonyl)phenoxy ⁇ decaneamido
• a C 1-32 alkylamino group e.g., methylamino, butylamino
• R may further have an organic substituent bonded by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom or may have a halogen atom.
• R 1 is preferably a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, a ureido group, a urethane group, or an acylamino group and more preferably a hydrogen atom, an alkyl group, or an aryl group.
• R is a hydrogen atom, an alkyl group or an aryl group
• the heat stability of the compound shown by formula (I) is particularly excellent.
• R 2 is the same group as illustrated above on R 1 and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, an acyl group, or a cyano group. Also, R 2 is more preferably an alkyl group or an aryl group.
• R 2 The preferred alkyl group shown by R 2 is shown by following formulae (L - 1) and (L - 2).
• R 21 has the same meaning as R in formula (I).
• R 41 and R 42 each represents an alkyl group and R 43 has the same meaning as R 1 in formula (I).
• the alkyl group shown by R 41 or R 42 is preferably an alkyl group having from 1 to 20 carbon atoms (e.g., methyl, ethyl, propyl, hexyl, nonyl, undecyl, tridecyl, and hexadecyl) and the alkyl groups each may further have a substituent.
• R 21 and R 43 each has the same meaning as R 1 in formula (I) and is preferably a hydrogen atom or an alkyl group.
• Preferred examples of the alkyl group are same as those illustrated above as the preferred examples of the alkyl group shown by R 41 and further has a substituent.
• R 2 is preferably an aryl group or a phenyl group and each group may further has a substituent.
• R 2 is most preferably the alkyl group shown by aforesaid formula (L - 2).
• R 31 and R 32 each represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, or a phenyl group.
• R 33 represents an alkyl group having not more than 6 carbon atoms (e.g., methyl, ethyl, trifluoromethyl, isorpopyl, benzyl, propyl, butyl, and cyclohexyl), an aryl group (e.g., phenyl, p-nitrophenyl, and p-methoxyphenyl), an acyl group (e.g., acetyl, propionyl, butyryl, trilfuoroacetyl, heptafluorobutyryl, benzoyl and pentafluorobutyryl), an alkoxycarbonyl group (e.g., methoxycarbonyl and isobutyloxycarbonyl), a carbamoyl group (e.g., N,N-dimethylcarbamoyl and N,N-diethylcarbamoyl), a sulfonyl group (e.g.,
• Examples of the linkage group shown by L in formula (I) are the group utilizing a cleavage reaction of hemiacetal described in U.S. Patents 4,146,396, 4,652,516, and 4,698,297, the timing group causing a cleavage reaction by utilizing an intramolecular nucleophilic reaction described in U.S. Patent 4,248,962, the timing group causing a cleavage reaction by utilizing the electron transfer reaction described in U.S. Patents 4,409,323 and 4,421,845, the group causing a cleavage reaction by utilizing the hydrolysis reaction of iminoketal described in U.S. Patent 4,546,073, and the group causing a cleavage reaction by utilizing the hydrolysis reaction of an ester described in West German Patent Publication (OLS) 2,626,317.
• OLS West German Patent Publication
• L is bonded to X at tge hetero atom included in L, such as, preferably, an oxygen atom, a sulfur atom, or a nitrogen atom.
• T - 1 wherein * represents a bonding hand at the left side of L of the compound shown by formula (I); ** represents a bonding hand at the right side of L of the compound shown by formula (I); Wi represents an oxygen atom, a, sulfur atom or (wherein R 67 represents a substituent);
• the group shown by B in formula (I) is the group leading to an oxidation-reduction group or leading to a coupler after cleaving the bond at the left side of B in formula (I).
• a yellow coupler residue e.g., an open-chain ketomethylene type coupler residue such as acylacetoanilide, malondianilide, etc.
• a magenta coupler residue e.g., a 5-pyrazolone type coupler residue, a pyrazolotriazole type coupler residue, and an imidazopyrazole type coupler residue
• a cyan coupler residue e.g., a phenol type coupler residue, a naphthol type coupler residue, the imidazole type coupler residue described in European Patent Publication (unexamined) 249453, and a pyrazolopyrimidine type coupler residue described in European Patent Publication (unexamined) 304001
• a non-coloring coupler residue e.g.,an indanone type coupler residue and an acetophenone type coupler residue.
• the group becoming a coupler may be the hterocyclic coupler residues described in U.S. Patents 4,315,070, 4,183,752, 4,174,969, 3,961,959,4,171,223 and JP-A-52-82423.
• the oxidation-reduction group is a group which can be cross-oxidized by the oxidation product of a color developing agent.
• a color developing agent examples thereof are hydroquinones, cetechols, pyrogallols, 1,4-naphthohydroquinones, 1,2-naphthohydroquinones, hydrazines, and sul- fonamidonaphthols. Practical examples thereof are described in JP-A-61-230135, JP-A-62-251746, JP-A-61-278852, U.S. Patents 3,364,022, 3379,529, 3,639,417, 4,684,604, and Journal of Organic Chemistry, 29, 588(1964).
• the group shown by B has a group releasing by reacting with the oxidation reaction of a color developing agent, that is the group bonded to the right side of B in formula (I).
• B is bonded to the group of the left side of B at the hetero atom included therein, such as, preferably, an oxygen atom or a nitrogen atom.
• a preferred group shown by B is the group shown by following formula (B - 1): wherein * represents a position bonding to the left aide of B in formula (I); ** represents a position bonding to the right side of B in formula (I); X, and X 4 each represents an oxygen atom or ... (wherein R 71 represents an aliphatic group, an aromatic group, or heterocyclic group); X 2 and X 3 each represents a methine group or a nitrogen atom; and b represents an integer of from 1 to 3 and bb represents 0, 1 or 2, at least one of b x X 2 and b x X 3 represents a methine group having a bonding hand shown by **. Also, when b represents 2 or 3, the plural X2s and X3s each may be the same or different.
• X 2 and X 3 each represents a methine group having a substituent, they include the case of forming a cyclic structure (e.g., a benzene ring or a pyridine ring) by the combination of them and the case of not forming such a cyclic structure.
• a cyclic structure e.g., a benzene ring or a pyridine ring
• Examples of the group shown by DI in formula (I) are are a tetrazolylthio group, a thiazolylthio group, an oxadiazolylthio group, a triazolylthio group, a benzimidazolylthio group, a benzothiazolylthio group, a tetrazolylseleno group, a benzoxazolylthio group, a benzotriazolyl group, a triazolyl group, and a benzimidazolyl group.
• Y represents a divalent linkage group having not more than 8 carbon atoms or a simple bonding hand
• R represents an aliphatic group having from 1 to 6 carbon atoms .or heterocyclic group
• Z 3 represents a non-metallicatomic group necessary for forming a heterocyclic ring together with carbon atom and nitrogen atom
• Z 4 represents a non-metallic atomic group necessary for forming a heterocyclic ring (a single ring or a condensed ring) together with nitrogen atom.
• heterocyclic ring examples include triazole, tetrazole, oxadiazole, thiadiazole, benzimidazole, and benzothiazole.
• tetrazole, 1,3,4-thiadiazole, 1,3,4-oxadiazole, and 1,2,4-triazole are particularly preferred.
• Z 4 preferably represents a non-metallic atomic group necessary for forming a 5- to 7-membered heterocyclic ring (a single ring or a condensed ring), which may be substituted, together with nitrogen atom.
• a heterocyclic ring examples include imidazole, 1,2,4-triazole, benztriazole, 1,2,3-triazole, pyrazole, indazole, imidazoiine-2-thion, 1,2,4-triazoline-3-thion, and 1,3,4-thiadiazoline-2-thion.
• 1,2,3-triazole and benztriazole are particularly preferred.
• heterocyclic ring shown by formula (Di - a) or (DI - b) has other substituent than Y-COOR at a position capable of being substituted
• examples thereof are an aliphatic group (having from 1 to 6 carbon atoms, e.g., methyl and ethyl), a halogen atom (e.g., chlorine, fluorine, and bromine), a heterocyclic group (having from 1 to 5 carbon atoms, a 3- to 6-membered ring having heteroatoms selected from oxygen atom, sulfur atom, and nitrogen atom, e.g., furyl, thienyl, and imidazolyl), a nitro group, a cyano group, an aromatic group (having from 6 to 10 carbon atoms, e.g., phenyl), an amino group, an alkylthio group (having from 1 to 10 carbon atoms, e.g., methylthio and ethylthio
• the divalent group shown by Y in formulae (DI - a) and (DI - b) is preferably an aliphatic group which may contain a bonding group having hetero-atom(s), such as an ether condensation, a thioether condensation, -NHCO-, - S0 2 -, -CO-, or -NHS0 2 -; an aromatic divalent linkage group, or a simple bonding hand.
• Examples of the divalent linkage group shown by Y are methylene, ethylene, propylene, -CH 2 0-CH 2 -, -SCH 2 CH 2 -, and -CH 2 SCH 2 -.
• the group shown by R is preferably an aliphatic group having from 1 to 6 carbon atoms, which may be substituted.
• the aliphatic group are methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isoamyl, sec-amyl, and t-amyl.
• examples of the substituent are an alkoxycarbonyl group (having from 2 to 6 carbon atoms, e.g., methoxycarbonyl, propoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, isopropoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, and 2-methoxyethoxycarbonyl), a carbamoyl group (having from 0 to 6 carbon atoms, e.g., N,N-diethylcarbamyl, N-methyl-N-ethylcarbamoyl, pyrrolidinocarbonyl, and piperidinocarbonyl), a halogen atom (e.g., chlorine and fluorine), a nitro group, a cyano group, an alkoxy group (having from 1 to 4 carbon atoms, e.g., methoxy, ethoxy, and methoxye
• an alkoxycarbonyl group having
• the coupler shown by formula (I) is of a non-diffusible type and it is particularly preferable that the non-diffusible group in included in R 1 , R 2 , L or B in formula (I).
• the couplers shown by formula (I) include the couplers shown by following formulae (II), (III), (IV), and (V) but in these couplers, the couplers shown by formulae (II) and (III) are particularly preferred in the point of heat stability and also the coupler shown by formula (II) is particularly preferred in the point of a high reactivity with the oxidation product of a color developing agent.
• R 1 , R 2 , X, L, B, DI, m, n, and p have the same meaning as in formula (I) and also, in formula (IV), it is excluded that two R 2 s bond to each other to form an aromatic ring.
• X 1 represents W represents an oxygen atom, a sulfur atom, or represents a group releasing Dl by an electron transfer along the conjugated system; and Dl R 31 , R 32 , R 33 , *, and ** have the same meaning as in formula (I).
• the compound shown by formula (I) may form a dimer or more polymer via a divalent or higher valent group at R, or R2...
• the compound shown by formula (I) forms a polymer
• the typical example thereof is a homopolymer or a copolymer of an addition polymerizable ethylenically unsaturated compound (coloring monomer) having the aforesaidcompound residue.
• the polymer has a recurring unit shown by following formula (VI).
• the polymer may contain one or more kinds of the aforesaid coloring recurring unit and also ray be a copolymer containing one or more kinds of non-coloring ethylenic monomers.
• R 34 represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, or chlorine atom; E represents -CONH-, -COO-, or a substituted or unsubstituted phenylene group; G represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted aralkylene group; T represents -CONH-, -NHCONH-, -NHCOO-, -NHCO-, -OCONH-, -NH-, -COO-, -OCO-, -CO-, -O-, -S0 2 -, -NHS0 2 -, or -S0 2 NH-; f, g, and t each represents 0 or 1; and QQ represents a compound residue formed by releasing a hydrogen atom from the compound shown by formula (I).
• a copolymer of the compound monomer giving the compound unit show by formula (VI) and a non-coloring ethylecial monomer shown below is preferred.
• the non-coloring ethylenical monomer which does not coupling with the oxidation product of an aromatic primary amine developing agent there are acrylic acid, a-chloroacrylic acid, a-aracrylic acid (e.g., methacrylic acid), the esters or amides induced from these acrylic acids (e.g., acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methylenebisacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, uraryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 8 -hydroxynnethacry
• acrylic acid esters methacrylic acid esters, and maleic acid esters are preferred.
• non-coloring ethylenic monomers described above can be used singly or as a combination thereof.
• methyl acrylate and butyl acrylate examples include methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, and methyl acrylate and diacetoneacrylamide.
• the non-coloring ethylenical monomer which is copoltmerized with the ethylenical monomer having the dye forming residue in this invention can be selected such that the physical properties and/or the chemical properties of the copolymer formed, such as the compatibility with gelatin, the flexibility, the thermal stability, etc., receive good influences.
• the polymer compound for use in this invention that is an oleophilic polymer compound obtained by the polymerization of a vinylic monomer giving the compound unit shown by aforesaid formula (VI), may be prepared by emulsion-dispersing the solution thereof in an organic solvent in an aqueous gelatin solution as a form of latex or may be directly prepared by a emulsion polymerization method.
• the 1H-pyrazolo[1,5-b]-1,2,4-triazole skeleton contained in the compound shown by formula (II) can be synthesized by the methods described in U.S. Patent 4,540,654, JP-A-60-172982, JP-A-60-215687, JP-A-60-197688, and JP-A-60-190779.
• the 1 H-pyrazolo[5,1-c]-1,2,4-triazole skeleton contained in the compound shown by formula (III) can be synthesized by the methods described in U.S. Patent 3,725,067, JP-B-47-27444, JP-B-48-30895, JP-A-61-18780, JP-A-62-33177, and JP-A-1-233285.
• the 1H-imidazo[1,2-b]pyrazoie skeleton contained in the compound shown by formula (IV) can be synthesized by the methods described in JP-A-59-162548, European Patent Publication (unexamined) 11974, and WO 86/02467.
• the 1H-pyrazolo[1,5-d]tetrazole skeleton contained in the compound shown by formula V can be synthesized by the method described in JP-A-60-33552.
• a coupling releasable group can be introduced as follows.
• compound (G) can be synthesized by treating a pyrazoloazole having no substituent at the coupling position with sulfur monochloride.
• Crystals deposited were collected by filrtation, immediately added to 1.0 liters of methanol, and after adding thereto 10.7 ml of pyridine, the resultant mixture was stirred for 4.5, hours at 50°C. Methanol was distilled off under reduced pressure to reduce the volume of the mixture to about 300 ml and crystals thus deposited were collected by filtration and after washing with methanol, were dried to provide 23.0 g of Intermediate (N).
• reaction mixture was extracted with the addition of ethyl acetate and 1 N hydrochloric acid and the organic layer formed was collected, washed with a saturated aqueous sodium chloride solution, and dried on anhydrous magnesium sulfate. After concentrating the product, the residue was purified by silica gel column chromatography (eluent: a mixture of chloroform and methanol) to provide 4:1 g of compound (13) as a glassy solid.
• the development inhibitor releasing coupler in this invention may be incorporated in any layer(s) of a color photographic material but is preferably incorporated in a light-sensitive silver halide emulsion layer and/or a layer adhacent thereto.
• the coupler is more preferably incorporated in a light-sensitive silver halide emulsion layer, and particularly preferably incorporated in a green-sensitive silver halide emulsion layer.
• the total addition amount of the coupler(s) in the color photographic material is usually from 3 x 10- 7 to 1 x 10- 3 mol/m 2 , preferably from 3 x 10- 6 to 5 x 10- 4 mo/lm 2 , and more preferably from 1 x 10- 5 to 3 x 10- 4 mol/m 2.
• the compound of formula (I) for use in this invention can be incorporated in a color photographic material by the same manner as the case of ordinary coupler as described below.
• the color photographic material of this invention has at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, and at least one red-sensitive silver halide emulsion layer on a support and there is no specific restriction on the number of the silver halide emulsion layers and light-insensitive emulsion layers and also the arrangement order of these layers.
• the silver halide color photographic material of this invention has at least one light-sensitive layer composed of plural silver halide emulsion layers each having a substantially same color sensitivity but having a different light sensitivity on a support, and the light-sensitive layer if a unit light-sensitive layer having a color sensitivity for any one one of blue light, green light, and red light.
• a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer are disposed on a support in this order from the support side in the arrangement of the unit light-sensitive layers.
• the order of the arrangement may be reversed depending on the application.
• an arrangement that a different unit light-sensitive layer is disposed between two light-sensitive layers each having the same color sensitivity can be employed.
• light-insensitive layer(s) such as interlayer, etc., may be formed between the aforesaid silver halide.
• the interlayer(s) may contain couplers, DIR compounds, etc., as described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037, and JP-A-61-20038 and further may contain a color mixing inhibitor as usually used.
• each unit light-sensitive layer As the plural silver halide emulsion layers constituting each unit light-sensitive layer, a double layer structure composed of a high-sensitive emulsion layer and a low-sensitive emulsion layer as described in West German Patent 1,121,470 or British Patent 923,045 can be preferably used. Usually, these layers are preferably arranged in such an order that the light sensitivity becomes lower towards the support and also a light-insensitive layer may be formed between these silver halide emulsion layers.
• a low- sensitiveemulsion layer may be disposed at aside far from a support and a high-sensitive emulsion layer may be disposed at a side near the support.
• a low-sensitive blue-sensitive emulsion layer (BL), a high-sensitive blue-sensitive emulsion layer (BH), a high-sensitive green-sensitive emulsion layer (GH), a low-sensitive green-sensitive emulsion layer (GL), a high-sensitive red-sensitive emulsion layer (RH), and a low-sensitive red-sensitive emulsion layer (RL) can be disposed on a support in this order from the farthest side of the support.
• the order of embodiments, the order of BH/BUGUGH/RH/RL or the order of BH/BUGH/GURURH can be employed.
• JP-B-55-34932 the term "JP-B” as used herein means an "examined published Japanese patent application”
• the order of a blue-sensitive emulsion layer, GH, RH, GL, and RL from the farthest side of the support can be employed.
• the order of a blue-sensitive emulsion layer, GL, RL, GH, and RH from the farthest side of the support can be also employed.
• a unit light-sensitive layer of three layer structure that the uppermost layer is a silver halide emulsion layer having the highest light sensitivity, an intermediate layer is a silver halide emulsion layer having a lower than that of the uppermost layer, and the lowermost layer is a silver halide emulsion layer having a lower light-sensitivity than that of the intermediate layer, that is, the light sensitivities of the three silver halide emulsion layers become successively lower towards the support may be employed.
• a same color-sensitive layer may be composed of an intermediate-sensitive emulsion layer, a high-sensitive emulsion layer, and a low-sensitive emulsion layer in this order from the farthest side of a support may be employed.
• the disposition order of a high-sensitive emulsion layer, a low-sensitive emulsion layer, and an intermediate emulsion layer or the disposition order of a high-sensitive emulsion layer may be employed.
• a same color-sensitive layer is composed of four or more layers
• the arrangement of the layers can be varied as described above.
• the silver halide contained in the photographic emulsion layers of the color photographic material of this invention is preferably is silver iodobromide, silver iodochloride, or silver iodochloro-bromide containing about not more than about 30 mol% silver iodide.
• the silver halide grains in the photographic emulsion may be those having a regular crystal form such as a cubic form, an octahedral form and a tetradecahedral form, those having an irregular crystal form such as a pherical form or a tabular from, those having a crystal defect such as twin planes, or those having the composite form of them....
• the silver halide grains may be either fine grains having grain sizes of less than about 0.2 microns or coarse grains having large grain sizes up to about 10 microns in the projected area diameter.
• the silver halide emulsion for use in this invention may be a polydisperse emulsion or a monodisperse emulsion.
• the silver halide photographic emulsions for use in this invention can be prepared by a method described, for example, in Research Disclosure (RD), No. 17643 (December, 1978), pages 22-23, "I. Emulsion Preparation and Types", ibid., No. 18716 (November, 1979), age 648, ibid., No. 307105 (November, 1989), pages 863-865, P. Glafkides, Chemie et Phisique Photographique, Paul Montel, 1967, C.F. Duffin, Photographic Emulsion Chemistry, published by Focal Press, 1966, and V. L. Zelikman et al, Making and Coating Photographic Emulsion, published by Focal Press, 1964.
• monodisperse emulsions as described in U.S. Patents 3,574,628 and 3,655,394 can be preferably used in this invention.
• Tabular grains having an aspect ratio of at least about 3 can be used in this invention.
• Tabular grain silver halide emulsions can be easily prepared by the methods described, e.g., in Gotoff, Photographic Science and Engineering, Vol. 14, pages 248-257(1970), U.S. Patents 4,434,226, 4,414,310, 4,433,048, 4,439,520, and British Patent 2,112,157.
• the individual silver halide grains may have either a homogeneous structure or a heterogeneous structure composed of a core and an outer shell differing in halogen composition or may have a layered structure. Furthermore, the silver halide grains may junctioned to other silver halide having a different halogen composition by epitaxial junction or to other compound than silver halide, e.g., silver thiocyanate, lead oxide, etc. Also, a mixture of silver, halide grains having various crystal forms may be used.
• the aforesaid silver halide emulsion may be of a surface latent image type of forming a latent image mainly on the surface thereof, an internal latent image type of forming a latent image in the inside of the grain, or a type of forming latent images on the surface and the inside of it.
• the internal latent image type emulsion may be a core/shell type internal latent image emulsion described in JP-A-63-264740.
• the thickness of the shell of the core/shell type silver halide gains differs according to the manner of the development process, etc., but us preferably from 3 to 40 nm, and particularly preferably from 5 to 20 nm.
• the silver halide emulsion is usually physically ripened, chemically ripened, and spectrally sensitized for use.
• Additives which are used in the aforesaid steps are described in Research' Disclosure, No. 17643, ibid., No. 18716, and ibid., No. 307105 as tabulated below.
• two or more kinds of silver halide emulsions each having at least one different characters in terms) of the grain sizes, the grain size distribution, the halogen composition, the grain form, and the sensitivity can be used in a same layer as a mixture thereof.
• silver halide grains having the fogged grain surface described in U.S. Patent 4,082,553, silver halide grains having the fogged grain inside described in U.S. Patent 4,626,498 and JP-A-59-214852, or colloidal silver can be preferably used for a light-sensitive silver halide emulsion layer and/or a substantially light-insensitive hydrophylic colloid layer.
• Silver halide grains having the fogged grain inside or fogged grain surface mean silver halide grains which can be unoformly (non-imagewise) developed regardless of non-exposed and exposed portions of the photographic material.
• the preparation methods of the silver halide grains having the fogged grain size or grain surface are described in U.S. Patent 4,626,498 and JP-A-59-214852.
• the silver halide forming the inner nucleus of the core/shell type silver halide grain having fogged grain side may be one having a same halogen composition as that of the shell portion or a different halogen composition of the latter.
• silver halide having the fogged grain inside or surface silver chloride, silver chlorobromide, silver iodobromide, or silver chloroiodo-bromide can be used.
• the mean grain size of these fogged silver halide grains is preferably from 0.01 to 0.75 pm, and particularly preferably from 0.05 to 0.6 pm.
• the form of the fogged silver halide grains and the silver halide grains may be regular grains.
• the emulsion of the fogged silver halide grains may be a polydisperse emulsion but is preferably monodisperse emulsion (at least 95% of the weight or the grain number of the silver halide grains have grain sizes within ⁇ 40% of the mean grain size thereof).
• a light-insensitive fine grain silver halide is preferably used.
• the light-insensitive fine grain silver halide is a silver halide fine grain which is not exposed at an imagewise exposure for obtaining dye images and is not substantially developed at development processing and it is preferred that the silver halide is not previously fogged.
• the fine grain silver halide has a silver bromide content of from 0 to 100% and, if necessary, contains silver chloride and/or silver iodide.
• the fine grain silver halide containing from 0.5 to 10 mol% of silver iodide is preferred.
• the mean grain size (the mean value of the circle-corresponding diameters of the projected areas) of the fine grain silver halide is preferably from 0.01 to 0.5 pm, and more particularly preferably from 0.02 to 0.2 pm.
• the fine grain silver halide can be prepared by a same method of preparing ordinary light-sensitive silver halide.
• the surface of the silver halide grains is not necessary optically sensitized and also is not necessarily spectrally sensitized.
• a known additive such as a triazole series compound, an azaindene series compound, a benzothiazolium series compound or a mercapto series compound is previously added to the silver halide.
• the layer containing the fine grain silver halide can preferably contain colloidal silver.
• the amount of the coated silver in the color photographic material of this invention is preferably not more than 6.0 g/m 2 , and most preferably not more than 4.5 g/m 2.
• the color photographic material of this invention contains a mercapto compound described in U.S. Patent 4,740,454, 4,788,132, JP-A-62-18539 and JP-A-1-283551:
• the color photographic material of this invention further contains a dye dispersed by the method described in WO(PCT) 88/04794A and Toku Hyo 1-502912 (the term "Toku Hyo” as used herein means an "unexamined published PCT patent application translated into Japanese language") or a dye described in EP 317,308A, U.S. Patent 4,421,555, and JP-A-1-259358.
• Preferred yellow couplers include those described in U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752, 4,248,961, 3,973,968, 4,314,023,and 4,511,649, JP-B-58-10739, British Patents 1,425,020 and 1,476,760, and European patent 249,473A.
• 5-pyrazolone series compounds and pyrazoloazole series compounds are preferred and those described in U.S. Patents 4,310,619, 4,351,897, 3,061,432, 3,725,064, 4,500,630, 4,540,654, and 4,556,630, European Patent 73,636,JP-A-60-33552, JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, and JP-A-60-185951, WO(PCT) 88/04795, Research Disclosure,No. 24220 (June, 1984), and ibid., No. 24230 (June, 1984) are particularly preferred.
• Cyan couplers which can be used in this invention include phenolic and naphtholic couplers.
• Preferred cyan couplers are described 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, 4,327,173, 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212, and 4,296,199, West German Patent Publication (OLS) 3,329,729, European Patents 121,365A and 249,453A, and JP-A-61-42658.
• OLS West German Patent Publication
• pyrazoloazole series cyan couplers described in JP-A-74-553, JP-A-64-554, JP-A-64-555, and JP-A-556 and imidazole series cyan couplers described in U.S. Patent 4,818,672 can be also used in this invention.
• Couplers which form dyes having a moderate diffusibility can be used in this invention and preferred such couplers are described in U.S. Patent 4,366,237, British Patent 2,125,570, European Patent 96,570, and West German Patent Publication (OLS) 3,234,533.
• Couplers for correcting unnecessary absorptions of colored dyes can be also used in this invention and preferred such couplers are described in Research Disclosure, No. 17643, VII-G, ibid., No. 307105, VII-G, U.S. Patents 4,163,670, 4,004,929, and 4,138,258, JP-B-57-39413, and British Patent 1,146,368. Furthermore, couplers for correcting unnecessary absorptions of colored dyes by fluorescent dyes released upon coupling described in U.S. Patent 4,774,181 and couplers having a dye precursor group capable of forming a dye by reacting with a developing agent as a releasable group described in U.S. Patent 4,777,120 are preferably used.
• Compouns releasing photographically useful residues with coupling can be preferably used in this invention.
• DIR couplers releasing a development inhibitor other than the DIR coupler of formula (I) for use in this invention can be also used in this invention and .preferred examples of such other DIR couplers are described in the patents described in Research Disclosure, No. 17643, VII-F and ibid., No. 307105, VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, and JP-A-63-37350, U.S. Patents 4,248,962 and 4,782,012.
• Couplers releasing bleach accelerators described in Research Disclosure, No. 11449, ibid., No. 24241, JP-A-61-201247 are effective for shortening the time of a processing step having a bleach faculty and, in particular, the effect of using such couplers is large in the case of adding the couplers to the color photographic material using aforesaid tabular silver halide grains.
• Couplers capable of imagewise releasing a nucleating agent or a development accelerator can be also used in this invention and preferred examples thereof are described in British Patents 2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840.
• couplers releasing a fogging agent, a development accelerator, a silver halide solvent, etc., by the oxidation reduction reaction with the oxidation product of a color developing agent described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, and JP-A-1-45687 are preferably used in this invention.
• the couplers for use in this invention can be introduced into the color photographic materials of this invention by various dispersion methods.
• the couplers can be incorporated in the silver halide emulsion by an oil drop-in-water dispersion method and examples of a high-boiling solvent which is used for the oil drop-in-water dispersion method are described in U.S. Patent 2,322,027.
• phthalic acid esters e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-5-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, and bis(1,1-diethylpropyl) phthalate
• phosphoric acid esters or phosphonic acid esters e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexydiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethy
• an organic solvent having a boiling point of higher than about 30 C, and preferably from 50 C to about 160°C can be used as an auxiliary solvent.
• Typical examples of the solvent are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.
• a latex dispersion method can be also used for incorporating the couplers in the emulsions in this invention and specific examples of the latex dispersion method, the effects thereof, and latexes for impregnation are described in U.S. Patent 4,199,363, West German Patent Publications (OLS) 2,541,274 and 2,541,230.
• phenethyl alcohol or various kinds of preservatives or antimolds such as 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxy ethanol, 2-(4-thiazolyl)benzimidazole, etc., described in JP-A-63-257747, JP-A-62-272248, and JP-A-1-80941 to the color photographic material of this invention.
• preservatives or antimolds such as 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxy ethanol, 2-(4-thiazolyl)benzimidazole, etc., described in JP-A-63-257747, JP-A-62-272248, and JP-A-1-80941 to the color photographic material of this invention.
• This invention can be applied to various color photographic materials.
• the invention can be applied for ordinary or cinne color negative films, color reversal films for slide or television, color photographic papers, color positive films, and color reversal papers.
• Suitable supports which can be used for the color photographic materials of this invention are described in Research Disclosure, No. 17643, page 28, ibid., No. 18716, page 647, right column to page 648, left column, and ibid., No. 307105, page 879.
• the total thickness of all hydrophilic colloid layers on the emulsion side is preferably 28 pm or less, more preferably 23 pm or less, particularly preferably 18 ⁇ m or less and the most preferably 16 ⁇ m or less.
• the film swelling rate T t is preferably 30 seconds or less, and more preferably 20 seconds or less.
• the film thickness is determined after being stored at a temperature of 25° C and a relative humidity of 55% (for 2 days).
• the film swelling rate T can be determined by a method known in the art, e.g., by means of a swellometer of the type as described in A. Green et al Photographic Science Engineering, vol. 19, No. 2, pages 124 to 129.
• T 1 ⁇ 2 is defined as the time taken until reaching 1/2 of the saturated film thickness, wherein the saturated film thickness of 90% of the most swollen film thickness reached when the light-sensitive material is processed with a color developer for 3 minutes and 15 seconds at 30° C.
• the film swelling rate T t can be adjusted by adding a hardening agent to gelatin as a binder or by changing the storing condition after coating.
• the swelling ratio of the color photographic material of this invention is preferably in the range of from 150 to 400%.
• the swelling ratio can be calculated according to the equation of (most swollen film thickness - film thickness)/film thickness from the most swollen film thickness under the aforesaid condition.
• a hydrophilic colloid layer having the total dry layer thickness of from 2 ⁇ m to 20 ⁇ m at the opposite side of the support to the emulsion layer-carrying side. It is also preferred that the back layer contains a light absorbent, a filter dye, a ultraviolet absorbent, an antistatic agent, a hardening agent, a binder, a plasticizer, a lubricant, a coating aid, a surface active agent.
• the swelling ratio of the back layer is preferably in the range of from 150 to 500%.
• the color photographic material of this invention can be processed by the ordinary process described in Research Disclosure, No. 17643, pages 28 to 29, ibid., No. 18716, page 651,left column to right column and ibid., No. 307105, pages 880 to 881.
• a color developer which is used for developing the color photographic material of this invention is an alkaline aqueous solution containing an aromatic primary amino color developing agent as the main component.
• an aminophenol series compound is useful but a p-phenylenediamine series compound is preferably used.
• Typical examples of the color developing agent are 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-3-amino-N-ethyl-N--hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-fl-methoxyethylaniline, and the sulfates, hydrochlorides, or p-toluenesulfonates of them.
• 3-methyl-4-amin-N-ethyl-N-,e-hydroxyethylaniline sulfate is particularly preferred.
• the aforesaid compounds can be used as a mixture thereof according to the purpose.
• the color developer generally contains a pH buffer agent such as a carbonate, a borate, or a phosphate of an alkali metal and a development inhibitor or an antifoggant such as a chloride, a bromide, an iodide, a benzimidazole, a benzothiazole, or a mercapto compound.
• a pH buffer agent such as a carbonate, a borate, or a phosphate of an alkali metal
• a development inhibitor or an antifoggant such as a chloride, a bromide, an iodide, a benzimidazole, a benzothiazole, or a mercapto compound.
• the color developer can further contain various kinds of preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines (such as N,N-biscarboxymethylhydrazine), phyenylsemicarbazides, triethanolamine, catecholsulfonic acids, etc.; organic solvents such as ethylene glycol, diethylene glycol, etc.; development accelerators such as benzyl alcohol, polyethyleneglycol, quaternary ammonium salts, amines, etc.; auxiliary developing agents such as 1-phenyl-3-pyrazolidone, etc.; dye-forming couplers; competing couplers; viscosity imparting agents; chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, etc., for example, ethylenediaminetetraacetic nitrilotriacetic acid, diethylenetriaminepentaacetic
• black-and-white developing agents such as dihydroxybenes (such as hydroquinone, etc.), 3-pyrazolidones (such as 1-phenyl-3-pyrazolidone, etc.), or aminophenols (such as N-methyl-p-aminophenol, etc.) can be used singly or as a combination thereof.
• the pH of these color developer and black-and-white developer is generally from 9 to 12.
• the replenishing amount for these developers depends upon the kind of the color photographic material being processed but is generally less than about 3 liters per one square meter of the color photographic material. The amount thereof can be reduced below 500 ml by reducing the bromide ion concentration in the replenisher. In the case of reducing the replenishing amount, it is preferred to prevent the occurrence of the evaporation and the air oxidation of the liquid by reducing the contact area of the processing bath with air.
• the contact area of the photographic processing liquid in a processing bath with air can be referred to as the opening ratio defined as follows.
• Opening ratio A (cm 2 )/B (cm 3 )
• the aforesaid opening ratio is preferably less than 0.1, and more preferably from 0.001 to 0.05.
• a method of reducing the opening ratio there are a method of forming a cover such as a floating lid on the surface of the photographic processing liquid in the processing bath, a method of using a mobile lid described in JP-A-1-82033, and a slit development processing method described in JP-A-63-216050.
• the reduction of the opening ratio can be preferably applied not only to both the color development and black-and-white development but also to subsequent many steps such as the steps of bleach, bleach-fix (blix), fix, wash, stabilization, etc.
• the replenishing amount can be reduced by using a means of restraining the accumulation of bromide ions in the developers.
• the time for the color development process is usually in the range of from 2 to 5 minutes but the processing time can be further shortened by employing a high temperature and high pH and using a color developing agent at a high concentration.
• the photographic emulsion layers are usually bleached after color development.
• the bleach process may be carried out simultaneously with a fix process (blix process) or may be carried out separately from a fix process.
• a process of applying a blix process after bleach process may be employed.
• it can be optionally practiced according to the purpose to practice the blix process using two baths, to practice a fix process before a blix process, or practice a bleach process after a blix process.
• bleaching agent for example, compounds of polyvalent metals such as iron(III), etc., peracids, quinones, nitro compounds, etc.
• Typical examples of the bleaching agent are organic complex salts of iron (III), e.g., the complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminipropanetetraacetic acid, glycol ether diaminetetraacetic acid, etc., or the complex salts of citric acid, tartaric acid, malic acid, etc., can be used.
• aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminipropanetetraace
• aminopolycarboxylic acid iron(III) complex salts as ethylenediaminetetraacetic acid iron(III) complex salt and 1,3-diaminopropanetetraacetic acid iron(III) complex salt are preferably used form the view points of quick processing and the prevention of environmental pollution. Furthermore, the aminopolycarboxylic acid iron(III) complex salt is particularly useful in both a bleach solution and a blix solution.
• the pH of the bleach solution or blix solution using such an aminopolycarboxylic acid iron(III) complex salt is usually from 4.0 to 8 but a lower pH may be employed for quickening the processing.
• the blix solution, and a prebath thereof can be used a bleach accelerator if necessary.
• the useful bleach accelerator are compounds having a mercapto group or a disulfide group described in U.S. Patent 3,893,858, 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-53-104232, JP-A-53-124424, JP-A-53-141623, and JP-A-53-28426, and Research Disclosure, No.
• Patent 3,706,561 iodides described in West German Patent 1,127,715 and JP-A-58-16235; polyoxyethylene compounds described in West German Patent 966,410 and 2,748,430; polyamine compounds described described in JP-B-45-8836, other compounds described in JP-A-49-40943, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506, and JP-A-58-163940; and bromide ions.
• the compounds having a mercapto group or a disulfide group are preferred in the view point of showing a large acceleration effect and the compounds described in U.S. Patent 3,893,858, West German Patent 1,290,812, and JP-A-53-95630 are particularly preferred. Furthermore, the compounds described in U.S. Patent 4,552,834 are preferred.
• the aforesaid bleaching accelerator may be incorporated in the color photographic material.
• the bleach accelerator is particularly effective.
• the bleach solution or the blix solution further contains an organic acid for preventing the occurrence of bleach stain in addition of the aforesaid compounds.
• a particularly preferred organic acid is a compound having an acid association constant (pKa) of from 2 to 5, such as acetic acid, propionic acid, hydroxyacetic acid, etc.
• a fixing agent which is used for a fix solution or a blix solution there are thiosulfates, thiocyanates, thioether series compounds, thioureas, a large amount of iodides, etc., but thiosulfates are generally used and in particular, ammonium thiosulfate is most widely used. Also, a combination of a thiosulfate and a thiocyanate, a thioether series compound, or a thiourea can be preferably used.
• fix solution or the blix solution As a preservative for the fix solution or the blix solution, sulfites, hydrogensulfites, carbonyl-hydrogen- sulfide addition products or the sulfinic compounds described in European Patent 294,769A are preferred. Furthermore, it is preferred that the fix solution or the blix solution contains various kinds of aminopolycarboxylic acids or organic solfonic acids for stabilizing the liquid.
• a compound having pka of from 6.0 to 9.0 preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, etc., in an amount of from 0.1 to 10 mol/liter for adjusting the pH thereof.
• the total time for the desilvering step is preferably as short as possible in the range of not causing poor desilvering.
• the time is preferably from one minute to 3 minutes, and more preferably from one minute to 2 minutes.
• the processing temperature is from 25° C to 500 C, and preferably from 35 ⁇ C to 45°C. In the aforesaid preferred temperature range, the desilvering rate is improved and the occurrence of stains after processing can be effectively prevented.
• stirring is strengthened as strong as possible.
• a practical method of strengthening stirring there are a method of applying jet stream of a processing liquid onto the surface of the emulsion layer of the color photographic material described in JP-A-62-183460, a method of increasing the stirring effect by using the rotation means described in JP-A-62-183461, a method of improving the stirring effect by transferring the color photographic material while contacting the surface of the emulsion layer with a wiper blade formed in a processing liquid to form turbid stream over the surface of the emulsion layer, and a method of increasing the circulating stream amount of the whole processing liquid.
• Such a means of improving stirring is effect in any of the bleach solution, the blix solution, and the fix solution.
• the improvement of stirring increases the rate of supplying a bleaching agent and a fixing agent into the emulsion layers, which results in increasing the desilvering rate. Also, the aforesaid means for improving stirring is more effective in the case of using a bleach accelerator and can greatly increase the bleach accelerating effect and dissolve the fix hindering action by the bleach accelerator.
• an automatic processor being suitably used for processing the color photographic materials of this invention has a conveying means for light-sensitive materials as described in JP-A-60-191257 JP-A-60-191258 and JP-A-60-191259, such a conveying means can remarkably reduce the amount of processing solution carried over from a bath to the succeeding bath as disclosed in JP-A-60-191257, to thereby inhibit the deterioration of the properties of the processing solution.
• Such as effect is particularly effective for reducing the processing time at each step or for reducing the replenishing rate of the processing solution.
• the thus desilvered silver halide color photographic materials of this invention are subjected to washing and/or stabilization.
• the amount of water being used for washing can be selected in a wide range depending on the characteristics (e.g., the kind of couplers, etc.) and the use of the color photographic material, the temperature of wash water, the number (stage number) of washing tanks, the replenishing system (e.g., countercurrent flow system or co-current flow system), and other various factors. Of these factors, the relation between the number of washing tanks and the amount of water in a multistage countercurrent flow system can be obtained according to the method described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pages 248 to 253 (May, 1955).
• the amount of washing water can be greatly reduced but bacteria would grow due to the increase of the retension time of water in the tanks and floating masses of bacterial would stick to the color photographic materials.
• the method of reducing calcium and magnesium ion concentrations described in JP-A-62-288838 can be used effectively.
• isothiazolone compounds or thiabendazoles described in JP-A-57-8542 chlorine series fungicides such as chlorinated sodium isocyanurate, etc., benzotriazole, and other fungicides described in Hiroshi Horiguchi, Bookin Boobaizai no Kagaku (Chemistry of Fungicides), edited by Eisei Gijutsu Gakkai, published bu Koogyo Kijutsu Kai, 1982, and Bookin Boobai Zai Jitan (Handbood of Bactericides and Fungicides), edited by Nippon Bookin Boobai Gakkai.
• the washing water in the processing of the color photographic materials of this invention has a pH value of from 4 to 9, and preferably from 5 to 8.
• the temperature of washing water and the washing time can be selected in broad ranges depending on the characteristics and the use of the color photographic material but in general they are selected in the ranges of from 15° C to 45° C in temperature and from 10 minutes to 20 seconds in washing time, and preferably from 25 C to 40 C in temperature and from 5 minutes to 30 seconds in washing time.
• the color photographic material of this invention may be directly processed with a stabilizer in place of the aforesaid washing step.
• a stabilizer for such a stabilization, any of the known techniques described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used.
• a stabilization process is further applied after applying the aforesaid washing step.
• a stabilizing bath containing a dye stabilizer and a surface active agent is used as a final bath for color photographic materials for in camera use.
• the dye stabilizer are aldehydes such as formalin, glutaraldehyde, etc., N-methylol compounds, hexamethylenetetramine, and aldehyde-sulfurous acid addition products.
• the stabilizing bath may also contain various chelating agents or bactericides.
• the overflow accompanying the replenishment of wash water and/or the stabilizing solution can be reused in other steps such as desilvering steps, etc.
• the silver halide color photographic material of this invention may contain a color developing agent for simplifying and quickening processing.
• a color developing agent is preferably used in the form of a precursor.
• examples of such a precursor are indoaniline compounds described in U.S. Patent 3,342,597, Schiff's base type compounds described in U.S. Patent 3,342,599, Research Dusclosure, No. 14850 and ibid., no. 15159, aldol compounds described in ibid., No. 13924, metal complexes described in U.S. Patent 3,719,492, and urethane compounds described in JP-A-53-135628.
• the silver halide color photographic materials of this invention may contain, if necessary, various 1-phenylpyrazolidaones for the purpose of accelerating color development. Typical examples of such compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.
• the various processing solutions are used at temperature of from 10° C to 50° C.
• the standard temperature range is normally from 33°C to 38°C.
• a higher temperature may be employed for accelerating processing to reduce the processing time.
• a lower temperature may be employed for improving the image quality and stabilizing the processing solutions.
• the silver halide color photographic material of this invention can be also applied to a heat-developable light-sensitive materials described in U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056, and European Patent 210,660A2.
• a multilayer color photographic material having the layers of the compositions shown below on an undercoated cellulose triacetate film support was prepared as Sample 101.
• the numerals are the coated amounts shown by a g/m 2 unit as converted silver amount for a silver halide emulsion and colloid silver, by a g/m 2 unit for couplers, aditives, and gelatin, and. a mol number per mol of silver halide in the same layer for a sensitizing dye.
• the sample contained B - 4,B - 5, W - 2, W - 3, F - 1, F - 2, F - 3, F - 4, F - 5, F - 6, F - 7, F - 8, F - 9, F - 10, F - 11, F - 12, F - 13, an iron salt, a lead salt, a gold salt, a platinum salt, an iridium salt, and a rhodium salt.
• the compounds used for the sample are as follows.
• Comparison Compound 3 (the coupler described in JP-A-61-28947):
• Comparison Compound 4 (the coupler described in JP-A-62-81638):
• the sample was processed by the steps shown below using an automatic processore (until the replenished amount of the processing solution became thrice the volume oft he mother liquid tank).
• compositions of the processing solutions used for the aforesaid steps are shown below.
• City water was passed through a mixed bed system column packed with an H-type strong acid cation exchange resin (Amberlite IR-120B, trade name, made by Rohm and Haas Co.) and an OH-type anion exchange resin (Amberlite IR-400, trade name, made by the same company) to reduce the calcium and magnesium ion concentrations below 3 mg/liter and then 20 mg/liter of sodium dichloroisocyanurate and 0.1 g g/liter of sodium sulfate were added to the water.
• the pH of the wash water was in the range of from 6.5 to 7.5.
• a multilayer color photographic material having layers of the compositions shown below on an undercoated triacetyl cellulose film support was prepared as Sample 201.
• the numerals shown below were the coating amount shown by a g/m 2 unit as silver converted for a silver halide emulsion and colloidal silver, the coating amount shown by a g/m 2 unit for couplers, additives, and gelatin, and the coating amount shown by mol number per mol of silver halide in the same layer for sensitizing dyes.
• the marks showing additive are as follows.
• UV Ultraviolet absorbent
• Solv High-boiling organic solvent
• ExF Dye
• ExS Sensitizing dye
• ExC Cyan coupler
• ExM Magenta coupler
• ExY yellow coupler
• Cpd Additive.
• 1,2-benzisothiazolon-3-one in a mean amount of 200 ppm to gelatin
• n-butyl-p-hydroxy benzoate in a mean amount of about 1,000 ppm to gelatin
• 2-phenoxy ethanol in a mean amount of about 1,000 ppm to gelatin
• 2-phenoxy ethanol in a mean amount of about 10,000 ppm to gelatin
• the sample contained B - 4, B - 5, F - 1, F - 2, F - 3, F - 4, F - 5, F - 6, F - 7, F - 8, F - 9, F - 10, F - 11, F - 12, F - 13, and also an iron salt, a lead salt, a gold salt, a platinum salt, an iridium salt, and a rhodium salt.
• the compounds used for the sample are as follows.
• Comparison Compound 5 (the coupler described in U.S. Patent 4,248,962):
• Comparison Compound 7 (the coupler described in JP-A-62-86361):
• compositions of the processing solutions are shown below.

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

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• 1990
  • 1990-11-28 JP JP32621090A patent/JPH04261529A/ja active Pending
• 1991
  • 1991-01-17 EP EP19910100511 patent/EP0438148A3/en not_active Withdrawn

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