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

Definitions

• This invention concerns silver halide color photographic materials, and more particularly silver halide color photographic materials which are improved in respect of color staining and color fogging.
• the above mentioned developing agent may undesirably be oxidized by the oxygen in the air and it is well known that the oxidized form of the developing agent reacts with the color couplers in the unexposed parts of the material or in the parts which have received a low level of exposure to form a dye so that color fogging occurs.
• hydroquinone based compounds has been suggested as a means of preventing the occurrence of undesirable color fogging and color staining.
• mono-n-alkylhydroquinones are disclosed in U.S. Patents 2,360,290, 2,419,613, 2,403,721 and 3,960,570, etc.
• mono-(branched alkyl)hydroquinones are disclosed in U.S. Patents 3,700,453 and 3,960,570
• dialkyl substituted hydroquinones are disclosed in U.S. Patents 2,728,659, 2,732,300, 3,243,294 and 3,700,453, British Patents 752,146, 1,571,445, and 2,005,040
• arylhydroquinones have been disclosed in U.S. Patent 2,418,613.
• hydroquinones substituted with sulfonamido groups are disclosed in U.S. Patent 4,584,264 but these compounds still do not have the ability to prevent the occurrence of color staining satisfactorily.
• hydroquinones which have electron attractive groups for example, hydroquinones which have been substituted with carbamoyl groups, are disclosed in Japanese Patent Application (OPI) No. 22237/82 but these compounds are readily oxidized during the manufacture and storage of the sensitive material and there are problems with changes in photographic performance and with the marked coloration of the oxidized forms.
• pyrogallol derivatives are suggested as anti-color staining agents in U. S. Patent 4.474,874. These have a marked inhibiting effect on color staining but they diffuse into layers to which they have not been added during the manufacture and storage of the sensitive material and this is disadvantageous in that it causes changes to occur the photographic performance of the other layers.
• a first object of the invention is to provide photosensitive materials which give rise to little color staining and color fogging.
• a second object of the invention is to provide photosensitive materials which contain anti-color staining agents which are not liable to form colored products during storage or development.
• a third object of the invention is to provide photosensitive materials which have excellent color reproduction properties and which have a photographic performance which is stable over long period of time with no change in the anti-color staining and anti-color fogging during manufacture and/or' storage.
• a fourth object of the invention is to provide photosensitive materials which have thin emulsion layers and intermediate layers.
• the distinguishing features of the compounds of this invention which are represented by the general formula (A) are that in the state in which the RED group is bonded to the Cp residual group, there is no reduction capacity or only a very weak reduction capacity, and that the ability of the RED group to reduce the oxidized form of the developing agent is initiated by its elimination from the Cp residual group.
• a first molecule of the oxidized form of the developing agent is consumed for releasing the RED group from the Cp residual group and a second molecule is consumed by the reduction due to the RED group and so more of the oxidized form of the developing agent is consumed by one molecule of these compounds than is the case with the compounds which reduce the oxidized form of the developer which have been used in the past (for example the compounds disclosed in the prior patents mentioned above).
• the capacity of the compound of this invention is not diminished in the initial development process and it is still able to realize its function during the color development process.
• Cp may be any group capable of releasing the RED-Ballast group in a coupling reaction with the oxidized form of a developing agent.
• Cp groups are represented by the general formulae (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7) or (Cp-8) which are shown below.
• R 54 , R ss , R 56 , R 57 , R 58 , R 59 , R 60 , R 61, and R 62 which may be the same or different, preferably have not more than a total of 15 carbon atoms.
• at least one of R s , and R 52 represents a linking group with the Sol group or the Sol group itself.
• R 41 represents an aliphatic group, aromatic group or heterocyclic group
• R 42 represents an aromatic group or a heterocyclic group
• R 43 , R 44 and R 45 represent hydrogen atoms, aliphatic groups, aromatic groups or heterocyclic groups.
• R 51 has the same significance as R 41
• R 52 and R 53 both have the same significance as R 42
• R 54 represents a group which has the same significance as R 41 , an group, an group, an group, an R 41 S- group, an R 43 0- group, an group, an R 43 OOC-group, an group or an N ⁇ C-group.
• R ss represents a group which has the same significance as R 41 .
• R 56 and R 57 each represents groups which have the same significance as the R 43 group, R 41 S-groups, R 43 O-groups, groups, groups.
• R 58 represents a group which has the same significance as R 41 .
• R 59 is a group which has the same significance as R 41 , an group, an group, an group, an group, an group, an R 41 0-group, an R 41 S-group, a halogen atom or an group.
• p is a number of value 0 to 3.
• the plurality of R 59 groups may be the same or different substituent groups.
• the R 59 groups may be divalent groups which are joined to form a ring structure. Examples of divalent groups for the formation of ring structures are indicated below. group, group or a group.
• R 60 represents a group which has the same significance as R 41 .
• R 61 represents a group which has the same significance as R 41
• R 62 represents a group which has the same significance as R 41 , an R 41 CONH-group, and R 41 OCONH-group, an R 41 SO 2 NH- group, an an group, an R 43 0-group, an R 41 S-group, a halogen atom or an group.
• h represents an integer of value 0 to 4. In cases where there is a plurality of R 62 groups these groups may be the same or different.
• the aliphatic groups mentioned above are saturated or unsaturated, chain or ring like, linear chain or branched chain, substituted or unsubstituted aliphatic groups which have from 1 to 20, and preferably from 1 to 10, carbon atoms.
• Typical examples are a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, a tert-butyl group, an iso-butyl group, a tert-amyl group, a hexyl group, a cyclohexyl group, a 2-ethylhexyl group, an octyl group, a 1,1,3,3-tetramethylbutyl group, and a decyl group.
• the aromatic groups have from 6 to 10 carbon atoms and are preferably substituted or unsubstituted phenyl groups.
• the heterocyclic groups are preferably 3-to 8-membered substituted or unsubstituted heterocyclic groups which have atoms selected from among nitrogen, oxygen and sulfur atoms as the hetero atoms and which may have from 1 to 12, and preferably from 1 to 8, carbon atoms.
• heterocyclic groups include a 2-pyridyl group, a 4-pyridyl group, a 2-thienyl group, a 2-furyl group, a 2-imidazolyl group, a pyrazinyl group, a 2-pyrimidinyl group, a 1-imidazolyl group, a 1-indolyl group, a phthalimido group, a 1.3,4-thiadiazol-2-yl group, a benzoxazol-2-yl group, a 2-quinolyl group, a 2,4-dioxo-1,3-imidazolidin-5-yl group, a 2,4-dioxo-1.3-imidazolidin-3-yl group, a succinimido group, a 1,2,4-triazol-2-yl group and a 1-pyrazolyl group.
• Typical substituents in cases where the aforementioned aliphatic groups, aromatic groups and heterocyclic groups have substituents include halogen atoms, R 47 O-group, R 43 S-group, groups, groups, groups, R 46 SO 2 -groups, R 47 OCO-groups, groups, group, groups which have the same significance as R 46 , groups, R 46 COO-groups, R 47 OSO 2 -groups, cyano groups and nitro groups.
• R 46 represents an aliphatic group, an aromatic group or a heterocyclic group
• R 47 , R 48 and R 49 each represents aliphatic groups, aromatic groups, heterocyclic groups or hydrogen atoms.
• the significance of the terms aliphatic group, aromatic group and heterocyclic group as used here is the same as that defined above.
• R s is preferably an aliphatic group or an aromatic group.
• R 52 , R 53 and R ss are preferably aromatic groups.
• R 54 is preferably an R 41 CONH-group or an group.
• R 56 and R 57 are preferably aliphatic groups or aromatic groups, R 41 O-groups or R 41 S-groups.
• R 58 is preferably an aliphatic group or an aromatic group.
• R 59 in general formula (Cp-6) is preferably a chlorine atom, an aliphatic group or an 41 CONH-group. Moreover, p preferably is an integer of from 0 to 2.
• R 60 is preferably an aromatic group.
• R 59 in general formula (Cp-7) is preferably an R 41 CONH-group.
• p in general formula (Cp-7) is preferably from 0 to 2.
• R. is preferably an aliphatic group or an aromatic group.
• the value of h is preferably 0 or 1.
• R. 2 is preferably an R 41 OCONH-group, an R 41 CONH-group or an R 41 SO 2 NH-group and the preferred substitution position of these groups is the 5- position of the naphthol ring.
• R s may be a tert-butyl group, a 4-methoxyphenyl group, a 2-furyl group, a phenyl group, a methyl group, a 2-chlorophenyl group or an acetoamidophenyl group.
• R 52 and R 53 may be 2-chloro-5-methoxycarbonylphenyl groups, 2-chloro-5-ethoxycarbonylphenyl groups, 2-chloroisopropoxycarbonylphenyl groups, 2-chloroacetoamidophenyl groups, 2-chloropropionamidophenyl groups, 2-methoxyphenyl groups, 2-methoxy-5-methoxycarbonylphenyl groups, 2-methoxy-5-ethoxycarbonylphenyl groups, 2-pyridyl groups, phenyl groups, 2-chloro-5-methanesulfonamido groups, 2,4-dichlorophenyl groups, 2-chloro-5-methoxycar- bonylethoxycarbonylphenyl groups, 2-chlorophenyl groups, or 2-butyloxyphenyl groups.
• R 14 may be a 3-acetoamidobenzamido group, a 5-phenoxyacetamidoanilino group, a 5-phenoxyacetamidobenzamido group, a 2-chloro-5-methylsuccinimidoanilino group, a 2,2-dimethylpropanimido group, a butanamido group, a pyrrolidino group, or an N,N-dimethylamino group.
• R ss may be a 2,4,6-trichlorophenyl group, a 2-chlorophenyl group, a 2,5-dichlorophenyl group, a 2,3-dichlorophenyl group, a 2,6-dichloro-4-methoxyphenyl group, or a 2,6-dichloro-4-methanesulfonylphenyl group.
• R 56 may be a methyl group, an ethyl group, an isopropyl group, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a 3-phenylureido group, a 3-meth ylureido group, a 2-phenoxyethoxy group, a 2-methoxyphenoxy group, or 2,4-dimethoxyphenoxy.group.
• R 57 may be a 3-phenoxypropyl group, a 3-(2-methoxyethoxyphenyl)propyl group, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a methyl group, an ethyl group, a propyl group, an iso-propyl group, a tert-butyl group, a 1-methyl-2-(2-ethoxy-5-methylphenylsulfonamido)ethyl group, a 1-methyl-2-(2-methoxyethoxyphenylsulfonamido)ethyl group, a 1,1-dimethyl-2-phenylsulfonamidoethyl group, a 3-methanesulfonamidophenyl group, a 3,5-dichlorophenyl group, a 3-nitrophenyl group, an ethylthio group or a phenylthio
• R s may be a 2-chlorophenyl group, a pentafluorophenyl group, a pentafluoropropyl group, a butyl group, a propyl group, an ethyl group, a methyl group or a furyl group.
• R 59 may be a chlorine atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, a butyl group, an iso-propyl group or a 2-phenoxyacetamido group.
• R 60 may be a 4-cyanophenyl group, a 2-cyanophenyl group, a 4-methanesulfonylphenyl group, a 4-ethanesulfonylphenyl group, a 4-ethoxycarbonylphenyl group, a 4-N,N-diethylsulfamoylphenyl group, a 3,4-dichlorophenyl group, or a 3-methoxycarbonylphenyl group.
• R. may be a butyl group, a 3-phenoxypropyl group, a 3-phenoxybutyl group, a 3-ethoxypropyl group, a 3-methoxy propyl group, a 2-methoxyphenyl group, a tert-butyl group, a 2,5-dimethoxyphenyl group, or a 2,5-dichlorophenyl group.
• R 62 may be an isobutyloxycarbonylamino group, an ethoxycarbonylamino group, a phenylsulfonylamino group, a methanesulfonamido group, a butanesulfonamido group, a 4-methylbenzenesulfonamido group, a benzamido group, a trifluoroacetamido group, a 3-phenylureido group, a butoxycarbonylamino group or an acetamido group.
• Sol group represents an alkali solubilizing group.
• Preferable alkali solubilizing group includes a hydroxy group, a carboxylic acid group or salts thereof, a sulfinic acid group or salts thereof, a sulfonic acid group or salts thereof, an amino group, a phosphinic acid group, a phosphonic acid group or salts thereof, etc.
• Sol group represents a salt, this may be, for example, a sodium salt, a potassium salt or an ammonium salt.
• Most preferable Sol group is a carboxylic acid group.
• R s , to R 62 each represents a linking group with a Sol group
• R 5 , to R 62 each represents a group wherein one or two hydrogen atoms in the preferable group represented by R 51 to R 62 link to the above described water solubilizing group.
• Representative groups represented by R 51 to R 62 are illustrated below.
• R s may be a 3-carboxyphenyl group, a 2-hydroxyphen yl group, a 4-hydroxyphenyl group, a 3,5-dicarboxyphenyl group, a 2-hydroxy-2-methylbutyl group, a 3-carboxypropyl group or a 2-hydroxyethyl group.
• R 52 and R 53 each may be a 2-chloro-4-hydroxyphenyl group, a 2-chloro-5-carboxyphenyl group, a 3,5-dicarboxyphenyl group, a 4-carboxyphenyl group, a 4-sulfophenyl group or a 3-(3-carboxy)propioneamido group.
• R 54 may be a 3-carboxypropioneamido group, a hydroxymethyl group, a carboxymethyl group, a carboxyethyl group or a sulfomethyl group.
• R ss may be a 4-(3-carboxy)propioneamidophenyl group, a 4-hydroxyphenyl group, a 3-carboxyphenyl group, a 3,5-dicarboxyphenyl group or a 2-hydroxyethyl group.
• R 56 may be a 2-hydroxyethyloxy group; a 2-carboxyethyloxy group, a carboxymethyloxy group, a 2-hydroxyphenoxy group, a 4-hydroxyphenoxy group or a 2,4-dihydroxyphenoxy group.
• R 57 may be a 2-carbamoylethyl group, a 1-methyl-2-carbamoylethyl group, a 2-sulfamoylethyl group, a 1-methylsulfoamoylethyl group, a 1-methyl-2-carboxyethyl group, a 2-(3-carboxypropioneamido)ethyl group, a carboxymethylthio group, a 3-carboxyphenyl gorup, a 3,5-dicarboxyphenyl group or a 4-hydroxyphenyl group.
• R 58 may be a 4-carboxyphenyl group, a 3-carboxyphenyl group, a 4-sulfophenyl group, a 2-carboxyethyl group, a 3,5-dicarboxyphenyl group, a 2,5-dihydroxyphenyl group, a 3-(3-carboxypropioneamido)-phenyl group, a carboxymethyl group or a 3-hydroxypropioneamido group.
• R 59 may be a 3-carboxypropioneamido group, a carboxy group, a hydroxy group, a sulfo group, a 2-carboxyethyloxy group, a carboxymethylthio group or a 3-hydroxypropioneamido group.
• R 60 and R., each may be the same group as R 58 .
• R 62 may be the same group as R 59 , a carboxymethoxycarbonylamino group, a hydroxymethoxycar- bonylamino group or a carboxymethoxysulfamoyl group.
• LV represents the (Time)p-RED-Ballast group in the general formula (A).
• RED-Ballast group represents a group which is releasable from Cp group and is capable of reducing the oxidized form of the developing agent.
• the preferred RED-Ballast groups in general formula (A) can be represented by the general formulae (B), (C) and (D) below.
• the arrow indicates the linking position with the Cp group and W represents an oxygen atom or a sulfur atom.
• Z represents an -OH group, -OCOR 1 group, -OSOR 1 group, -OSO 2 R 1 group, -NHR 1 group, -NR 2 SOR 1 group and/or an -NR 2 SO 2 R 1 group located in positions ortho and/or para to the linking group W.
• R 1 represents an aliphatic group, an aromatic group or a heterocyclic group
• R 2 represents a hydrogen atom or an aliphatic group and t is an integer of value from 1 to 3.
• Y represents a substituent on the benzene ring as defined below and m is an integer of value from 0 to 3.
• Ballast represents a group which is fast to diffusion and n is an integer of value 1 or 2. However, the sum total of t, m and n is not greater than 5.
• X represents an electron attractive group, such as acyl groups e.g., an acetyl group, a benzoyl group, etc., alkylsulfonyl groups, e.g., a methylsulfonyl group, -, etc., arylsulfonyl group, e.g., a p-toluenesulfonyl group, a p-bromobenzenesulfonyl group, etc.
• acyl groups e.g., an acetyl group, a benzoyl group, etc.
• alkylsulfonyl groups e.g., a methylsulfonyl group, -, etc.
• arylsulfonyl group e.g., a p-toluenesulfonyl group, a p-bromobenzenesulfonyl group, etc.
• the groups represented by Z are substitued in a position ortho and/or para to the nitrogen atom and moreover Z, R l , R 2 , Y, the Ballast group and, m and n don the same significane as in general formula (B).
• the timing group which is represented by (Time)p is a divalent or trivalent organic group which bonds the -RED-Ballast part to the coupling part of Cp. These two parts are bonded together directly when p is zero.
• the mechanism by which the -RED-Ballast group is released when the (Time)p group is present can be, for example, that which is seen with a photographically useful group (referred to below as a PUG) releasing timing type coupler.
• This may involve, for example, the methods in which a PUG is released by means of a post elimination intramolecular nucleophilic substitution reaction as disclosed in U.S. Patent 4,248,962, the methods in which a PUG is released by means of a post elimination electron transfer along a conjugated system as disclosed in U.S. Patent 4,409,323 and Japanese Patent Application (OPI) Nos. 154234/82 (Research Disclosure No. 21228) and 188035/82, the methods in which a PUG is released as a result of a post elimination intramolecular nucleophilic substitution reaction occurring by means of a nucleophilic group which is newly formed by an electron transfer along a conjugated system as disclosed in Japanese Patent Application (OPI) Nos. 56837/82 and 209740/83, or the methods in which a PUG is released by the post elimination cleavage of a hemiacetal as disclosed in Japanese Patent Application Nos. 75475/84 and 89719/84.
• the Ballast group is preferably an organic group having 8 or more of carbon atoms and more preferably 16 or more of carbon atoms.
• the compounds of general formula (A) of this invention may form dimers, trimers or polymers at the Ballast position.
• the aliphatic group, aromatic group and heterocyclic group substituent groups and Y and the substituent groups in the general formulae (A) to (D) are halogen atoms, hydroxyl groups, nitro groups, cyano groups, aliphatic groups, aromatic groups, heterocyclic groups, aliphatic oxy groups, aromatic oxy groups, aliphatic thio groups, aromatic thio groups, unsubstituted or substituted amino groups, carbonyl groups, sulfonyl groups, sulfoxide groups, aliphatic oxycarbonyl groups, aromatic oxycarbonyl groups, aliphatic oxysulfonyl groups, aromatic oxysulfonyl groups, carbamoyl groups, sulfamoyl groups, acyloxy groups, acylamino groups, sulfonamido groups, ureido groups, sulfamoylamino groups, aliphatic oxycar- bonylamino groups, etc.
• the compounds of this invention can be included in the layers of sensitive material, for example, in the photosensitive emulsion layers (blue sensitive layers, green sensitive layers and red sensitive layers) or in the layers adjacent to these layers (for example, in the intermediate layers which are adjacent to different color sensitive emulsion layers and intermediate layers between color sensitive emulsion layers which are essentially the same), the protective layers and anti-halation agents containing layers, etc. but they are preferably included in the intermediate layers between emulsion layers which have different color sensitivities.
• the compounds of this invention may be used conjointly with conventional anti-color mixing agents such as the hydroquinones, catechols, gallic acids, etc.
• the amount added is from 1 x 10 -7 to 1 x 10 mol per square meter, preferably from 10 to 3 X 10 mol per square meter and most desirably from 1 x 10 -5 to 1 ⁇ 10 -3 mol per square meter.
• the amount is from 1 ⁇ 10 -4 to 1 mol, preferably from 3 ⁇ 10 -4 to 3 ⁇ 10 -1 mol, and most desirably from 1 x 10 to 1 ⁇ 10 -1 mol, per mol of silver contained in the layer.
• This compound is synthesized by the route indicated below.
• the silver halide which is contained in the photographic emulsion layers of the photographic materials in which the invention is employed is preferably a silver iodobromide, silver iodochloride or a silver iodochlorobromide which contains less than about 30 mol% of silver iodide.
• Silver iodobromides which contain from about 2 mol% to about 25 mol% of silver iodide are especially desirable.
• the silver halide grains in the photographic emulsion may have a regular crystalline form, such as a cubic, octahedral or tetradecahedral form, an irregular crystalline form such as a spherical or plate-like form, they may have crystal defects such as twinned crystal planes, etc., or they may have a complex form incorporating these forms.
• the silver halide grain size may be such as to include fine grains ' of less than about 0.2 microns and large grains of which the projected area diameter reaches about 10 microns and they may be in the form of a polydisperse emulsion or a mono-disperse emulsion.
• the silver halide photographic emulsions which can be used in the invention can be prepared using the methods disclosed, for example, in Research Disclosure (RD) No. 17643 (December, 1978), pages 22-23, "I. Emulsion Prepara tion” (Emulsions preparation and types) and RD No. 18716 (November, 1979), page 648, and the methods described by P. Glafkides in Chimie et Physique Photographique, Paul Montel, 1967, by G.F. Duffin in Photographic Emulsion Chemis , Focal Press, 1966, and by Zelikman et al. in Making and Coating Photographic Emulsion, Focal Press, 1964, etc.
• plate-like grains such that the aspect ratio is greater than about 5 can be used in the invention.
• Plate-like grains can be prepared easily using the method disclosed by Gutoff on pages 248-257 of volume 14 of Photographic Science and Engineering (1970), and the methods disclosed in U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520 and in British Patent 2,112,157, etc.
• the crystal structure may be uniform or the inner and outer parts may have a different halogen composition to provide a layered type of structure.
• the silver halides of different compositions may be joined, for example, with an epitaxial junction, or they may be joined with a compound other than silver halide such as silver thiocyanate or lead oxide.
• Silver halide emulsions which have been physically ripened, chemically ripened and spectrally sensitized.are normally used.
• the additives used in processes of this type are disclosed in Research Disclosure Nos. 17643 and 18716 and the locations of these materials in the said publications are summarized in the table below.
• the preferred yellow couplers are those disclosed, for example, in U.S. Patents 3,933,501, 4,022,620, 4,326,024 and 4,401,752, Japanese Patent Publication No. 10739/83 and British Patents 1,425,020 and 1,476,760, etc.
• 5-Pyrazolone and pyrazoloazole based compounds are preferred for the magenta couplers and those 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), Japanese Patent Application (OPI) No. 33552'85, Research Disclosure No. 24230 (June, 1984), Japanese Patent Application (OPI) No. 43659/85 and U.S. Patents 4.500.630 and 4,540,654, etc. are especially desirable.
• Phenol 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, 4,327,173, 3,446,622, 4,333,999. 4,451,559 and 4,427,767, West German Patent Laid Open No. 3,329,729. European Patents 121,365A and 161,626A, etc. are preferred.
• the colored couplers for correcting the unrequired absorptions of the colored dyes disclosed in section VII-G of Research Disclosure No. 17643, U.S. Patent 4,163,670, Japanese Patent Publication No. 39413/82, U.S. Patents 4,004,929 and 4,138,258 and British Patent 1,146,368 are preferred.
• Couplers disclosed in U.S. Patent 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Laid Open) No. 3,234,533 are preferred as couplers of which the colored dye has suitable diffusion properties.
• Couplers which release residual groups which are useful photographically on coupling are preferred in this invention.
• the DIR couplers which release development inhibitors disclosed in the patents disclosed in sections VII-F of the aforementioned Research Disclosure (RD) No. 17643, Japanese Patent Application (OPI) Nos. 151944/82, 154234/82 and 184248/85 and U.S. Patent 4,248,962 are preferred.
• couplers which can be used in the light sensitive materials of this invention include the competitive couplers disclosed in U.S. Patent 4,130,427, etc., the polyequivalent couplers disclosed in U.S. Patents 4,283,472, 4,338,393 and 4,310,618, etc., the DIR redox compound releasing couplers disclosed in Japanese Patent Application (OPI) No. 185950/85, etc. and the coulers which release a dye of which the color is restored after elimination as disclosed in European Patent 173,302A.
• OPI Japanese Patent Application
• the couplers used in the invention can be introduced into the photosensitive material using the various known methods of dispersion.
• Suitable supports which can be used in the invention are disclosed, for example, on page 28 of the aforementioned Research Disclosure (RD) No. 17643 and in the section from the right hand column of page 647 to the left hand column on page 648 of Research Disclosure (RD) No. 18716.
• Color photographic materials in accordance with this invention can be developed using the normal methods of development as disclosed on pages 28 and 29 of the aforementioned Research Disclosure - (RD) No. 17643 and in the section from the left hand column to the right hand column of page 651 of Research Disclosure (RD) No. 18716.
• a color developer which is used for the development of the color photographic materials of this invention is an alkaline aqueous solution preferably containing an aromatic primary amine color developing agent as the main component.
• an aminophenolic compound may be useful but a p-phenylenediamine series compound is preferably used.
• Typical examples thereof are 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesul fonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline and the sulfates, hydrochlorides, or p-toluenesulfonates of them. They can be used singly or as a mixture thereof.
• the color developer generally contains a pH buffer such as the carbonates, borates, or phosphates of an alkali metal and a development inhibitor or an antifoggant such as bromides, iodides, benzimidazoles, benzothiazoles, and mercapto compounds.
• a pH buffer such as the carbonates, borates, or phosphates of an alkali metal
• a development inhibitor or an antifoggant such as bromides, iodides, benzimidazoles, benzothiazoles, and mercapto compounds.
• the developer may contain various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine-(1,4-diazabicyclo[2,22]octanes, etc.; organic solvents such as ethylene glycol, diethylene glycol, etc.; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salt. amines, etc.; dye forming couplers, competing couplers, fogging agents such as sodium borohydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone.
• preservatives such as hydroxylamine, diethylhydroxylamine, sulfites hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine-(1,4-diazabicyclo[2,22]oc
• tackifiers such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, etc. (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid.
• chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, etc. (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid.
• a black and white development is usually performed before the color development.
• dihydroxybenzenes such as hydroquinone, etc.
• 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, etc.
• aminophenols such as N-methyl-p-aminophenol, etc.
• the pH of the color developer and black and white developer is generally from 9 to 12.
• the amount of the replenishers for these developers depends upon the kind of color photographic material being used but is generally less than 3 liters per square meters 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 amount of replenisher, it is preferred to reduce the contact area of the surface of the processor with air for preventing the evaporation of liquid and occurrence of the air oxidation of liquid. Also, by employing a means for preventing the deposition of bromide ions in the developer, the amount of the replenisher can be reduced.
• the photographic emulsion layers after color development are generally bleached.
• the bleach processing may be performed simultaneously with (bleach-fix or blix processing) or separately from a fix processing. Furthermore, for quickening the processing, blix processing may be performed after bleaching. Moreover, processing of continuous blixing using two tanks, fixing before blixing, or bleaching after blixing may be performed according to the purposes.
• bleaching agent compounds of multivalent metals such as iron (111), cobalt (III), chromium (IV), copper (II), etc., as well as peroxides, quinones, nitro compounds are used.
• Typical bleaching agents are ferricyanides, perchromates, organic complex salts of iron (111) or cobalt (III), such as the complex salts of aminipolycarboxylic acids, such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, etc., or citric acid, tartaric acid, malic acid, etc., persulfates, bromates, permanganates, nitrobenzenes, etc.
• ethylenediaminetetraacetic acid iron (111) complex salts as well as aminopolycarboxylic acid iron (III) complex salts and persulfates are preferred from the viewpoint of quick processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron (III) complex salts are particularly useful for bleach solution and blix solution.
• the pH of the blix solution using the aminopolycarboxylic acid iron (111) complex salt is usually from 5.5 to 8 but the pH may be further lowered for quickening the processing.
• a bleach accelerator can be, if necessary, used.
• Specific examples of such bleach accelerators are compounds having a mercapto group or disulfide group described in U.S. Patent 3,893,858, West German Patents 1,290,812 and 2,059,988, Japanese Patent Application (OPI) Nos. 32736/78, 57..1/78, 37418/78, 72623/78, 95630/78, 95631/78, 10423/78, 124424/78, 141623/78, and 28426/78, Research Disclosure, No. 17129 (July, 1978), etc.; thiazolizine derivatives described in Japanese Patent Application (OPI) No.
• the compounds having a mercapto group or a disulfide group are preferred from the viewpoint of obtaining a high accelerating effect and in particular, the compounds described in U.S. patent 3,893,858, West German Patent 1,290,812, and Japanese Patent Application (OPI) No. 95630/78 are preferred. Furthermore, the compounds described in U.S. Patent 4,552,834 are preferably used in this invention.
• the bleach accelerator may be incorporated in the color photographic materials of this invention. These bleach accelerators are particularly useful in the case of blixing color photographic materials for photographing.
• thiosulfates there are thiosulfates, thiocyanates, thioether series compounds, thioureas, a large amount of iodides but thiosulfate are generally used and in particular, ammonium thiosulfate is most widely used.
• a sulfite, a hydrogensulfite, or a carbonyl hydrogensulfite is preferred.
• the silver halide color photographic material is generally washed and/or stabilized after desilvering.
• the amount of wash water for the wash step can be widely changed according to various conditions such as the characteristics (e.g., the kind of the couplers, etc.) of the color photographic materials, the washing temperature, the number (stage number) of wash tanks, the replenisher system such as a countercurrent system or ordinary current system, and others.
• the relation between the number of wash tanks and the amount of water in the multistage countercurrent system can be determined by the method shown in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, 248-253 (May, 1955).
• the amount of wash water can be greatly reduced but there occurs a problem of drawing bacteria and attaching of floats thus formed on the light-sensitive materials by the increase of retension time.
• the pH of wash water in processing of the color photographic materials of this invention is of from 4 to 9, and preferably from 5 to 8.
• the washing temperature and washing time can be desirably selected according to the characteristics and uses of the light-sensitive materials of this invention but are generally in the ranges of from 15 to 45°C and from 20 seconds to 10 minutes, and preferably from 25 to 40°C and 30 seconds to 5 minutes.
• the color photographic materials of this invention can be directly subjected to a stabilization processing in place of the aforesaid wash process.
• a stabilization processing known methods described in Japanese Patent Application (OPI) Nos. 8543/82, 14834/83, and 220345/85 can be all used.
• the color photographic materials are, as the case may be, further stabilized and as such an example, there are a stabilization bath containing formalin and a surface active agent, which is used as the final bath for color photographic materials for photographing.
• a stabilizing bath can contain a chelating agent and an antifungal agent.
• the overflow liquid obtained with the replenishing of the aforesaid wash and/or stabilization liquid can be reused in a desilvering step and other steps.
• the silver halide color photographic materials of this invention may contain a color developing agent for simplifying and quickening processing.
• a color developing agent for simplifying and quickening processing.
• various precursors for color developing agent are Sciff base type compounds described in U.S. Patent 3,342,599 and Research Disclosure Nos. 14850 and 15159, indoaniline series compounds described in U.S. Patent 3,342,597, also compounds described in Research Disclosure, No. 13924, metal complexes described in U.S. Patent 3,719,492, and urethane compounds described in Japanese Patent Application (OPI) No. 135628/78.
• the silver halide color photographic materials of this invention may further contain various kinds of 1-phenyl-3-pyrazolidones for accelerating color development. Typical compounds are described in Japanese Patent Application (OPI) Nos. 64339/81, 144547/82, and 115438/83.
• Various processing solutions in this invention are used at from 10°C to 50°C.
• the standard processing temperature is from 33°C to 38°C but a higher temperature may be employed for quickening the processing and a lower temperature may be employed for improving the image quality and stability of processing solutions.
• processing using a cobalt intensification or hydrogen peroxide intensification described in West German Patent 2,226,770 and U.S. Patent 3,674,499 may be performed.
• Sample 101 a multi-layer color photographic material consisting of each of the layers of which the compositions are indicated below on an undercoated cellulose triacetate film support was prepared in order to evaluate the effectiveness of the compounds of this invention.
• the amount of the sensitizing dyes used are expressed as the number of mols per mol of silver halide which is present in the same layer.
• Second Layer Fine Silver Bromide Grains (average grain diameter 0.07 ⁇ m) 0.15 g /m 2
• Second Layer Low Speed Red-Sensitive Emulsion Layer
• Silver lodobromide Emulsion (2 mol% silver iodide, average grain size 0.3 ⁇ m) 0.4 g/m 2 as silver
• Coupler C-3 0.06 g/m 2
• Coupler C-4 0.06 g / m 2
• Coupler C-2 0.03 g / m 2
• Silver lodobromide Emulsion (5 mol% silver iodide, average grain size 0.5 ⁇ m) 0.7 gm 2 as silver Sensitizing Dye I 1.0 ⁇ 10 -4
• Coupler C-3 0.24 g/m 2
• Coupler C-4 0.24 g/m 2
• Coupler C-2 0.04 g/m 2
• Coupler C-6 0.05 g/m 2
• Coupler C-7 0.1 g/m 2
• Coupler C-9 0.2 g/m 2
• Coupler C-5 0.03 g/m 2
• Coupler C-1 0.03 g/m 2
• Coupler C-9 0.25 g/m 2
• Coupler C-1 0.03 g/m 2
• Coupler C-10 0.15 g / m 2
• Coupler C-5 0.01 g/m 2
• Coupler C-11 1 0.01 g / m 2
• Coupler C-12 0.03 g / m 2
• Coupler C-13 0.20 g/m 2
• Coupler C-1 0.02 g/m 2
• Coupler C-15 0.02 g/m 2
• Twelfth Layer High Speed Blue-Sensitive Emulsion Layer
• Silver lodobromide Emulsion (10 mol% silver iodide, average grain size 1.5 ⁇ ) 0.5 g/m 2 as silver
• Coupler C-14 0.25 g/m 2
• UV-1 0.1 g/m 2
• a surfactant was added as a coating promotor to each layer as well as the components indicated above.
• the sample prepared in the way outlined above was sample 101.
• Samples 102 to 106 were prepared by replacing the Compound Cpd-A (Compound (9) of U.S. Patent 2.701.197) in the sixth layer of Sample 101 with equimolar amounts of the Comparative Compounds B-1 to B-5, respectively.
• Samples 107 to 111 were prepared by replacing the Compound Cpd-A in the sixth layer of Sample 101 with equimolar amounts of the compounds A-2, A-3, A-7, A-11 and A-26 of this invention.
• Samples 101 to 111 were subjected to a red image exposure and color processed in the way described below. After processing the density of the samples was measured using a red filter and a green filter and the color turbidity, the value obtained by subtracting the magenta fog density from the magenta density at an exposure at which the cyan density measured with a red filter was (fog + 1.5), was as shown in Table 1.
• the development process was carried out as follows.
• compositions of the processing baths used in each process were as follows:
• Sample 201 was prepared by coating photosensitive layers of which the compositions were as indicated below to form a multi-layer structure on a cellulose triacetate film on which an undercoating layer had been established.
• the amount coated is expressed in terms of grams of silver per square meter, in the case of couplers, additives and gelatin the amount coated is expressed in terms of grams per square meter and the amounts of the sensitizing dyes used are expressed in terms of the number of mols per mol of silver halide in the same layer. In the case of solvent the amount coated is expressed in terms of cc/m 2 .
• Twelfth Layer High Speed Blue-Sensitive Emulsion Layer
• Emulsion stabilizer Cpd-3 (0.04 g per square meter) and surfactant Cpd-4 (0.02 g per square meter) were added as coating promotors to each layer as well as the components indicated above.
• SoLv-1 TricresyL phosphate SoLv-2 DibutyL phthalate
• Samples 202 to 206 were prepared by replacing compound Cpd-1 in the fifth layer of Sample 201 with equimolar amountsof the comparative compound B-1 to B-5, respectively.
• Sample 207 was prepared by replacing compound Cpd-1 in the fifth layer of Sample 201 with Cpd-A, which was used as a comparative compound in Sample 101 of Example 1.
• Samples 208 to 212 were prepared by replacing compound Cpd-1 in the fifth layer of Sample 201 with equimolar amounts of the compounds A-1, A-3, A-5, A-7 and A-27 according to this invention, respectively.
• Samples 201 to 210 were subjected to a red image exposure and a color development process as indicated below.
• the density of the processed samples was measured with a red filter and a green filter and the color turbidity, a value obtained by subtracting the magenta fog density from the magenta density at an exposure at which the cyan density measured with the red filter was (fog + 1.5), was as shown in column I in Table 2.
• color development process used here was that described as color development process A below.
• compositions of the processing baths were as follows:
• Town water was treated by passage through a mixed bed type column packed with an H-type strongly acidic cation exchange resin ("Amberlite !R-120B", made by the Rohm and Haas Co.) and an OH-type anion exchange resin ("Amberlite IR-400", made by the same company), the calcium and magnesium ion contents being reduced to less than 3 mg/liter, after which 20 mg/liter of sodium dichloroisocyanurate and 1.5 g/liter of sodium sulfate were added.
• H-type strongly acidic cation exchange resin (“Amberlite !R-120B”, made by the Rohm and Haas Co.)
• an OH-type anion exchange resin (“Amberlite IR-400”, made by the same company
• the pH of this liquid was within the range 6.5 to 7.5.
• Processing was carried out in an automatic developing machine using the method indicated below until the total amount of replenishment of the color developer bath reached 3 times the original bath tank capacity.
• compositions of the processing baths were as follows:
• Town water was treated by passage through a mixed bed type column packed with an H-type strongly acidic cation exchange resin ("Amberlite IR-120B", made by the Rohm and Haas Co.) and an OH-type anion exchange resin ("Amberlite IR-400", made by the same company), the calcium and magnesium ion contents being reduced to less than 3 mg/liter, after which 20 mg/liter of sodium dichloroisocyanurate and 1.5 giliter of sodium sulfate were added.
• H-type strongly acidic cation exchange resin (“Amberlite IR-120B”, made by the Rohm and Haas Co.)
• an OH-type anion exchange resin (“Amberlite IR-400”, made by the same company
• the pH of this liquid was within the range 6.5 to 7.5.
• Photosensitive sheet A was prepared by coating the layers indicated below sequentially on a transparent poly(ethylene terephthalate) film.
• Photosensitive Sheet B and Photosensitive Sheets C and D for comparative purposes were prepared in the same way with the following differences.
• photosensitive sheet A This was the same as photosensitive sheet A except that layers 7 and 8 of photosensitive sheet A were not coated.
• a cover sheet was prepared by coating the layers indicated below sequentially on a transparent polyester support.
• Layer 6 which contained the anti-color staining agents in the Photosensitive Sheets A to C prepared here. was provided in order to prevent reaction between the oxidized form of the developer and the release of the yellow dye when the oxidized form of the developer formed in layer 5, which contains the green sensitive silver halide emulsion, diffuses, passing through the layer 6 towards the layer 7, which contains a yellow dye releasing redox compound which is not connected with the silver halide emulsion layer 5 (this would not result in magenta color turbidity, which is to say that the layer 6 prevents the mixing of yellow with the magenta and prevents any deterioration of the magenta hue).
• the performance of the layer 6 which contains the anti-color staining agent in the photosensitive sheets A, B and C can be assessed by means of the value of Db-Db (Photosensitive Sheet D), which is to say by the color turbidity.
• Photosensitive Sheet A, in which a compound of this invention was used had a much lower color turbidity than the Photosensitive Sheets B and C prepared for comparison, thus it clearly demonstrated between anti-color staining performance.
• a multi-layer color photosensitive material consisting of each of the layers of which the compositions are indicated below on an undercoated cellulose triacetate film support was prepared as Sample 401.
• a gelatin layer (dry film thickness 2 ⁇ ) containing: Black Colloidal Silver 0.25 g/m 2
• a gelatin layer (dry film thickness 1 ⁇ ) containing: Compound Cpd-C 0.05 g/m 2
• a gelatin layer (dry film thickness 1 ⁇ ) containing: Silver bromide emulsion which had been spectrally sensitized with'the sensitizing dyes S-1 and S-2 (average grain size 0.3 ⁇ , Agl content 4 mol%) 0.5 g/m 2 as silver
• Coupler F-1 0.2 g / m 2
• Coupler F-2 0.05 g/m2
• a gelatin layer (dry film thickness 2.5 ⁇ ) containing: Silver bromide emulsion which had been spectrally sensitized with the sensitizing dyes S-1 and S-2 (average grain size 0.6 ⁇ , Agl content 3 mol%) 0.8 g/m 2 as silver
• Coupler F-1 0.55 g/m 2
• Coupler C-2 0.14 g/m 2
• a gelatin layer (dry film thickness 1 containing: Compound Cpd-C 0.1 g/m 2
• a gelatin layer (dry film thickness 1 ⁇ ) containing: Silver iodobromide emulsion containing the sensitized dyes S-3 and S-4 (average grain size 0.3 ⁇ , Agl content 4 mol%) 0.7 g/m 2 as silver Coupler F-3 0.20 g/m 2
• Coupler F-5 0.10 g/m2
• a gelatin layer (dry film thickness 2.5 ⁇ ) containing: Silver iodobromide emulsion containing the sensitized dyes S-3 and S-4 (average grain size 0.6 ⁇ , Agl content 2.5 mol%) 0.7 g/m 2 as silver Coupler F-4 0.10 g / m 2
• Coupler F-5 0.10 g/m 2
• a gelatin layer (dry film thickness 1 ⁇ ) containing: Compound Cpd-C 0.05 g/m 2
• a gelatin layer (dry film thickness 1 ⁇ ) containing: Yellow Colloidal Silver 0.1 g/m 2 Compound Cpd-C 0.02 g/m 2
• a gelatin layer (dry film thickness 1.5 ⁇ ) containing: Silver iodobromide emulsion containing the sensitized dye S-5 (average grain size 0.3 ⁇ , Agl content 2 mol%) 0.6 g/m 2 as silver
• Coupler F-7 0.4 gim 2
• a gelatin layer (dry film thickness 3 ⁇ ) containing: Silver iodobromide emulsion containing the sensitized dye S-6 (average grain size 0.6 ⁇ , Agl content 2 mol%) 1.1 g/m 2 as silver
• Coupler F-6 0.4 g/m2
• Coupler F-8 0.8 g/m 2
• a gelatin layer (dry film thickness 2 ⁇ ) containing: Ultraviolet Absorber U-1 0.02.g/m2
• a gelatin layer (dry film thickness 2.5 ⁇ ) containing: Fine Grained Silver lodobromide Emulsion (of which the surface had been fogged; iodide content 1 mol%, average grain size 0.06 ⁇ ) 0.1 g/m 2 as silver
• a gelatin hardener H-1 (the same as used in Example 1) and a surfactant were added to each layer as well as the above-mentioned components.
• Sample 402 and 403 were prepared using equimolar amounts of the comparative compounds B-2 and B-3 of Example 1 in place of the Cpd-C in the second, fifth and eighth layer of Sample 401.
• Samples 404 to 406 were prepared using equimolar amounts of the compounds A-2, A-3 and A-11, respectively, in place of Cpd-C in the second, fifth and eighth layers of Sample 401.
• the Samples 401 to 406 prepared in the way described above were subjected to a red image exposure using a wedge with which the gray density varied continuously and then to a reversal development of the type outlined below.
• compositions of the processing baths were as follows:
• the maximum color density (Dmax) and the minim color density (Dmin) obtained densitometrically using a red filter were measured for each of the processed samples. Furthermore, the maximum color densities of the blue sensitive layer and the green sensitive layer were each measured using a blue filter and a green filter.
• a multi-layer printing paper with the layer structure shown in Table 5 was formed on a paper support which had been laminated on both sides with polyethylene.
• the coated liquids were prepared in the way indicated below.
• This emulsion was mixed with the aforementioned emulsified dispersion to form a solution which formed the first layer coating liquid with the composition shown in Table 5.
• the coating liquids for the second to the seventh layers were prepared using a similar method to that used for the first layer coating liquid.
• 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardener for each layer.
• the spectral sensitizing dyes indicated below were used for the various layers.
• the compound indicated below was added at the rate of 2.6 X 10 -3 mol per mol of silver halide to the red sensitive emulsion layer.
• 1-(5-methylureidophenyl)-5-mercaptotetrazole was added at the rate of 8.5 x 10 mol, 7.7 ⁇ 10 -4 mol and 2.5 ⁇ 10 -4 mol per mol of silver halide to prepare the blue, green and red sensitive emulsion layers, respectively.
• 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added at the rate of 1.2 X 10 mol and 1.1 ⁇ 10-5 -2 mol per mol of silver halide to the blue and green sensitive emulsion layers, respectively.
• the dyes indicated below were added to the emulsion layers prevent the occurrence of irradiation.
• Samples 502 and 503 were prepared using an equimolar amount of the comparative compound B-2 of Example 1 and the compound Cpd-A of Sample 101 in place of the compound (d) in the second and fourth layers of Sample 501.
• Samples 504 to 506 were prepared using the compounds A-3, A-10 and A-14 of this invention in place of the compound (d) in the second and fourth layers of Sample 501.
• the above mentioned photosensitive materials were processed continuously (in a running test) using a paper processor in accordance with the processing treatment indicated below until the amount of replenisher used was twice the color development tank capacity. Subsequently the above mentioned photosensitive materials were given a red image exposure and developed using the same processing baths.
• compositions of the processing baths were as follows:
• the replenishing system was carried out by a so-called countercurrent replenishing system wherein the replenisher for the 2nd wash was introduced into 2nd wash (2) and the overflow liquid from 2nd wash (2) was introduced into 2nd wash (1).
• composition of each processing solution used in the aforesaid processing step was as follows.
• the pH was adjusted with hydrochloric acid or potassium hydroxide.
• the pH was adjusted with either hydrochloric acid or sodium hydroxide.
• the pH was adjusted with hydrochloric acid or sodium hydroxide.
• the pH was adjusted with hydrochloric acid or potassium hydroxide.
• the pH was adjusted with hydrochloric acid or aqueous ammonia.
• City water was passed through a mixed bed system column packed with a H-type strong cation exchange resin (Amberlite IR-120B), trade name, made by Rhom and Haas Co.) and an OH-type anion exchange resin (Amberlite IR-400 made by Rhom and Haas Co.) to reduce the concentrations of calcium and magnesium less than 3 ml/liter and then 20 mgiliter of sodium dichloroisocyanurate and 1.5 g/liter of sodium sulfate were added thereto.
• the pH of the solution was in the range of from 6.5 to 7.5.
• the maximum color density (Dmax) and the minimum density (Dmin) were measured using a red filter. Also, the maximum color densities of the blue-sensitive layer and the green-sensitive layer of each sample were measured using a blue filter and green filter, respectively. The results were almost same as those shown in Table 4 above.
• a multilayer silver halide photographic material (Sample 601) having the following layers on a paper support having polyethylene coating on both surfaces thereof was prepared.
• the coating compositions for the layers were prepared as follows.
• the coating compositions for layer 2 to layer 7 were also prepared by similar manners as above.
• each layer is shown below.
• the numerals are coated amount (g/m 2 ), wherein the silver halide emulsion is shown by the calculated silver amount.
• the polyethylene coating at the emulsion layer carrying side contained white pigment (TiO 2 ) and a bluish dye.)
• Cpd-13 and Cpd-14 were used as irradiation preventing dyes.
• each layer contained Alkanol XC (made by DuPont), sodium alkylbenzenesulfonate, succinic acid ester, and Magefacx F-120 (made by Dainippon Ink and Chemicals, Inc.) as dispersing agent and coating aid.
• Cpd-15 and Cpd-16 were used as the stabilizers for silver halide.
• the emulsions used are as follows.
• Samples 602 and 603 were prepared.
• composition of the processing solutions were as follows.
• UVTEX-CK trade name, made by Ciba-Geigy

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• 1987
  • 1987-11-20 JP JP29467787A patent/JPS64548A/ja active Pending
• 1988
  • 1988-03-25 EP EP88104867A patent/EP0284099A3/en not_active Withdrawn

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