Silver halide color photographic light sensitive material

A magenta coupler and a light sensitive silver halide color photographic material containing the coupler are disclosed. The magenta coupler is represented by formulas ##STR1## wherein R.sub.1 is a hydrogen atom or a substituent, R.sub.2, R.sub.3 and R.sub.4 each represents a hydrogen atom or a substituent, L is an alkylene group, n is 0 or 1, R.sub.5 and R.sub.6 each represents a hydrogen atom or a substituent, where R.sub.5 and R.sub.6 may be condensed to form a cycle, and X is a hydrogen atom or an atom or a group that can be released upon the reaction with an oxidation product of color developing agent.

FIELD OF THE INVENTION 
This invention relates to a silver halide color photographic light 
sensitive material containing a magenta coupler and, particularly, to a 
silver halide color photographic light sensitive material in which a color 
reproducibility and color reproducibility can be excellent and a dye image 
stable against heat and light can be obtained when containing a novel 
pyrazoloazole type magenta coupler therein. 
BACKGROUND OF THE INVENTION 
As for the couplers generally applicable to silver halide color 
photographic light sensitive materials, there have been known couplers 
including, for example, the yellow couplers each comprising a open-chained 
ketomethylene type compound, the magenta couplers each comprising a 
pyrazolone or pyrazoloazole type compound and the cyan couplers each 
comprising a phenol or naphthol type compound. Among them, a 5-pyrazolone 
compound has very often been used for the magenta couplers so far. 
The known pyrazolone magenta couplers are described in, for example, U.S. 
Pat. Nos. 2,600,788 and 3,519,429 and Japanese Patent Publication Open to 
Public Inspection (hereinafter referred to as JP OPI Publication) Nos. 
49-111631 (1974) and 57-35858 (1982). However, the dyes made of the 
pyrazolone magenta couplers have produced an undesirable side-absorption 
which has been demanded for the improvements, as described in `The Theory 
of the Photographic Process`, the 4th Ed., Macmillan Publishing Co., 1977, 
pp.356-358; `Fine Chemical`, Vol.14, No.8, CMC Press, pp.38-41; and the 
Lecture Transcription published at the 1985 Annual convention of the 
Society of Photographic Science of Japan, pp.108-110. 
As described in the above-given literatures, the dyes made of the 
pyrazoloazole type magenta couplers do not produce any side-absorption. 
The above-given literatures, U.S. Pat. Nos. 3,725,067, 3,758,309 and 
3,810,761 and so forth describe that the couplers of this type are 
excellent. 
However, the light-fastness of azomethine dyes made of the couplers are so 
seriously low that the characteristics of color photographic light 
sensitive materials, particularly those of print type color photographic 
light sensitive materials are seriously spoiled. 
The studies and researches have been tried for improving the 
light-fastness. For example, JP OPI Publication Nos. 59-125732 (1984), 
61-282845 (1986), 61-292639 (1986) and 61-279855 (1986) disclose the 
techniques of making combination use of a pyrazoloazole type coupler and a 
phenol type compound or a phenylether compound and JP OPI Publication Nos. 
61-72246 (1986), 62-208048 (1987), 62-157031 (1987) and 163351 (1988) 
disclose the techniques of making combination use of a pyrazoloazole type 
coupler and an amine type compound. 
Further, JP OPI Publication No. 63-24256 (1988) proposes for a 
pyrazoloazole type magenta coupler having an alkyloxyphenyloxy group. 
In the above-given techniques, the light-fastness of magenta dye images are 
still unsatisfactory and the improvements thereof have been eagerly 
demanded. 
SUMMARY OF THE INVENTION 
This invention has been made for solving the above-mentioned problems. It 
is an object of the invention is to provide a silver halide color 
photographic light sensitive material excellent in color reproducibility 
and color developability and remarkably improved in light-fastness of 
magenta dye images. 
The silver halide color photographic light sensitive material of the 
present invention contains a magenta coupler represented by the Formula I, 
or II, particularly I-a or II-a, or III-a or III-b. 
##STR2## 
In the formulas R.sub.1 is a hydrogen atom or a substituent, R.sub.2, 
R.sub.3 and R.sub.4 each represents a hydrogen atom or a substituent, L is 
an alkylene group, n is 0 or 1, R.sub.5 and R.sub.6 each represents a 
hydrogen atom or a substituent, where R.sub.5 and R.sub.6 may be condensed 
to form a cycle, and X is a hydrogen atom or an atom or a group that can 
be released upon the reaction with an oxidation product of color 
developing agent. 
##STR3## 
In the formulas R.sub.1 is a hydrogen atom or a substituent, R.sub.2 
represents a hydrogen atom or a substituent, R.sub.5 and R.sub.6 each 
represents a hydrogen atom or a substituent, where R.sub.5 and R.sub.6 may 
be condensed to form a cycle, and X is a hydrogen atom or an atom or a 
group that can be released upon the reaction with an oxidation product of 
color developing agent. 
##STR4## 
In the formulas R.sub.11 is a hydrogen atom or a substituent, R.sub.12, 
R.sub.13, R.sub.14, R.sub.15 and R.sub.16 represents a hydrogen atom or a 
substituent, Y represents a group 
##STR5## 
R.sub.17, R.sub.18, R.sub.19, R.sub.20, R.sub.21, R.sub.22 and R.sub.23 
each represents a hydrogen atom or a substituent, where R.sub.19 and 
R.sub.20 may be condensed to form a cycle, and X is a hydrogen atom or an 
atom or a group that can be released upon the reaction with an oxidation 
product of color developing agent. 
In the above-given Formulas R.sub.1, is a hydrogen atom or a substituent. 
The substituent is selected without specific restriction. The preferable 
examples thereof include a straight or branched alkyl group having carbon 
atoms of 1 to 8, for example, a methyl, ethyl, i-propyl, t-butyl, 
neopentyl and pentadecyl group; a cycloalkyl group having 3 to 10 carbon 
atoms, for example, a cyclopropyl, cyclopentyl and cyclohexyl group; an 
alkoxy group such as a methoxy and ethoxy group; an aryloxy group such as 
a phenoxy and naphtyloxy group; an aryl group such as a phenyl and naphtyl 
group; an alkylthio group such as methylthio and dodecylthio group; an 
arylthio group such as a phenylthio group; an acylamino group such as an 
acetylamino and benzoylamino group; a ureido group such as a 
phenylcarbamoyl and dimethylcarbamoyl group; an alkoxycarbonylamino group 
such as an ethoxycarbabonylamino group; an aryloxycarbonyl group such as a 
phenoxycarbonylamino group; an amino group such as a dimethylamino and 
anilino group. These groups may have a substituent. 
R.sub.2, R.sub.3 and R.sub.4 each represents a hydrogen atom or a 
substituent. There is no specific limitation in selecting the substituent 
and preferable example thereof is that mentioned for R.sub.1, especially 
an alkyl group. The preferable example of R.sub.2, R.sub.3 and R.sub.4 is 
a hydrogen atom and an alkyl group, especially a methyl group. 
L is an alkylene group, preferable example of which is a straight or 
branched alkylene group having 1 to 18 carbon atoms, such as, an 
methylene, ethylene, 1-methylethylene, 1,1-dimethylpropylene group. The 
alkylene group may be substituted with any substituting group, example of 
which includes an aryl group such as a phenyl and naphtyl group; an amino 
group such as a methylamino, diethylamino and anilino group; a sulfonamide 
group such as a methanesulfonamide and phenylsulfonamide group; a sulfonyl 
group such as a butylsulfonyl and phenylsulfonyl group; an alkoxy group 
such as methoxy and butoxy group; an aryloxy group such as 
2-methylphenyloxy, 4-chlorophenyloxy group; an alkylthio group such as an 
octylthio and isopropyl group; an acylamino group such as a benzoylamino 
and dodecanoylamino group; an arylthio group such as a phenylthio and 
1-naphtylthio group; an alkenyl group such as a vinyl and propenyl group; 
a cycloalkeny group such as cyclopropyl and cyclohexyl group; a hydroxy 
group; a carboxy group; a halogen atom such as a bromine and chlorine 
atom. 
There is no specific limitation for a substituent represented by R.sub.5 
and R.sub.6 and typical examples include an alkyl, aryl alkenyl, 
cycloalkyl, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, 
phosphonyl, phosphinyl, acyl, carbamoyl, sulfamoyl, alkoxycarbonyl, 
aryloxycarbonyl group and a spiro compound residual group and hydrocarbon 
compound residual group having a bridge. 
The preferable example of R.sub.5 and R.sub.6 is hydrogen atom, a sulfonyl 
group, a phosphonyl group and an acyl group respectively. 
In the more preferable embodiment of the invention R.sub.5 and R.sub.6 are 
the same. 
The alkyl groups mentioned above include, preferably, those having 1 to 32 
carbon atoms and they may be straight-chained or branched. As for the aryl 
groups, a phenyl group or a substituted phenyl group are preferred. 
The alkenyl groups mentioned above include, preferably, those having 2 to 
32 carbon atoms. The cycloalkyl groups include, desirably, those having 3 
to 12 carbon atoms and, preferably, those having 5 to 7 carbon atoms. The 
alkenyl groups may be straight-chained or branched. 
The sulfonyl groups mentioned above include, for example, an alkylsulfonyl 
group and an arylsulfonyl group; 
The sulfinyl groups include, for example, an alkylsulfinyl group and an 
arylsulfinyl group; 
The phosphonyl groups include, for example, an alkylphosphonyl group and an 
arylphosphonyl group; 
The phosphinyl groups include, for example, an alkylphosphinyl group and an 
arylphosphinyl group; 
The acyl groups include, for example, an alkylcarbonyl group and an 
arylcarbonyl group; 
The carbamoyl groups include, for example, an alkylcarbamoyl group and an 
arylcarbamoyl group; 
The sulfamoyl groups include, for example, an alkylsulfamoyl group and an 
arylsulfamoyl group; 
The heterocyclic groups include, preferably, those having 5- to 7-members 
and, typically, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group 
and a 2-benzothiazolyl group; 
The spiro compound residual groups include, for example, a 
spiro[3.3]heptane-1-yl; and 
The hydrocarbon compound residual groups having a bridge include, for 
example, a bicyclo[2.2.1]heptane-1-yl, tricyclo[3.3.1.1.sup.3,7 
]decane-1-yl and 7,7-dimethylbicyclo[2.2.1]heptane-1-yl. 
Each of the groups for R.sub.5 and R.sub.6 include those each further 
having a substituent. 
A preferable example of Y includes 
##STR6## 
X is an atom or a group capable of splitting off upon reaction with the 
oxidized product of a color developing agent (a splitting off group). The 
splitting off group include, for example, a halogen atom and each of the 
groups of alkoxy, aryloxy, acyloxy, arylthio, alkylthio, sulfonamido, 
acylamino, and 
##STR7## 
wherein Z is atoms selected from a carbon oxygen, nitrogen, or sulfur atom 
to complete a 5- or 6 membered cycle with the nitrogen atom. 
Examples of the split off groups are illustrated. 
Halogen atom: Chlorine, bromine and fluorine atom; 
Alkoxy group: Ethoxy, benzyloxy, ethylcarbamoylmethoxy and 
tetradecylcarbamoylmethoxy group. 
Aryloxy group: Phenoxy, 4-methoxyphenoxy and 4-nitrophenoxy group; 
Acyloxy group: Acetoxy, myristoyloxy and benzoyloxy group; 
Arylthio group: Phenylthio, 2-buthoxy-5-octylphenylthio, and 
2,5-dihexylphenylthio group; 
Alkylthio group: Methylthio, octylthio, hexadecylthio, benzylthio, 
2-(diethylamino)ethylthio, ethoxycarbonylmethylthio, ethoxyethylthio and 
phenoxyethylthio; 
Sulfonamido group: Methanesulfonamido and benzenesulfonamide; Acylamino 
group: Heptafluorobutaneamido and pentachlorophenylcarbonylamino group. 
Group represented by 
##STR8## 
is exemplified. 
##STR9## 
The preferable splitting off group is a halogen atom and more preferably a 
chlorine atom. 
The Formulae III and IV are explained in detail. 
R.sub.11 is a hydrogen atom or a substituent. The substituent is not 
specifically limited. The preferable examples thereof include a straight 
or branched alkyl group having carbon atoms of 1 to 18, for example, a 
methyl, ethyl, i-propyl, t-butyl, neopentyl and pentadecyl group; a 
cycloalkyl group having 3 to 10 carbon atoms, for example, a cyclopropyl, 
cyclopentyl and cyclohexyl group; an alkoxy group such as a methoxy and 
ethoxy group; an aryloxy group such as a phenoxy and naphtyloxy group; an 
aryl group such as a phenyl and naphtyl group; an alkylthio group such as 
methylthio and dodecylthio group; an arylthio group such as a phenylthio 
group; an acylamino group such as an acetylamino and benzoylamino group; a 
ureido group such as a phenylcarbamoyl and dimethylcarbamoyl group; an 
alkoxycarbonylamino group such as an ethoxycarbabonylamino group; an 
aryloxycarbonyl group such as a phennoxycarbonylamino group; an amino 
group such as a dimetylamino and anilino group. These groups may have a 
substituent. 
R.sub.12, R.sub.13, R.sub.14, R.sub.15, R.sub.16, R.sub.17, R.sub.18, 
R.sub.19, R.sub.20, R.sub.21, R.sub.22 and R.sub.23 is a hydrogen atom or 
a substituent. The substituent is not specifically limited and example 
thereof includes those exemplified for R.sub.11. As for R.sub.12 to 
R.sub.16, R.sub.19, R.sub.20, R.sub.22 and R.sub.23 an unsubstituted or 
substituted alkyl is especially preferable. As for R.sub.17, R.sub.18 and 
R.sub.21 an alkyl aryl, alkoxy and aryloxy group is preferable. 
The representative examples of the magenta coupler are illustrated. 
##STR10## 
The typical synthesizing examples of the above-mentioned pyrazoloazole type 
magenta couplers relating to the invention will now be given below.

SYNTHESIS EXAMPLE 
Synthesis of Exemplified Compound M-14 
Synthesis Procedures 
##STR11## 
Synthesis of Intermediate 1 
To 2,2-bis(hydroxymethyl)propionic acid of 40.2 g, 120 ml of acetic acid 
anhydrite are added and they are allowed to stir for 2 hours at 70.degree. 
C. The reactant was poured into a mixture of 10 ml of 0.6 N hydrochloric 
acid and 100 g of ice and the resultant was extracted by adding 300 ml of 
ethylacetate after stirring for one hour. Obtained organic phase was 
washed with water twice, dried with magnesium sulfate anhydrite, and then 
solvent of the organic phase was removed by evaporation at reduced 
pressure. The obtained oily result was recrystallized from toluene to give 
the Intermediate 1 of white crystal in an amount of 47.4 g. The chemical 
structure was confirmed by .sup.1 HNMR, IR spectroscopic analysis and FD 
mass spectroscopic analysis. 
Synthesis of Intermediate 5 
After mixture of 200 ml of toluene and 47 ml of thionyl chloride was added 
to 47.4 g of the Intermediate 1, they were refluxed with heating for 4 
hours. Toluene and excess thionyl chloride were removed by evaporation to 
obtain the Intermediate 2 of brown oil in an mount of 51.4 g. 
To the Intermediate 3 in an amount of 43.5g, 450 ml of acetonitrile and 
51.4 g of the Intermediate 2 were added and they were refluxed with 
heating for 3 hours and cooled to room temperature. After removing organic 
solvent, to the resulted oily product 400 ml of toluene and 6 ml of 
concentrated sulfuric acid were added, and they were refluxed with heating 
for 2 hours. After the reaction liquid was cooled to room temperature, 500 
ml of ethyl acetate was added thereto, and further sodium hydrogen 
carbonate was added until the water phase becomes to show weak alkaline, 
and then organic phase was separated. The resulted organic phase was 
washed with water, dried with magnesium sulfate anhydrite, and solvent was 
removed by evaporation at reduced pressure. The resultant was refined 
through silica gel chromatography to obtain 54.6 g of pale yellow oil 
Intermediate 6. 
The chemical structure was confirmed by .sup.1 HNMR, IR spectroscopic 
analysis and FD mass spectroscopic analysis. 
Synthesis of Intermediate 7 
To 54.6 g of the Intermediate 5, 300 ml of acetic acid anhydrite was added, 
excess acetic acid anhydrite was removed at normal pressure after refluxed 
with heating for 3 hours. To the resultant, 200 ml of methanol was added 
and further 60 ml of concentrated sulfuric acid was added dropwise. They 
were refluxed with heating for 3 hours. After the reaction the reaction 
liquid was cooled to room temperature, and was kept standing for a day 
after removing deposited crystal sulfur by filtration. Deposited crystal 
was separated by filtration to obtain 46 g of crystal, to the crystal, 
1000 ml of ethylacetate and 80 ml of saturated aqueous solution of sodium 
hydrogen carbonate, and they were stirred with heating for 1 hour. Then 
the organic phase was dried and organic solvent was removed therefrom by 
evaporation at reduced pressure. The resultant was refined by 
crystallization from a mixture solvent of ethyl acetate and hexane to 
obtain 38.3 g of white crystal Intermediate 7. 
The structure thereof was confirmed by .sup.1 HNMR, FD mass-spectral 
analysis and IR spectral analysis. 
Synthesis of Exemplified Compound M-14 
After dissolving 38.3 g of the Intermediate 7 in 300 ml of tetrahydrofuran, 
the solution was cooled to 5.degree. C. To the solution 15.2 g of 
N-chlorosumlinimide was added as a solid state little by little, the 
mixture was stirred for 2 hours at 5.degree. to 7.degree. C. After 
removing solvent by evaporation at reduce pressure to the reactant 700 ml 
of ethylacetate and 150 ml of water was added then organic phase is 
separated. The organic phase was dried and therefrom ethyl acetate was 
removed by evaporation at reduced pressure. The resultant was 
recrystallized from a mixture solvent of ethylacetate and hexane to obtain 
41.8 g of the Intermediate 8. 
After addition of 31.8 g of n-hexane, 300 ml of toluene and 15.0 g of 
p-toluenesufonic acid to 41.9 g of the Intermediate 8, the mixture was 
refluxed with heating for 15 hours, was cooled to room temperature 
thereafter, and the organic phase was separated after adding 300 ml of 
water. The separated organic phase was washed with aqueous solution of 
sodium hydrogen carbonate, and was dried with magnesium sulfite anhydrite, 
and organic solvent was removed by evaporation at reduced pressure. The 
obtained oily product was refined through silica gel chromatography and 
further was recrystallized from a mixture solvent of ethylacetate and 
hexane to obtain 40.7 g of white crystal M-14. 
The structure thereof was confirmed by .sup.1 HNMR, FD mass-spectral 
analysis and IR spectral analysis. 
Synthesis of Exemplified Compound M-75 
Synthesis Procedures 
##STR12## 
Synthesis of Intermediate 9 
To 2,2-bis(hydroxymethyl)propionic acid of 40.2 g, 120 ml of acetic acid 
anhydrite are added and they are allowed to stir for 2 hours at 70.degree. 
C. The reactant was poured into a mixture of 10 ml of 0.6 N hydrochloric 
acid and 100 g of ice and the resultant was extracted by adding 300 ml of 
ethylacetate after stirring for one hour. Obtained organic phase was 
washed with water twice, dried with magnesium sulfate anhydrite, and then 
solvent of the organic phase was removed by evaporation at reduced 
pressure. The obtained oily result was recrystallized from toluene to give 
the Intermediate 9 of white crystal in an amount of 47.4 g. The chemical 
structure was confirmed by .sup.1 HNMR, IR spectroscopic analysis and FD 
mass spectroscopic analysis. 
Synthesis of Intermediate 13 
After mixture of 200 ml of toluene and 47 ml of thionyl chloride was added 
to 47.4 g of the Intermediate 9, they were refluxed with heating for 4 
hours. Toluene and excess thionyl chloride were removed by evaporation to 
obtain the Intermediate 10 of brown oil in an mount of 51.4 g. 
To the Intermediate 11 in an amount of 43.5g, 450 ml of acetonitrile and 
51.4 g of the Intermediate 10 were added and they were refluxed with 
heating for 3 hours and cooled to room temperature. After removing organic 
solvent, to the resulted oily product 400 ml of toluene and 6 ml of 
concentrated sulfuric acid were added, and they were refluxed with heating 
for 2 hours. After the reaction liquid was cooled to room temperature, 500 
ml of ethyl acetate was added thereto, and further sodium hydrogen 
carbonate was added until the water phase becomes to show weak alkaline, 
and then organic phase was separated. The resulted organic phase was 
washed with water, dried with magnesium sulfate anhydrite, and solvent was 
removed by evaporation at reduced pressure. The resultant was refined 
through silica gel chromatography to obtain 54.6 g of pale yellow oil 
Intermediate 13. 
The chemical structure was confirmed by .sup.1 HNMR, IR spectroscopic 
analysis and FD mass spectroscopic analysis. 
Synthesis of Intermediate 15 
To 54.6 g of the Intermediate 13, 300 ml of acetic acid anhydrite was 
added, excess acetic acid anhydrite was removed at normal pressure after 
refluxed with heating for 3 hours. To the resultant, 200 ml of methanol 
was added and further 60 ml of concentrated sulfuric acid was added 
dropwise. They were refluxed with heating for 3 hours. After the reaction 
the reaction liquid was cooled to room temperature, and was kept standing 
for a day after removing deposited crystal sulfur by filtration. Deposited 
crystal was separated by filtration to obtain 46 g of crystal, to the 
crystal, 1000 ml of ethylacetate and 80 ml of saturated aqueous solution 
of sodium hydrogen carbonate, and they were stirred with heating for 1 
hour. Then the organic phase was dried and organic solvent was removed 
therefrom by evaporation at reduced pressure. The resultant was refined by 
crystallization from a mixture solvent of ethyl acetate and hexane to 
obtain 38.3 g of white crystal Intermediate 15. 
The structure thereof was confirmed by .sup.1 HNMR, FD mass-spectral 
analysis and IR spectral analysis. 
Synthesis of Exemplified Compound M-75 
After dissolving 38.3 g of the Intermediate 15 in 300 ml of 
tetrahydrofuran, the solution was cooled to 5.degree. C. To the solution 
15.2 g of N-chlorosumlinimide was added as a solid state little by little, 
the mixture was stirred for 2 hours at 5.degree. to 7.degree. C. After 
removing solvent by evaporation at reduce pressure to the reactant 700 ml 
of ethylacetate and 150 ml of water was added then organic phase is 
separated. The organic phase was dried and therefrom ethyl acetate was 
removed by evaporation at reduced pressure. The resultant was 
recrystallized from a mixture solvent of ethylacetate and hexane to obtain 
41.9 g of the Intermediate 16. 
After addition of 15.4 g of 2-dodecanone, 800 ml of toluene and 5.2 g of 
p-toluenesufonic acid to 10.0 g of the Intermediate 16, the mixture was 
refluxed with heating for 8 hours, was cooled to room temperature 
thereafter, and was washed with 5% aqueous solution of sodium hydrogen 
carbonate, and organic solvent was removed by evaporation at reduced 
pressure. The obtained oily product was refined through silica gel 
chromatography to obtain 8.9 g of pale oil M-75. 
The chemical structure thereof was confirmed by .sup.1 HNMR, FD 
mass-spectral analysis and IR spectral analysis. 
It is preferred to contain the magenta coupler in a silver halide emulsion. 
The magenta coupler may be contained therein in a well-known method. For 
example, the magenta coupler relating to the invention can be contained in 
a silver halide emulsion in the following manner. The magenta coupler of 
the invention is dissolved in a high boiling organic solvent having a 
boiling point of not lower than 175.degree. C. such as tricresyl phosphate 
and dibutyl phthalate or a low boiling solvent such as ethyl acetate and 
butyl propionate independently or, if required, in the mixture thereof 
independently or in combination, and the resulting solution is mixed with 
an aqueous gelatin solution containing a surfactant. After that, the 
resulting mixture is emulsified by making use of a high-speed rotary mixer 
or a colloid-mill and the emulsified mixture is then added into the silver 
halide emulsion. 
The magenta coupler of the invention may usually be used in an amount 
within the range of 1.times.10.sup.-3 to 1 mol and, preferably, 
1.times.10.sup.-2 to 8.times.10.sup.-1 mols per mol of silver halide. 
It is also allowed to use the magenta couplers of the invention with other 
kinds of magenta couplers in combination. 
It is further allowed to use the magenta couplers of the invention with an 
image stabilizer. The preferable examples of the stabilizer include phenol 
compounds, phenylether compounds, amine compounds, and chlate compounds, 
and concretely, the exemplified compounds GG-1 through G-54, disclosed in 
pages 133-137 of JP OPI Publication No. 62-215272, the exemplified 
compounds (a-1) to (a-8), (b-1) to (b-6), (c-1) to (c-7), IIIa-1 to 
IIIa-15, IV-1 to IV-22, V-1 to V-10 and VI-1 to VI-5 disclosed in pages 23 
to 29 of JP OPI Publication No. 4-95952, the exemplified compounds A-1 to 
A-28 disclosed in pages 11 to 13 of JP OPI Publication No. 60-262159, the 
exemplified compounds PH-1 to PH-29 disclosed in pages 8-10 of JP OPI 
Publication No. 61-145552, the exemplified compounds B-1 to B- 21 
disclosed in pages 6-7 of JP OPI Publication No. 1-306846, the exemplified 
compounds I-1 to I-13, I'-1 to I'-8, II-1 to II-12, II-1 to II-21, III-8 
to III-14, IV-1 to IV-24, and V-1 to V-17 disclosed in pages 10-18 of JP 
OPI Publication No. 2-958, the exemplified compounds II-1 to II-33 
disclosed in pages 10-11 of JP OPI Publication No. 3-39956, the 
exemplified compounds B-1 to B-65 disclosed in pages 8-11 of JP OPI 
Publication No. 2-167543, and the exemplified compounds (1) to (120) 
disclosed in pages 4-7 of JP OPI Publication No. 63-95439. 
The image stabilizers may be used in an amount of, desirably, 5 to 400 mol 
% and, preferably, 10 to 250 mol % of the pyrazoloazole type magenta 
couplers of the invention. 
It is desired that the pyrazoloazole type magenta couplers of the invention 
and the above-mentioned image stabilizers are used in one and the same 
layer. It is, however, allowed to use the image stabilizers in the layer 
adjacent to a layer containing the above-mentioned couplers. 
The silver halides desirably used in the invention are comprised of silver 
chloride, silver chlorobromide or silver chloroiodobromide and, further, 
they may also be comprised of a combined mixture such as the mixture of 
silver chloride and silver bromide. 
The preferable silver halide component of the silver halide emulsion used 
in the present invention includes silver chloride, silver chlorobromide or 
silver chloroiodobromide. The emulsion may be a mixture of, for example, 
silver chlioride and silver bromide. 
In the silver halide emulsions applicable to the invention, it is allowed 
to use any one of silver halides such as silver bromide, silver 
iodobromide, silver iodochloride, silver chlorobromide, silver 
chloroiodobromide and silver chloride which can be used in ordinary silver 
halide emulsions. 
The silver halide grains may be either those having the uniform 
distribution of silver halide compositions inside the grains or those of 
the core/shell type having the different silver halide compositions 
between the inside of the grains and the surface layers of the grains. 
The silver halide grains may be either those capable of forming a latent 
image mainly on the surfaces thereof or those capable of forming a latent 
image mainly inside the grains thereof. 
The silver halide grains may be either those having a regular crystal form 
such as a cube, octahedron or tetradecahedron or those having an irregular 
crystal form such as a globular or tabular form. It is allowed to use the 
grains having any ratios of {100} planes to {111} planes. 
These grains may also have a mixed crystal form or may be mixed with the 
grains having various crystal forms. 
The silver halide grains applicable there to are to have a grain size 
within the range of, desirably, 0.05 to 30 .mu. and, preferably, 0.1 to 20 
.mu.. 
The silver halide emulsions having any grain size distributions may be 
used. It is, therefore, allowed to use either the emulsions having a wide 
grain size distribution (hereinafter referred to as `polydisperse type 
emulsions`) or the independent or mixed emulsions having a narrow grain 
size distribution (hereinafter referred to as `monodisperse type 
emulsions`). It is, further, allowed to use the mixtures of the 
polydisperse type and monodisperse type emulsions. 
The couplers applicable to the invention include a colored coupler capable 
of displaying a color compensation effect and the compounds capable of 
releasing a photographically useful fragment such as a development 
retarder, a development amlelerator, a bleach amlelerator, a developing 
agent, a silver halide solvent, a color toner, a layer hardener, a 
foggant, an antifoggant, a chemical sensitizer, a spectral sensitizer and 
a desensitizer. Among these compounds, it is also allowed to use the 
so-called DIR compounds capable of releasing a development retarder in the 
course of carrying out a development and improving the sharpness and 
graininess of an image. 
The above-mentioned DIR compounds include those containing a retarder 
directly coupled to the coupling position thereof and those containing a 
retarder coupled to the coupling position through a divalent group and 
capable of releasing the retarder either upon intramolecular nucteophilic 
reaction or upon intramolecular electron-transfer reaction, produced in a 
group split off upon coupling reaction, (the latter compounds are 
hereinafter referred to as `timing DIR compounds`). The retarders 
applicable thereto include those becoming diffusible upon splitting off 
and those not having a diffusibility so much, independently or in 
combination so as to meet the purposes of application. 
The above-mentioned couplers are to make a coupling reaction with the 
oxidized products of an aromatic primary amine developing agent and these 
couplers may also be used in combination with a colorless coupler not 
forming any dyes (hereinafter referred to as `competing coupler`) as a 
dye-forming coupler. 
The yellow couplers preferably applicable to the invention include, for 
example, the well-known acylacetanilide type couplers. Among these 
couplers, benzoyl acetanilide type and pivaloyl acetanilide type compounds 
may advantageously be used. 
The cyan couplers preferably applicable to the invention include, for 
example, phenol type and naphthol type couplers. 
It is also allowed to use a color-fog inhibitor for the purposes of 
preventing a color stain, a sharpness deterioration and/or a rough 
graininess, which may be produced by transferring the oxidized products of 
an developing agent or an electron transferrer between the emulsion layers 
of a light sensitive material (i.e., between the same color-sensitive 
layers and/or between the different color-sensitive layers). 
An image stabilizer capable of preventing the deterioration of a dye image 
may be applied to the light sensitive materials of the invention. The 
compounds preferably applicable thereto are described in, for example, RD 
17643, Article VII-J. 
For the purposes of preventing any fog from being produced by a electric 
discharge generated by frictionally static-charging a light sensitive 
material and preventing an image from being deteriorated by UV rays, a UV 
absorbent may also be contained in the hydrophilic colloidal layers 
thereof such as the protective layers and interlayers. 
For the purpose of preventing a magenta-dye forming coupler from being 
deteriorated by formalin in the course of preserving a light sensitive 
material, a formalin scavenger may further be used in the light sensitive 
material. 
The invention can preferably be applied to a color negative film, a color 
paper, a color reversal film and so forth. 
The invention will be detailed with reference to the following preferred 
embodiments. 
EXAMPLE 1-1 
Sample 101 of multilayered silver halide color photographic light sensitive 
materials was prepared in the manner that over to a polyethylene-laminated 
paper support containing polyethylene on one side thereof and titanium 
oxide on the other side thereof, each of the layers having the 
compositions shown in the following table were coated thereover on the 
side of the polyethylene layer containing titanium oxide. 
The coating solutions were each prepared in the following manner. 
Coating solution for the 1st layer 
Ethyl acetate of 60 ml was added and dissolved into 26.7 g of yellow 
coupler (EY-1), 10.0 g of dye-image stabilizer (ST-1), 6.67 g of a 
dye-image stabilizer (ST-2), 0.67 g of antistaining agent (HQ-1) and 6.67 
g of high-boiling organic solvent (DNP). The resulting solution was 
emulsified and dispersed in 220 ml of an aqueous 10% gelatin solution 
containing 7 ml of an aqueous 20% surfactant (SU-2) solution by making use 
of a supersonic homogenizer, so that a yellow coupler dispersed solution 
could be prepared. 
______________________________________ 
Amount 
added 
Layer Composition (g/m.sup.2) 
______________________________________ 
7th layer Gelatin 1.00 
(Protective 
layer) 
6th layer Gelatin 0.40 
(UV abosorbing 
UV absorbent (UV-1) 0.10 
layer) UV absorbent (UV-2) 0.04 
UV absorbent (UV-3) 0.16 
Antistaining agent (HQ-1) 
0.01 
DNP 0.20 
PVP 0.03 
Anti-irradiation dye (AIC-1) 
0.02 
5th layer Gelatin 1.30 
(Red-sensitive 
Red-sensitive silver chlorobromide 
0.21 
layer) emulsion (Em-R) 
Cyan coupler (EC-1) 0.24 
Cyan coupler (EC-2) 0.08 
Dye-image stabilizer (ST-1) 
0.20 
Antistaining agent (HQ-1) 
0.01 
HBS-1 0.20 
DOP 0.20 
4th layer Gelatin 0.94 
(UV absorbing 
UV absorbent (UV-1) 0.28 
layer) UV absorbent (UV-2) 0.09 
UV absorbent (UV-3) 0.38 
Antistaining agent (HQ-1) 
0.03 
DNP 0.40 
3rd layer Gelatin 1.40 
(Green- Green-sensitive silver chlorobromide 
0.17 
sensitive emulsion (Em-G) 
layer) Magenta coupler (EM-1) 
0.75* 
DNP 0.43 
Dye-image stabilizer (ST-3) 
0.75* 
Anti-irradiation dye (AIM-1) 
0.01 
2nd layer Gelatin 1.20 
(Interlayer) 
Antistaining agent (HQ-2) 
0.03 
Antistaining agent (HQ-3) 
0.03 
Antistaining agent (HQ-4) 
0.05 
Antistaining agent (HQ-5) 
0.23 
DIDP 0.06 
Antimold (F-1) 0.002 
1st layer Gelatin 1.20 
(Blue-sensitive 
Blue-sensitive silver chlorobromide 
0.26 
layer) emulsion (Em-B) 
Yellow coupler (EY-1) 0.80 
Dye-image stabilizer (ST-1) 
0.30 
Dye-image stabilizer (ST-2) 
0.20 
Antistaining agent (HQ-1) 
0.02 
Anti-irradiation dye (AIY-1) 
0.01 
DNP 0.20 
Support Polyethylene-laminated paper sheet 
______________________________________ 
*milli-mol/m.sup.2 
Amounts of the silver halide emulsions added were each shown in terms of 
the silver contents. 
The chemical structures of the compounds applied to each of the 
above-mentioned layers were as follows. 
##STR13## 
DOP: Dioctyl phthalate DNP: Dinonyl phthalate 
DIDP: Diisodecyl phthalate 
PVP: Polyvinyl pyrrolidone 
##STR14## 
Blue-sensitive silver halide emulsion (Em-B) 
This was a monodisperse type cubic silver chlorobromide emulsion having an 
average grain size of 0.85 .mu.m, a variation coefficient of 0.07 and a 
silver chloride content of 99.5 mol %. 
______________________________________ 
Sodium thiosulfate 
0.8 mg/mol of AgX 
Chloroauric acid 0.5 mg/mol of AgX 
Stabilizer STAB-1 
6 .times. 10.sup.-4 
mols/mol of AgX 
Sensitizing dye BS-1 
4 .times. 10.sup.-4 
mols/mol of AgX 
Sensitizing dye BS-2 
1 .times. 10.sup.-4 
mols/mol of AgX 
______________________________________ 
Green-sensitive silver halide emulsion (Em-G) 
This was a monodisperse type cubic silver chlorobromide emulsion having an 
average grain size of 0.43 .mu.m, a variation coefficient of 0.08 and a 
silver chloride content of 99.5 mol %. 
______________________________________ 
Sodium thiosulfate 
1.5 mg/mol of AgX 
Chloroauric acid 1.0 mg/mol of AgX 
Stabilizer STAB-1 
6 .times. 10.sup.-4 
mols/mol of AgX 
Sensitizing dye GS-1 
4 .times. 10.sup.-4 
mols/mol of AgX 
______________________________________ 
Red-sensitive silver halide emulsion (Em-R) 
This was a monodisperse type cubic silver chlorobromide emulsion having an 
average grain size of 0.50 .mu.m, a variation coefficient of 0.08 and a 
silver chloride content of 99.5 mol %. 
______________________________________ 
Sodium thiosulfate 
1.8 mg/mol of AgX 
Chloroauric acid 2.0 mg/mol of AgX 
Stabilizer STAB-1 
6 .times. 10.sup.-4 
mols/mol of AgX 
Sensitizing dye RS-1 
1 .times. 10.sup.-4 
mols/mol of AgX 
______________________________________ 
The variation coefficient is calculated by the following formulae; 
##EQU1## 
wherein r.sub.i is a grain size of each grain, ans n.sub.i is number of 
the grains. Grain size means a dimeter of the grain in case that the grain 
is sphere, or a dimeter of a circle having the same area converted from 
respective grain in case that the grain is other than sphere such as 
cubic. 
The chemical structures of the compounds applied to each of the monodiserse 
type cubic emulsions were as follows. 
##STR15## 
Next, Samples 102 through 113 were each prepared in the same manner as in 
Sample 101, except that the coupler EM-1 of the 3rd layer was replaced by 
the same mols of the coupler of the invention shown in Table-3. 
The resulting samples were each exposed to green light through a wedge in 
an ordinary procedures and they were then processed in the following 
processing steps. 
______________________________________ 
Processing step Temperature Time 
______________________________________ 
Color developing 
35.0 .+-. 0.3.degree. C. 
45 sec 
Bleach-fixing 35.0 .+-. 0.5.degree. C. 
45 sec 
Stabilizing 30 to 34.degree. C. 
90 sec 
Drying 60 to 80.degree. C. 
60 sec 
______________________________________ 
The compositions of each of the processing solution will be given below. 
The processing solutions were each replenished in an amount of 80 ml per 
m.sup.2 of a subject silver halide color photographic light sensitive 
material. 
______________________________________ 
Tank Replenishing 
Color developer solution solution 
______________________________________ 
Deionized water 800 ml 800 ml 
Triethanol amine 10 g 18 g 
N,N-diethyl hydroxyl amine 
5 g 9 g 
Potassium chloride 2.4 g 
1hydroxyethylidene-1,1- 
1.0 g 1.8 g 
diphosphoric acid 
N-ethyl-N-b-methanesulfonamidoethyl- 
5.4 g 8.2 g 
3-methyl-4-aminoaniline sulfate 
Fluorescent whitening agent, 
1.0 g 1.8 g 
(a 4,4'-diaminostilbene sulfonic 
acid derivative) 
Potassium carbonate 27 g 27 g 
______________________________________ 
Add water to make in total of 1000 ml 
Adjust pH values of the tank solution to be 10.0 and of the replenisher to 
be 10.60, respectively. 
Bleach-fixer (The same in both of the tank solution and the replenishing 
solution) 
______________________________________ 
Ferric ammonium ethylenediamine 
60 g 
tetraacetate, dehydrate 
Ethylenediaminetetraacetic acid 
3 g 
Ammonium thiosulfate (in an aqueous 
100 ml 
70% solution) 
Ammonium sulfite (in an aqueous 
27.5 ml 
40% solution) 
Add water to make in total of 
1000 ml 
Adjust pH with potassium carbonate 
pH 5.7 
or glacial acetic acid to be 
______________________________________ 
Stabilizer (The same in both of the tank solution and the replenisher) 
______________________________________ 
5-chloro-2-methyl-4-isothiazoline-3-one 
1.0 g 
Ethylene glycol 1.0 g 
1-hydroxyethylidene-1,1- 2.0 g 
diphosphonic acid 
Ethylenediaminetetraacetic acid 
1.0 g 
Ammonium hydroxide (in an aqueous 
3.0 g 
20% solution) 
Fluorescent whitening agent 
1.5 g 
(a 4,4'-diaminostilbene sulfonic 
acid derivative) 
Add water to make in total of 
1000 ml 
Adjust pH with sulfuric acid or 
pH 7.0 
potassium hydroxide to be 
______________________________________ 
The following evaluation were each carried out by making use of the samples 
which were continuously processed. 
&lt;Light-fastness&gt; 
The resulting samples were each exposed to a Xenon fade-o-meter for 7 days 
and the dye image residual percentage (%) thereof at the initial density 
of 1.0 were found out. 
&lt;Dmax&gt; 
The maximum color densities thereof were measured. 
The results thereof are shown in Table 3. 
TABLE 3 
______________________________________ 
Light- 
Sample Magenta fastness 
No. couplers Dmax (residual %) 
______________________________________ 
101 EM-1 1.96 55 
102 M-13 2.15 72 
103 M-14 2.35 70 
104 M-15 2.24 70 
105 M-18 2.07 75 
106 M-24 2.20 71 
107 M-54 2.41 75 
108 M-75 2.20 71 
109 M-77 2.09 70 
110 M-80 2.18 72 
111 M-82 2.23 73 
112 M-84 2.15 72 
113 M-88 2.24 73 
______________________________________ 
Samples No.102 through No.113 each shown in Table 3, are improved in both 
of developability and light-fastness as compared with the comparative 
sample 101. 
EXAMPLE 1-2 
Samples No.114 through No.122 were each prepared in the same manner as in 
Sample No.101 of Example 1-1, except that the magenta coupler in the third 
layer was replaced with the same mol of each coupler shown in the Table 4. 
The same evaluation as Example 1-1 was each carried out by making use of 
the resulting samples. The results thereof are shown in Table 4. 
TABLE 4 
______________________________________ 
Light- 
Sample Magenta fastness 
No. couplers Dmax (residual %) 
______________________________________ 
114 EM-2 2.44 13 
115 M-1 2.57 61 
116 M-4 2.53 63 
117 M-6 2.49 67 
118 M-7 2.51 60 
119 M-55 2.54 63 
120 M-61 2.51 65 
121 M-64 2.48 61 
122 M-60 2.57 60 
______________________________________ 
Samples No.115 through No.122 each shown in Table 4, are remarkably 
improved in both of developability and light-fastness as compared with the 
comparative sample 114. 
EXAMPLE 1-3 
Samples No.123 through No.131 were each prepared in the same manner as in 
Sample No.101 of Example 1-1, except that the magenta coupler in the third 
layer was replaced with the same mol of each coupler shown in the Table 5. 
The same evaluation as Example 1-1 was each carried out by making use of 
the resulting samples. The results thereof are shown in Table 5. 
TABLE 5 
______________________________________ 
Light- 
Sample Magenta fastness 
No. couplers Dmax (residual %) 
______________________________________ 
123 EM-3 1.75 47 
124 M-38 2.07 65 
125 M-40 2.08 67 
126 M-44 2.11 70 
127 M-45 1.97 64 
128 M-96 1.93 67 
129 M-97 1.97 70 
130 M-101 1.86 70 
131 M-103 2.05 68 
______________________________________ 
Samples No.124 through No. 131 each shown in Table 5, are remarkably 
improved in both of developability and light-fastness as compared with the 
comparative sample 123. 
EXAMPLE 1-3 
The reflective absorption spectrum of Samples 101 to 113 of the Example 1-1 
was observed to evaluate spectroscopic absorption characteristics 
.lambda.max and Abs600. The result is summarised in Table 6. 
TABLE 6 
______________________________________ 
Sample Magenta 
No. couplers .lambda.max 
Abs600 
______________________________________ 
101 EM-1 547 0.42 
102 M-13 548 0.34 
103 M-14 545 0.36 
104 M-15 548 0.35 
105 M-18 550 0.36 
106 M-24 546 0.34 
107 M-54 552 0.35 
108 M-75 547 0.34 
109 M-77 548 0.35 
110 M-80 549 0.34 
111 M-82 550 0.33 
112 M-84 552 0.37 
113 M-88 554 0.38 
______________________________________ 
As apparent from the Table 6, samples 102 to 113 containing the coupler of 
the invention show improvement in color reproduction characteristics since 
they have reduced absorption at 600 nm having sharp spectrum in comparison 
with the comparative sample 101. 
EXAMPLE 2 
In the following examples, the amounts of ingredients are those per square 
meter of the light-sensitive material, unless otherwise indicated. The 
amounts of a silver halide and colloidal silver are each indicated as the 
amount of silver. 
One side (the right side) of a cellulose triacetate film support was 
subbed. On the other side (the backing side) of the support, layers of the 
following compositions were provided in sequence. 
--Backing side 
______________________________________ 
1st layer 
Alumina sol AS-100 (aluminum oxide, 
0.8 g 
manufactured by Nissan 
Chemical Industry, Ltd.) 
2nd layer 
Cellulose acetate 100 g 
Stearic acid 10 mg 
Finely divided silica 50 mg 
(average particle size: 0.2 .mu.m) 
______________________________________ 
Then, on the right side of the support that had been subbed, layers of the 
following compositions were provided in sequence, whereby a multilayer 
color photographic light-sensitive material (Sample No. 201) was obtained. 
--Right side 
______________________________________ 
1st layer: Anti-halation layer (HC) 
Black colloidal silver 
0.15 g 
UV absorber (UV-4) 
0.20 g 
Colored cyan coupler (CC-1) 
0.02 g 
High-boiling solvent (DOP) 
0.20 g 
High-boiling solvent (TCP) 
0.20 g 
Gelatin 1.6 g 
2nd layer: Intermediate layer (IL-1) 
Gelatin 1.3 g 
3rd layer: Low-speed red-sensitive emulsion layer (R-L) 
Silver iodobromide emulsion 
0.4 g 
(average grain size: 0.3 .mu.m, 
average iodine content: 
2.0 mol %) 
Silver iodobromide emulsion 
0.3 g 
(average grain size: 0.4 .mu.m, 
average iodine content: 
8.0 mol %) 
Sensitizing dye (RS-2) 
3.2 .times. 10.sup.-4 
(mol/mol silver) 
Sensitizing dye (RS-3) 
3.2 .times. 10.sup.-4 
(mol/mol silver) 
Sensitizing dye (RS-4) 
0.2 .times. 10.sup.-4 
(mol/mol silver) 
Cyan coupler (EC-3) 
0.50 g 
Cyan coupler (EC-4) 
0.13 g 
Colored cyan coupler (CC-1-) 
0.07 g 
DIR compound (D-1) 
0.006 g 
DIR compound (D-22) 
0.01 g 
High-boiling solvent (DOP) 
0.55 g 
Gelatin 1.0 g 
4th layer: High-speed red-sensitive emulsion layer (R-H) 
Silver iodobromide emulsion 
0.9 g 
(average grain size: 0.7 .mu.m, 
average iodine content: 
7.5 mol %) 
Sensitizing dye (RS-2) 
1.7 .times. 10.sup.-4 
(mol/mol silver) 
Sensitizing dye (RS-3) 
1.6 .times. 10.sup.-4 
(mol/mol silver) 
Sensitizing dye (RS-4) 
0.1 .times. 10.sup.-4 
(mol/mol silver) 
Cyan coupler (EC-4) 
0.23 g 
Colored cyan coupler (CC-1) 
0.03 g 
DIR compound (D-2) 
0.02 g 
High-boiling solvent (DOP) 
0.25 g 
Gelatin 1.0 g 
5th layer: Intermediate layer (IL-2) 
Gelatin 0.8 g 
6th layer: Low-speed green-sensitive emulsion layer (G-L) 
Silver iodobromide emulsion 
0.6 g 
(average grain size: 0.4 .mu.m, 
average iodine content: 
8.0 mol %) 
Silver iodobromide emulsion 
0.2 g 
(average grain size: 0.3 .mu.m, 
average iodine 
content: 2.0 mol %) 
Sensitizing dye (GS-2) 
6.7 .times. 10.sup.-4 
(mol/mol silver) 
Sensitizing dye (GS-3) 
0.8 .times. 10.sup.-4 
(mol/mol silver) 
Magenta coupler (EM-4) 
0.45 g 
Colored magenta coupler (CM-1) 
0.10 g 
DIR compound (D-3) 
0.02 g 
High-boiling solvent (TCP) 
0.7 g 
Gelatin 1.0 g 
7th layer: High-speed green-sensitive emulsion layer (G-H) 
Silver iodobromide emulsion 
0.9 g 
(average grain size: 0.7 .mu.m; 
average iodine content: 
7.5 mol %) 
Sensitizing dye (GS-4) 
1.1 .times. 10.sup.-4 
(mol/mol silver) 
Sensitizing dye (GS-5) 
2.0 .times. 10.sup.-4 
(mol/mol silver) 
Sensitizing dye (GS-6) 
0.3 .times. 10.sup.-4 
(mol/mol silver) 
Magenta coupler (EM-4) 
0.35 g 
Colored magenta coupler (CM-I) 
0.04 g 
DIR compound (D-3) 
0.004 g 
High-boiling solvent (TCP) 
0.35 g 
Gelatin 1.0 g 
8th layer: Yellow filter layer (YC) 
Yellow colloidal silver 
0.1 g 
Additive (HS-1) 0.07 g 
Additive (HS-2) 0.07 g 
Additive (SC-1) 0.12 g 
High-boiling solvent (TCP) 
0.15 g 
Gelatin 1.0 g 
9th layer: Low-speed blue-sensitive emulsion layer (B-L) 
Silver iodobromide emulsion 
0.25 g 
(average grain size: 0.3 .mu.m; 
average iodine content: 
2.0 mol %) 
Silver iodobromide emulsion 
0.25 g 
(average grain size: 0.4 .mu.m; 
average iodine content: 
8.0 mol %) 
Sensitizing dye (S-9) 
5.8 .times. 10.sup.-4 
(mol/mol silver) 
Yellow coupler (EY-2) 
0.6 g 
Yellow coupler (EY-3) 
0.32 g 
DIR compound (D-1) 
0.003 g 
DIR compound (D-22) 
0.006 g 
High-boiling solvent (TCP) 
0.18 g 
Gelatin 1.3 g 
10th layer: High-speed blue-sensitive emulsion layer (B-H) 
Silver iodobromide emulsion 
0.5 g 
(average grain size: 0.8 .mu.m; 
average iodine content: 
8.5 mol %) 
Sensitizing dye (BS-4) 
3 .times. (mol/mol silver) 
Sensitizing dye (BS-5) 
1.2 .times. 10.sup.-4 
(mol/mol silver) 
Yellow coupler (EY-2) 
0.18 g 
Yellow coupler (EY-3) 
0.10 g 
High-boiling solvent (TCP) 
0.05 g 
Gelatin 1.0 g 
11th layer: 1st protective layer (PRO-1) 
Silver iodobromide emulsion 
0.3 g 
(average grain size: 0.08 .mu.m) 
UV absorber (UV-4) 
0.07 g 
UV absorber (UV-5) 
0.10 g 
Additive (HS-1) 0.2 g 
Additive (HS-2) 0.1 g 
High-boiling solvent (DOP) 
0.07 g 
High-boiling solvent (DBP) 
0.07 g 
Gelatin 0.8 g 
12th layer: 2nd protective layer (PRO-2) 
Compound A 0.04 g 
Compound B 0.004 g 
Polymethyl methacrylate 
0.02 g 
(average particle size: 3 .mu.m) 
Methyl methacrylate/ethyl 
0.13 g 
methacrylate/methacrylic acid 
copolymer (weight ratio: 3:3:4, 
average particle size: 3 .mu.m) 
______________________________________ 
The light sensitive material sample 201 further contains compounds SU-1 and 
SU-4, viscosity adjusting agent, hardeners HH-1 and HH-3, a stabilizer 
ST-1, antifoggants AF-1 and AF-2 (two kinds of AF-2 were employed; one had 
a weight average molecular weight of 10,000 and the other with a weight 
average molecular weight of 1,100,000), dyes AI-1, AI-2 and DI-1 (content: 
9.4 g/m.sup.2). 
The silver iodobromide emulsion contained in the 10th layer was prepared by 
the double-jet method as described below. 
Silver iodobromide emulsion was prepared by double jet method to grow seed 
grains of monodispersed silver iodobromide grains having an average grain 
size of 0.33 .mu.m and an average silver iodide content of 2 mol %. 
To the solution G-1, of which the temperature, pAg and pH had been kept at 
70.degree. C., 7.8 and 7.0, respectively, a 0.34 mol-equivalent amount of 
seed grains were added with stirring. 
&lt;Preparation of internal high iodide phase-core phase&gt; 
Then, solutions H-1 and S-1 were added over a period of 86 minutes at an 
accelerated flow rate so that the flow rate immediately before the start 
of addition would be 3.6 times as high as that immediately after the start 
of addition. The ratio of the flow rate of solution H-1 to that of S-1 was 
kept at 1:1. 
&lt;Preparation of external low iodide phase-shell phase&gt; 
Subsequently, while keeping pAg and pH at 10.1 and 6.0, respectively, 
solutions H-2 and S-2 were added over a period of 65 minutes at an 
accelerated flow rate so that the flow rate immediately before the start 
of addition would be 5.2 times as high as that immediately after the start 
of addition. The ratio of the flow rate of solution H-1 to that of S-1 was 
kept at 1:1. 
During the formation of the silver halide grains, pAg and pH were 
controlled with an aqueous potassium bromide solution and a 56% aqueous 
acetic acid solution. The so-formed grains were washed with water by the 
conventional flocculating method. Gelatin was then added to make the 
grains redispersed, and pH and pAg were controlled at 40.degree. C. to 5.8 
and 8.06, respectively. 
The emulsion consisted of monodispersed, octahedral silver iodobromide 
grains with an average grain size of 0.80 .mu.m, a variation coefficient 
of 12.4% and a silver iodide content of 8.5 mol %. 
______________________________________ 
&lt;G-1&gt; 
Ossein gelatin 100.0 g 
Compound-I (10 wt % methanol solution) 
25.0 ml 
28% aqueous ammonium solution 
440.0 ml 
56% aqueous acetic acid solution 
660.0 ml 
Water was added to make the total quantity 
5,000.0 ml. 
&lt;H-1&gt; 
Ossein gelatin 82.4 g 
Potassium bromide 151.6 g 
Potassium iodide 90.6 g 
Water was added to make the total quantity 
1030.5 ml. 
&lt;S-1&gt; 
Silver nitrate 309.2 g 
28% aqueous ammonia solution 
Equivalent 
Water was added to make the total quantity 
1030.5 ml. 
&lt;H-2&gt; 
Ossein gelatin 302.1 g 
Potassium bromide 770.0 g 
Potassium iodide 33.2 g 
Water was added to make the total quantity of 
3776.8 ml. 
&lt;S-2&gt; 
Silver nitrate 1133.0 g 
28% aqueous ammonia solution 
Equivalent 
amount 
Water was added to make the total quantity 
3776.8 ml. 
______________________________________ 
Emulsions differing in average grain size and silver iodide content were 
prepared in substantially the same manner as mentioned above, except that 
the average size of seed grains, temperature, pAg, pH, flow rate, addition 
time and halide composition were varied. 
Each of the resulting emulsions was a core/shell type emulsion consisting 
of monodispersed grains with a variation coefficient of 20% or less. Each 
emulsion was chemically ripen to an optimum level in the presence of 
chloroauric acid and ammonium thiocyanate, and then spectrally sensitized 
with a sensitizing dye, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 
1-phenyl-5-mercaptotetrazole. 
Chemical structures of compounds used in each layer are shown. 
##STR16## 
DOP: Dioctyl phthalate DBP: Dibutyl phthalate 
TCP: Tricredyl phthalate 
##STR17## 
Sample Nos. 202 to 219 were prepared in substantially the same manner as in 
the preparation of Sample No. 101, except that the magenta couplers in the 
6th and 7th layers were replaced with those shown in Table 8. 
Each sample was exposed to white light through a step wedge, and processed 
according to the following procedures (Developing Process I). 
Processing steps 
______________________________________ 
Procedure Time Temperature 
Repl. Amount* 
______________________________________ 
Color developing 
3'15" 38 .+-. 0.3.degree. C. 
780 ml 
Bleaching 45" 38 .+-. 2.0.degree. C. 
150 ml 
Fixing 1'30" 38 .+-. 2.0.degree. C. 
830 ml 
Stabilizing 
60" 38 .+-. 5.0.degree. C. 
830 ml 
Drying 1' 55 .+-. 5.0.degree. C. 
-- 
______________________________________ 
*The amount of a replenisher is that per square meter of a lightsensitive 
material. 
The compositions of the processing liquids were as follows. 
&lt;Color Developer&gt; 
______________________________________ 
Water 800 ml 
Potassium carbonate 30 g 
Sodium bicarbonate 2.5 g 
Potassium sulfite 3.0 g 
Sodium bromide 1.3 g 
Potassium iodide 1.2 mg 
Hydroxylamine sulfate 2.5 g 
Sodium chloride 0.6 g 
4-amino-3-methyl-N-ethyl-N-(.beta.-hydroxyethyl) 
4.5 g 
aniline sulfate 
Diethylenetriaminepentacetic acid 
3.0 g 
Potassium hydroxide 1.2 g 
______________________________________ 
Water was added to make the total quantity 11, and pH was controlled to 
10.06 with potassium hydroxide or 20% sulfuric acid. 
&lt;Color Developer Replenisher&gt; 
______________________________________ 
Water 800 ml 
Potassium carbonate 35 g 
Sodium bicarbonate 3 g 
Potassium sulfite 5 g 
Sodium bromide 0.4 g 
Hydroxylamine sulfate 3.1 g 
4-amino-3-methyl-N-ethyl-N-(.beta.-hydroxyethyl) 
6.3 g 
aniline sulfate 
Potassium hydroxide 2 g 
Diethylenetriaminepentacetic acid 
3.0 g 
______________________________________ 
Water was added to make the total quantity 11, and pH was controlled to 
10.18 with potassium hydroxide or 20% sulfuric acid. 
&lt;Bleacher&gt; 
______________________________________ 
Water 700 ml 
Ferric ammonium 1,3-diaminopropanetetracetate (III) 
125 g 
Ethylenediaminetetracetic acid 
2 g 
Sodium nitrate 40 g 
Ammonium bromide 150 g 
Glacial acetic acid 40 g 
______________________________________ 
Water was added to make the total quantity 11, and pH was controlled to 4.4 
with aqueous ammonia or glacial acetic acid. 
&lt;Bleacher Replenisher&gt; 
______________________________________ 
Water 700 ml 
Ferric ammonium 1,3-diaminopropanetetracetate (III) 
175 g 
Ethylenediaminetetracetic acid 
2 g 
Silver nitrate 50 g 
Ammonium bromide 200 g 
Glacial acetic acid 56 g 
______________________________________ 
After adjusting pH to 4.0 with aqueous ammonia or glacial acetic acid, 
water was added to make the total quantity 11. 
&lt;Fixer&gt; 
______________________________________ 
Water 800 ml 
Ammonium thiocyanate 120 g 
Ammonium thiosulfate 150 g 
Sodium sulfite 15 g 
Ethylenediaminetetracetic acid 
2 g 
______________________________________ 
After adjusting pH to 6.2 with aqueous ammonia or glacial acetic acid, 
water was added to make the total quantity 11. 
&lt;Fixer Replenisher&gt; 
______________________________________ 
Water 800 ml 
Ammonium thiocyanate 150 g 
Ammonium thiosulfate 180 g 
Sodium sulfite 20 g 
Ethylenediaminetetracetic acid 
2 g 
______________________________________ 
After adjusting pH to 6.5 with aqueous ammonia or glacial acetic acid, 
water was added to make the total quantity 11. 
&lt;Stabilizer and Stabilizer Replenisher&gt; 
______________________________________ 
Water 900 ml 
Compound 2.0 g 
##STR18## 
[Dimethylol urea 0.5 g 
Hexamethylene tetramine 0.2 g 
1,2-benzisothiazoline-3-on 
0.1 g 
Siloxane (L-77, manufactured by UCC) 
0.1 g 
Aqueous ammonia 0.5 ml 
______________________________________ 
Water was added to make the total quantity 1, and pH was adjusted to 8.5 
with 50% sulfuric acid or aqueous ammonia. 
Sample Nos. 201 to 219 were exposed to white light through a step wedge 
(specifically designed for sensitometry), and processed in the same way as 
mentioned above, except that the pH of the developer was varied to 9.90 
(Developing Process II). 
For each of the processed samples, maximum density of magenta dye was 
measured with green light by means of optical densitometer PDA-6 
(manufactured by Konica Corporation). Maximum color density, relative 
sensitivity and pH influence are shown in Table 8. The evaluation for pH 
influence is given by a ratio of maximum densty obtained by Developing 
process I to maximum densty obtained by Developing process II, that is, 
##EQU2## 
TABLE 8 
______________________________________ 
Magenta Maximum Relative 
pH 
Sample Coupler Density Sensitivity 
influence 
______________________________________ 
201 EM-4 2.38 100 63 
202 M-1 2.56 125 84 
203 M-2 2.64 131 82 
204 M-3 2.47 129 85 
205 M-4 2.49 126 86 
206 M-5 2.42 124 85 
207 M-6 2.50 130 87 
208 M-7 2.41 125 87 
209 M-9 2.43 124 84 
210 M-10 2.44 126 83 
211 M-55 2.60 130 82 
212 M-56 2.54 126 87 
213 M-57 2.55 128 84 
214 M-58 2.63 132 81 
215 M-59 2.47 125 87 
216 M-64 2.44 119 88 
217 M-71 2.42 109 85 
218 M-72 2.45 114 84 
219 M-73 2.44 121 84 
______________________________________ 
The Relative Sensitivity is a value of reciprocal number of exposure 
necessary to give a density of fog density plus 0.10, and shown relatively 
taking the sample 201 as 100. The values of relative sensitivity and 
maximum density are measured for the samples processed by Developing 
Processing I. 
As is evident from the results, the samples No. 202 to 219 containing the 
coupler of the invention are remarkably improved in maximum density, 
sensitivity and pH influence in comparison with Sample 201 containing a 
conventional coupler EM-4.