Silver halide color photographic material

FIELD OF TEE INVENTION
The present invention relates to a silver halide color photographic material, and particularly to a silver halide color photographic material containing a novel yellow color forming coupler (hereinafter referred to as a yellow coupler). The material can provide improved color reproducibility, color image fastness to light and heat, and processing dependency.
BACKGROUND OF TEE INVENTION
Silver halide color photographic materials are subjected to color development after exposure, which allows dye forming couplers to react with oxidation products of aromatic primary amine developing agents and form color images.
In this method, the color images are generally reproduced by the subtractive color process. In this process, couplers for forming yellow, magenta and cyan dyes are used Which are dispersed in silver halide emulsion layers different in color sensitivity. Of these couplers, acylacetanilide-type couplers such as pivaloyl-type yellow couplers, and benzoyl-type yellow couplers and malondianilide-type couplers are widely known as the yellow couplers.
The pivaloyl-type yellow couplers can provide excellent hue and color image fastness, and have been used mainly in color print materials. However, they exhibit the disadvantage of low molecular extinction coefficients and low coupling activities. Also with respect to hue and color image fastness, further developments have been desired to meet recently higher demands.
The benzoyl-type yellow couplers have been used mainly in negative films for shooting, because of their high molecular extinction coefficients and high activities. However, they are broad in their absorption wave forms and provide low fastness of formed dye images, such that further developments have also been desired.
The malondianilide-type yellow couplers are described, for example, in U.S. Patents 4,149,886, 4,095,984 and 4,477,563. They are inferior to the above-described benzoyl-type couplers in hue and image fastness. Therefore, they are only used as couplers of the development inhibitor releasing-type and have limited applications.
Couplers in which the disadvantages of the malondianilide-type couplers have been improved are described in European Patent 447020A1. However, even those couplers have not reached a fully satisfactory level in all of the color forming properties, hue and color image fastness.
There is a strong desire to develop couplers having a satisfactory combination of high molecular extinction coefficient, high color forming properties, excellent hue and the excellent color image fastness.
Various uses of high boiling organic solvents, antifading agents and color forming accelerators have been studied to compensate for the disadvantages of the yellow couplers of the types described above. For example, methods for improving the hue by use of high boiling organic solvents are described in JP-A-63-241547 (the term "JP-A" as used herein means an "unexamined published Japanese patent application") and JP-A-63-256952, and methods for improving color image fastness are described in U.S. Pat. No. 4,745,049, JP-A-64-11262, JP-A-64-17056, JP-A-64-10247, JP-A-64-50048 and JP-A-2-4239. Methods for improving color image fastness by use of antifading agents are described, for example, in JP-A-61-2151, JP-A-61-6652, JP-A-l-196049 and JP-A-1-284853. Further, methods using water-insoluble, organic solvent-soluble polymers to improve the color image fastness are described in JP-A-64-50049.
However, materials or methods which can fully meet increasingly heightened demands have not yet been reached, even by the above-described methods. Further improvements in couplers, or techniques for use thereof, are still strongly desired.
SUMMARY OF TEE INVENTION
Therefore, an object of the present invention is to develop a novel yellow coupler having a combination of a high molecular extinction coefficient, high color forming properties, excellent hue and excellent color image fastness, and to provide a silver halide color photographic material which provides excellent color reproducibility, color image fastness and processing dependency using that coupler.
The above-described object of the present invention can be obtained by the silver halide color photographic materials described below. In a first embodiment there is provided a silver halide color photographic material comprising a yellow color forming silver halide emulsion layer formed on a support, said layer containing at least one yellow color forming coupler represented by the following general formula (I) dispersed by dissolution in a high boiling organic solvent in a weight ratio of the high boiling organic solvent to the yellow color forming coupler of 0.6 or more: ##STR2## wherein X represents an organic residue necessary for forming a nitrogen-containing heterocycle with a nitrogen atom; Y represents an aromatic group or a heterocyclic group; Z represents a group which is eliminatable by reaction of the coupler represented by general formula (I) with an oxidation product of a developing agent; and ##STR3## is hereinafter referred to as A.
In a preferred embodiment, the high boiling organic solvent has a dielectric constant of 6.0 or less.
In an even more preferred embodiment, the high boiling organic solvent is represented by one of the following general formulae (S-1) to (S-5): ##STR4##
In formula (S-1), R.sub.1, R.sub.2 and R.sub.3 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group or an aryloxy group. In formula (S-2), R.sub.4 and R.sub.5 each independently represents an alkyl group, a cycloalkyl group or an aryl group, R.sub.6 represents a halogen atom such as F, Cl, Br or I, an alkyl group, an alkoxy group, an aryloxy group or an alkoxycarbonyl group, and a represents an integer of 0 to 3, with the proviso that when a is 2 or more, a plurality of R.sub.6 s may be the same or different. In formula (S-3), Ar represents an aryl group, b represents an integer of 1 to 6, and R.sub.7 represents a b-valent hydrocarbon group or a hydrocarbon group bonded through an ether linkage to each other. In formula (S-4), R.sub.8 represents an alkyl group or a cycloalkyl group, c represents an integer of 1 to 6, and R.sub.9 represents a c-valent hydrocarbon group or a hydrocarbon group bonded through an ether linkage. In formula (S-5), d represents an integer of 2 to 6, R.sub.10 represents d-valent hydrocarbon group (excluding an aromatic group), and R.sub.11 represents an alkyl group, a cycloalkyl group or an aryl group.
In another embodiment, the yellow color forming silver halide emulsion layer contains a water-insoluble polymer.
In even another embodiment, the weight ratio of the water-insoluble polymer to the yellow coupler in the yellow color forming silver halide emulsion layer is 0.2 or more.
In a further embodiment, at least one cyan color forming silver halide emulsion layer, at least one magenta color forming silver halide emulsion layer and at least one of said yellow color forming silver halide emulsion layer, which are different from one another in color sensitivity, are formed on the support.

DETAILED DESCRIPTION OF THE INVENTION
In the couplers represented by general formula (I) the nitrogen-containing heterocycle represented by A has one or more carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 2 to 12 atoms, and may be saturated or unsaturated, a single ring or a condensed ring, and substituted or unsubstituted. The ring may contain an oxygen atom, a sulfur atom or a phosphorus atom in addition to the nitrogen atom. More than one atom may be contained in each of these heteroatoms. The number of the ring members is 3 or more, preferably 3 to 12, and more preferably 5 or 6.
Specific examples of the heterocycles represented by A include pyrrolidino, piperidino, morpholino, 1-imidazolidinyl, 1-pyrazolyl, 1-piperazinyl, 1-indolinyl, 1,2,3,4-tetrahydroquinoxaline-1-yl, 1-pyrrolinyl, pyrazolidine-1-yl, 2,3-dihydro-1-indazolyl, isoindoline-2-yl, 1-indolyl, 1-pyrrolyl, benzothiazine-4-yl, 4-thiazinyl, benzodiazine-1-yl, aziridine-1-yl, benzooxazine-4-yl, 2,3,4,5-tetrahydroquinolyl and phenoxazine-10-yl.
In general formula (I), the aromatic group represented by Y has 6 or more carbon atoms, and preferably 6 to 10 carbon atoms, and may be substituted or unsubstituted. Particularly preferred examples of such aromatic groups include phenyl and naphthyl.
In general formula (I), the heterocyclic group represented by Y has one or more carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 2 to 5 carbon atoms, and may be saturated or unsaturated, and substituted or unsubstituted. Preferred examples of the heteroatoms include a nitrogen atom, a sulfur atom and an oxygen atom. The number of the ring members is preferably 5 or 6, but others may be used. The ring may be either a single ring or a condensed ring. Specific examples of the heterocyclic groups represented by Y include 2-pyridyl, 4-pyrimidinyl, 5-pyrazolyl, 8-quinolyl, 2-furyl and 2-pyrrolyl.
When the groups represented by A and Y in general formula (I) each have substituents, examples of the substituents include halogen atoms such as fluorine and chlorine, alkoxycarbonyl groups having 2 to 30, preferably 2 to 20 carbon atoms, such as methoxycarbonyl, dodecyloxycarbonyl and hexadecyloxycarbonyl groups, acylamino groups having 2 to 30, preferably 2 to 20 carbon atoms, such as acetamido, tetra-decaneamido, 2-(2,4-di-t-amylphenoxy)butaneamido and benzamido groups, sulfonamido groups having 1 to 30, preferably 1 to 20 carbon atoms, such as methanesulfonamido, dodecanesulfonamido, hexadecanesulfonamido and benzenesulfonamido groups, carbamoyl groups having 2 to 30, preferably 2 to 20 carbon atoms, such as N-butylcarbamoyl and N,N-diethylcarbamoyl groups, sulfamoyl groups having 1 to 30, preferably 1 to 20 carbon atoms, such as N-butylsulfamoyl, N-dodecylsulfamoyl, N-hexadecylsulfamoyl and N-3-(2,4-di-t-amylphenoxy)butylsulfamoyl groups, alkoxy groups having 1 to 30, preferably 1 to 20 carbon atoms, such as methoxy and dodecyloxy groups, N-acylsulfamoyl groups having 2 to 30, preferably 2 to 20 carbon atoms, such as N-propanoylsulfamoyl and N-tetradecanoylsulfamoyl groups, sulfonyl groups having 1 to 30, preferably 1 to 20 carbon atoms, such as methanesulfonyl, octanesulfonyl and dodecanesulfonyl groups, alkoxycarbonylamino groups having 1 to 30, preferably 1 to 20 carbon atoms, such as methoxycarbonylamino and tetradecyloxycarbonylamino groups, a cyano group, a nitro group, a carboxyl group, aryloxy groups having 6 to 20, preferably 6 to 10 carbon atoms, such as phenoxy and 4-chlorophenoxy groups, alkylthio groups having 1 to 30, preferably 1 to 20 carbon atoms, such as methylthio and dodecylthio groups, ureido groups having 1 to 30, preferably 1 to 20 carbon atoms, such as a phenylureido group, aryl groups having the same meaning as described when Y represents an aromatic group, heterocyclic groups having the same meaning as described when Y represents a heterocyclic group, a sulfo group, alkyl groups having 1 to 30, preferably 1 to 20 carbon atoms, which are straight, branched, cyclic, saturated, unsaturated, substituted or unsubstituted, such as methyl, ethyl, isopropyl, cyclopropyl, trifluoromethyl, cyclopentyl, dodecyl and 2-hexyloctyl groups, acyl groups having 1 to 30, preferably 2 to 20 carbon atoms, such as acetyl and benzoyl groups, arylthio groups having 6 to 20, preferably 6 to 10 carbon atoms, such as a phenylthio group, sulfamoylamino groups having 0 to 30, preferably 0 to 20 carbon atoms, such as N-butylsulfamoylamino and N-dodecylsulfamoylamino groups, N-acylcarbamoyl groups having 2 to 30, preferably 2 to 20 carbon atoms, such as a N-dodecanoylcarbamoyl group, N-sulfonylcarbamoyl groups having 1 to 30, preferably 2 to 20, carbon atoms, such as N-hexadecanesulfonylcarbamoyl, N-benzenesulfonylcarbamoyl and N-(2-octyloxy-5-tert-octylbenzenesulfonyl)carbamoyl groups, N-sulfamoylcarbamoyl groups having 1 to 30, preferably 1 to 20 carbon atoms, such as N-(ethylsulfamoyl)carbamoyl and N-{3-(2,4-di-t-amylphenoxy)propylsulfamoyl}carbamoyl groups, N-sulfonylsulfamoyl groups having 0 to 30, preferably 1 to 20 carbon atoms, such as N-dodecanesulfonylsulfamoyl and N-benzenesulfonylsulfamoyl groups, N-carbamoylsulfamoyl groups having 1 to 30, preferably 1 to 20 carbon atoms, such as N(ethylcarbamoyl)sulfamoyl and N-{3-(2,4-di-t-amyl-phenoxy)propylcarbamoyl}sulfamoyl groups, N-(N-sulfonylcarbamoyl)sulfamoyl groups having 1 to 30, preferably 1 to 20 carbon atoms, such as N-(dodecanesulfonylcarbamoyl)sulfamoyl and N-(2-octyloxy-5-t-octylbenzenesulfonylcarbamoyl)sulfamoyl groups, 3-sulfonylureido groups having 1 to 30, preferably 1 to 20 carbon atoms, such as 3-hexadecanesulfonylureido and 3-benzenesulfonylureido groups, 3-acylureido groups having 2 to 30, preferably 2 to 20 carbon atoms, such as 3-acetylureido and 3-benzoylureido groups, 3-acylsulfamido groups having 1 to 30, preferably 1 to 20 carbon atoms, such as 3-propionylsulfamido and 3-(2,4-dichlorobenzoyl)sulfamido groups, 3-sulfonylsulfamido groups having 0 to 30, preferably 1 to 20 carbon atoms, such as 3-methanesulfonylsulfamido and 3-(2-methoxyethoxy-5-t-octylbenzenesulfonyl)sulfamido groups, a hydroxyl group, acyloxy groups having 1 to 30, preferably 1 to 20 carbon atoms, such as propanoyloxy and tetradecanoyloxy groups, sulfonyloxy groups having 0 to 30, preferably 0 to 20 carbon atoms, such as dodecanesulfonyloxy and 2-octyl-oxy-5-t-octylbenzene-sulfonyloxy groups and aryloxycarbonyl groups having 7 to 20, preferably 7 to 10 carbon atoms, such as a phenoxycarbonyl group.
When the groups represented by A have substituents, preferred examples of the substituents include the halogen atoms, alkoxy groups, acylamino groups, carbamoyl groups, alkyl groups, sulfonamido groups and nitro groups, of the groups enumerated above. However, unsubstituted groups are also preferred examples.
When the groups represented by Y have substituents, preferred examples of the substituents include the halogen atoms, alkoxycarbonyl groups, sulfamoyl groups, carbamoyl groups, sulfonyl groups, sulfonamido groups, acylamino groups, alkoxy groups, aryloxy groups, N-acylcarbamoyl groups, N-sulfonylcarbamoyl groups, N-sulfamoylcarbamoyl groups, N-sulfonylsulfamoyl groups, N-acylsulfamoyl groups, N-carbamoylsulfamoyl groups and N-(N-sulfonylcarbamoyl)sulfamoyl groups.
The group represented by Z in general formula (I) may be any of coupling eliminatable groups previously known. Preferred examples thereof include nitrogen-containing heterocyclic groups which are bonded to coupling positions at the nitrogen atoms, aromatic oxy groups, aromatic thio groups, heterocyclically oxy groups, heterocyclic thio groups, acyloxy groups, carbamoyloxy groups, alkylthio groups and halogen groups. These eliminatable groups may be any of photographic useful groups or precursors thereof such as development inhibitors, development accelerators, desilverization accelerators, fogging agents, dyes, hardening agents, couplers, developing agent oxidation product scavengers, fluorescent dyes, developing agents and electron transfer agents, and non-photographically useful groups.
The nitrogen-containing heterocyclic group represented by Z is preferably a substituted or unsubstituted heterocyclic group of a single or condensed ring. Examples thereof include succinimido, maleinimido, phthalimido, diglycolimido, pyrrolino, pyrazolyl, imidazolyl, 1,2,4-triazole-1-yl (or 4-yl ), 1-tetrazolyl, indolyl, benzopyrazolyl, benzimidazolyl, benzotriazolyl, imidazolidine-2,4-dione-3-yl (or 1-yl), oxazolidine-2,4-dione-3-yl, thiazolidine-2,4-dione-3-yl, imidazoline-2-one-1-yl, oxazoline-2-one-3-yl, thiazoline-2-one-3-yl, benzooxazoline-2-one-3-yl, 1,2,4-triazolidine-3,5-dione-4-yl, 2-pyridone-l-yl, morpholine-3,5-dione-4-yl, 1,2,3-triazole-1-yl and 2-imidazoline-5-one group.
When the heterocyclic groups have substituents, examples of the substituents include the substituents enumerated for the above-described groups represented by A.
Preferred examples of the nitrogen-containing heterocyclic groups represented by include 1-pyrazolyl, imidazolyl, 1,2,3-triazole-l-yl, benzotriazolyl, 1,2,4-triazole-l-yl, oxazolidine-2,4-dione-3-yl, 1,2,4-triazolidine-3,5-dione-4-yl and imidazolidine-2,4-dione-3-yl. These groups may also be substituted.
The aromatic oxy group represented by Z is preferably a substituted or unsubstituted phenoxy group. When the phenoxy group has a substituent, examples of the substituents include the substituents enumerated for the above-described groups represented by Y. Preferred examples thereof include those groups having at least one electron attractive substituent, such as the sulfonyl, alkoxycarbonyl, sulfamoyl, halogen, carboxyl, carbamoyl and nitro groups.
The aromatic thio group represented by Z is preferably a substituted or unsubstituted phenylthio group. When the phenylthio group has a substituent, examples of the substituents include the substituents enumerated for the above-described groups represented by Y. In the case of the phenylthio group, it is preferred that at least one substituent is alkyl, alkoxy, sulfonyl, alkoxycarbonyl, sulfamoyl, halogen, carbamoyl or nitro.
When Z represents the heterocyclic oxy group, the heterocyclic moiety has the same meaning as described above when Y represents a heterocyclic group.
The heterocyclic thio group represented by Z is preferably a 5- or 6-membered unsaturated heterocyclic thio group. Examples thereof include tetrazolylthio, 1,3,4-thiazolylthio, 1,3,4-oxadiazolylthio, 1,3,4-triazolylthio, benzoimidazolylthio, benzothiazolylthio and 2-pyridylthio groups. When these groups have substituents, examples of the substituents include the substituents enumerated for the above-described heterocyclic groups represented by Y. Of those, particularly preferred substituents include aromatic groups, alkyl groups, alkylthio groups, acylamino groups, alkoxycarbonyl groups and aryloxycarbonyl groups.
Examples of the acyloxy group represented by Z include an aromatic acyloxy group having 7 to 11 carbon atoms, and preferably is benzoyloxy group, or an aliphatic acyloxy group having 2 to 20, preferably 2 to 10 carbon atoms, which may have a substituent. Specific examples of the substituents include the substituents enumerated for the above-described aromatic groups represented by Y. It is preferred that at least one substituent is a halogen atom, a nitro group, an aryl group, an alkyl group or an alkoxy group.
The carbamoyloxy group represented by Z is preferably an aliphatic, aromatic, heterocyclic or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Examples thereof include N,N-diethylcarbamoyloxy, N-phenylcarbamoyl-morpholinocarbonyloxy, 1-imidazolylcarbonyloxy and N,N-dimethylcarbamoyloxy, wherein detailed descriptions of alkyl, aromatic and heterocyclic groups have the same meanings as defined in the above descriptions for Y.
The alkylthio group represented by Z preferably has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Details of the alkylthio group are the same as defined in the above description for Y.
Preferred examples of the groups represented by Z in general formula (I) include 5- or 6-membered nitrogen-containing heterocyclic groups which are bonded to coupling positions at the nitrogen atoms, aromatic oxy groups, 5- or 6-membered heterocyclic oxy groups and 5- or 6-membered heterocyclic thio groups.
The groups represented by Y in general formula (I) are preferably aromatic groups. A phenyl group having at least one substituent at the ortho position is particularly preferred. Examples of the substituents include the substituents mentioned for the abovedescribed aromatic groups represented by Y.
When the group represented by Y in general formula (I) is the phenyl group having at least one substituent at the ortho position, a halogen atom, an alkoxy group, an alkyl group or an aryloxy group is particularly preferred as the substituent at the ortho position.
Of the couplers represented by general formula (I), particularly preferred couplers are represented by the following general formula (II): ##STR5## wherein Y and Z have the same meanings as described in general formula (I); X.sub.1 represents an organic residue necessary for forming a nitrogen-containing heterocycle with --C(R.sub.1 R.sub.2)--N--; R.sub.1 and R.sub.2 each represents a hydrogen atom or a substituent; and ##STR6## is hereinafter referred to as B.
Preferred examples and specific examples of Y and Z are the same as described above for general formula (I).
Specific examples of the heterocyclic groups represented by B in general formula (II), add examples of the substituents thereof, include the heterocyclic groups and substituents described for A in general formula (I). Preferred examples thereof are also the same as described for A in general formula (I). It is particularly preferred that these nitrogen-containing heterocyclic groups are benzene condensed rings.
Of the couplers represented by general formula (II), more preferred couplers are represented by the following general formula (III): ##STR7## wherein R.sub.3 represents a hydrogen atom or a substituent; R.sub.4, R.sub.5 and R.sub.6 represent substituents; Z has the same meaning as described for general formula (I); m and n each represent an integer of 0 to 4; with the proviso that when m and n each represent an integer of 2 or more, R.sub.4 and R.sub.6, which may be the same or different, may combine to form a ring.
Examples of the substituents represented by R.sub.3 and R.sub.4 in general formula (III) are the same as the examples of the substituents of the groups represented by A in general formula (I). Preferred examples of the groups represented by R.sub.3 include hydrogen, alkoxy and aryl, and preferred examples of the groups represented by R.sub.4 include halogen, alkoxy, acylamino, carbamoyl, alkyl, sulfonamido and nitro. m is preferably an integer of 0 to 2, more preferably, 0 or 1.
Examples of the substituents represented by R.sub.5 and R.sub.6 in general formula (III) include the same examples as described for the substituents of the groups represented by Y in general formula (I). R.sub.5 is preferably halogen, alkoxy, alkyl or aryloxy. Preferred examples of the groups represented by R.sub.6 include the same examples as described for the preferred substituents of the groups represented by Y in general formula (I). n is preferably an integer of 0 to 2, more preferably, 1 or 2.
The couplers represented by general formulae (I), (II) and (III) may combine at X, Y and Z through divalent or higher valent groups to form dimers or polymers. In this case, the number of the carbon atoms may be excluded from the range defined above for each of the substituents.
Specific examples of the couplers represented by general formula (I) include, but are not limited to, the following compounds.
##STR8## No. R.sub.3 m R.sub.4 R.sub.5 n R.sub.6 Z 1 H 0 -- OCH.sub.3 1 ##STR9## ##STR10## 2 " " -- OC.sub.18 H.sub.37 (n) 1 ##STR11## " 3 " " -- OC.sub.12 H.sub.25 (n) 1 5-SO.sub.2 NHCONHC.sub.3 H.sub.7 " 4 " " -- ##STR12## 1 ##STR13## " 5 H 0 -- ##STR14## 1 5-SO.sub.2 NHCOC.sub.2 H.sub.5 ##STR15## 6 " " -- ##STR16## 1 5-SO.sub.2 NHCOC.sub.2 H.sub.5 " 7 " " -- ##STR17## 1 5-SO.sub.2 NHCOCH.sub.3 " 8 " " -- ##STR18## 1 ##STR19## " 9 " " -- ##STR20## 1 ##STR21## " 10 H 0 -- ##STR22## 1 5-CONHSO.sub.2 C.sub.12 H.sub.25 ##STR23## 11 " " -- ##STR24## 1 4-SO.sub.2 NHCOC.sub.9 H.sub.19 " 12 " " -- " 2 4-Cl-5-CONHSO.sub.2 C.sub.16 H.sub.33 (n) " 13 " " -- " 2 3-Cl-5-C ONHCOC.sub.11 H.sub.23 " 14 " " -- OCH.sub.3 2 3-Cl-5-CONHSO .sub.2 C.sub.12 H.sub.25 (n) " 15 H 0 -- OC.sub.16 H.sub.33 (n) 1 ##STR25## ##STR26## 16 " " -- ##STR27## 1 ##STR28## " 17 " " -- OCH(CH.sub.3).sub.2 1 ##STR29## " 18 " " -- OC.sub.18 H.sub.37 (n) 1 ##STR30## " 19 H 0 -- ##STR31## 1 ##STR32## ##STR33## 20 " " -- OC.sub.2 H.sub.5 1 " ##STR34## 21 " " -- OC.sub.18 H.sub.37 (n) 2 4-Cl-5-CONHSO.sub.2 C.sub.12 H.sub.25 ##STR35## 22 " " -- " 1 ##STR36## " 23 H 0 -- ##STR37## 1 ##STR38## ##STR39## 24 " " -- OCH(CH.sub.3).sub.2 1 ##STR40## " 25 CH.sub.3 " -- OC.sub.2 H.sub.5 1 ##STR41## " 26 H " -- OC.sub.18 H.sub.37 (n) 1 ##STR42## ##STR43## 27 H 0 -- ##STR44## 1 ##STR45## ##STR46## 28 " 0 -- OC.sub.16 H.sub.33 (n) 1 5-SO.sub.2 NHCOC.sub.2 H.sub.5 ##STR47## 29 " 0 -- Cl 1 5 -CONHSO.sub.2C.sub.16 H.sub.33 (n) ##STR48## 30 " 0 -- " 1 ##STR49## ##STR50## 31 H 0 -- Cl 1 ##STR51## ##STR52## 32 " 0 -- " 2 4 -Cl-5-COOC.sub.12 H.sub.25 ##STR53## 33 " 0 -- " 2 ##STR54## ##STR55## 34 " 0 -- " 1 5 -SO.sub.2 NHC.sub.12 H.sub.25 " 35 " 0 -- " 1 5-SO.sub.2 NHSO.sub.2 C.sub.16 H.sub.33 (n) ##STR56## 36 H 1 5-NO.sub.2 Cl 1 ##STR57## ##STR58## 37 " 2 5,7-Br " 1 5 -NHSO.sub.2 C.sub.16 H.sub.33 (n) " 38 " 0 -- C.sub.18 H.sub.37 (n) 1 ##STR59## ##STR60## 39 " 0 -- " 1 " ##STR61## 40 " 0 -- ##STR62## 1 ##STR63## " 41 H 1 5-Cl Cl 1 5-NH SO.sub.2 C.sub.16 H.sub.33 ##STR64## 42 ##STR65## 1 5-NO.sub.2 OC.sub.14 H.sub.29 1 ##STR66## ##STR67## 43 H 1 5-Br Cl 1 ##STR68## ##STR69## 44 H 1 " " 1 " ##STR70## 45 " 1 5-Cl " 1 5 -NHSO.sub.2 C.sub.12 H.sub.25 ##STR71## 46 H 1 5-NO.sub.2 Cl 1 5 -NHSO.sub.2 C.sub.12 H.sub.25 ##STR72## 47 " 0 -- " 1 ##STR73## ##STR74## 48 " 1 5-OCH.sub.3 " 2 4 -Cl-5-COOC.sub.12 H.sub.25 ##STR75## 49 " 1 5-NO.sub.2 CF.sub.3 1 ##STR76## ##STR77## 50 H 0 -- OC.sub.2 H.sub.5 1 5-SO.sub.2 C.sub.12 H.sub.25 ##STR78## 51 " 0 -- Cl 1 ##STR79## " 52 C.sub.2 H.sub.5 0 -- " 1 ##STR80## ##STR81## 53 H 0 -- " 1 ##STR82## ##STR83## 54 H 0 -- Cl 1 5 -SO.sub.2 NHCOC.sub.11 H.sub.23 ##STR84## 55 H 0 -- ##STR85## 1 ##STR86## ##STR87## 56 H 1 Br ##STR88## 1 ##STR89## " 57 H 0 -- ##STR90## 1 ##STR91## " 58 H 0 -- ##STR92## 1 5-SO.sub.2 NHC.sub.14 H.sub.29 ##STR93## 59 " " -- ##STR94## 1 5-SO.sub.2 NHCONHC.sub.12 H.sub. 25 ##STR95## 60 " " -- ##STR96## 1 5-SO.sub.2 C.sub.16 H.sub.33 (n) ##STR97## 61 " " -- ##STR98## 1 ##STR99## ##STR100## 62 H 0 -- ##STR101## 1 ##STR102## ##STR103## 63 " 1 5-NO.sub.2 " 1 " ##STR104## 64 " 1 5-NHSO.sub.2 CH.sub.3 ##STR105## 1 5-SO.sub.2 NH.sub.2 ##STR106## 65 " 0 -- ##STR107## 2 ##STR108## " 66 CH.sub.3 1 5-Br ##STR109## 1 ##STR110## ##STR111## 67 H 0 -- ##STR112## 1 ##STR113## ##STR114## 68 " 1 5-Br OC.sub.12 H.sub.25 1 ##STR115## " 69 " 0 -- ##STR116## 1 ##STR117## " 70 " 0 -- ##STR118## 1 ##STR119## ##STR120## ##STR121## No. ##STR122## Y Z 71 ##STR123## ##STR124## ##STR125## 72 ##STR126## ##STR127## " 73 ##STR128## ##STR129## ##STR130## 74 ##STR131## ##STR132## ##STR133## 75 ##STR134## ##STR135## ##STR136## 76 ##STR137## ##STR138## ##STR139## 77 ##STR140## ##STR141## ##STR142## 78 ##STR143## ##STR144## SCH.sub.2 COOH 79 ##STR145## ##STR146## ##STR147## 80 " " ##STR148## (81) ##STR149## (82) ##STR150## n/m = 50/50 (weight ratio) (average molecular weight: 25,000) PG,28
The compounds of the present invention can be synthesized by methods generally known in the art or similar methods.
For example, the compounds can be synthesized by the following synthesis route: ##STR151##
In the above synthesis, X, Y and Z have the same meanings as described above for general formula (I); R.sub.10 represents a halogen atom such as chlorine, --OH, an alkoxy group such as methoxy or ethoxy or a phenoxy group such as phenoxy or 4-nitrophenoxy; and Hal represents a halogen.
Under reaction conditions of (a), when R.sub.10 is --OH, a dehydrating condensing agent such as N,N-dicyclghexylcarbodiimide or N,N-diisopropylcarbodiimide is used. When R.sub.10 is a halogen atom, the reaction is conducted in the presence of a dehydrohalogenating agent. The dehydrohalogenating agents used include organic bases such as triethylamine, diisopropylethylamine, pyridine, guanidine and butoxypotassium, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium hydride and potassium carbonate. In the reaction of compound 3 to compound 4, a halogenating agent is used as (b). Examples of halogenating agents include bromine, chlorine, N-bromosuccinimide and N-chlorosuccinimide. In the reaction of compound 4 to the end product, a dehydrohalogenating agent is generally used as (c). Examples thereof include the organic and inorganic bases described above. In each reaction, a reaction solvent is used. Examples of the solvents include chlorine type solvents such as dichloromethylene, aromatic type solvents such as benzene, chlorobenzene and toluene, amide type solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, nitrile type solvents such as acetonitrile and propionitrile, ether type solvents such as tetrahydrofuran and ethylene glycol diethyl ether, sulfone type solvents such as dimethyl sulfone and sulfolane and hydrocarbon type solvents such as cyclohexane and n-hexane.
The compounds of the present invention can also be synthesized by methods other than the above-described synthesis route. One example is the method described in 5 J. Org. Chem., 29, 2932 (1964). In some cases, product is converted to a desired end product by further conversion of a functional group. The modification of the synthesis route and additional reaction can be appropriately selected.
Specific syntheses are described below. Other example compounds can be synthesized in a similar manner.
SYNTHESIS EXAMPLE 1
Synthesis of Example Compound (54)
Synthesis was conducted by the following method: ##STR152##
3.5 g of compound (6) and 14 g of compound (7) were dissolved in 100 ml of N,N-dimethylformamide and 0 ml of acetonitrile. To the resulting solution, 40 ml of an acetonitrile solution in which 6 g of N,N'-dicyclohexylcarbodiimide was dissolved, was added dropwise at room temperature. After reaction for 2 hours, precipitated N,N-dicyclohexylurea was separated by filtration. The filtrate was poured on 500 ml of water, and extracted with 500 ml of ethyl acetate. The oil layer was collected using a separatory funnel, and washed with water, followed by drying with Glauber's salt. The solvent was distilled off under reduced pressure, and hexane was added to the residue, followed by crystallization. As a result, 17.2 g of compound (8) was obtained.
16 g of compound (8) was mixed with 150 ml of dichloromethane. 10 ml of dichloromethane solution containing 4.8 g of bromine was added dropwise under ice cooling (5.degree. to 10.degree. C.). After reaction for 10 minutes, the reaction product was transferred into a separatory funnel, and washed with water. The oil layer, a solution containing compound (9), was collected to use in a subsequent step.
8.1 g of 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine and 8.8 ml of triethylamine were added to 160 ml of N,N-dimethylformamide. The dichloromethane solution of compound (9) obtained above was added dropwise to this solution at room temperature. After reaction for 1 hour, 500 ml of ethyl acetate was added. The resulting solution was transferred into a separatory funnel, and washed with water. After neutralization with diluted hydrochloric acid, the solution was washed with water again, and the oil layer was separated. The solvent was distilled off under reduced pressure, and the residue was separated and purified by column chromatography. Silica gel was used as a packing, and ethyl acetate/hexane (1/1) was used as an elute. Fractions containing desired example compound (54) were collected, and the solvent was distilled off under reduced pressure to obtain 15.2 g of waxy example compound (54).
SYNTHESIS EXAMPLE 2
Synthesis of Example Compound (2)
Synthesis was conducted in a manner similar to that of Synthesis Example 1 described above, with the exception that compound (7) was substituted with an equimolar amount of the following compound (10): ##STR153##
The end product was purified by column chromatography to obtain 18.3 g of waxy example compound (2).
The couplers of the present invention are used preferably in an amount of 0.01 to 10 mmol/m.sup.2, more preferably in an amount of 0 05 to 5 mmol/m.sup.2 and most preferably in an amount of 0.1 to 3 mmol/m.sup.2.
Silver halides are used with respect to the couplers of the present invention in a molar ratio of 0.1 to 100, preferably in a molar ratio of 0.5 to 20, more preferably in a molar ratio of 1.5 to 10, and most preferably in a molar ratio of 2.0 to 6.0.
In the present invention, various conventional dispersing methods can be used to introduce lipophilic photographic organic compounds such as couplers into photographic materials.
According to the oil-in-water dispersion method described in U.S. Pat. No. 2,322,027, the lipophilic photographic organic compounds can be dissolved in high boiling organic solvents having a boiling point of about 175.degree. C. or more at atmospheric pressure such as phthalates, phosphates, benzoates, fatty acid esters, amides, phenols, alcohols, carboxylic acids, N,N-dialkylanilines, hydrocarbons, oligomers and polymers, and/or low boiling organic solvents having a boiling point of about 30.degree. to about 160.degree. C. at atmospheric pressure such as esters (e.g., ethyl acetate, butyl acetate, ethyl propionate, .beta.-ethoxyethyl acetate and methyl cellosolve acetate), alcohols (e.g., sec-butyl alcohol), ketones (e.g., methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone), amides (e.g., dimethylformamide and N-methylpyrrolidone) and ethers (e.g., tetrahydrofuran and dioxane), followed by dispersion by emulsification in hydrophilic colloids such as gelatin.
The high boiling organic solvents used in the present invention may be in any of liquid, waxy and solid forms. As the high boiling organic solvents used for the above-described yellow couplers of the present invention, the high boiling organic solvents having a dielectric constant (25.degree. C., 1 atm., 10 KHz) of 6.0 or less, preferably 3.5 to 5.5, are preferred among others in terms of the best hue of color forming dyes and fastness to light.
Further, with respect to color forming properties and other photographic characteristics, the high boiling solvents represented by any of the above-described general formulae (S-1) to (S-5) are preferably used. For the object of the present invention, the high boiling organic solvents having a dielectric constant of 6.0 or less and represented by any of the above-described general formulae (S-1) to (S-5) are more preferred.
General formulae (S-1) to (S-5) are hereinafter described. ##STR154##
In general formula (S-1), R.sub.1, R.sub.2 and R.sub.3 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group or an aryloxy group. ##STR155##
In general formula (S-2), R.sub.4 and R.sub.5 each independently represents an alkyl group, a cycloalkyl group or an aryl group, R.sub.6 represents a halogen atom such as F, Cl, Br or I, an alkyl group, an alkoxy group, an aryloxy group or an alkoxycarbonyl group, and a represents an integer of 0 to 3, with the proviso that when a is 2 or more, a plurality of R.sub.6 s may be the same or different. ##STR156##
In general formula (S-3), Ar represents an aryl group, b represents an integer of 1 to 6, and R.sub.7 represents a b-valent hydrocarbon group or a hydrocarbon group bonded through an ether linkage to each other. ##STR157##
In general formula (S-4), R.sub.8 represents an alkyl group or a cycloalkyl group, c represents an integer of 1 to 6, and R.sub.9 represents a c-valent hydrocarbon group or a hydrocarbon group bonded through an ether linkage to each other. ##STR158##
In general formula (S-5), d represents an integer of 2 to 6, R.sub.10 represents d-valent hydrocarbon group (excluding an aromatic group), and R.sub.11 represents an alkyl group, a cycloalkyl group or an aryl group.
Specific examples of the high boiling organic solvents used in the present invention are enumerated below:
Compounds represented by formula (S-1); ##STR159##
Compounds represented by formula (S-3); ##STR160##
Compounds represented by formula (S-4 ); ##STR161##
Compounds represented by formula (S-5); ##STR162##
Other high boiling organic solvents which can be used according to the present invention in addition to those described above, and/or methods for producing them are described, for example, in U.S. Pat. Nos. 2,322,027, 2,533,514, 2,772,163, 2,835,579, 3,676,137, 3,912,515, 3,936,303, 4,080,209, 4,127,413, 4,193,802, 4,239,851, 4,278,757, 4,363,873, 4,483,918 and 4,745,049, European Patent 276,319A, JP-A-48-47335, JP-A-51-149028, JP-A-61-84641, JP-A-62-118345, JP-A-62-247364, JP-A-63-167357, JP-A-64-68745 and JP-A-1-101543.
The weight ratio of the high boiling organic solvents, to the yellow couplers of the present invention is 0.6 or more, preferably 0.6 to 5.0, more preferably 0.8 to 4.0, and most preferably 1.0 to 3.0.
A weight ratio of less than 0.6 causes a remarkable deterioration in light fastness, and a weight ratio exceeding 5.0 is liable to produce the problems of deterioration in film property and generation of stains formed by a lapse of time after processing. If gelatin is applied in an increased amount to avoid deterioration of the film property, the problem of prolonged drying time arises.
In order to further improve the light fastness of yellow images formed from the yellow couplers of the present invention as well as other yellow couplers, it is preferred that water-insoluble polymers are added to the silver halide emulsion layers containing the yellow couplers.
The water-insoluble polymers which can be used in the present invention include the polymers described in PCT International Publication No. WO88/00723 and JP-A-63-44658.
However, any polymers may be used in the present invention, so long as they are water-insoluble. Vinyl polymers in which repeating units have --(C.dbd.O)-- linkages and polyester type polymers are preferably used.
As to vinyl monomers preferably used for synthesis of the polymers used in the present invention, two or more types of monomers are used as comonomers, corresponding to various purposes (for example, an improvement in solubility). For control of color forming property or solubility, an acid group-containing monomer may be used as the comonomer, so long as the copolymer does not become water-soluble. Further, a monomer having two or more cross-linkable ethylenic unsaturated components can be used. As such monomers, those described in JP-A-60-151636 are preferably used.
When the hydrophilic monomer (which means here a monomer providing a water-soluble homopolymer) is used as the comonomer in the vinyl monomer, there is no particular limitation on the ratio of the hydrophilic monomer to the synthesized copolymer, so long as the copolymer does not become water-soluble. However, usually the ratio will preferably be 40 mol % or less, more preferably 20 mol % or less, and most preferably 10 mol % or less. Furthermore, when the hydrophilic comonomer which is copolymerized with the monomer, has an acid group, the ratio of the comonomer having the acid group to the copolymer is usually 20 mol % or less, and preferably 10 mol % or less, from the viewpoint of image keeping quality. However, it is most preferred that such a comonomer is not used.
The monomer components contained in the polymers are preferably methacrylates, acrylamides and methacrylamides. Acrylamides and methacrylamides are most preferred.
The number average molecular weight of the polymers which can be used in the present invention is preferably 5,000 to 150,000, and more preferably 10,000 to 100,000.
The water-insoluble polymer in the present invention is a polymer having a solubility of 3 g or less, preferably 1 g or less, to 100 g of distilled water (25.degree. C.).
Specific examples of the polymers used in the present invention are shown below, but the scope of the present invention is not limited thereto. The copolymerization ratios of the copolymers in the specific examples shown below are molar ratios.
P-1: Polymethyl methacrylate
P-2: Polyethyl methacrylate
P-3: Polyisopropyl methacrylate
P-4: Polymethyl chloroacrylate
P-5: Poly(2-tert-butylphenyl acrylate)
P-6: Poly(4-tert-butylphenyl acrylate)
P-7: Ethyl methacrylate-n-butyl acrylate copolymer (70:30)
P-8: Methyl methacrylate-a-crylonitrile copolymer (65:35)
P-9: Methyl methacrylate-styrene copolymer (90:10)
P-10: N-tert-Butylmethacrylamide-methyl methacrylate-acrylic acid copolymer (60:30:10)
P-11: Methyl methacrylate-styrene-vinylsulfonamide copolymer (70:20:10)
P-12: Methyl methacrylate-cyclohexyl methacrylate copolymer (50:50)
P-13: Methyl methacrylate-acrylic acid copolymer (95:5)
P-14: Methyl methacrylate-n-butyl methacrylate copolymer (65:35)
P-15: Methyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:10)
P-16: Poly(N-sec-butylacrylamide)
P-17: Poly(N-tert-butylacrylamide)
P-18: Cyclohexyl methacrylate-methyl methacrylate copolymer (60:40)
P-19: n-Butyl methacrylate-methyl methacrylate-acrylamide copolymer (20:70:10)
P-20: Diacetoneacrylamide-methyl methacrylate copolymer (20:80)
P-21: N-tert-Butylacrylamide-methyl methacrylate copolymer (40:60)
P-22: Poly(N-n-butylacrylamide)
P-23: tert-Butyl methacrylate-N-tert-butylacrylamide co
polymer (50:50)
P-24: tert-Butyl methacrylate-methyl methacrylate co
polymer (70:30)
P-25: Poly(N-tert-butylmethacrylamide)
P-26: N-tert-Butylacrylamide-methyl methacrylate copolymer (60:40)
P-27: Methyl methacrylate-acrylonitrile copolymer (70:30)
P-28: Methyl methacrylate-styrene copolymer (75:25)
P-29: Methyl methacrylate-hexyl methacrylate copolymer (70:30)
P-30: Poly(4-biphenylacrylate)
P-31: Poly(2-chlorophenyl acrylate)
P-32: Poly(4-chlorophenyl acrylate)
P-33: Poly(pentachlorophenyl acrylate)
P-34: Poly(4-ethoxycarbonylphenyl acrylate)
P-35: Poly(4-methoxycarbonylphenyl acrylate)
P-36: Poly(4-cyanophenyl acrylate)
P-37: Poly(4-methoxyphenyl acrylate)
P-38: Poly(3,5-dimethyladamantyl acrylate)
P-39: Poly(3-dimethylaminophenyl acrylate)
P-40: Poly(2-naphthyl acrylate)
P-41: Poly(phenyl acrylate)
P-42: Poly(N,N-dibutylacrylamide)
P-43: Poly(isohexylacrylamide)
P-44: Poly(isooctylacrylamide)
P-45: Poly(N-methyl-N-phenylacrylamide)
P-46: Poly(adamantyl methacrylate)
P-47: Poly(sec-butyl methacrylate)
P-48: N-tert-Butylacrylamide-acrylic acid copolymer (97:3)
P-49: Poly (2-chloroethyl methacrylate) (2-cyanoethyl methacrylate)
P-50: Poly
P-51: Poly (2-cyanomethylphenyl methacrylate)
P-52: Poly (4-cyanophenyl methacrylate)
P-53: Poly (cyclohexyl methacrylate)
P-54: Poly(2-hydroxypropyl methacrylate)
P-55: Poly(4-methoxycarbonylphenyl methacrylate)
P-56: Poly(3,5-dimethyladamantyl methacrylate)
P-57: Poly(phenyl methacrylate)
P-58: Poly(4-butoxycarbonylphenylmethacrylamide)
P-59: Poly(4-carboxyphenylmethacrylamide)
P-60: Poly(4-ethoxycarbonylphenylmethacrylamide)
P-61: Poly(4-methoxycarbonylphenylmethacrylamide)
P-62: Poly(cyclohexyl chloroacrylate)
P-63: Poly(ethyl chloroacrylate)
P-64: Poly(isobutyl chloroacrylate)
P-65: Poly(isopropyl chloroacrylate)
P-66: Poly(phenylacrylamide)
P-67: Poly(cyclohexylacrylamide)
P-68: Poly(phenylmethacrylamide)
P-69: Poly(cyclohexylmethacrylamide)
P-70: Poly(butylene adipate)
In the present invention, the amount of the water-insoluble polymer used in the silver halide color photographic material is 0.02 to 2.0, and preferably 0.2 to 2.0, by weight ratio to the yellow coupler contained in a light-sensitive layer of the photographic material. In order to improve both the light fading and the color forming properties, however, it is more preferred that the weight ratio is 0.4 to 1.5.
Methods for allowing the yellow couplers and the water-insoluble polymers of the present invention to be contained in the same layers are hereinafter described.
In the present invention, it is preferred that the coupler and the water-insoluble polymer are allowed to coexist and be finely dispersed. More preferably, the coupler and the water-insoluble polymer exist in the same drop of oil. For example, a latex of the polymer can be impregnated with the coupler of the present invention by the so-called loadable latex method (see U.S. Pat. No. 4,203,716). The methods of using organic solvent-soluble polymers described in PCT International Publication No. WO88/00723 and U.S. Pat. No. 5,006,453 can be used as more preferable methods. Namely, the polymer, the high boiling organic solvent and the coupler of the present invention are completely dissolved in an auxiliary organic solvent, and the resulting solution is dispersed in a fine particle form in water, preferably in an aqueous solution of a hydrophilic colloid, more preferably in an aqueous solution of gelatin, by means of ultrasound or a colloid mill with the aid of a dispersing agent.
The yellow couplers of the present invention are preferably used in combination with conventional antifading agents. Typical examples of such antifading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, spiroindanes, p-alkoxyphenols, hindered phenols such as bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating or alkylating phenolic hydroxyl groups of these compounds.
Specific examples of the organic antifading agents are described in the following patent documents.
The hydroquinones are described in U.S. Pat. Nos. 2,360,290, 2,418,613, 2,675,314, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944, 4,430,425, 2,710,801 and 2,816,028, and British Patent 1,363,921. The 6-hydroxychromans, 5-hydroxycoumarans and spirochromans are described in U.S. Pat. Nos. 3,432,300, 3,573,050, 3,574,626, 3,698,909 and 3,764,337, and JP-A-52-152225. The spiroindanes are described in U.S. Pat. No. 4,360,589. The p-alkoxyphenols are described in U.S. Pat. No. 2,735,765, British Patent 2,066,975, JP-A-59-10539 and JP-B-57-19765 (the term "JP-B" as used therein means an "examined Japanese patent publication").
The hindered phenols are described in U.S. Pat. Nos. 3,700,455 and 4,228,235, JP-A-52-72225 and JP-B-52-6623. The gallic acid derivatives, the methylenedioxybenzenes and the aminophenols are each described in U.S. Pat. Nos. 3,457,079 and 4,332,886 and JP-B-56-21144. The hindered amines are described in U.S. Pat. Nos. 3,336,135 and 4,268,593, British Patents 1,326,889, 1,354,313 and 1,410,846, JP-B-51-1420, JP-A-58-114036, JP-A-59-53846 and JP-A-59-78344.
Of the above-described antifading agents, preferred are the hindered phenols represented by the following general formula (IV) and the bisphenols represented by the following general formula (V). ##STR163##
In general formula (IV), R.sup.11 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an allyl group, an acyl group or a silyl group; and R.sup.12 and R.sup.13 are straight or branched alkyl groups of 3 to 8 carbon atoms, which are bonded preferably through secondary or tertiary carbon, more preferably through tertiary carbon. Specific examples of such alkyl groups include n-butyl, iso-propyl, tert-butyl and tert-amyl. Further, the alkyl groups may have appropriate substituents at any positions of the alkyl chains. R.sup.14 may be any group, as long as it is a monovalent organic group. Furthermore, R.sup.14 may contain a hindered phenol or bisphenol moiety. ##STR164##
In general formula (V), R.sup.15 and R.sup.16 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an allyl group, an acyl group, a phosphonyl group, a phosphinyl group or a sulfonyl group, and R.sup.15 and R.sup.16 may combine through the above-described group to form a ring R.sup.17, R.sup.18, R.sup.20 and R.sup.21 represent straight or branched alkyl groups of 1 to 8 carbon atoms. Specific examples include methyl, ethyl, n-propyl, iso-propyl, tert-butyl, tert-amyl, cyclohexyl, 1-methyl. Cyclohexyl and cyclopentyl. The above-described alkyl groups may have appropriate substituents including halogen atoms. R.sup.19 is a hydrogen atom or a straight or branched alkyl group of 1 to 8 carbon atoms. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, tertamyl and cyclohexyl.
Specific examples of the hindered phenols and bisphenols preferably used in the present invention include, but are not limited to, the following compounds: ##STR165##
The silver halides used in the silver halide photographic materials of the present invention include silver chloride, silver chloroiodide, silver chloro(iodo)bromide, silver bromide and silver iodobromide. In particular, silver chlorobromide or silver chloride substantially free from silver iodide and containing 90 mol % or more (more preferably 98 mol % or more) of silver chloride is preferably used for rapid processing.
In the photographic materials according to the present invention, it is preferred that the dyes decolorizable by processing (oxonol dyes among others) described in European Patent 0,337,490A2, pages 27 to 76 are added to hydrophilic colloidal layers so that the optical reflection density of the photographic materials at 680 nm reaches 0.70 or more, or that 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with dihydric to tetrahydric alcohols (for example, trimethylolethane) is added to water-resistant resin layers of supports, for an improvement in sharpness of images.
In the photographic materials of the present invention, compounds for improving the keeping quality of color images described in European Patent 0,277,589A2 are preferably used in combination with the couplers. In particular, they are preferably used in combination with pyrazoloazole couplers or pyrrolotriazole couplers.
Namely, in order to prevent the production of stains caused by the formation of a forming dye due to reaction of a color developing agent remaining in a film or an oxidation product thereof with a coupler during storage after processing, and other side effects, it is preferred to use a compound (F) which is chemically bonded to an aromatic amine developing agent remaining after color development to form a chemically inactive, substantially colorless compound, and/or a compound (G) which is chemically bonded to an oxidation product of an aromatic amine color developing agent remaining after color development to form a chemically inactive, substantially colorless compound.
Further, it is preferred that antifungal agents such as those described in JP-A-63-271247, be added to the photographic materials of the present invention to prevent various molds and bacteria from breeding in the hydrophilic colloidal layers and deteriorating images.
A white-polyester support or a support provided with a white pigment-containing layer on the side coated with silver halide emulsion layers, may be used as supports for the photographic material of the present invention. Furthermore, in order to improve sharpness, an antihalation layer is preferably formed on the side coated with silver halide emulsion layers, or on the back surface, of the support. In particular, it is preferred that the transmission density be established within the range of 0.35 to 0.8 so that the display can be appreciated with both reflected light and transmitted light.
The photographic materials of the present invention may be exposed to visible light or infrared light. Exposing methods may be either low illuminance exposure or high illumination exposure for a short time. In particular, in the latter case, a laser scanning exposing method in which the exposing time is shorter than 10.sup.-4 second is preferred.
In exposing, the band stop filter described in U.S. Pat. No. 4,880,726 is preferably used, whereby optical color mixing is eliminated and color reproducibility is markedly improved.
It is preferred that the color photographic materials of the present invention be subjected to color development, bleach-fixing and washing (or stabilizing), after exposure. The bleaching and fixing may be carried out separately, not using the single bath process as described above.
Silver halide emulsions, other materials such as additives and photographic constituent layers such as layer arrangements applied to the photographic materials of the present invention, and processing methods and additives for processing applied to treat the photographic materials, which are preferably used, are described in the following patents shown in Table 1, particularly in European Patent 0,355,660A2 (JP-A-2-139544).
TABLE 1______________________________________PhotographicConstituents,etc. JP-A-62-215272 JP-A-2-33144 EP0,355,660A2______________________________________Silver Halide Page 10, upper Page 28, Page 45, lineEmulsions right column, upper right 53 to page line 6 to page column, line 47, line 3; 12, lower left 16 to page page 47, line column, line 5; 29, lower 20 to line 22 page 12, lower right column, right column, line 11; page line 4 from the 30, line 2 to bottom to page line 5 13, upper left column, line 17Solvents for Page 12, lower -- --Silver left column,Halides line 6 to line 14; page 13, upper left column, line 3 from the bottom to page 18, lower left column, the last lineChemical Page 12, lower Page 29, lower Page 47, lineSensitizers left column, right column, 4 to line 9 line 3 from line 12 to the bottom to the last line lower right column, line 5 from the bottom; page 18, lower right column, line 1, to page 22, upper right column, line 9 from the bottomSpectral Page 22, upper Page 30, upper Page 47, lineSensitizers right column, left column, 10 to line 15(Spectrally line 8 from the line 1 to lineSensitizing bottom to page 13Methods) 38, the last lineEmulsion Page 39, upper Page 30, upper Page 47, lineStabilizers left column, left column, 16 to line 19 line 1 to page line 14 to 72, upper right upper right column, the column, line 1 last lineDevelopment Page 72, lower -- --Accelerators left column, line 1 to page 91, upper right column, line 3Color Page 91, upper Page 3, upper Page 4, lineCouplers right column, right column, 15 to line 27;(Cyan, line 4 to page line 14 to page 5, lineMagenta, 121, upper page 18, upper 30 to page 28,Yellow left column, left column, the last line;Couplers) line 6 the last line; page 45, line page 30, upper 29 to line 31; right column, page 47, line line 6 to page 23 to page 63, 35, lower line 50 right column, line 11Color Page 121, upper -- --Development left column,Increasing line 7 to pageAgents 125, upper right column, line 1Ultraviolet Page 125, upper Page 37, lower Page 65, lineAbsorbers right column, right column, 22 to line 31 line 2 to page line 14 to 127, lower left page 38, upper column, the left column, last line line 11Antifading Page 127, lower Page 36, upper Page 4, lineAgents right column, right column, 30 to page 5,(Image Stabi- line 1 to page line 12 to line 23; pagelizers) 137, lower left page 37, upper 29, line 1 to column, line 8 left column, page 45, line line 19 25; page 45, line 33 to line 40; page 65, line 2 to line 21.High Boiling Page 137, lower Page 35, lower Page 64, lineand/or Low left column, right column, 1 to line 51Boiling line 9 to page line 14 toOrganic 144, upper page 36, upperSolvents right column, left column, the last line line 4 from the bottomDispersing Page 144, lower Page 27, lower Page 63, lineMethods of left column, right column, 51 to pagePhotographic line 1 to page line 10 to 64, line 56Additives 146, upper page 28, upper right column, left column, line 7 the last line; page 35, lower right column, line 12 to page 36, upper right column, line 7Hardeners Page 146, upper -- -- right column, line 8 to page 155, lower left column, line 4Developing Page 155, lower -- --Agent left column,Precursors line 5 to lower right column, line 2Development Page 155, lower -- --Restrainer- right column,Releasing line 3 to lineCompounds 9Supports Page 155, lower Page 38, upper Page 66, line right column, right column, 29 to page line 19 to page line 18 to 67, line 13 156, upper left page 39, upper column, line 14 left column, line 3Photographic Page 156, upper Page 28, upper Page 45, lineMaterial left column, right column, 41 to line 52Layer line 15 to page line 1 to lineConstitution 156, lower 15 right column, line 14Dyes Page 156, lower Page 38, upper Page 66, line right column, left column, 18 to line 22 line 15 to page line 12 to 184, lower upper right right column, column, line the last line 7Color Mixing Page 185, upper Page 36, upper Page 64, lineInhibitors left column, right column, 57 to page line 1 to page line 8 to line 65, line 1 188, lower 11 right column, line 3Gradation Page 188, lower -- --Modifiers right column, line 4 to line 8Stain Page 188, lower Page 37, upper Page 65, lineInhibitors right column, left column, 32 to page line 9 to page the last line 66, line 17 193, lower to lower right right column, column, line line 10 13Surfactants Page 201, lower Page 18, upper -- left column, right column, line 1 to page line 1 to page 210, upper 24, lower right column, right column, the last line the last line; page 27, lower left column, line 10 from the bottom to lower right column, line 9Fluorine- Page 210, lower Page 25, upper --Containing right column, left column,Compounds line 1 to page line 1 to page(Antistatic 222, lower left 27, lowerAgents, Coat- column, line 5 right column,ing Aids, line 9Lubricants,AdhesionInhibitors)Binders Page 222, lower Page 38, upper Page 66, line(Hydrophilic left column, right column, 23 to line 28Colloids) line 6 to page line 8 to line 225, upper left 18 column, the last lineTackifiers Page 225, upper -- -- right column, line 1 to page 227, upper right column, line 2Antistatic Page 227, upper -- --Agents right column, line 3 to page 230, upper left column, line 1Polymer Page 230, upper -- --Latices left column, line 2 to page 239, the last lineMatting Page 240, upper -- --Agents left column, line 1 to upper right column, the last line______________________________________ Note: The cited portions of JPA-62-215272 include the contents of the amendment dated March, 16, 1987 which is given in the end of the publication. In addition, of the abovedescribed color couplers, as yellow couplers, socalled short wave type yellow couplers are also preferably used, and ar described in JPA-63-231451, JPA-63-123047, JPA-63-241547, JPA-1-173499, JPA-1-213648 and JPA-1-250944.
Cyan couplers preferably used include the diphenylimidazole cyan couplers described in JP-A-2-33144, the 3-hydroxypyridine cyan couplers described in European Patent 0,333,185A2 including the coupler made 2-equivalent by giving a chlorine eliminatable group to a 4-equivalent coupler of coupler (42), and couplers (6) and (9), which are particularly preferred, and the cyclic active methylene cyan couplers described in JP-A-64-32260 including couplers (3), (8) and (34) which are particularly preferred.
As a method for processing the silver halide color photographic materials using the high silver chloride emulsions containing at least 90 mol % of silver chloride, the method described on page 27, upper left column, to page 34, upper right column, of JP-A-2-207250 is preferably applied.
The present invention will be further illustrated in greater detail with reference to the following examples, which are, however, not to be construed as limiting the invention.
The structures of high boiling organic solvents used in the following examples, other than those compounds represented by general formulae (S-1) to (S-5), are as follows: ##STR166##
EXAMPLE 1
Using a triacetyl cellulose support having an under coat, monolayer photographic material 101 for evaluation having the following layer constitution, was prepared.
Preparation of Emulsion Layer Coating Solution
To 1.85 mmol of a coupler, 10 cc of ethyl acetate and 40% by weight (to the coupler) of trioctyl phosphate (a high boiling organic solvent, hereinafter also referred to as "an oil"), were added to dissolve the coupler. The resulting solution was dispersed by emulsification in 33 g of a 14% aqueous solution of gelatin containing 3 cc of a 10% solution of sodium dodecylbenzenesulfonate. On the other hand, a silver chlorobromide emulsion (silver bromide: 70 mol %) was sulfur sensitized and mixed -with the above-described emulsified product to prepare a coating solution so as to give the following composition. As a hardener, sodium salt of 1-oxy-3,5-dichloro-s-triazine was used.
Layer Constitution
The layer constitution of the sample used in this experiment is shown below. Numerals indicate coated weights (g/m.sup.2).
______________________________________SupportTriacetyl CelluloseSupportEmulsion LayerSilver Chlorobromide 4.0 mmol(described above)Coupler (see Table 2) 1.0 mmolSolvent (see Table 2) (40% by weight of coupler)Gelatin 5.2 gProtective LayerGelatin 1.3 gAcrylic Modified Copoly- 0.17 gmer of PolyvinylAlcohol (degree of modifi-cation: 17%)Liquid Paraffin 0.03 g______________________________________
The above-described photographic material was subjected to imagewise exposure using an optical wedge, and thereafter processed according to the following processing stages.
______________________________________Processing Stages Temperature TimeProcessing Stage (.degree.C.) (min)______________________________________Color Development 33 2Bleach-Fixing 33 1.5Washing 33 3Composition of Processing SolutionsColor Developing SolutionDistilled Water 800 mlTriethanolamine 8.1 gDiethylhydroxylamine 4.2 gPotassium Bromide 0.6 gSodium Hydrogencarbonate 3.9 gSodium Sulfite 0.13 gN-Ethyl-N-(.beta.-methanesulfonamido- 5.0 gethyl)-3-methyl-4-aminoanilineSulfatePotassium Carbonate 18.7 gWater to make 1000 mlpH 10.25Bleach-Fixing SolutionDistilled Water 400 mlAmmonium Thiosulfate (700 g/liter) 150 mlSodium Sulfate 18.0 gEthylenediaminetetraacetic Acid 55.0 g(III) AmmoniumSodium Ethylenediaminetetraacetate 5.0 gWater to make 1000 mlpH 6.7______________________________________
Then, samples 102 to 165 were prepared in the same manner as with sample 101 with the exception that couplers were changed so as to become equimolar to sample 101, and the kinds and the amounts of oils used (the weight ratios of the oils to the couplers) were changed as shown in Table 2. These samples were exposed, followed by processing, in the same manner as the above-described sample 101.
For the processed samples, the yellow color forming density was measured through a blue color filter to prepare sensitometry curves. The maximum color forming density (Dmax) was read from these curves. The Dmax value mainly depends on the molecular extinction coefficient and coupling activity of the yellow coupler. Accordingly, a coupler showing an increase in this value can be said to be an excellent coupler high in color forming property.
Then, in order to evaluate the color image fastness of the above-described samples against light, the samples were irradiated with Xe light of 100,000 luxes (by an intermittent irradiation process of 3-hour irradiation/1-hour putting out lights) for 14 days, and then the density was measured again. The density of residual color images at Dmax portions was determined by percentage as evaluated values, which are shown in Table 2.
TABLE 2__________________________________________________________________________ Oil Color Forming Property Fading Xe,14 daysSample Coupler Kind Amount (Dmax) (residual rate) Remark__________________________________________________________________________101 ExY-1 S-110 0.4 1.28 74 Comparison102 ExY-1 S-110 0.6 1.43 67 Comparison103 ExY-1 S-110 1.0 1.51 53 Comparison104 ExY-1 S-102 0.4 1.27 83 Comparison105 ExY-1 S-102 0.6 1.48 79 Comparison106 ExY-1 S-102 1.0 1.52 74 Comparison107 ExY-1 S-201 0.4 1.46 80 Comparison108 ExY-1 S-201 0.6 1.51 73 Comparison109 ExY-1 S-201 1.0 1.53 62 Comparison110 ExY-1 S-502 0.4 1.35 75 Comparison111 ExY-1 S-502 0.6 1.42 69 Comparison112 ExY-1 S-502 1.0 1.50 56 Comparison113 (2) S-110 0.4 1.94 41 Comparison114 (2) S-110 0.6 1.97 75 Invention115 (2) S-110 0.8 1.99 82 Invention116 (2) S-110 1.0 2.00 87 Invention117 (2) S-110 2.0 2.01 91 Invention118 (2) S-102 0.4 1.93 35 Comparison119 (2) S-102 0.6 1.97 71 Invention120 (2) S-102 0.8 2.02 78 Invention121 (2) S-102 1.0 2.04 83 Invention122 (2) S-102 2.0 2.03 86 Invention123 (2) S-201 0.4 1.97 32 Comparison124 (2) S-201 0.6 2.02 67 Invention125 (2) S-201 0.8 2.04 74 Invention126 (2) S-201 1.0 2.04 79 Invention127 (2) S-201 2.0 2.03 83 Invention128 (2) S-502 0.4 1.96 34 Comparison129 (2) S-502 0.6 1.98 69 Invention130 (2) S-502 0.8 1.99 75 Invention131 (2) S-502 1.0 2.00 81 Invention132 (2) S-502 2.0 2.00 85 Invention133 (2) S-407 0.4 1.92 35 Comparison134 (2) S-407 0.6 1.95 70 Invention135 (2) S-407 1.0 1.96 76 Invention136 (2) S-301 0.4 1.94 32 Comparison137 (2) S-301 0.6 1.98 68 Invention138 (2) S-301 1.0 1.99 75 Invention139 (1) S-111 0.4 2.08 37 Comparison140 (1) S-111 0.6 2.09 72 Invention141 (1) S-111 1.0 2.10 84 Invention142 (1) S-104 0.4 2.12 32 Comparison143 (1) S-104 0.6 2.13 69 Invention144 (1) S-104 1.0 2.13 76 Invention145 (1) S-205 0.4 2.14 30 Comparison146 (1) S-205 0.6 2.14 66 Invention147 (1) S-205 1.0 2.14 73 Invention148 (29) S-111 0.4 2.16 46 Comparison149 (29) S-111 1.0 2.18 90 Invention150 (16) S-111 0.4 2.04 43 Comparison151 (16) S-111 1.0 2.07 88 Invention152 (25) S-111 0.4 1.93 45 Comparison153 (25) S-111 1.0 1.95 89 Invention154 (8) S-111 0.4 2.04 48 Comparison155 (8) S-111 1.0 2.06 91 Invention156 (37) S-111 0.4 1.96 28 Comparison157 (37) S-111 1.0 2.02 70 Invention158 (2) S-601 0.4 1.84 43 Comparison159 (2) S-601 1.0 1.87 73 Invention160 (2) S-602 0.4 1.88 18 Comparison161 (2) S-602 1.0 1.90 57 Invention162 (2) S-125 0.4 1.98 35 Comparison163 (2) S-125 1.0 2.04 80 Invention164 (2) S-130 0.4 2.01 39 Comparison165 (2) S-130 1.0 2.05 78 Invention__________________________________________________________________________ExY-1 ##STR167## ##STR168## The results shown in Table 2 reveal that coupler Ex-Y for comparisonhas a tendency to be improved in color forming property as the amounts ofthe high boiling organic solvents used increase, but the light fastnessdecreases. Thus, the conventional acylacet-anilide-type couplersincluding the pivaloyl-type yellow couplers tend to be improved in lightfastness with decreases in the amounts used of the high boiling organic
In contrast, the results shown in Table 2 reveal that the couplers of the present invention exhibit color forming density as high as 1.4 to 1.5 times that of ExY-1, regardless of the amounts of the high boiling organic solvents used.
Further, the color image fastness against light is significantly improved when the amounts of the high boiling organic solvents used (the weight ratios of the solvents to the couplers) are 0.6 or more. This fact can not be anticipated at all from the light fading behavior of the acylacetanilide-type yellow couplers described above.
As is described above, when the high boiling organic solvents are used in weight ratios to the couplers of 0.6 or more with the yellow couplers of the present invention, it becomes possible to realize the high color forming property and the excellent light fastness at the same time.
EXAMPLE 2
Using a triacetyl cellulose support having an under coat, monolayer photographic material 201 was prepared for evaluation having the following layer constitution.
Preparation of Emulsion Layer Coating Solution
To 1.85 mmol of a coupler, 10 cc of ethyl acetate, and 40% by weight (to the coupler) of tricresyl phosphate (a high boiling organic solvent), were added to dissolve the coupler. The resulting solution was dispersed by emulsification in 33 g of a 14% aqueous solution of gelatin containing 3 cc of a 10% solution of sodium dodecylbenzene-sulfonate. On the other hand, a silver chlorobromide emulsion was prepared; cubic, a 3:7 mixture (silver molar ratio) of a large-sized emulsion having a mean grain size of 0.88 .mu.m and a small-sized emulsion having a mean grain size of 0.70 .mu.m, coefficients of variation in grain size distribution for the respective emulsions being 0.08 and 0.10, each emulsion comprising silver halide grains in which 0.3 mol % of silver bromide is localized on part of the surface of each grain and the remainder is silver chloride. Each of blue sensitizing dyes A and B shown below was added to this emulsion in an amount of 2.0.times.10.sup.-4 mol per mol of silver for the large-sized emulsion, and in an amount of 2.5.times.10.sup.-4 mol per mol of silver for the small-sized emulsion. Chemical sensitization of this emulsion was carried out by adding a sulfur sensitizing agent and a gold sensitizing agent. This emulsion and the abovedescribed emulsified product were mixed with each other to prepare a coating solution so as to give the following composition. As a hardener, sodium salt of 1-oxy-3,5-dichloro-s-triazine was used.
Layer Constitution
The layer constitution of the sample used in this experiment is shown below. Numerals indicate coated weights (g/m.sup.2).
__________________________________________________________________________SupportTriacetyl Cellulose SupportEmulsion LayerSilver Chlorobromide (described above) 3.0 mmolCoupler (see Table 3) 1.0 mmolSolvent (see Table 3) (40% by weight of coupler)Gelatin 5.5 gProtective LayerGelatin 1.5 gAcrylic Modified Copolymer of Polyvinyl Alcohol 0.15 g(degree of modification: 17%)Liquid Paraffin 0.03 gBlue-Sensitive Emulsion LayerSensitizing Dye A ##STR169##andSensitizing Dye B ##STR170##ExY-2 ##STR171## ##STR172##__________________________________________________________________________
The above-described photographic material was subjected to exposure through an optical wedge, and thereafter processed according to the following stages.
______________________________________Processing Stages Temperature TimeProcessing Stage (.degree.C.) (sec)______________________________________Color Development 35 45Bleaching-Fixing 35 45Stabilizing (1) 35 20Stabilizing (2) 35 20Stabilizing (3) 35 20Stabilizing (4) 35 20Drying 80 60Four-tank countercurrent system from stabilizing (4)to stabilizing (1) was employed.______________________________________
The composition of each processing solution was as follows:
______________________________________Color Developing SolutionWater 800 ml1-Hydroxyethylidene-1,1-diphosphonic 0.8 mlAcid (60%)Triethanolamine 8.0 gSodium Chloride 1.4 gPotassium Bromide 0.03 gN,N-Diethylhydroxylamine 4.6 gPotassium Carbonate 27 gSodium Sulfite 0.1 gN-Ethyl-N-(.beta.-methanesulfonamidoethyl)- 4.5 g3-methyl-4-aminoaniline 3/2 SulfateMonohydrateLithium Sulfate (anhydrous) 2.7 gFluorescent Brightener 2.0 g(4,4'-diaminostilbene type)Water to make 1000 mlpH (by adding potassium hydroxide) 10.25Bleach-Fixing SolutionWater 400 mlAmmonium Thiosulfate (700 g/liter) 100 mlSodium Sulfite 18 gEthylenediaminetetraacetic Acid 55 gFe(III) AmmoniumDisodium Ethylenediaminetetraacetate 3 gGlacial Acetic Acid 9 gWater to make 1000 mlpH 5.4Stabilizing SolutionBenzoisothiazoline-3-one 0.02 gPolyvinylpyrrolidone 0.05 gWater to make 1000 mlpH 7.0______________________________________
Then, samples 202 to 269 were prepared in the same manner as sample 201, with the exception that the types of couplers, and the types and amounts of high boiling organic solvents (the weight ratios of the solvents to the couplers) were changed as shown in Table 3. When the couplers of the present invention were used, the total amounts applied were reduced to 70% by weight of that of sample 201. These samples were also exposed, followed by processing, in the same manner as with the above-described sample 201.
For the processed samples, the yellow color forming density and the magenta component density in yellow were measured through a blue color filter and a green color filter, respectively, to prepare respective sensitometry curves. The magenta component at a yellow color forming density of 1.5, which is determined by the following equation from these curves, was taken as a measure for indicating hue, D.sub.G /D.sub.B.
Magenta Component=100.times.Magenta Density/Yellow Color Forming Density
The magenta component on yellow color forming is decreased, as this value is lowered. A lowered value shows that hue is excellent.
The color image fastness against light was evaluated the same manner as with Example 1, with the proviso that the residual rate was indicated by a value at an initial density of 1.5.
TABLE 3__________________________________________________________________________ Fading High Boiling Organic Solvent Hue (DG/DB) (residual rate)Sample Coupler Kind Dielectric Const. Amount (%) (%) Remark__________________________________________________________________________201 ExY-1 S-102 7.33 0.4 7.2 70 Comparison202 ExY-1 S-102 7.33 1.0 7.0 59 Comparison203 ExY-1 S-124 5.08 0.4 6.9 65 Comparison204 ExY-1 S-124 5.08 1.0 6.7 48 Comparison205 ExY-1 S-110 4.80 0.4 6.7 58 Comparison206 ExY-1 S-110 4.80 1.0 6.3 42 Comparison207 ExY-1 S-111 4.46 0.4 6.7 69 Comparison208 ExY-1 S-111 4.46 1.0 6.4 60 Comparison209 ExY-1 S-201 6.45 0.4 7.0 62 Comparison210 ExY-1 S-201 6.45 1.0 6.8 45 Comparison211 ExY-1 S-203 5.18 0.4 6.9 65 Comparison212 ExY-1 S-203 5.18 1.0 6.6 61 Comparison213 ExY-2 S-102 7.33 0.4 5.1 55 Comparison214 ExY-2 S-102 7.33 1.0 4.8 40 Comparison215 ExY-2 S-110 4.80 0.4 4.7 50 Comparison216 ExY-2 S-110 4.80 1.0 4.4 36 Comparison217 ExY-2 S-201 6.45 0.4 4.9 52 Comparison218 ExY-2 S-201 6.45 1.0 4.7 39 Comparison219 (1) S-110 4.80 0.4 5.7 30 Comparison220 (1) S-110 4.80 0.6 4.5 59 Invention221 (1) S-110 4.80 0.8 4.0 72 Invention222 (1) S-110 4.80 1.0 3.7 80 Invention223 (1) S-110 4.80 1.5 3.5 84 Invention224 (1) S-110 4.80 2.0 3.3 87 Invention225 (1) S-201 6.45 0.4 6.3 25 Comparison226 (1) S-201 6.45 0.6 5.8 53 Invention227 (1) S-201 6.45 0.8 5.5 62 Invention228 (1) S-201 6.45 1.0 5.3 70 Invention229 (1) S-201 6.45 2.0 5.0 78 Invention230 (1) S-601 13.45 0.4 7.4 42 Comparison231 (1) S-601 13.45 0.6 7.2 62 Invention232 (1) S-601 13.45 1.0 6.9 70 Invention233 (1) S-601 13.45 2.0 6.7 73 Invention234 (1) S-602 2.06 0.4 6.9 22 Comparison235 (1) S-602 2.06 0.6 5.6 48 Invention236 (1) S-602 2.06 1.0 5.2 57 Invention237 (1) S-603 10.6 0.4 7.2 47 Comparison238 (1) S-603 10.6 0.6 7.0 65 Invention239 (1) S-603 10.6 1.0 6.8 71 Invention240 (2) S-101 7.68 0.4 6.6 29 Comparison241 (2) S-101 7.68 1.0 5.8 78 Invention242 (2) S-102 7.33 0.4 6.4 31 comparison243 (2) S-102 7.33 1.0 5.6 82 Invention244 (2) S-104 6.64 0.4 6.3 37 Comparison245 (2) S-104 6.64 1.0 5.4 86 Invention246 (2) S-124 5.08 0.4 6.2 35 Comparison247 (2) S-124 5.08 1.0 5.0 84 Invention248 (2) S-109 5.86 0.4 6.2 32 Comparison249 (2) S-109 5.86 1.0 4.5 81 Invention250 (2) S-110 4.80 0.4 5.8 35 Comparison251 (2) S-110 4.80 1.0 4.0 86 Invention252 (2) S-111 4.46 0.4 5.9 37 Comparison253 (2) S-111 4.46 1.0 4.1 89 Invention254 (2) S-112 3.87 0.4 5.8 38 Comparison255 (2) S-112 3.87 1.0 4.0 85 Invention256 (2) S-201 6.45 0.4 6.6 28 Comparison257 (2) S-201 6.45 1.0 5.8 75 Invention258 (2) S-209 6.45 0.4 6.7 32 Comparison259 (2) S-209 6.45 1.0 5.8 80 Invention260 (2) S-203 5.18 0.4 6.2 30 Comparison261 (2) S-203 5.18 1.0 5.0 77 Invention262 (2) S-206 4.17 0.4 6.1 33 Comparison263 (2) S-206 4.17 1.0 4.7 79 Invention264 (2) S-301 4.49 0.4 6.1 30 Comparison265 (2) S-301 4.49 1.0 4.6 76 Invention266 (2) S-502 3.96 0.4 6.0 31 Comparison267 (2) S-502 3.96 1.0 4.2 75 Invention268 (2) S-407 3.84 0.4 6.0 33 Comparison269 (2) S-407 3.84 1.0 4.2 74 Invention__________________________________________________________________________
The results shown in Table 3 reveal that coupler ExY-1 for comparison has a high D.sub.G /D.sub.B value and has undesirable hue. This value does not largely vary, even if the amounts of the high boiling organic solvents are changed.
On the other hand, the results shown in Table 3 reveal that coupler ExY-2 for comparison shows a relatively low D.sub.G /D.sub.B value, even when the amounts of the high boiling organic solvents used are small, and is superior to coupler ExY-1 in hue. However, even this coupler did not show the tendency of the hue to be further largely improved by increasing the amounts of the high boiling organic solvents.
Further, the results reveal that ExY-2 is inferior to ExY-1 in light fastness. Furthermore, it was observed that the couplers were both deteriorated in light fastness by increasing the amount of the high boiling organic solvent.
In contrast, with respect to the yellow couplers of the present invention, a greater effect of improving the hue (a drop in D.sub.G /D.sub.B value) was observed by increasing the amounts of the high boiling organic solvents used. This tendency is pronounced at the high boiling organic solvents having a dielectric constant of 6.0 or less (for example, S-110, S-124, S-111, S-203 and S-206).
Further, this tendency is particularly pronounced with alkyl phosphates (for example, S-110 and S-111), which can be said to be the high boiling organic solvents preferable to improve the hue of the couplers of the present invention.
Furthermore, for any of the high boiling organic solvents, an improvement in light fastness is observed by increasing the amounts of the high boiling organic solvents used. Of the high boiling organic solvents, the solvents represented by general formulae (S-1) to (S-5) are highly effective.
EXAMPLE 3
A paper support, both sides of which were laminated with polyethylene, was subjected to corona discharge treatment and then provided with a gelatin underlayer containing sodium dodecylbenzenesulfonate. Various photographic constituent layers were further applied thereto. Thus, a multilayer color photographic paper sample 300 having the following layer constitution was prepared. Coating solutions were prepared as follows:
Preparation of Coating Solution for First Layer
132.0 g of yellow coupler (ExY), 15.0 g of color image stabilizer (Cpd-1), 7.5 g of color image stabilizer (Cpd-2) and 16.0 g of color image stabilizer (Cpd-3), were dissolved in 25 g of solvent (Solv-1), 25 g of solvent (Solv-2) and 180 cc of ethyl acetate. The resulting solution was emulsified and dispersed in 1000 g of a 10% aqueous solution of gelatin containing 60 cc of 10% sodium dodecylbenzenesulfonate and 10 g of citric acid, to prepare an emulsified dispersion A. This emulsified dispersion A and the silver chlorobromide emulsion prepared in Example 2 were mixed with each other to prepare a coating solution for a first layer so as to have the composition shown below. The amount of emulsion applied indicates a coated weight converted to silver.
Coating solutions for the second to seventh layers were prepared in the same manner as to the coating solution for the first layer. As a gelatin hardener for each layer, the sodium salt of 1-oxy-3,5-dichloro-s-triazine was used.
Cpd-14 and Cpd-15 were added to each layer to total amounts of 25.0 mg/m.sup.2 and 50.0 mg/m.sup.2, respectively.
In silver chlorobromide emulsions of other respective light-sensitive emulsion layers, the following color sensitizing dyes were used. ##STR173## 4.0.times.10.sup.-4 mol per mol of silver halide for a large-sized emulsion, and 5.6.times.10.sup.-4 mol per mol of silver halide for a small-sized emulsion. ##STR174## 7.0.times.10.sup.-5 mol per mol of silver halide for a large-sized emulsion, and 1.0.times.10.sup.-4 mol per mol of silver halide for a small-sized emulsion. ##STR175## 0.9.times.10.sup.-4 mol per mol of silver halide for a large-sized emulsion, and 1.1.times.10.sup.-4 mol per mol of silver halide for a small-sized emulsion.
The following compound was further added in an amount of 2.6.times.10.sup.-3 mol per mol of silver halide: ##STR176##
Further, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in amounts of 8.5.times.10.sup.-5 mol, 7.7.times.10.sup.-4 mol and 2.5.times.10.sup.-4 mol per mol of silver halide, respectively.
Furthermore, 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in amounts of 1.times.10.sup.-4 mol and 2.times.10.sup.-4 mol per mol of silver halide, respectively.
The following dyes were added to the emulsion layers for prevention of irradiation. The numerical values in parentheses indicate coated weights. ##STR177##
Layer Constitution
The composition of each layer is hereinafter shown. The numerals indicate coated weights (g/m.sup.2). For the silver halide emulsions, the numerals indicate coated weights converted to silver.
Support
The support was paper laminated with polyethylene (polyethylene on the side of the first layer containing a white pigment (TiO.sub.2) and a ,bluing dye (ultramarine)).
__________________________________________________________________________First Layer (Blue-Sensitive Emulsion Layer)Silver Chlorobromide Emulsion 0.27Described AboveGelatin 1.36Yellow Coupler (ExY) 0.68Color Image Stabilizer (Cpd-1) 0.08Color Image Stabilizer (Cpd-2) 0.04Color Image Stabilizer (Cpd-3) 0.08Solvent (Solv-1) 0.13Solvent (Solv-2) 0.13Second Layer (Color Mixing Preventing Layer)Gelatin 1.00Color Mixing Inhibitor (Cpd-4) 0.08Solvent (Solv-7) 0.03Solvent (Solv-2) 0.25Solvent (Solv-3) 0.25Third Layer (Green-Sensitive Emulsion Layer)Silver Chlorobromide Emulsion Cubic, a 1:3 mixture (Ag molar ratio) 0.13a large-sized emulsion having a mean grain size of 0.55 .mu.m and asmall-sized emulsionhaving a mean grain size of 0.39 .mu.m, coefficients of variation ingrainsize distribution being 0.1 and 0.08, respectively, each emulsioncontainingsilver halide in which 0.8 mol % of AgBr is localized on part of thesurface ofeach grain and the remainder being silver chloride.Gelatin 1.45Magenta Coupler (ExM) 0.16Color Image Stabilizer (Cpd-5) 0.15Color Image Stabilizer (Cpd-2) 0.03Color Image Stabilizer (Cpd-6) 0.01Color Image Stabilizer (Cpd-7) 0.01Color Image Stabilizer (Cpd-8) 0.08Solvent (Solv-3) 0.50Solvent (Solv-4) 0.15Solvent (Solv-5) 0.15Fourth Layer (Color Mixing Preventing Layer)Gelatin 0.70Color Mixing Inhibitor (Cpd-4) 0.05Solvent (Solv-7) 0.02Solvent (Solv-2) 0.18Solvent (Solv-3) 0.18Fifth Layer (Red-Sensitive Emulsion Layer)Silver Chlorobromide Emulsion Cubic, a 1:4 mixture (Ag molar ratio) 0.20a large-sized emulsion having a mean grain size of 0.50 .mu.m and asmall-sized emulsionhaving a mean grain size of 0.41 .mu.m, coefficients of variation ingrainsize distribution being 0.09 and 0.11, respectively, each emulsioncontainingsilver halide in which 0.8 mol % of AgBr is localized on part of thesurface ofeach grain and the remainder being silver chloride.Gelatin 0.85Cyan Coupler (ExC) 0.33Ultraviolet Light Absorber (UV-2) 0.18Color Image Stabilizer (Cpd-9) 0.01Color Image Stabilizer (Cpd-10) 0.01Color Image Stabilizer (Cpd-11) 0.01Solvent (Solv-6) 0.22Color Image Stabilizer (Cpd-8) 0.01Color Image Stabilizer (Cpd-6) 0.01Solvent (Solv-1) 0.01Color Image Stabilizer (Cpd-1) 0.33Sixth Layer (Ultraviolet Light Absorbing Layer)Gelatin 0.55Ultraviolet Light Absorber (UV-1) 0.38Color Image Stabilizer (Cpd-12) 0.15Color Image Stabilizer (Cpd-5) 0.02Seventh Layer (Protective Layer)Gelatin 1.13Acrylic Modified Copolymer of Polyvinyl 0.05Alcohol (degree of modification: 17%)Liquid paraffin 0.02Color Image Stabilizer (Cpd-13) 0.01__________________________________________________________________________ExY Yellow Coupler: ##STR178##A 1:1 mixture (molar ratio) of ##STR179##ExM Magenta Coupler: ##STR180##ExC Cyan Coupler:A 3:7 mixture (molar ratio) of ##STR181##(Cpd-1) Color Image Stabilizer: ##STR182##(Cpd-2) Color Image Stabilizer: ##STR183##(Cpd-3) Color Image Stabilizer: ##STR184##(Cpd-4) Color Mixing Inhibitor: ##STR185##(Cpd-5) Color Image Stabilizer: ##STR186##(Cpd-6) Color Image Stabilizer: ##STR187##(Cpd-7) Color Image Stabilizer: ##STR188##(Cpd-8) Color Image Stabilizer: ##STR189##(Cpd-9) Color Image Stabilizer: ##STR190##(Cpd-10) Color Image Stabilizer: ##STR191##(Cpd-11) Color Image Stabilizer: ##STR192##(Cpd-12) Color Image Stabilizer: ##STR193##(Cpd-13) Color Image Stabilizer: ##STR194##(Cpd-14) Antiseptic agent: ##STR195##(Cpd-15) Antiseptic agent: ##STR196##
A 1:5:10:5 mixture (weight ratio) of (1), (2), (3) and (4). ##STR197##
(UV-2) Ultraviolet Light Absorber
A 1:2:2 mixture (weight ratio) of (1), (2) and (3). ##STR198##
The above-described photographic material 300 was subjected to imagewise exposure using an optical wedge for three-color separation sensitometry. Then, continuous processing (running test) was carried out according to the following processing stages using a paper processor until the replenishment rate of the processing solutions reached twice the tank capacity of color development.
______________________________________ Replenish-* TankProcessing Temperature Time ment Rate CapacityStage (.degree.C.) (sec) (ml) (liter)______________________________________Color 35 45 161 10DevelopmentBleach-Fixing 35 45 218 10Rinsing (1) 35 30 -- 5Rinsing (2) 35 30 -- 5Rinsing (3) 35 30 360 5Drying 80 60______________________________________ *Replenishment rate per m.sup.2 of lightsensitive material
Three-tank countercurrent system from rinsing (3) to rinsing (1) was employed.
The composition of each processing solution was as follows:
______________________________________ Tank Solution Replenisher______________________________________Color Developing SolutionWater 800 ml 800 mlEthylenediaminetetraacetic 3.0 g 3.0 gAcidDisodium 4,5-Dihydroxy- 0.5 g 0.5 gbenzene-1,3-disulfonateTriethanolamine 12.0 g 12.0 gPotassium Chloride 2.5 g --Potassium Bromide 0.01 g --Potassium Carbonate 27.0 g 27.0 gFluorescent Brightener 1.0 g 2.5 g(WHITEX 4, Sumitomo ChemicalCo., Ltd.)Sodium Sulfite 0.1 g 0.2 gDisodium-N,N-bis(sulfonate- 5.0 g 8.0 gethyl) hydroxylamineN-Ethyl-N-(.beta.-methanesulfon- 5.0 g 7.1 gamidoethyl)-3-methyl-4-aminoaniline.3/2 Sulfate.MonohydrateWater to make 1000 ml 1000 mlpH (25.degree. C., with potassium 10.05 10.45hydroxide and sulfuric acid)Bleach-Fixing Solution (tank solution and replenisher being the same)Water 600 mlAmmonium Thiosulfate (700 g/liter) 100 mlAmmonium Sulfite 40 gEthylenediaminetetraacetic Acid 55 gFe(III) AmmoniumIron Ethylenediaminetetraacetate 5 gAmmonium Bromide 40 gNitric Acid (67%) 30 gWater to make 1000 mlpH (25.degree. C., with acetic acid and 5.8aqueous ammonia)Rinsing Solution (tank solution and replenisher being the same)Chlorinated Sodium Isocyanurate 0.02 gDeionized Water (electric conduc- 1000 mltivity: 5 .mu.s/cm or less)pH 6.5______________________________________
Then, samples 301 to 385 were prepared in the same manner as with sample 300, with the exception that couplers, polymers (the amounts used are indicated by the percentages by weight to the couplers), and high boiling organic solvents (the amounts used are indicated by the weight ratios to the couplers) shown in Table 4 were substituted for yellow coupler (ExY), color image stabilizer (Cpd-1) and solvent (Solv-2), respectively.
Three sheets of each sample were exposed using an optical wedge for three-color separation sensitometry, followed by processing using processing solutions brought to a running state by use of the above-described sample 300. After processing, the yellow color forming density was measured for each sample through a blue color filter to prepare a sensitometry curve.
The yellow color forming density (Dmax) of each sample at exposure at which sample 300 gives a density of 2.20 (corresponding to the maximum color forming density), was read from the sensitometry curve, and the average values of three sheets are shown in Table 4 as evaluated values.
Then, one of the above-described sheets was irradiated with Xe light of 100,000 luxes (by intermittent irradiation of 3 hours in light/1 hour in the dark) for 28 days, and then the yellow density was measured again to determine the residual rate of color images. For the residual rate of color images, the residual rate at an initial density of 1.5 was indicated by percentage as an evaluated value of light fastness.
Further, another one of the above-described sheets was stored at 80.degree. C. at a relative humidity of 70% for 28 days, and subsequently the residual rate of color images was determined in the same manner as described above as an evaluated value of dark fastness.
These evaluated values are shown in Table 4.
TABLE 4__________________________________________________________________________ Color High Boiling Forming Light Fading Dark Fading Solvent Polymer Property Xe 80.degree. C., 70%Sample Coupler Kind Amount Kind Amount (%) Dmax 28 days (%) 28 days (%) Remark__________________________________________________________________________301 ExY-1 S-201 0.4 -- -- 2.17 65 60 Comparison302 ExY-1 S-201 0.6 -- -- 2.22 61 62 Comparison303 ExY-1 S-201 1.0 -- -- 2.29 57 65 Comparison304 ExY-1 S-201 0.4 P-17 10 2.08 76 62 Comparison305 ExY-1 S-201 0.4 P-17 20 1.68 80 63 Comparison306 ExY-1 S-201 0.6 P-17 10 2.14 71 64 Comparison307 ExY-1 S-201 0.6 P-17 20 1.75 75 64 Comparison308 ExY-1 S-201 1.0 P-17 10 2.21 67 67 Comparison309 ExY-1 S-201 1.0 P-17 20 2.08 71 68 Comparison310 ExY-1 S-201 1.0 P-17 30 1.92 74 68 Comparison311 ExY-1 S-201 1.0 P-17 50 1.74 78 69 Comparison312 ExY-2 S-110 0.4 -- -- 2.04 65 65 Comparison313 ExY-2 S-110 1.0 -- -- 2.32 52 68 Comparison314 ExY-2 S-110 0.4 P-17 10 1.87 73 68 Comparison315 ExY-2 S-110 0.4 P-17 20 1.58 77 69 Comparison316 ExY-2 S-110 1.0 P-17 10 2.24 64 70 Comparison317 ExY-2 S-110 1.0 P-17 20 1.73 68 71 Comparison318 (2) S-201 0.4 -- -- 2.25 48 87 Comparison319 (2) S-201 0.6 -- -- 2.27 67 90 Invention320 (2) S-201 1.0 -- -- 2.28 75 92 Invention321 (2) S-201 0.4 P-17 10 2.24 55 89 Comparison322 (2) S-201 0.4 P-17 20 2.24 57 89 Comparison323 (2) S-201 0.4 P-17 50 2.17 60 90 Comparison324 (2) S-201 0.6 P-17 10 2.26 74 92 Invention325 (2) S-201 0.6 P-17 20 2.25 83 92 Invention326 (2) S-201 0.6 P-17 50 2.21 88 93 Invention327 (2) S-201 1.0 P-17 20 2.27 88 94 Invention328 (2) S-201 1.0 P-17 50 2.27 90 95 Invention329 (2) S-201 1.0 P-17 100 2.24 92 96 Invention330 (2) S-201 0.4 P-2 20 2.24 56 89 Comparison331 (2) S-201 1.0 P-2 20 2.26 85 94 Invention332 (2) S-201 0.4 P-70 20 2.23 54 87 Comparison333 (2) S-201 1.0 P-70 20 2.25 82 92 Invention334 (2) S-110 0.4 -- -- 2.23 55 90 Comparison335 (2) S-110 0.6 -- -- 2.25 72 92 Invention336 (2) S-110 1.0 -- -- 2.25 81 93 Invention337 (2) S-110 0.4 P-17 10 2.23 62 92 Comparison338 (2) S-110 0.4 P-17 20 2.23 64 93 Comparison339 (2) S-110 0.4 P-17 50 2.21 66 94 Comparison340 (2) S-110 1.0 P-17 20 2.25 86 94 Invention341 (2) S-110 1.0 P-17 50 2.25 90 95 Invention342 (2) S-110 1.0 P-17 100 2.24 95 97 Invention343 (2) S-102 0.4 -- -- 2.25 53 88 Comparison344 (2) S-102 0.6 -- -- 2.27 70 91 Invention345 (2) S-102 1.0 -- -- 2.28 78 92 Invention346 (2) S-102 0.4 P-67 10 2.25 59 90 Comparison347 (2) S-102 0.4 P-67 20 2.24 62 91 Comparison348 (2) S-102 0.4 P-67 50 2.22 64 91 Comparison349 (2) S-102 1.0 P-67 20 2.28 82 93 Invention350 (2) S-102 1.0 P-67 50 2.27 88 93 Invention351 (2) S-102 1.0 P-67 100 2.25 94 94 Invention352 (1) S-111 0.4 -- -- 2.19 49 88 Comparison353 (1) S-111 0.6 -- -- 2.21 68 90 Invention354 (1) S-111 1.0 -- -- 2.22 79 91 Invention355 (1) S-111 0.4 P-17 20 2.18 56 89 Comparison356 (1) S-111 0.6 P-17 20 2.20 75 90 Invention357 (1) S-111 1.0 P-17 20 2.22 86 92 Invention358 (1) S-203 0.4 -- -- 2.21 50 90 Comparison359 (1) S-203 0.6 -- -- 2.23 69 93 Invention360 (1) S-203 1.0 -- -- 2.24 81 95 Invention361 (1) S-203 0.4 P-67 20 2.20 58 93 Comparison362 (1) S-203 0.6 P-67 20 2.23 78 95 Invention363 (1) S-203 1.0 P-67 20 2.24 89 97 Invention364 (1) S-203 1.0 P-67 50 2.21 92 98 Invention365 (29) S-110 0.4 -- -- 2.24 45 85 Comparison366 (29) S-110 0.6 -- -- 2.27 68 90 Invention367 (29) S-110 1.0 -- -- 2.28 80 92 Invention368 (29) S-110 0.4 P-17 20 2.20 52 89 Comparison369 (29) S-110 0.6 P-17 20 2.25 74 92 Invention370 (29) S-110 1.0 P-17 20 2.27 86 94 Invention371 (29) S-110 1.0 P-17 50 2.24 91 96 Invention372 (8) S-110 0.4 -- -- 2.18 43 88 Comparison373 (8) S-110 0.6 -- -- 2.20 69 90 Invention374 (8) S-110 1.0 -- -- 2.21 82 90 Invention375 (8) S-110 0.4 P-17 20 2.16 53 91 Comparison376 (8) S-110 0.6 P-17 20 2.20 75 93 Invention377 (8) S-110 1.0 P-17 20 2.21 84 94 Invention378 (8) S-110 2.0 P-17 100 2.21 93 96 Invention379 (15) S-110 0.4 -- -- 2.08 35 91 Comparison380 (15) S-110 0.6 -- -- 2.14 62 93 Invention381 (15) S-110 1.0 -- -- 2.18 85 94 Invention382 (15) S-110 0.4 P-17 20 2.01 48 92 Comparison383 (15) S-110 0.6 P-17 20 2.10 75 95 Invention384 (15) S-110 1.0 P-17 20 2.17 91 95 Invention385 (15) S-110 2.0 P-17 50 2.16 94 96 Invention__________________________________________________________________________
The results shown in Table 4 reveal that the yellow couplers of the present invention are significantly improved in light fastness when the high boiling organic solvents are used in weight ratios to the couplers of 0.6 or more, as shown in Examples 1 and 2.
Even when each of the polymers is added to coupler ExY-1 for comparison, the light fastness is improved. However, although this effect increases with increasing the amount of the polymer added, a reduction in color forming property is induced at the same time. Accordingly, when the couplers for comparison are used, the amount of the polymer which can be added for an improvement in light fading has a limitation.
On the other hand, the light fastness is also improved by adding the polymers to the couplers of the present invention. When the high boiling organic solvents are used in amounts to the couplers of less than 0.6, the level of the light fastness of the coupler for comparison is not reached. However, when the high boiling organic solvents are used in weight ratios to the couplers of 0.6 or more, a light fastness equivalent to or higher than that of the coupler for comparison is attained. Further increases in the amounts of the polymers cause the realization of a higher light fastness without lowering the color forming property.
Further, the same samples as described above were processed by use of the above-described processing stages, and running processing was continued until the replenishment rate of the developing solution reached 5 times the tank capacity, followed by evaluations in the same manner as to those described above. The results thereof revealed that the samples of the present invention had a lower drop in the maximum color forming density than the samples for comparison. This shows that the samples of the present invention are excellent because of little processing dependency.
Furthermore, the results shown in Table 4 reveal that significant improvements in color image fastness in the dark also become possible by using the yellow couplers of the present invention.
EXAMPLE 4
Samples were prepared in the same manner as with Example 3, with the exception that HP-5, BP-14 or BP-15 was substituted for color image stabilizer (Cpd-2) in the blue-sensitive emulsion layer of each sample of Example 3. These samples were also evaluated in the same manner as with Example 3.
Also in this case, the couplers of the present invention were confirmed to show a particularly high light fastness when the high boiling organic solvents were used in weight ratios to the couplers of 0.6 or more.
As has been described in the foregoing Examples 1 to 4, it becomes possible to provide the photographic materials excellent in color reproducibility, color forming property, color image fastness and processing dependency by using the couplers of the present invention with the high boiling organic solvents which are used in weight ratios to the couplers of 0.6 or more.
In particular, the color image fastness can be more improved by using the polymers in amounts of 20% by weight or more based on the couplers.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Number	Name	Date
4668611	Nakamura et al.	May 1987
4770983	Ogawa et al.	Sep 1988
5001045	Furutachi et al.	Mar 1991
5028519	Norigaki et al.	Jul 1991
5071738	Mizukura et al.	Dec 1991
5100771	Mihayashi et al.	Mar 1992
5213958	Motoki et al.	May 1993
5294527	Deguchi	Mar 1994
5328817	Nakagawa et al.	Jul 1994

Silver halide color photographic material

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

Agents

CPC

US Classifications

Field of Search

US

International Classifications

Abstract

Description

Claims

Priority Claims (1)

Parent Case Info

US Referenced Citations (9)

Divisions (1)