Silver halide photographic light-sensitive material containing a novel yellow coupler

FIELD OF THE INVENTION
The present invention relates to a silver halide photographic light-sensitive material, more particularly to a silver halide photographic light-sensitive material that uses a novel 2-equivalent yellow coupler having an excellent color forming property and causing less fog, and having an improved dispersing stability in emulsion as well.
BACKGROUND OF THE INVENTION
Yellow couplers are an essential component of a color photographic light-sensitive material, and 2-equivalent yellow couplers are used in the industry to obtain a maximum dye density and photographic sensitivity with a minimum amount of silver. As an coupling-off substituent in such 2-equivalent yellow couplers, there has been known an aryloxy group described in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 87650/1975 and U.S. Pat. No. 3,408,194; an oxazolyloxy group described in Japanese Pat. O.P.I. Publication No. 131325/1976; a chroman-4-oxy group in the same Publication NO. 139333/1976; a tetrazolyloxy group in the same Publication No. 43426/1977; a 5-pyrazolyloxy group in the same Publication No. 150631/1977; a nitrogen-containing heterocyclic group in the same Publication No. 115219/1977; urazol group and hydantoin group in Japanese Pat. Examined Publication No. 33410/1976; and an arylthio group in U.S. Pat. No. 3,227,554.
On the other hand, requirements for coupler properties come to increasingly severe as the silver halide photographic light-sensitive material advances, and improvement in color forming efficiency is also required of the 2-equivalent yellow couplers. To meet with the requirement, there have been made various attempts in designing a coupler molecule, including proposals to introduce an alkoxycarbonyl group, or, a N-substituted or non-substituted alkylsulfonamide group or arylsulfonamide group as a ballast component. However, improvement in color forming property is not yet attained. A 2-equivalent yellow coupler with a hydantoin group as the coupling-off substituent is known to have an excellent color forming property, but it has disadvantage in poor solubility and unstable dispersibility in emulsion; therefore, improvement in these properties is strongly desired. Meanwhile, it is desired to reduce an amount of benzyl alcohol used in a color developer solution, or not to use it at all, in order to prevent environmental pollution and a problem caused by formation of tar in a developer solution. But, such reduction or nonuse of benzyl alcohol tends to lower the color forming property. Therefore, it is of much value to develop a yellow coupler which exhibits an excellent color forming property even in a developer solution containing little or no benzyl alcohol. But it cannot be said that study of the yellow coupler has been actively conducted with the view of solving the above problems.
SUMMARY OF THE INVENTION
The present invention has been achieved by taking notice of the above conditions. The primary object of the present invention is to provide a silver halide photographic light-sensitive material containing a novel 2-equivalent yellow coupler which causes less fog and exhibits an excellent color forming property even in a developer solution containing little or no benzyl alcohol.
The secondary object of the present invention is to provide a silver halide photographic light-sensitive material containing a novel 2-equivalent yellow coupler excellent in solubility and dispersion stability when incorporated in an emulsion.
The above objects of the invention have been attained, in a silver halide photographic light-sensitive material comprising a support bearing thereon at least one silver halide emulsion layer, by a silver halide photographic light-sensitive material in which at least one of said silver halide emulsion layers contains a coupler represented by the following Formulas (I), (II) or (III): ##STR2## wherein R.sub.1 and R.sub.2 independently represent an alkyl group, cycloalkyl group or aryl group; R.sub.3 and R.sub.4 independently represent an alkyl group or cycloalkyl group; B represents a group capable of being substituted at a benzene ring; m represents an integer from 0 to 3; and X represents an acylamino group, sulfonamide group, oxycarbonyl group, carbamoyl group, sulfamoyl group, carbonyloxy group, oxycarbonylamino group, ureido group or sulfonyloxy group. ##STR3## wherein R.sub.5 represents an alkyl group or cycloalkyl group; R.sub.6 and R.sub.7 represent independently an alkyl group or cycloalkyl group, and R.sub.9 represents a hydrogen atom, alkyl group or cycloalkyl group, provided that the total carbon number of R.sub.6, R.sub.7 and R.sub.8 is 7 or less; X is the same as defined in Formula (I); and Y represents a halogen atom, amino group, alkylthio group or arylthio group. ##STR4## wherein R.sub.9 represents an aryl group; R.sub.10 and R.sub.11 independently represent an alkyl group or cycloalkyl group, provided that the total carbon number of the two is 9 or less; X and Y are the same as defined in Formulas (I) and (II).
DETAILED DESCRIPTION OF THE INVENTION
Examples of the alkyl group represented by R.sub.1 in Formula (I) include linear or branched-chain alkyl groups such as methyl, ethyl, isopropyl, t-butyl and dodecyl groups.
Examples of the cycloalkyl group represented by R.sub.1 include cyclopropyl, cyclohexyl and adamantyl groups. These alkyl and cycloalkyl groups represented by R.sub.1 include ones having a substituent such as a halogen atom, aryl group, alkoxy group, aryloxy group, alkylsulfonyl group, acylamino group and hydroxy group. Of these groups, branched alkyl groups such as t-butyl group are preferable as R.sub.1.
Examples of the aryl group represented by R.sub.1 in Formula (I) include a phenyl group and p-(t-octyl)phenyl group. These aryl groups may have a substituent such as a halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, nitro group, cyano group and acylamino group.
Examples of the alkyl group, cycloalkyl and aryl group each represented by R.sub.2 in Formura (I) include the same groups as specified in respect to R.sub.1. These alkyl, cycloalkyl and aryl groups represented by R.sub.2 may have the same substituent as specified in respect to R.sub.1. Of them, linear or branched alkyl groups are preferred as R.sub.2.
Examples of the alkyl group represented by R.sub.3 in Formula (I) include linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl and dodecyl groups.
Examples of the cycloalkyl group represented by R.sub.3 include cyclopropyl and cyclohexyl groups. These alkyl and cycloalkyl groups represented by R.sub.3 include ones having a substituent such as a halogen atom, aryl group, alkoxy group, aryloxy group, hydroxy group, acyloxy group, acylamino group, carbamoyl group, alkylcarbamoyl group, alkyloxycarbamoyl group, aryloxycarbamoyl group, alkylsulfonyl group and arylsulfonyl group.
Examples of the alkyl group and cycloalkyl group each represented by R.sub.4 include the same groups as R.sub.3. The alkyl and cycloalkyl groups represented by R.sub.4 include ones having the same substituent as specified in respect to R.sub.3.
Examples of the group capable of being replaced at a benzene ring and represented by B in Formula (I) are a halogen atom, alkyl group, alkoxy group, aryloxy group, acyloxy group, acylamino group, carbamoyl group, alkylsulfonamide group, arylsulfonamide group, sulfamoyl group and imide group. m represents an integer from 0 to 3; B may be the same or different, provided that m is 2 or more.
Examples of the alkyl group represented by R.sub.5 in Formula (II) include a methyl group, ethyl group, isopropyl group, t-butyl group and dodecyl group. These alkyl groups represented by R.sub.5 may have a substituent such as a halogen atom, aryl group, alkoxy group, aryloxy group, alkyloxy group, acyloxy group and acylamino group.
Examples of the cycloalkyl group represented by R.sub.5 include a cyclopropyl group, cyclohexyl group and adamantyl group.
R.sub.5 is preferably a branched alkyl group. In Formula (II), X is the same as defined in Formula (I).
Examples of the alkyl group and cycloalkyl group each represented by R.sub.6, R.sub.7 or R.sub.8 in Formula (II) are a methyl group, ethyl group, isopropyl group, hexyl group, cyclopentyl group and cyclohexyl group.
These alkyl and cycloalkyl groups each represented by R.sub.6, R.sub.7 or R.sub.8 may have a substituent such as a halogen atom (e.g., chlorine atom or bromine atom), alkoxy group (e.g., methoxy, ethoxy or isopropoxy group), cycloalkyloxy group (e.g., cyclopentyloxy group), alkylthio group (e.g., methylthio group), alkylsulfonylamino group (e.g., methanesulfonylamino or n-buthanesulfonylamino group), alkylcarbonylamino group (e.g., acetylamino group), alkoxycarbonyl group (e.g., methoxycarbonyl or ethoxycarbonyl group) and heterocyclic group (e.g., terahydrofuryl, furyl or propanesaltonyl group).
Other than the above alkyl and cycloalkyl groups, R.sub.8 represents a hydrogen atom.
R.sub.6, R.sub.7 and R.sub.8 may be in any combination with one another, provided that each of which represents the above group; the total carbon number of R.sub.6, R.sub.7 and R.sub.8 is 7 or less.
Examples of the halogen atom represented by Y in Formula (II) are a fluorine atom, chlorine atom, bromine atom and iodine atom.
The amino group represented by Y may be mono-substituted or di-substituted with groups such as alkyl, aryl, acyl and sulfonyl group; and examples of such amino group include a methylamino group, dimethylamino group, ethylamino group, isopropylamino group, dodecylamino group, phenylamino group, acetylamino group and benzylamino group.
Examples of the alkylthio group represented by Y are a methylthio group and arylthio group, and examples of the arylthio group represented by Y include a phenylthio group.
Y is preferably a halogen atom, particularly preferably a chlorine atom.
Examples of the aryl group represented by R.sub.9 in Formula (III) include an aryl group having 6 to 30 carbon atoms such as a phenyl group. This aryl group may have a substituent such as a halogen atom, trifluoromethyl group, alkoxy group, aryloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylamino group, dialkylamino group, anilino group, alkylcarbonylamino group or arylcarbonylamino group. Of them, an alkoxy group is preferred, a methoxy group is particularly preferred.
Examples of the alkyl and cycloalkyl groups each represented by R.sub.10 or R.sub.11 in Formura (III) include a methyl group, ethyl group, isopropyl group, hexyl group, cyclopentyl group and cyclohexyl group.
These alkyl and cycloalkyl groups each represented by R.sub.10 or R.sub.11 may have a substituent such as a halogen atom (e.g., chlorine or bromine atom), alkoxy group (e.g., methoxy, ethoxy or isopropoxy group), cycloalkyloxy group (e.g., cyclopentyloxy group), alkylthio group (e.g., methylthio group), alkylsufonylamino group (e.g., methanesulfonamide or n-buthanesulfonylamide group), alkylcarbonylamino group (e.g., acetylamino group), alkoxycarbonyl group (e.g., methoxycarbonyl or ethoxycarbonyl group) and heterocyclic group (e.g., tetrahydrofuryl, furyl or propanesaltonyl group).
R.sub.10 and R.sub.11 may be in any combination, provided that they represent the above groups; and the total carbon number of the two is 9 or less.
In Formulas (I) (II) and (III), X represents an acylamino group, sulfonamide group, oxycarbonyl group, carbamoyl group, sufamoyl group, carbonyloxy group, oxycarbonylamino group, ureido group and sulfonyloxy group; and X is preferably selected from the following groups represented by Formuras (1) to (11). ##STR5## wherein R.sub.12 represents an alkyl group, cycloalkyl group or aryl group; R.sub.13 and R.sub.14 independently represent a hydrogen atom or a group represented by R.sub.12 ; and L represents a divalent organic linking group.
Examples of the alkyl and cycloalkyl groups each represented by R.sub.12, R.sub.13 or R.sub.14 include a linear or branched alkyl and cycloalkyl groups (e.g., methyl, n-butyl, cyclohexyl, 2-ethylhexyl, n-dodecyl or n-hexadecyl group). Examples of the aryl group represented by R.sub.12, R.sub.13 or R.sub.14 include an aryl group having 6 to 22 carbon atoms (e.g., phenyl or 1-naphthyl group).
These alkyl and cycloalkyl groups each represented by R.sub.12, R.sub.13 or R.sub.14 may have a substituent such as a halogen atom (e.g., chlorin or bromine atom), aryl group (e.g., phenyl or 4-t-butylphenyl group), aryloxy group (e.g., phenoxy, p-methylphenoxy or 2,4-di-t-amylphenoxy group), alkoxy group (e.g., methoxy, ethoxy, i-propyloxy or n-dodecyloxy group), cycloalkyloxy (e..g, cyclohexyloxy group), alkylthio group (e.g., methylthio group), alkylsulfonylamino group (e.g., methanesulfonylamino or n-butanesulfonylamino group) and alkylcarbonylamino group (e.g., acetylamino or 3-(2,4-di-t-amylphenoxy)butanoylamino group).
The aryl group represented by R.sub.12, R.sub.13 or R.sub.14 may have a substituent such as an alkyl group or the same group that can be introduced in the alkyl or cycloalkyl group represented by R.sub.12, R.sub.13 or R.sub.14.
L in Formulas (4) and (10) represents a divalent organic linking group being a alkylene or arylene group. Examples of the alkylene group include linear or branched alkylene groups having 1 to 10 carbon atoms (e.g., methylene, ethylene, methylethylene, propylene, dimethylmethylene, butylene and hexylene groups). Examples of the arylene group represented by L include arylene groups having 6 to 14 carbon atoms (e.g., 1,2-phenylene, 1,4-phenylene and 1,4-naphthylene groups).
Each of the couplers represented by Formulas (I), (II) and (III) may link with one another via a polyvalent group to form a dimer, oligomer or much larger low polymer. In this case, the carbon number range defined for the forgoing substituents may not be applicable.
Typical examples of the 2-equivalent yellow couplers of the invention represented by Formulas (I), (II) and (III) are shown below, but the scope of the invention is not limited to these examples.
##STR6## No. R.sub.1 R.sub.2 R.sub.3 R.sub.4 X (Substitutional position) 1 tC.sub.4 H.sub.9 CH.sub.3 C.sub.4 H.sub.9 CH.sub.3 NHSO.sub.2 C.sub.16 H.sub.33 (5) 2 tC.sub.4 H.sub.9 CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.3 NHSO.sub.2 C.sub.16 H.sub.33 (5) 3 tC.sub.4 H.sub.9 CH.sub.3 ##STR7## CH.sub.3 NHSO.sub.2 C.sub.16 H.sub.33 (5) 4 tC.sub.4 H.sub.9 CH.sub.3 C.sub.4 H.sub.7 CH.sub.3 ##STR8## 5 t C.sub.4 H.sub.9 C.sub.16 H.sub.33 CH.sub.3 CH.sub.3 NHSO.sub.2 C.sub.4 H.sub.9 (5) 6 tC.sub.4 H.sub.9 CH.sub.3 CH.sub.2 CH.sub.2 (CH.sub.3).sub.2 CH.sub.3 ##STR9## 7 t C.sub.4 H.sub.9 CH.sub.3 C.sub.6 H.sub.13 CH.sub.3 ##STR10## 8 t C.sub.4 H.sub.9 CH.sub.3 ##STR11## CH.sub.3 ##STR12## 9 t C.sub.4 H.sub.9 ##STR13## CH.sub.3 CH.sub.3 ##STR14## 10 t C.sub.4 H.sub.9 CH.sub.3 CH.sub.2 CH.sub.2 OH.sub.3 CH.sub.3 ##STR15## 11 t C.sub.4 H.sub.9 CH.sub.3 ##STR16## CH.sub.3 ##STR17## 12 t C.sub.4 H.sub.9 CH.sub.3 C.sub.4 H.sub.9 CH.sub.3 ##STR18## 13 t C.sub.4 H.sub.9 CH.sub.3 CH.sub.3 CH.sub.3 NHCOC.sub.11 H.sub.23 (5) 14 tC.sub.4 H.sub.9 CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.3 ##STR19## 15 t C.sub.4 H.sub.9 CH.sub.3 CH.sub.3 CH.sub.3 ##STR20## 16 t C.sub.4 H.sub.9 CH.sub.3 ##STR21## CH.sub.3 ##STR22## 17 t C.sub.4 H.sub.9 CH.sub.3 C.sub.4 H.sub.9 CH.sub.3 ##STR23## 18 t C.sub.4 H.sub.9 CH.sub.3 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR24## 19 t C.sub.4 H.sub.9 CH.sub.3 CH.sub.2 OH CH.sub.3 ##STR25## 20 t C.sub.4 H.sub.9 CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 CH.sub.3 ##STR26## 21 t C.sub.4 H.sub.9 ##STR27## CH.sub.3 CH.sub.3 NHCO(CH.sub.2).sub.3 SO.sub.2 C.sub.12 H.sub.25 (5) 22 tC.sub.4 H.sub.9 CH.sub.3 ##STR28## CH.sub.3 ##STR29## 23 t C.sub.4 H.sub.9 CH.sub.3 C.sub.4 H.sub.9 CH.sub.3 CO.sub.2 C.sub.12 H.sub.25 (5) 24 tC.sub.4 H.sub.9 CH.sub.3 C.sub.4 H.sub.9 CH.sub.3 ##STR30## 25 t C.sub.4 H.sub.9 CH.sub.3 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 CH.sub.3 ##STR31## 26 t C.sub.4 H.sub.9 CH.sub.3 CH.sub.3 CH.sub.3 ##STR32## 27 t C.sub.4 H.sub.9 CH.sub.3 CH.sub.3 CH.sub.3 CONHC.sub.12 H.sub.25 (5) 28 tC.sub.4 H.sub.9 C.sub.2 H.sub.5 C.sub.4 H.sub.9 CH.sub.3 ##STR33## 29 t C.sub.4 H.sub.9 CH.sub.3 CH.sub.3 CH.sub.3 NHCOOC.sub.16 H.sub.33 (5) 30 ##STR34## CH.sub.3 C.sub.4 H.sub.9 CH.sub.3 ##STR35## 31 ##STR36## CH.sub.3 CH.sub.3 CH.sub.3 NHCO(CH.sub.2).sub.3 SO.sub.2 C.sub.12 H.sub.25 (5) 32 ##STR37## CH.sub.3 CH.sub.3 CH.sub.3 ##STR38## 33 ##STR39## CH.sub.3 C.sub.4 H.sub.9 CH.sub.3 NHSO.sub.2 C.sub.16 H.sub.33 (5) 34 ##STR40## CH.sub.3 C.sub.4 H.sub.9 CH.sub.3 CO.sub.2 C.sub.12 H.sub.25 (5) 35 ##STR41## CH.sub.3 CH.sub.3 CH.sub.3 CO.sub.2 C.sub.12 H.sub.25 (5) 36 ##STR42## CH.sub.3 ##STR43## CH.sub.3 CO.sub.2 C.sub.12 H.sub.25 (5) 37 ##STR44## CH.sub.3 CH(CH.sub.3).sub.2 CH.sub.3 ##STR45## 38 ##STR46## CH.sub.3 C.sub.4 H.sub.9 CH.sub.3 ##STR47## 39 ##STR48## CH.sub.3 ##STR49## CH.sub.3 SO.sub.2 NHC.sub.16 H.sub.33 (5) 40 ##STR50## CH.sub.3 CH.sub.3 C.sub.4 H.sub.9 CONHC.sub.12 H.sub.25 (5) 41 ##STR51## CH.sub.3 C.sub.4 H.sub.9 CH.sub.3 ##STR52## 42 ##STR53## CH.sub.3 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 CH.sub.3 OCOC.sub.11 H.sub.23 (5) 43 ##STR54## CH.sub.3 ##STR55## CH.sub.3 OCO.sub.2 C.sub.16 H.sub.33 (5) 44 ##STR56## 45 ##STR57## 46 ##STR58## ##STR59## No. R.sub.5 Y ##STR60## X (Substitutional position) 47 (t)C.sub.4 H.sub.9 Cl ##STR61## ##STR62## 48 (t)C.sub.4 H.sub.9 ##STR63## ##STR64## ##STR65## 49 (t)C.sub.4 H.sub.9 Cl ##STR66## ##STR67## 50 (t)C.sub.4 H.sub.9 Cl ##STR68## ##STR69## 51 (t)C.sub.4 H.sub.9 Cl ##STR70## ##STR71## 52 (t)C.sub.4 H.sub.9 SCH.sub.3 ##STR72## ##STR73## 53 (t)C.sub.4 H.sub.9 Cl ##STR74## ##STR75## 54 (t)C.sub.4 H.sub.9 Cl ##STR76## NHCO(CH.sub.2).sub.3 SO.sub.2 C.sub.12 H.sub.25 (5) 55 (t)C.sub.4 H.sub.9 F ##STR77## NHCO(CH.sub.2).sub.3 SO.sub.2 C.sub.10 H.sub.21 (5) 56 (t)C.sub.4 H.sub.9 NHSO.sub.2 CH.sub.3 ##STR78## CONHC.sub.12 H.sub.25 (5) 57 (t)C.sub.4 H.sub.9 Cl ##STR79## ##STR80## 58 (t)C.sub.4 H.sub.9 Cl ##STR81## COOC.sub.12 H.sub.25 (5) 59 (t)C.sub.4 H.sub.9 Cl ##STR82## ##STR83## 60 (t)C.sub.4 H.sub.9 Cl ##STR84## NHSO.sub.2 C.sub.16 H.sub.33 (5) 61 (t)C.sub.4 H.sub.9 Cl ##STR85## ##STR86## 62 (t)C.sub.4 H.sub.9 Cl ##STR87## NHCOOC.sub.16 H.sub.33 (5) 63 (t)C.sub.4 H.sub.9 Cl ##STR88## ##STR89## 64 (t)C.sub.4 H.sub.9 Cl ##STR90## ##STR91## 65 (t)C.sub.4 H.sub.9 Cl ##STR92## OCOC.sub.11 H.sub.23 (5) 66 (t)C.sub.4 H.sub.9 Cl ##STR93## ##STR94## 67 (t)C.sub.4 H.sub.9 Cl ##STR95## ##STR96## 68 (t)C.sub.4 H.sub.9 Cl ##STR97## CONHC.sub.12 H.sub.25 (5) 69 (t)C.sub.4 H.sub.9 Cl ##STR98## NHCONHC.sub.12 H.sub.25 (5) ##STR99## No. R.sub.9 Y ##STR100## X (Substitutional position) 70 ##STR101## Cl ##STR102## NHSO.sub.2 C.sub.16 H.sub.33 (5) 71 ##STR103## Cl ##STR104## NHSO.sub.2 C.sub.16 H.sub.33 (5) 72 ##STR105## Cl ##STR106## NHSO.sub.2 C.sub.16 H.sub.33 (5) 73 ##STR107## Cl ##STR108## ##STR109## 75 ##STR110## F ##STR111## ##STR112## 76 ##STR113## Cl ##STR114## COOC.sub.8 H.sub.17 (5) 77 ##STR115## Cl ##STR116## COOC.sub.8 H.sub.17 (5) 78 ##STR117## Cl ##STR118## NHSO.sub.2 C.sub.12 H.sub.25 (5) 79 ##STR119## Cl ##STR120## ##STR121## 80 ##STR122## Cl ##STR123## ##STR124## 81 ##STR125## Cl ##STR126## ##STR127## 82 ##STR128## Cl ##STR129## NHCOOC.sub.16 H.sub.33 (5) 83 ##STR130## Cl ##STR131## CONHC.sub.12 H.sub.25 (5) 84 ##STR132## Cl ##STR133## CONHC.sub.12 H.sub.25 (5) 85 ##STR134## Cl ##STR135## ##STR136## 86 ##STR137## Cl ##STR138## OCOC.sub.11 H.sub.23 (5) 87 ##STR139## Cl ##STR140## OSO.sub.2 C.sub.16 H.sub.33 (5) 88 ##STR141## F ##STR142## OCOC.sub.16 H.sub.33 (5) 89 ##STR143## Cl ##STR144## NHCONHC.sub.12 H.sub.25 (5) 90 ##STR145## Cl ##STR146## ##STR147## 91 ##STR148## Cl ##STR149## ##STR150##
The yellow couplers of the invention can be synthesized by known methods. The following are examples of typical methods for synthesizing couplers of the invention.
Synthesis 1 (synthesis of Example Coupler 15)
A solution of 12.8 g of -chloro- -pivaloyl-2-methoxy-5-( -methyl- -dodecylsulfonylpropanoylamino) acetanilide, 3.3 g of 1,5-dimethylhydantoin and 3.8 g of potassium carbonate in 100 ml of acetone was refluxed for 6 hours upon continued heating. Then, acetone was removed by vacuum distillation. The residue was dissolved in 200 ml of ethylacetate and washed three times with 100 ml of 3-N hydrochloric acid. The organic layer was then separated and dried with magnesium sulfate. After filtering off the insoluble matter, the solvent was removed by vacuum distillation. The product was purified by column chromatography to obtain 9.1 g of Example Coupler 15. The yield was 62%.
Synthesis 2 (synthesis of Example Coupler 35)
A solution of 10.4 g of -chloro- -(4-methoxybenzoyl)-2-methoxy-5-dodecyloxycarbonylacetanilide and 6.4 g of potassium 1,5-dimethylhydantoin in 150 ml of acetone was refluxed for 8 hours upon continued heating. Then, after-treatments were carried out in the same procedure as in Synthesis 1. Purification by column chromatography gave 6.7 g (yield: 55%) of Example Coupler 35.
The structures of Example Couplers 15 and 35 were identified by NMR spectrums, IR spectrums and mass spectrums.
Synthesis 3 (synthesis of Example Coupler 49)
There was added 6.6 g of potassium carbonate to 100 ml of acetone solution containing 25.1 g of .alpha.-chloro-.alpha.-pivaloyl-2-chloro-5-(.alpha.-methyl-.beta.-dodecylsulfonylpropanoylamino)acetanilide and 6.1 g of 1,5-dimethyl-2,4-dioxoimidazoline, and the mixture was refluxed for 3 hours upon heating. After filtering off the insoluble matter, acotone was distilled out from the filtrate, and then ethyl acetate was added thereto. The solution was washed with an aqueous solution of potassium carbonate, followed by washing with water and neutralizing with a dilute hydrochloric acid. After drying with magnesium sulfate, ethylacetate was removed by vacuum distillation. The residue was recrystallized from 100 ml of methanol to obtain the objective compound. The yield was 20.8 g (72%). The structure was identified by means of NMR, IR and mass spectrums.
Synthesis 4 (synthesis of Example Coupler 70)
A solution of 10 g of .alpha.-bromo-.alpha.-(4methoxybenzoyl)-2-chloro-5-hexadecanylsulfonylaminoacetanilide, 4.8 g of potassium 1,5,5-trimethyl-2,4-dioxoimidazolidine and 50 ml of DMF was heated at 60.degree. C. for 3 hours. After completion f the reaction, 100 ml of water was added thereto, then ethyl acetate was added for extraction. The organic portion was washed with an aqueous solution of potassium carbonate, rinsed with water and neutralized with a dilute hydrochloric acid. After drying the solution with magnesium sulfate, ethyl acetate was removed by vacuum distillation, and the resulting residue was recrystallized from 50 ml of methanol to obtain the objective compound. The yield was 7.26 g (68%). The structure was identified by NMR, IR and mass spectrums.
The other couplers of the invention were synthesized from corresponding raw materials by the same procedures as in Synthesises 1 to 4.
The yellow couplers of the invention may be used singly or in combination of two or more. Further, they may be used together with a noninventive yellow coupler of pivaloylacetanilide type or benzoylacetanilide type.
In incorporating the yellow couplers of the invention in a silver halide photographic emulsion, the couplers are first dissolved singly or in combination in a high boiling organic solvent such as tricresyl phosphate or dibutyl phthalate, each which has a boiling point above 175.degree. C., or in a low boiling organic solvent such as ethyl acetate or butyl propionate, or a mixture thereof. The solution is mixed with an aqueous solution of gelatin containing a surfactant and then dispersed with a high-speed rotary mixer or colloid mill. The dispersion is directly added to a silver halide photographic emulsion, then the emulsion is coated on a support and dried; or the dispersion is allowed to set and divided into portions, after removing the low boiling organic solvent by means such as washing, it is added to an emulsion to be coated and dried on a support.
In general, the yellow couplers of the invention are preferably used in an amount of 10 to 300 g per mol of silver halide, but the addition amount may vary according to specific requirements.
The silver halide photographic light-sensitive material of the invention may be of any kind and for any use. Silver halides usable in the invention are silver chloride, silver bromide, silver iodide, silver bromochloride, silver bromoiodide and silver bromochloroiodide.
The silver halide photographic light-sensitive material may contain color couplers other than the yellow couplers of the invention in order to form multicolor images.
In the silver halide photographic light-sensitive material of the invention, there may be arbitrarily contained a variety additives such as an antistain agent, image stabilizer, hardener, plasticizer, polymer latex, formalin scavenger, mordant, development accelerator, development retarder, fluorescent whitening agent, matting agent, solvent, antistatic agent and surfactant.
In addition, the silver halide photographic light-sensitive material comprising the yellow coupler of the invention may contain an ultra violet absorbent so that stability of yellow images can be further improved.

EXAMPLES
The present invention is hereunder described in more detail with examples, but the embodiments of the invention are not limited to these examples.
EXAMPLE 1
10.0 g each of the yellow couplers of the invention shown in Table 1 (denoted by the number given to each example coupler) and the comparative couplers represented by Y-1 to Y-4 was dissolved at 50.degree. C. in a mixture of 2.0 ml of dibutyl phthalate and 20 ml of ethyl acetate. The solution thus prepared was mixed with 5 ml of 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate made by Du pont) and 100 ml of 5% aqueous gelatin, the mixture was then emulsified by being passed through a colloid mill several times to prepare an emulsion for each of the foregoing couplers. Thus, Samples 1 to 8 of the invention and Comparative Samples 1 to 4 were obtained.
These emulsion samples were stored for 48 hours at 20.degree. C., then the condition of each coupler was visually observed through a 20-power magnifier. The results are shown in Table 1.
TABLE 1______________________________________ Coupler conditionSample No. Coupler after storage______________________________________Sample of the 1 Example 70 No precipitationinvention 2 Coupler 71 No precipitation 3 72 No precipitation 4 73 No precipitation 6 75 No precipitation 7 76 No precipitation 8 78 No precipitationComparative 1 Comparative Y-1 Slight precipitationSample 2 coupler Y-2 Slight precipitation 3 Y-3 Heavy precipitation 4 Y-4 Heavy precipitation______________________________________
It is understood from the results shown in Table 1 that Samples 1 to 8 of the invention do not cause precipitation of couplers; that is, the couplers of the invention are excellent in dispersion stability when stored in an emulsion state. ##STR151##
EXAMPLE 2
3.0.times.10.sup.- mols each of the yellow couplers of the invention shown in Table 2 (denoted by the number given to each example coupler) and the comparative couplers represented by Y-5 and Y-6 was dissolved at 50.degree. C. in a mixture of dibutyl phthalate in an amount corresponding to 1/4 the weight of each yellow coupler and 40 ml of ethyl acetate . The solution was mixed with 10 ml of 10% aqueous solution of Alkanol B and 200 ml of 5% aqueous gelatin, the mixtures was then emulsified by being passed through a colloid mill several times. Twelve kinds of dispersion (A) containing respective couplers were thus prepared, and their turbidities were measured with a integrating sphere type turbidimeter made by Nippon Seimitsu Kogaku, Ltd. Then, each 1/2 the volume of the dispersion (A) was stored at 40.degree. C. for 8 hours to obtain dispersion (B), turbidities of these dispersions were measured in the same manner as in Example 1. The results of the measurements are shown in Table 2.
Next, the dispersions (A) and (B) were each added to 500 ml of silver chlorobromide emulsion, then each of the emulsions so prepared was coated on a polyethylene laminated paper to a coating weight of 0.25 g AgX/m.sup.2 and dried to obtain Samples 9 to 16 consisting of silver halide color photographic light-sensitive materials of the invention and Comparative Samples 5 and 6.
Each sample was exposed through an optical wedge in a normal manner and processed according to the following developing procedure and recipes of processing solutions.
______________________________________[Processing] Temperature TimeColor developing .sup. 38.degree. C. 3 min 30 secBleach-fixing .sup. 33.degree. C. 1 min 30 secWashing .sup. 33.degree. C. 3 minDrying 50 to 80.degree. C. 2 min______________________________________[Composition of color developer]Benzyl alcohol 12 mlDiethylene glycol 10 mlPotassium carbonate 25 gSodium bromide 0.6 gAnhydrous sodium sulfite 2.0 gHydroxylamine sulfate 2.5 gN-ethyl-N-.beta.-methanesulfonamidoethyl-3-methyl- 4.5 gaminoaniline sulfateWater was added to make 1 l, then pH was adjusted to10.2 with NaOH.[Composition of bleach-fixer]Ammonium thiosulfate 120 gSodium metabisulfite 15 gAnhydrous sodium sulfite 3 gAmmonium ferric EDTA 65 gWater was added to make 1 l, then pH was adjusted to6.7 to 6.8.______________________________________
The maximum color density of dye images formed on each sample through the above processes was measured together with the sensitivity of each sample. The results are shown in Table 2. ##STR152##
TABLE 2__________________________________________________________________________ Samples using Samples using Dispersion (A) Dispersion (B) Turbidity (ppm) Maximum MaximumSample No. Coupler Dispersion (A) Dispersion (B) Sensitivity turbidity Sensitivity turbidity__________________________________________________________________________Sample of the ExampleInvention coupler 9 47 22 31 118 2.47 110 2.2410 49 13 25 131 2.62 122 2.3711 51 17 30 127 2.58 119 2.3312 54 19 27 120 2.57 109 2.2513 55 11 22 122 2.52 113 2.2914 57 25 45 128 2.55 121 2.2715 59 20 36 130 2.60 121 2.3816 65 15 33 117 2.46 106 2.22Comparative ComparativeSample coupler 5 Y-5 42 100 100 2.02 78 1.65 6 Y-6 35 91 105 1.98 55 1.58__________________________________________________________________________ *The sensitivity is expressed by the value relative to that of Comparativ Sample 1 which is set at 100.
It can be seen in Table 2 that the samples of the invention yield higher maximum color densities than the comparative samples in both dispersions (A) and (B), and cause less deterioration in sensitivity and maximum color density in samples that use dispersion (B). This means that the couplers of the invention have an excellent dispersion stability not only right after the preparation of dispersion but also after the storage of dispersion.
EXAMPLE 3
Dispersions (A) and (B) were prepared in the same manner as in Example 2 using the yellow couplers of the invention shown in Table 3 (denoted by the number given to each example coupler) and the following comparative couplers Y-7 to Y-10, and then their turbidities were measured.
Each of these dispersions was added to an silver chlorobromide emulsion; the emulsion was then coated on a polyethylene laminated paper, and dried to prepare samples. ##STR153##
The samples prepared as above were exposed through an optical wedge and processed according to the following developing procedure and recipes of processing solutions.
______________________________________Processing step Temperature TimeColor developing 38.degree. C. 3 min 30 secBleach-fixing 38.degree. C. 1 min 30 secWashing 38.degree. C. 2 min 0 secStabilizing 38.degree. C. 1 min 0 sec______________________________________[Composition of color developer A]Benzyl alcohol 15 mlSodium hexametaphosphate 3.00 gAnhydrous sodium sulfite 1.85 gSodium bromide 1.40 gPotassium bromide 0.50 gBorax (Na.sub.2 B.sub.4 O.sub.7 E10H.sub.2 O) 39.10 gN-ethyl-N-[2-(methanesulfonamidoethyl)-3-methyl- 4.5 g4-aminoaniline sulfateWater was added to make 1 l, then pH was adjusted to10.3 with NaOH.[Composition of bleach-fixer]Ammonium ferric EDTA 61.0 gDiammonium EDTA 5.0 gAmmonium thiosulfate 124.5 gSodium metabisulfite 13.3 gSodium bisulfite 2.7 gWater was added to 1 l, then pH was adjusted to 6.5.[Composition of stabilizer]Glacial acetic acid 20 ml______________________________________
800 ml of water was added, and pH was adjusted to 3.5 to 4.0 with sodium acatate trihydrate, then the total volume was made up to 1l.
Color developer B was prepared with the same composition as in Color developer A, except that the amount of benzyl alcohol was decreased to 1.0 ml.
The turbidities of the dispersions and the evaluation results of dye images formed by color developing are shown in Table 3.
TABLE 3__________________________________________________________________________ Developer (A) Turbidity (ppm) Dispersion (A) Dispersion Dispersion MaximumSample No. Coupler (A) (B) Fog Sensitivity density Fog__________________________________________________________________________17(Invention) 1 28 32 0.02 100 2.53 0.0318(Invention) 4 26 29 0.02 103 2.55 0.0319(Invention) 10 30 33 0.03 101 2.52 0.0320(Invention) 15 20 22 0.02 105 2.61 0.0221(Invention) 17 24 25 0.02 104 2.58 0.0322(Invention) 23 31 35 0.03 102 2.56 0.0323(Invention) 24 33 35 0.03 101 2.51 0.0224(Invention) 25 28 31 0.02 104 2.58 0.0325(Invention) 28 36 39 0.04 101 2.54 0.0226(Invention) 32 29 33 0.02 101 2.51 0.03 7(Comparison) Y-7 50 132 0.02 80 2.17 0.03 8(Comparison) Y-8 65 129 0.03 69 1.90 0.03 9(Comparison) Y-9 63 180 0.03 59 1.73 0.0310(Comparison) Y-10 48 125 0.04 78 1.84 0.04__________________________________________________________________________ Developer (A) Developer (B) Dispersion (B) Dispersion (B) Maximum Maximum Sample No. Sensitivity density Fog Sensitivity density__________________________________________________________________________ 17(Invention) 100 2.48 0.03 96 2.28 18(Invention) 103 2.54 0.02 94 2.31 19(Invention) 100 2.50 0.03 94 2.30 20(Invention) 104 2.59 0.03 98 2.35 21(Invention) 103 2.57 0.03 97 2.33 22(Invention) 101 2.51 0.02 96 2.24 23(Invention) 101 2.49 0.02 95 2.29 24(Invention) 102 2.56 0.02 95 2.29 25(Invention) 101 2.51 0.03 98 2.28 26(Invention) 100 2.46 0.03 96 2.21 7(Comparison) 70 1.72 0.03 51 1.38 8(Comparison) 68 1.69 0.02 53 1.31 9(Comparison) 52 1.50 0.02 50 1.30 10(Comparison) 71 1.77 0.02 64 1.44__________________________________________________________________________ *The sensitivity is expressed by a value relative to those of Sample 1 in Dispersion (A) and Dispersion (B) of Developer (A) which are set at 100 respectively.
As apparent from Table 3, Comparative Samples 7 to 10 are inferior in dispersion stability on storing and poor in sensitivity and maximum density when developed in Developer (A) containing benzyl alcohol. Moreover, when they were developed with Developer (B) containing less benzyl alcohol, a sensitivity drop and a noticeable deterioration in maximum density were observed.
Contrary to the above, Samples 17 to 26 using the yellow couplers of the invention are good in dispersion stability and capable of providing a higher sensitivity and maximum density without causing a substantial lowering in maximum density when Developer (A) is used. Further, these samples exhibit a better color forming property and a less tendency to lower the maximum density than the comparative samples even when processed in Developer (B) containing a reduced amount of benzyl alcohol.
EXAMPLE 4
On a paper support laminated with polyethylene on both sides were coated in sequence the layers having the following compositions respectively in order to prepare Sample 27 of a multicolor silver halide photographic light-sensitive material of the invention.
______________________________________1st layer: blue-sensitive silver halide emulsion layerMonodispersed silver bromochloride 3.2 mg/100 cm.sup.2emulsion containing 99.5 mol % (in terms of silver)or more of AgClExample Compound 1 6.7 mg/100 cm.sup.2Dibutyl phthalate 3.5 mg/100 cm.sup.2Gelatin 13.5 mg/100 cm.sup.22nd layer: intermediate layerA gelatin layer containing 0.5 mg/100 cm.sup.2HQ-1Dibutyl phthalate 0.5 mg/100 cm.sup.2Gelatin 9.0 mg/100 cm.sup.23rd layer: green-sensitive silver halide emulsion layerMonodispersed silver bromochloride 2.5 mg/100 cm.sup.2emulsion containing 99.5 mol % (in terms of silver)or more of AgClMagenta coupler (M-1) 3.5 mg/100 cm.sup.2Dibutyl phthalate 3.0 mg/100 cm.sup.2Gelatin 12.0 mg/100 cm.sup.24th layer: intermediate layerA gelatin layer containing 0.7 mg/100 cm.sup.2UV-absorbent (UV-1)Dibutyl phthalate 6.0 mg/100 cm.sup.2HQ-1 0.5 mg/100 cm.sup.2Gelatin 12.0 mg/100 cm.sup.25th layer: red-sensitive silver halide emulsion layerMonodispersed silver bromochloride 3.0 mg/100 cm.sup.2emulsion containing 99.5 mol % (in terms of silver)or more of AgClCyan coupler (C-1) 4.2 mg/100 cm.sup.2Tricresyl phosphate 3.5 mg/100 cm.sup.2Gelatin 11.5 mg/100 cm.sup.26th layer: protective layerA gelatin layer containing 8.0 mg/100 cm.sup.2Gelatin______________________________________
Next, Samples 28 to 37 of the invention and Comparative Samples 11 to 16 were prepared in the same manner as in Sample 27, except that Example Compound 1 was replaced by an equivalent amount of each of the couplers shown in Table 4.
Each of these samples were subjected to exposure through an optical wedge in an usual manner and then processed according to the following developing procedure and recipes of processing solution.
______________________________________Processing step Temperature TimeColor developing 35.0 .+-. 0.3.degree. C. 45 secBleach-fixing 35.0 .+-. 0.5.degree. C. 45 secStabilizing 30 to 34.degree. C. 90 secDrying room temperature (25.degree. C.) drying______________________________________[Composition of color developer]Water 800 mlTriethanolamine 10 gN,N'-diethylhydroxylamine 5 gPotassium bromide 0.02 gPotassium chloride 2 gPotassium sulfite 0.3 g1-hydroxyethylidene-1,1-diphosphonic acid 1.0 gEDTA 1.0 gDisodium catechol-3,5-disulfonate 1.0 gN-ethyl-N-.beta.-methanesulfonamidoethyl-3-methyl- 4.5 g4-aminoaniline sulfateFluorescent whitening agent (4,4'-diaminostilbene 10 gdisulfonate)Potassium carbonate 27 gWater was added to make 1 l, then pH was adjusted to10.10.[Composition of bleach-fixer]Ammonium ferric EDTA dihydrate 60 gEDTA 3 gAmmonium thiosulfate (70% aqueous solution) 100 mlAmmonium sulfite (40% aqueous solution) 27.5 mlWater was added to make 1 l, then pH was adjusted to6.2 with potassium carbonate or glacial acetic acid.[Composition of stabilizer]5-chloro-2-methyl-4-isothiazoline-3-one 1.0 gEthylene glycol 1.0 g1-hydroxyethylidene-1,1-diphosphonic acid 2.0 gEDTA 1.0 gAmmonium hydroxide (20% aqueous solution) 3.0 gAmmonium sulfite 3.0 gFluorescent whitening agent 1.5 g(4,4'-diaminostilbenedisulfonate)Water was added to make 1 l, then pH was adjusted to7.0 with sulfuric acid or potassium hydroxide.______________________________________
The maximum dye density and fog of images formed were measured together with the sensitivity of the sample. The results are shown in Table 4. The sensitivity is expressed by a value relative to that of Comparative Sample 11 which is set at 100.
TABLE 4______________________________________Sample No. Coupler Fog Sensitivity Maximum density______________________________________27(Invention) 1 0.03 145 2.4128(Invention) 4 0.02 148 2.4429(Invention) 13 0.03 145 2.4030(Invention) 15 0.03 150 2.5131(Invention) 23 0.02 148 2.4632(Invention) 25 0.03 148 2.4233(Invention) 28 0.03 146 3.3934(Invention) 47 0.04 120 2.1835(Invention) 50 0.03 120 2.2736(Invention) 60 0.05 131 2.2537(Invention) 65 0.03 122 2.2011(Comparison) Y-5 0.06 100 1.5112(Comparison) Y-6 0.07 105 1.5513(Comparison) Y-7 0.04 92 1.6214(Comparison) Y-8 0.07 101 1.9115(Comparison) Y-9 0.06 98 1.9316(Comparison) Y-10 0.06 103 2.21______________________________________
It is understood from the results shown in Table 4 that the samples of the invention are capable of forming dye images of higher maximum dye density and less fog than the comparative samples, in addition to having a higher sensitivity; thereby it is proved that the couplers of the invention are excellent in color forming property.
As apparent from the results shown in Table 4, the couplers of the invention, unlike the comparative couplers, are capable of providing a sufficient color density even when processed with a developer containing no benzyl alcohol.
EXAMPLE 5
There were sequentially coated on a triacetate film support the following layers having respective compositions to prepared Comparative Sample 17 of a multilayered color photographic light-sensitive material.
__________________________________________________________________________1st layer: antihalation layer (HC)A layer containing black colloidal silver.2nd layer: intermediate layer (IL)A gelatin layer containing a dispersion of 2,5-di-t-octylhydroquinone.3rd layer: low speed red-sensitive silver halide emulsionlayer (RL)Monodispersed emulsion containing AgBrI having an 1.8 g/m.sup.2average grain size of 0.30 .mu.m and an AgI content of (in terms of silver)6.0 mol % (Emulsion 1)Sensitizing dye I 6 .times. 10.sup.-5 mol/mol AgSensitizing dye II 1.0 .times. 10.sup.-5 mol/mol AgCyan coupler (C-2) 0.06 mol/mol AgColored cyan coupler (CC-1) 0.003 mol/mol AgDIR compound (D-1) 0.0015 mol/mol AgDIR compound (D-2) 0.002 mol/mol Ag4th layer: high speed red-sensitive silver halide emulsionlayer (RH)Monodispersed emulsion containing AgBrI having an 1.3 g/m.sup.2average grain size of 0.5 .mu.m and an AgI content of 7.0 (in terms of silver)mol % (Emulsion II)Sensitizing dye I 3 .times. 10.sup.-5 mol/mol AgSensitizing dye II 1.0 .times. 10.sup.-5 mol/mol AgCyan coupler (C-2) 0.02 mol/mol AgColored cyan coupler (CC-1) 0.0015 mol/mol AgDIR compound (D-2) 0.001 mol/mol Ag5th layer: intermediate layer (IL)A gelatin layer with the same composition as 2nd layer.6th layer: low speed green-sensitive silver halide emulsionlayer (GL)Emulsion I 1.5 g/m.sup.2 (in terms of silver)Sensitizing dye III 2.5 .times. 10.sup.-5 mol/mol AgSensitizing dye IV 1.2 .times. 10.sup.-5 mol/mol AgMagenta coupler (CM-2) 0.050 mol/mol AgColored magenta coupler (CM-1) 0.009 mol/mol AgDIR compound (D-1) 0.0010 mol/mol AgDIR compound (D-3) 0.0030 mol/mol Ag7th layer: high speed green-sensitive silver halideemulsion layer (GH)Emulsion II 1.4 g/m.sup.2 (in terms of silver)Sensitizing dye III 1.5 .times. 10.sup.-5 mol/mol AgSensitizing dye IV 1.0 .times. 10.sup.-5 mol/mol AgMagenta coupler (M-2) 0.020 mol/mol AgColored magenta coupler (CM-1) 0.002 mol/mol AgDIR compound (D-3) 0.0010 mol/mol Ag8th layer: yellow filter layer (YC)A gelatin layer containing a dispersion of yellowcolloidal silver and 2,5-di-t-octylhydroquinone.9th layer: low speed blue-sensitive silver halide emulsionlayer (BL)Monodispersed emulsion containing AgBrI having an 0.9 g/m.sup.2average grain size of 0.48 .mu.m and an AgI content of (in terms of silver)6.0 mol % (Emulsion III)Sensitizing dye V 1.3 .times. 10.sup.-5 mol/mol AgComp. yellow coupler (Y-3) 0.29 mol/mol AgTricresyl phosphate 0.7 ml/m.sup.210th layer: high speed blue-sensitive silver halideemulsion layer (BH)Monodispersed emulsion containing AgBrI having an 0.5 g/m.sup.2average grain size of 0.8 .mu.m and an AgI content of 15 (in terms of silver)mol % (Emulsion IV)Sensitizing dye V 1.0 .times. 10.sup.-5 mol/mol AgComp. yellow coupler (Y-3) 0.29 mol/mol AgDIR compound (D-2) 0.0015 mol/mol AgTricresyl phosphate 0.2 ml/m.sup.211th layer: 1st protective layer (Pro-1)A gelatin layer containing silver iodobromide (AgI: 1mol %, average grain size: 0.07 .mu.m, coating weight interms of silver: 0.5 g/m.sup.2) and UV absorbents UV-3and UV-4 (1:1).12th layer: 2nd protective layer (Pro-2)A gelatin layer containing polymethylmethacrylatepowder (average particle size: 1.5 .mu.m) and formalinscavenger (HS-1).__________________________________________________________________________
In addition to the above component, a gelatin hardener (H-1) and a surfactant were added to each layer.
Further, samples shown in Table 5 were prepared in the same manner as in Comparative Sample 17, except that the Comparative coupler Y-3 used in the 9th and 10th layers of Comparative Sample 17 was replaced by couplers shown in Table 5.
Components used in above samples are as follows:
______________________________________Sensitizing dye I:Anhydro-5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)thiacarbocyaninehydroxideSensitizing dye II:Anhydro-9-ethyl-3,3'-di-(3-sulfopropyl)-4,5,4',5'-dibenzothiacarbocyaninehydroxideSensitizing dye III:Anhydro-5,5'-diphenyl-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyaninehydroxideSensitizing dye IV:Anhydro-9-ethyl-3,3'-di-(3-sulfopropyl)-5,6,5',6'-dibenzoxacarbocyaninehydroxideSensitizing dye V:Anhydro-3,3'-di-(3-sulfopropyl)-4,5-benzo-5'-methoxythiacyaninehydroxide______________________________________ ##STR154##
The samples prepared as above were exposed through an optical wedge and processed according to the following developing procedure and recipes of processing solution.
______________________________________Processing step (at 38.degree. C.) Time______________________________________Color developingBleaching 3 min 15 secWashing 6 min 30 secFixing 3 min 15 secWashing 6 min 30 secStabilizing 3 min 15 secDrying 1 min 30 sec______________________________________Composition of each processing solution is asfollows:______________________________________[Color developer]4-amino-3-methyl-N-ethyl-N- 4.75 g(.beta.-hydroxyethyl)aniline sulfateAnhydrous sodium sulfite 4.25 gHydroxylamine 1/2 sulfate 2.0 gAnhydrous potassium carbonate 37.5 gSodium bromide 1.3 gTrisodium nitrilotriacetate monohydrate 2.5 gPotassium hydroxide 1.0 gWater was added to make 1 l.[Bleacher]Ammonium ferric EDTA 100.0 gDiammonium EDTA 10.0 gAmmonium bromide 150.0 gGlacial acetic acid 10.0 mlWater was added to make 1 l, then pH was adjusted to6.0 with aqueous ammonia.[Fixer]Ammonium thiosulfate 175.0 gAnhydrous sodium sulfite 8.5 gSodium metasulfite 2.3 gWater was added to make 1 l, then pH was adjusted to6.0 with acetic acid.[Stabilizer]Formalin 1.5 mlKoniducks (made by Konica Corp.) 7.5 mlWater was added to make 1 l.______________________________________
The evaluation results are shown in Table 5.
TABLE 5______________________________________ Coupler Maximum RelativeSample No. No. .DELTA.Fog*.sup.1 density sensitivity______________________________________17 (Comparison) Y-3 +0.04 2.18 9218 (Comparison) Y-6 +0.05 2.24 9438 (Invention) 7 .+-.0 2.38 10039 (Invention) 33 .+-.0 2.43 10540 (Invention) 34 .+-.0 2.36 9841 (Invention) 35 +0.01 2.46 10842 (Invention) 36 +0.02 2.44 10643 (Invention) 37 +0.01 2.52 11144 (Invention) 38 +0.01 2.43 10645 (Invention) 39 .+-.0 2.44 10846 (Invention) 40 +0.01 2.49 11047 (Invention) 41 +0.02 2.41 9948 (Invention) 42 +0.01 2.39 10149 (Invention) 43 .+-.0 2.38 98______________________________________ *.sup.1 Difference in fog from Sample 38 *.sup.2 Relative sensitivity when the sensitivity of Sample 38 is set at 100.
It can be found from Table 5 that the couplers of the invention can raise the density and sensitivity without facilitating occurrence of fog as compared with the comparative couplers.
EXAMPLE 6
Comparative Sample 19(A) of a multilayered color photographic material was prepared by forming layers of the same configuration and composition as Comparative Sample 17 of Example 5 on a triacetyl cellulose film support, except that Y-1 was used as a comparative coupler instead of Y-3.
Comparative Sample 19 (B) of a multilayered color photographic material was prepared in the same manner as in Comparative Sample 19 (A), except that a coupler dispersion maintained at 40.degree. C. for 8 hours after the preparation was used instead of a freshly prepared coupler dispersion used in Comparative Sample 19 (A).
Further, comparative samples and samples of the invention were prepared in the same way as the above, except that the couplers shown in Table 6 were used instead of Comparative coupler Y-1 used in the 9th and 10th layers of Comparative Samples 19 (A) and (B).
Each sample prepared as above was subjected to exposure through an optical wedge in a normal manner, followed by processing according to the developing procedure and recipes of processing solution in Example 5.
The image formed on each sample was evaluated for the maximum dye density, as well as the measurement of sensitivity on each sample. The results are shown in Table 6.
TABLE 6__________________________________________________________________________ Samples using fresh Samples using stored coupler Dispersion (A) coupler Dispersion (B) Maximum MaximumSample No. Coupler Sensitivity density Sensitivity density__________________________________________________________________________Sample of the 50 Example 71 109 2.28 105 2.22invention 51 Coupler 72 110 2.32 104 2.24 53 75 111 2.30 105 2.25Comparative 19 Comparative Y-1 100 2.12 85 1.72Sample 20 coupler Y-2 105 2.19 89 1.81 21 Y-4 94 1.82 72 1.58__________________________________________________________________________ *The sensitivity is expressed by a value relative to that of Comparative Sample 19 (A) which is set at 100.
It is understood from the results shown in Table 6 that in both Samples (A) and (B), the samples of the invention can provide maximum dye densities higher than those of the comparative samples and cause less deterioration in sensitivity and maximum dye density between Samples (A) an d(B) than the comparative samples. This proves that the couplers of the invention are excellent in dispersion stability immediately after the preparation of couplers dispersion and even after the standing of coupler dispersion.
EXAMPLE 7
On a subbed triacetyl cellulose film support were formed the following layers in order to prepared Comparative Sample 22 of multilayered color photographic material. The coating weight of each component is in g/m.sup.2.
______________________________________1st layer: antihalation layerUV absorbent (UV-3) 0.3UV absorbent (UV-4) 0.4High boiling solvent (Oil-1) 1.0Black colloidal silver 0.24Gelatin 2.02nd layer: intermediate layer2,5-di-t-octylhydroquinone 0.1High boiling solvent (Oil-1) 0.2Gelatin 1.03rd layer: low speed red-sensitive silver halideemulsion layerSilver iodobromide emulsion spectrally sensitized 0.5by red sensitizing dyes S-1 and S-2(AgI: 4.0 mol %, average grain size: 0.25 .mu.m)Coupler (C-1) 0.1 molHigh boiling solvent (Oil-2) 0.6Gelatin 1.34th layer: high speed red-sensitive silver halideemulsion layerSilver iodobromide emulsion spectrally sensitized 0.8by red sensitizing dyes S-1 and S-2(AgI: 2.0 mol %, average grain size: 0.6 .mu.m)Coupler (C-1) 0.2 molHigh boiling solvent (Oil-2) 1.2Gelatin 1.85th layer: intermediate layer2,5-di-t-octylhydroquinone 0.1High boiling solvent (Oil-1) 0.2Gelatin 0.96th layer: low speed green-sensitive silver halideemulsion layerSilver iodobromide emulsion spectrally sensitized by 0.6green sensitizing dyes S-3 and S-4(AgI: 4.0 mol %, average grain size: 0.25 .mu.m)Coupler (C-2) 0.04 molCoupler (C-3) 0.01 molHigh boiling solvent (Oil-3) 0.5Gelatin 1.47th layer: high speed green-sensitive silver halideemulsion layerSilver iodobromide emulsion spectrally sensitized by 0.9green sensitizing dyes S-3 and S-4(AgI: 2.0 mol %, average grain size: 0.6 .mu.m)Coupler (C-2) 0.10 molCoupler (C-3) 0.02 molHigh boiling solvent (Oil-3) 1.0Gelatin 1.58th layer: intermediate layerThe same as 5th layer.9th layer: yellow filter layerYellow colloidal silver 0.1Gelatin 0.92,5-di-t-octylhydroquinone 0.1Hydroquinone 0.1High boiling solvent (Oil-1) 0.210th layer: low speed blue-sensitive silver halideemulsion layerSilver iodobromide emulsion spectrally sensitized 0.6by blue sensitizing dyes S-5(AgI: 4.0 mol %, average grain size: 0.35 .mu.m)Comparative coupler (Y-7) 0.3 molHigh boiling solvent (Oil-3) 0.6Gelatin 1.311th layer: high speed blue-sensitive silver halideemulsion layerSilver iodobromide emulsion spectrally sensitized 0.9by blue sensitizing dyes S-5(AgI: 2.0 mol %, average grain size: 0.9 .mu.m)Comparative coupler (Y-7) 0.5 molHigh boiling solvent (Oil-3) 1.4Gelatin 2.112th layer: 1st protective layerUV absorbent (UV-3) 0.3UV absorbent (UV-4) 0.4High boiling solvent (Oil-3) 0.6Gelatin 1.22,5-di-t-octylhydroquinone 0.113th layer: 2nd protective layerEmulsion of nonlight-sensitive silver halide grains 0.3containing silver iodobromide having a silver iodide (in termscontent of 1 mol % and an average grain size (- r) of of silver)0.08 .mu.m.Polymethylmethacrylate powder (dia.: 1.5 .mu.m) 0.05Surfactant (Su-1) 0.005Gelatin 0.7______________________________________
In addition to the above compounds, a gelatin hardener (H-1) and a surfactant were added to each of the foregoing layers. As a solvent for couplers, tricresyl phosphate was used. ##STR155##
Further, multilayered color photographic material samples were prepared in the same manner as in Comparative Sample 22, except that the yellow couplers used in the 10th and 11th layers were varied as shown in Table 7.
The samples were exposed through an optical wedge and then processed according to the following developing procedure and recipes of processing solution.
______________________________________Reversal processing step Time Temperature______________________________________1st developingWashing 6 min 38.degree. C.Reversing 2 min 38.degree. C.Color developing 2 min 38.degree. C.Conditioning 6 min 38.degree. C.Bleaching 2 min 38.degree. C.Fixing 6 min 38.degree. C.Washing 4 min 38.degree. C.Stabilizing 4 min 38.degree. C.Drying 1 min room temp.______________________________________Composition of each processing solution was asfollows:______________________________________[1st developer]Sodium tetrapolyphosphate 2 gSodium sulfite 20 gHydroquinone monosulfonate 30 gSodium carbonate monohydrate 30 g1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 gPotassium bromide 2.5 gpotassium thiocyanate 1.2 gPotassium iodide (0.1% solution) 2 mlWater to make 1000 ml[Reversing solution]Hexasodium nitrilotrimethylene phophonate 3 gStannous chloride dihydrate 1 gp-aminophenol 0.1 gSodium hydroxide 8 gGlacial acetic acid 15 mlWater to make 1000 ml[Color developer]Sodium tetrapolyphosphate 3 gSodium sulfite 7 gSodium orthophosphate (12 hydrate) 36 gPotassium bromide 1 gPotassium iodide (0.1% solution) 90 mlSodium hydroxide 3 gCitrazinic acid 1.5 gN-ethyl-N-.beta.-methanesulfonamidoethyl-3-methyl-4- 11 gaminoaniline sulfate3,2-ethylenedithioethanol 1 gWater to make 1000 ml[Conditioner]Sodium sulfite 12 gSodium EDTA (dihydrate) 8 gThioglycerin 0.4 mlGlacial acetic acid 3 mlWater to make 1000 ml[bleacher]Sodium EDTA (dihydrate) 2.0 gAmmonium ferric EDTA (dihydrate) 120.0 gAmmonium bromide 100.0 gWater to make 1000 ml[Fixer]Ammonium thiosulfate 80.0 gSodium sulfite 5.0 gSodium bisulfite 5.0 gWater to make 1000 ml[Stabilizer]Formalin (37 wt % solution) 5.0 mlKoniducks (made by Konica Corp.) 5.0 mlWater to make 1000 ml______________________________________
The samples processed with the above processing solutions were evaluated for the maximum density (D max) with blue light. The results are shown in Table 7.
TABLE 7______________________________________ MaximumSample No. Coupler No. .DELTA.Fog*.sup.1 density______________________________________22 (Comparison) Y-1 +0.03 2.9823 (Comparison) Y-2 +0.02 2.9224 (Comparison) Y-3 +0.06 3.0325 (Comparison) Y-4 +0.05 3.0126 (Comparison) Y-6 +0.06 3.154 (Invention) 2 .+-.0 3.2855 (Invention) 3 +0.02 3.3156 (Invention) 4 +0.01 3.3257 (Invention) 12 +0.01 3.3058 (Invention) 23 +0.01 3.2959 (Invention) 24 +0.02 3.2760 (Invention) 26 +0.02 3.3561 (Invention) 27 +0.01 3.3062 (Invention) 33 +0.02 3.39______________________________________ *.sup.1 Difference in fog from Sample 45
As shown in Table 7, the yellow couplers of the invention can provide a good dye density without causing a rise in fogging.

Number	Date	Country
1-262776	Oct 1989	JPX
1-266009	Oct 1989	JPX
1-266010	Oct 1989	JPX

Number	Name	Date
4266019	Kobayashi et al.	May 1981
4269936	Arai et al.	May 1981
4404274	Arai et al.	Sep 1983
4791050	Ogawa et al.	Dec 1988

Number	Date	Country
267491	May 1988	EPX
2322615	Nov 1973	DEX

Silver halide photographic light-sensitive material containing a novel yellow coupler

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