Silver halide color photographic light-sensitive material

A silver halide color photographic light-sensitive material comprising a silver halide emulsion layer containing a cyan coupler represented by the following general formula [I]. The color photographic material is improved in sensitivity, density of cyan image, density losing of cyan image due to processing by a fatigued bleach or bleach-fix solution. ##STR1##

FIELD OF THE INVENTION 
The present invention relates to a silver halide color photographic 
light-sensitive material, in particular, to a silver halide color 
photographic light-sensitive material capable of providing a cyan dye 
image indicating satisfactory spectral absroption property and free from 
dye loss, even if treated with a bleaching bath or bleach-fixing bath 
which has been fatigued in the course of running treatment. 
BACKGROUND OF THE INVENTION 
With a silver halide color photographic light-sensitive material, a dye 
image is usually formed in the following manner: first, silver halide 
particles, which underwent exposing, are reduced by an aromatic primary 
amine color developing agent; next, the resultant oxidation product of the 
color developing agent couples with couplers respectively forming yellow, 
magenta, and cyan dyes. 
Couplers widely used for forming the cyan dye are phenol cyan couplers and 
naphthol cyan couplers. 
The recent photographic industry witnessed a phenomenon resulting from the 
rapid progress in color photography has prompted a drastic increase in the 
amount of color negative films being treated, where the bleaching bath or 
bleach-fixing bath readily develops fatigue in the course of running 
treatment. 
It was found that a naphthol compound conventionally widely used as a cyan 
coupler for a color negative film has a disadvantage; when such a film is 
treated with a fatigued bleaching bath or bleach-fixing bath, a cyan dye 
once formed reverts to a leuco matter, resulting in dye loss. To solve 
these problems, cyan couplers having a phenylureide group in the 
2-position on a phenol was developed as described in Japanese Patent Open 
to Public Inspection (hereinafter referred to a Japanese Patent O.P.I. 
Publication) Nos. 21139/1972, 65134/1981, 204543/1982, 204544/1982, 
204545/1982, 98731/1983, 187928/1983 and the like. This cyan coupler 
drastically improved the dye loss. However, these cyan couplers have a 
disadvantage regarding color reproduction; in relation to spectral 
absorption property, the dyes formed from these couplers, when compared 
with dyes formed from naphthol couplers, have a maximum absorption 
wavelength in a relatively shortwave range, hence greater absorption in 
the green range to a shortwave range. Human vision is especially sensitive 
to a green light. Therefore, even marginal reduction in green absorption 
contributes to greater improve in color reproduction as appreciated by 
human vision. This is because further improved cyan couplers are required. 
SUMMARY OF THE INVENTION 
The first object of the present invention is to provide a highly sensitive, 
silver halide color photographic light-sensitive material being capable of 
forming a cyan image with high color density. 
The second object of the invention is to provide a silver halide color 
photographic light-sensitive material being capable of forming a cyan 
image free from dye loss even when using a bleaching bath or bleach-fixing 
bath fatigued in the course of running treatment. 
The third object of the invention is to provide a silver halide color 
photographic light-sensitive material being capable of forming a cyan dye 
image which has a satisfactory spectral absorption property and of which 
maximum absorption range is in a comparatively longer wavelength side. 
The fourth object of the invention is to provide a silver halide color 
photographic light-sensitive material being capable of forming a cyan dye 
image and manufactured at a relatively low cost. 
The fifth object of the invention is to provide a silver halide color 
photographic light-sensitive material excelling in dispersion stability 
and capable of forming a cyan image. 
These objects of the invention are attained by a silver halide color 
photographic light-sensitive material comprising a silver halide emulsion 
layer containing a cyan coupler represented by the following general 
formula I: 
##STR2## 
(wherein R.sub.1 represents a substituted or not substituted alkyl or a 
substituted or not-substituted aryl group, and Z represents a group 
represented by the following formula [II], [III], [IV] or [V]) 
##STR3## 
(wherein R.sub.2, R.sub.3 and R.sub.5 independently represent a hydrogen 
atom, a substituted or not substituted alkyl group, or substituted or not 
substituted aryl group, R.sub.2 and R.sub.3 may be the same or different 
from each other; W.sub.1 represents a group having a .sigma.p value of 
Hammet's rule of not less than 0.4, W.sub.4 represents a group having a 
.sigma.p value of Hammet's rule of not less than O, W.sub.1 and W.sub.2 
may be the same or different from each other; R.sub.4 represents an alkyl 
group, an aryl group, an alkoxy group, an aryloxy group, an alkylamino 
group or aryl amino group, which may be subsituted or not substituted.) 
R.sub.1 in general formula [I] represents an alkyl or aryl group. The 
specific alkyl group is an alkyl group having 1 to 20 carbon atoms, and 
such an alkyl group may have a substituent. The preferred alkyl group is a 
group represented by the following general formula [VI]. 
##STR4## 
(wherein Y represents --O--, --S--, or --SO.sub.2 --; R.sub.6 represents 
an alkylene group with 1 to 20 carbon atoms (such as a methylene, 
1,1-ethylene, 1,1-propylene, 1,3-propylene, 2-methyl-1,1-propylene, 
1,1-pentylene, 1,1-heptylene, 1,1-nonylene, 1,1-undecylene, 
1,1-tridecylene, or 1,1-pentadecylene group); R.sub.7 represents a halogen 
atom (such as a chlorine or fluorine atom); or a hydroxy group, or an 
alkyl group with 1 to 20 carbon atoms (such as a methyl, ethyl, 
tert-butyl, tert-pentyl, cyclopentyl, tert-octyl, or pentadecyl group); or 
an alkoxy group (such as a methoxy, ethoxy, isopropoxy, butoxy, hexyloxy, 
or dodecyloxy group); an alkylsulfonamido group (such as a 
methanesulfonamido, ethanesulfonamido, butanesulfonamido, 
octylsulfonamido, or hexadecylsulfonamido group), or an arylsulfonamido 
group (such as a benzenesulfonamido, m-chlorobenzenesulfonamido, 
toluenesulfonamido, p-methoxybenzenesulfonamido, or 
p-dodecyloxybenzenesulfonamido group); or an alkylsulfamoyl group (such as 
a butylsulfamoyl, tert-butylsulfamoyl, or dodecylsulfamoyl group); or an 
arylsulfamoyl group (such as a benzenesulfamoyl, toluenesulfamoyl, or 
dedecyloxybenzenesulfamoyl group); or an alkylsulfonyl group (such as a 
methanesulfonyl, or butanesulfonyl group); or an arylsulfonyl group (such 
as a benzenesulfonyl, p-benzyloxyphenylsulfonyl, or 
p-hydroxyphenylsulfonyl group); or an alkoxycarbonyl group (such as an 
ethoxycarbonyl, butoxycarbonyl, or hexadecyloxycarbonyl group); l 
represent an integer 1 to 4, preferably, 1 or 2; when l is greater than 2, 
R.sub.7 S may be identical or different with each other.) 
According to the invention, a preferred aryl group represented by R.sub.1 
in general formula [I] is a phenyl group, wherein the phenyl group may 
have a substituent which is represented by R.sub.7 in general formula [VI] 
R.sub.2, R.sub.3 and R.sub.5 in general formulas [II] through [V] 
independently represent a hydrogen atom, or an alkyl group (for example, 
an alkyl or alkenyl group with 1 to 18 carbon atoms, or an aryl group, 
(for example an aralkyl or aralkenyl group; or an aryl group with 6 to 12 
carbon atoms). The alkyl group, alkenyl group, aralkyl group, aralkenyl 
group or aryl group represented any of R.sub.2, R.sub.3 and R.sub.5 may 
have a such a substituent as a halogen atom such as fluorine, chlorine, or 
bromine atom, nitro group, cyano group, hydroxy group, alkoxy group, 
acyloxy group, acylamino group, sulfonamido group, sulfamoyl group, 
sulfonyl group, carboxy group or sulfo group, or another group. 
Additionally, the alkyl group, alkenyl group, aralkyl group, or aralkenyl 
group represented any of R.sub.2, R.sub.3 and R.sub.5 may be either 
straight-chained or branched. 
W.sub.1 represents a group of which .sigma.p value according to Hammett's 
is greater than 0.4. The examples of such a group include a 
trifluoromethyl group, cyano group, formyl group, acyl group (COR.sub.8), 
alkoxycarbonyl group, aryloxycarbonyl group (--COOR.sub.8), sulfonyl group 
(--SO.sub.2 R.sub.8), and sulfamoyl group 
##STR5## 
What are represented by R.sub.8, R.sub.9 and R.sub.10 are respectively 
identical with those the previously defined with R.sub.2, R.sub.3 and 
R.sub.5. W.sub.2 represents a group of which .sigma.p value according to 
Hammett's rule is 0 is larger (for example, 0.0). The examples of such a 
group include a halogen atom, (F, Cl, Br, and I), a trifluoromethyl group, 
a cyano group, or a substituted or unsubstituted group of carbamoyl group, 
##STR6## 
formyl, acyl, alkoxycarbonyl, arylxycarbonyl, sulfonyl and sulfamoyl. 
R.sub.4 represents an alkyl group, aryl group, alkoxy group, aryloxy 
group, alkylamino group or arylamino group. Among these groups, the alkyl 
and aryl portions are identical with those previously defined for R.sub.2, 
R.sub.3 and R.sub.5. 
The typical examples of the cyan coupler of the invention are listed below. 
However, the scope of the invention is not limited only to these examples. 
Me represents CH.sub.3. 
__________________________________________________________________________ 
##STR7## 
Coupler No. 
R.sub.1 Z 
__________________________________________________________________________ 
##STR8## OCH.sub.2 CO.sub.2 CH.sub.3 
2 
##STR9## OCH.sub.2 COCH.sub.3 
3 
##STR10## OCH.sub.2 CN 
4 
##STR11## OCH.sub.2 CF.sub.3 
5 
##STR12## 
##STR13## 
6 
##STR14## 
##STR15## 
7 
##STR16## 
##STR17## 
8 
##STR18## OCOOCH.sub.3 
9 
##STR19## 
##STR20## 
10 
##STR21## 
##STR22## 
11 
##STR23## OSO.sub.2 C.sub.2 H.sub.5 
12 
##STR24## OCONHC.sub.12 H.sub.25 
13 
##STR25## 
##STR26## 
14 
##STR27## OCH.sub.2 SO.sub.2 NHCH.sub.3 
15 
##STR28## OCH.sub. 2 NO.sub.2 
16 
##STR29## 
##STR30## 
17 
##STR31## 
##STR32## 
18 
##STR33## OCOCH.sub.2 CH.sub.2 Cl 
19 
##STR34## 
##STR35## 
20 
##STR36## 
##STR37## 
21 
##STR38## 
##STR39## 
22 
##STR40## OCH.sub.2 CO.sub.2 CH.sub.2 CO.sub.2 
CH.sub.3 
23 
##STR41## OCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.2 OH 
24 
##STR42## 
##STR43## 
25 
##STR44## 
##STR45## 
26 
##STR46## OCH.sub.2 COOH 
27 
##STR47## OCH.sub.2 COOCH.sub.2 SO.sub.2 NHC.sub.4 
H.sub.9 
28 
##STR48## OCH.sub.2 COOC(CH.sub.3).sub.3 
29 
##STR49## OCH.sub.2 COOC.sub.6 H.sub.13 
30 
##STR50## OCH.sub.2 COOCH.sub.2 (CF.sub.2 CF.sub.2). 
sub.2 H 
31 
##STR51## 
##STR52## 
32 
##STR53## OCH.sub.2 COOC.sub.2 H.sub.5 
33 
##STR54## 
##STR55## 
34 
##STR56## 
##STR57## 
35 
##STR58## 
##STR59## 
36 
##STR60## OCH.sub.2 COOCH.sub.2 CH.sub.2 OCH.sub.2 
CH.sub.2 OCH.sub.3 
37 
##STR61## OCH.sub.2 COO(CH.sub.2 CH.sub.2 O).sub.4 
C.sub.4 H.sub.9 (t) 
38 
##STR62## OCH.sub.2 COOCH.sub.2 CH.sub.2 OCH.sub.2 
CH.sub.2 OC.sub.6 H.sub.13 
__________________________________________________________________________ 
Tye cyan coupler of the invention is readily synthesized according to the 
following procedure. 
Synthetic scheme 
##STR63## 
Synthesis example-1 (synthesis of coupler No. 1) 
5.0 g of compound [1] synthesized according to the procedure described in 
Japanese Patent Publication No. 45142/1974 was dissolved in 50 ml of 
methanol, into which 1.0 g of Raney nickel, whereby the mixture was 
subjected to catalytic hydrogenation under the conditions of a normal 
temperature and normal pressure. 
Once the reaction was complete, the catalyst was removed by filtration, and 
then the solvent was distilled away, whereby the residue was rinsed with a 
mixture solvent of ethyl acetate and n-hexane. As a result, 3.7 g of 
compound [2] in the form of crude crystals (yield, 85%) was abtained. The 
compound was dissolved in 40 ml of ethyl acetate, into which 2.5 of 
N,N-dimethylaniline was added, whereby ethyl acetate solution (20 ml) 
containing 7.6 g of 2-(2,4-di-tert-amylphenoxy)hexanoylchloride was added 
dropwise into the solution at a room temperature. The solution was 
subjected to stirring for five hours. To the reaction solution was added 
50 ml of ethyl acetate, and the solution was rinsed with water and 
condensed under reduced pressure, whereby the residue was recrystallized 
using a mixture solvent of ethyl acetate and n-hexane, resulting in 7.1 g 
(yield, 71%) of compound [3]. The melting point, mp, of this compound is 
108.degree. to 110.degree. C. This compound was dissolved in 100 ml of 
acetone, to which 2.1 g of potassium carbonate and 3.1 g of ethyl 
bromoacetate were added, thereby the solution was refluxed for two hours 
by heating. Once the reaction was complete, insoluble matters were 
filtered out, and the solution was condensed under reduced pressure. Ethyl 
acetate was added to the residue, which was rinsed with water, and then 
the solvent was distilled away, thus 7.3 g (yield, 90%) of compound [4a] 
in the form of oil was obtained. 
20.6 g of compound [4a] was dissolved in 200 ml of methanol, to which a 
solution (20 ml) containing 2.7 g of sodium hydroxide was added. The 
mixture solution was stirred for one hour at a room temperature. Once the 
reaction was complete, the reaction solution was condensed under reduced 
pressure, and to which water was added, and made acid with hydrochloric 
acid, thereby extraction was performed using ethyl acetate. After rinsing 
with water, solvent was distilled away, thereby 100 ml of methanol and one 
or two droplets of condentrated sulfuric acid was added to the residue, 
which was refluxed by heating for four hours. 
Once the reaction was complete, the resultant solution was condensed under 
reduced pressure, thereby the residue was recrystallized with n-hexane, 
thus providing 15.5 g (yield, 86%) of compound [5a]. The mp of this 
compound is 128.degree. to 130.degree. C. 5.3 g of compound [5a] was 
dissolved in 30 ml of chloroform, whereby 1.1 ml of concentrated nitric 
acid (d=1.38) was added dropwise to the chloroform solution cooled by ice 
water, and then the solution was stirred for 30 minutes. Once the reaction 
was complete, the reaction product was rinsed with water and condensed 
under reduced pressure. Then, the residue was purified by means of silica 
gel column chromatography. As a result, 5.0 g (yield, 87%) of compound 
[6a] in the form of oil was obtained. This compound was dissolved in 150 
ml of methanol, thereby the solution was subjected to catalytic 
hydrogenation using palladium catalyst supported on carbon carrier under 
the conditions of a normal temperature and normal pressure. 
Once the reaction was complete, the catalyst was filtered out, and the 
remaining solution was condensed under reduced pressure, thereby to the 
residue were added 30 ml of acetonitrile, 20 mg of imidazole, and 2.0 g of 
phenyl 3-cyano-4-chlorophenylcarbamate, and the mixture was refluxed for 
two hours by heating. The reaction solution was cooled, thereby 
precipitated crystals were filtered off and recrystallized with 
acetonitrile. Thus, 3.4 g (yield, 53%) of coupler No. 1 was obtained. The 
mp of this coupler is 143.degree. to 145.degree. C. The structure of the 
coupler was identified by means of NMR, IR, and MASS techniques. 
Synthesis example-2 (synthesis of coupler No. 2) 
10 g of compound [3] was dissolved in 150 ml of acetone, to which 3.9 g of 
potassium cabonate and 2.6 g of chloracetone were added, whereby the 
solution was refluxed for three hours by heating. Once the reaction was 
complete, the insoluble matters were filtered out, and then the solution 
was condensed under reduced pressure, whereby to the residue was added 100 
ml of methanol, to which were added aqueous solution (20 ml) containing 
1.2 g of sodium hydroxide, and the solution was stirred for one hour at a 
room temperature. Once the reaction was complete, the solution was 
condensed under reduced pressure, and to which water was added, thereby 
the condensed solution was made acid with hydrochloric acid, and then 
extraction was performed using ethyl acetate. After rising with water, 
solvent was distilled away, thereby the residue was purified by means of 
silica gel column chromatography. As a result, 9.5 g (yield, 98%) of 
compound [5b] in the form of oil was obtained. This compound was dissolved 
in 100 ml of chloroform, to which 2.0 ml of condensed nitric acid (d=1.38) 
was added dropwise, thereby the solution was heated to 40.degree. C. and 
stirred for 30 minutes. Once the reaction was complete, the resultant 
mixture was rinsed with water and condensed under reduced pressure, 
thereby the residue was purified by means of silica gel column 
chromatography. As a result, 5.4 g (yield, 52%) of compound [6b] in the 
form of oil was obtained. This compound was dissolved in 300 ml of 
methanol, thereby the solution was subjected to catalytic hydrogenation 
using palladium catalyst supported on carbon carrier under the conditions 
of a normal temperature and normal pressure. Once the reaction was 
complete, the catalyst was filtered out, and the remaining solution was 
condensed under reduced pressure, thereby to the residue were added 60 ml 
of acetonitrile, 30 mg of imidazole, and 3.2 g of phenyl 
3-cyano-4-chlorophenylcarbamate, and the mixture was refluxed for two 
hours by heating. The reaction solution was cooled, thereby precipitated 
crystals were filtered off. And then, the crude crystals were heated and 
rinsed with a mixture solvent of ethyl acetate and n-hexane, and 
recrystallized with acetonitrile, thus 4.4 g (yield, 59%) of coupler No. 2 
was prepared. This coupler has the mp of 164.degree. to 166.degree. C. The 
structure of the coupler was identified by means of NMR, IR, and MASS 
techniques. 
A silver halide color photographic light-sensitive material prepared using 
any of the couplers according to the invention (hereinafter referred to as 
the couplers of the invention) specified above may contain a dye forming 
coupler which has been conventionally used in the art. 
A cyan dye forming coupler used in embodying the invention may be used in 
compliance with a conventional method and purposes which are commonly 
observed when using a cyan dye forming coupler in photography. 
Generally, the cyan coupler of the invention is contained in a silver 
halide emulsion layer and/or an adjacent non-light-sensitive layer. 
Typically, the cyan coupler of the invention is incorporated into a silver 
halide emulsion, whereby the emulsion is applied and dried onto a support, 
in order to prepare a silver halide color photographic light-sensitive 
material comprising a silver halide emulsion layer containing the cyan 
coupler. Such a silver halide color photographic light-sensitive material 
may be either fo a monochromatic or multi-color application. In a 
multi-color application, the cyan coupler of the invention is usually 
incorporated into a red-sensitive emulsion or non-sensitized emulsion. The 
cyan coupler may be contained in an emulsion layer that is sensitive to 
three primary color spectrums other than of red. 
Each component for forming a dye image according to the invention comprises 
a single emulsion layer or multi-emulsion layer which is sensitive to a 
specific spectral band. 
The layers, including the image forming component layer above, for 
composing a silver halide color photographic light-sensitive material may 
be arranged in various orders known in the photographic art. A typical 
multi-color silver halide color photographic light-sensitive material 
comprises a support, disposed thereon, a cyan dye-image forming component 
comprising at least one red-sensitive silver halide emulsion layer having 
at least one cyan dye forming coupler, in which at least one cyan coupler 
is the cyan coupler of the invention; a magenta dye-image forming 
component comprising at least one green-sensitive silver halide emulsion 
layer having at least one magenta dye forming coupler; and a yellow 
dye-image forming component comprising at least one blue-sensitive silver 
halide emulsion layer having at least one yellow dye forming coupler. 
Such a photographic light-sensitive material may have additional layers, 
such as a filter layer, intermediate layer, and subbing layer. 
When preparing a silver halide color photographic light-sensitive material 
by using the coupler of the invention, additional layers are necessary; 
they are a light-sensitive layer containing yellow dye forming coupler, 
and a light-sensitive layer containing magenta dye forming coupler. 
The useful yellow dye forming couplers are those conventionally known in 
the art; for example, those represented by the following general formula 
[VII]. 
##STR64## 
(wherein R.sub.11 represents an alkyl or aryl group; R.sub.12, an aryl 
group; Z, a hydrogen atom, or a group being capable of splitting off by 
reaction with an oxidation product of a color developing agent.) 
The examples of Z in general formula [VII] are groups represented by the 
following general formula [VIII] or [IX]. 
##STR65## 
(wherein F represents a group of non-metal atoms being capable of forming 
a five- or six-membered ring.) 
##STR66## 
(wherein R.sub.13 represents an aryl group, and, preferably, a substituted 
phenyl group.) 
The useful magenta dye forming couplers are those conventionally known in 
the art; for example, those represented by the following general formula 
[X], [XI] or [XII]. 
##STR67## 
(wherein R.sub.14 represents an alkylcarbonyl group, aryl carbonyl group, 
or aryl group; R.sub.15, a monovalent group; Z, a hydrogen atom, or a 
group being capable of splitting off by reaction with an oxidation product 
of a color developing agent.) 
##STR68## 
(wherein R.sub.16 represents an alkyl group or aryl group; R.sub.17, an 
alkyl group, aryl group, or alkylthio group; Z, a group being capable of 
splitting off by reaction with an oxidation product of a color developing 
agent.) 
##STR69## 
(wherein R.sub.18 represents a monovalent group; R.sub.19, an alkyl group, 
aryl group, acylamino group, or alkoxy group; Z, a hydrogen atom, or a 
group being capable of splitting off by reaction with an oxidation product 
of a color developing agent.) 
The cyan dye forming coupler of the invention may be used together with 
another cyan dye forming coupler. 
The useful cyan dye forming couplers are those conventionally known in the 
art; for example, those represented by the following general formula 
[XIII], or [XIV]. 
##STR70## 
(wherein R.sub.20 represents an alkyl group or aryl group; R.sub.21, an 
acylamino group, alkoxycarbonylamino group, sulfonamido group, or ureide 
group; Z, a hydrogen atom, or a group being capable of splitting off by 
reaction with an oxidation product of a color developing agent.) 
##STR71## 
(wherein R.sub.22 represents an alkyl group; R.sub.22, an aryl group; 
R.sub.23, an alkyl group; Z, a hydrogen atom, or a group being capable of 
splitting off by reaction with an oxidation product of a color developing 
agent.) 
The typical examples of yellow, magenta and cyan couplers represented 
respectively by general formulas [VII], [X], [XI], [XII] and [XIV] are the 
following compounds. However, the scope of the invention is not limited 
only to these examples. These couplers are arbitrarily selected in 
compliance with a requirement, and two or more couplers of a specific dye 
may be combinedly used. 
##STR72## 
To incorporate the cyan coupler of the invention as well as the respective 
couplers according to the invention into a silver halide light-sensitive 
material, a conventionally known method may be observed. In one of known 
methods, the cyan coupler of the invention or the respective couplers 
according to the invention is dissolved in a mixture solution containing a 
known high-boiling solvent, and a low-boiling solvent such as butyl 
acetate and butyl propionate, thereby the resultant solution is blended 
with aqueous gelatin solution containing a surfactant. Next, the blended 
solution is subjected to emulsification with a high-speed mixer, colloid 
mill, or ultrasonic dispersion apparatus, whereby the dispersion is added 
to silver halide, in order to prepare a silver halide emulsion used in 
embodying the invention. 
The useful high-boiling solvents are those conventionally known in the art; 
for exampole, those represented by the following general formula [XV], 
[XVI], [XVII], [XVIII], or [XIX]. 
##STR73## 
(wherein B represents a halogen atom, or an alkoxy group having 1 to 20 
carbon atoms, or --COOR.sub.24 ; R.sub.24, an alkyl or phenyl group having 
1 to 20 carbon atoms; p, an integer from 0 to 3; when p is 2 or 3, those 
represented by p may be identical or different with each other.) 
General formula [XVI] 
EQU O=P(-OR.sub.25).sub.3 
(wherein R.sub.25 is synonymous with R.sub.24 in thepreviously mentioned 
general formula [XV].) 
##STR74## 
(wherein R.sub.26 and R.sub.27 independently represent an alkyl or phenyl 
group having 1 to 20 carbon atoms; R.sub.28, a hydrogen atom, an alkyl or 
phenyl group having 1 to 20 carbon atoms; R.sub.27 and R.sub.28 may form a 
five- or six-membered ring together with a group of non-metal atoms.) 
General formula [XVIII] 
EQU R.sub.29 COOR.sub.25 
(wherein R.sub.29 represents an alkyl group having 1 to 20 carbon atoms; 
R.sub.25 is synonymous with R.sub.25 in the previously defined general 
formula [XVI].) 
##STR75## 
(wherein R.sub.30 represents an alkyl group having 1 to 20 carbon atoms; 
m, an integer from 1 to 3; when m is 2 or three, those represented by 
R.sub.30 may be identical with or different from each other.) 
The typical examples of high-boiling solvents represented by general 
formulas [XV], [XVI], [XVII], [XVIII] and [XIX] are the following 
compounds. However, the scope of the invention is not limited only to 
these examples. These high-boiling solvents are arbitrarily selected in 
compliance with sa requirement, and two or more couplers of a specific dye 
may be combinedly used. 
##STR76## 
A silver halide color photographic light-sensitive material prepared 
according to the invention may, in compliance with a specific requirement, 
incorporate a colored coupler for color correction, a DIR (development 
inhibitor releasing) coupler, a non-colored coupler for improving hues of 
the material, or various additives conventionally used, such as an 
ultraviolet absorber, and an agent for stable photographic performance. 
The useful colored couplers include a colored magenta coupler, and a 
colored cyan coupler; these couplers are represented by the following 
general formulas [XX] and [XXI]. 
General formula [XX] 
EQU M-N=N-Ar 
(wherein M represents a residue group formed by removing one hydrogen atom 
from an active site on a magenta coupler; Ar, an aryl group.) 
General formula [XXI] 
EQU C(J).sub.q.sup.. N=N-Ar 
(wherein C represents a residue group formed by removing a hydrogen atom 
from an active site on a phenol class or naphthol class cyan coupler; J, a 
bivalent bonding group; Ar, an aryl group; and q, 0 or 1, respectively.) 
A preferred example of M in general formula [XX] is a magenta coupler 
represented by general formula [X] or [XI] above (R.sub.14 represents a 
substituted phenyl group). A preferred example of C in general formula 
[XXI] is a cyan coupler represented by general formula [XII] above. A 
preferred example of q is 1. 
Colored magenta couplers and colored cyan couplers respectively represented 
by general formulas [XX] and [XXI] include the following compounds. 
However, the scope of the invention is not limited only to these examples. 
More than two of the respective type of colored couplers may be combinedly 
used. 
##STR77## 
The useful DIR couplers are represented by the following general formula 
[XXII]. 
General formula [XXII] 
EQU C.sub.p --J').sub.q I 
(wherein C.sub.p represents a residue group having a site which is capable 
of coupling to an oxidation product of a color developing agent, and one 
hydrogen atom removed from the site; J' represents a bivalent group which 
is capable of being released from C.sub.p by reaction with an oxidation 
product of a color developing agent and releasing I by, for example, 
intramolecular nucleophilic substitution reaction, or electron transfer, 
or hydrolysis; I represents a development inhibitor and q is 0 or 1.) 
The typical preferred DIR couplers are listed below. However, the scope of 
the invention is not limited only to these examples. A relevant DIR 
coupler is selected in compliance with a specific requirement. More than 
two couplers may be combinedly used if necessary. 
##STR78## 
The useful ultraviolet absorbers are those represented by the following 
general formulas [XXIII] and [XXIV]. 
##STR79## 
(wherein R.sub.31 represents an alkyl group having 1 to 20 carbon atoms; 
R.sub.32, a halogen atom; r, and integer 1 or 2; and s, an integer 0 or 1, 
when r is 2, those represented by R.sub.31 may be identical with or 
different from each other.) 
##STR80## 
(wherein R.sub.33 represents an aryl group, or vinyl group; R.sub.34 and 
R.sub.35 independently represent a cyano group, alkoxycarbonyl group, or 
arylsulfonyl group.) 
The typical examples of a useful ultraviolet absorber are listed below. 
However, the scope of the invention is not limited only to these examples. 
More than two of the examples may be combinedly used if necessary. 
##STR81## 
The useful stabilizing agents include an anti-fogging agent, and a dye 
image stabilizer, and represented by the following general formulas [XXV], 
[XXVI] and [XXVII]. 
##STR82## 
(wherein R.sub.36 and R.sub.37 independently represent a hydrogen atom, or 
an alkyl group having 1 to 20 carbon atoms; R.sub.38, an alkyl or sulfone 
group having 1 to 20 carbon atoms; t, an integer 1 or 2; when t is 2, 
those represented by R.sub.38 may be identical or different with each 
other; R.sub.37 and R.sub.38 may form a five- or six-membered ring 
together with a group of non-metal atoms.) 
##STR83## 
(wherein R.sub.36, R.sub.37 and R.sub.38 are synonymous with R.sub.36, 
R.sub.37 and R.sub.38 in the previously specified general formula [XXV]; 
t', an integer 1 or 2; when t' is 2, those represented by may be identical 
or different with each other; R.sub.38 may form a five- or six-membered 
ring at the ortho position.) 
##STR84## 
(wherein R.sub.39 represents an alkyl group, phenoxycarbonyl group, 
benzenesulfonamide group or alkylsulfonamide group; a, integer 1 to 3; 
when a is 2 or 3, those represented by R.sub.39 may be identical or 
different with each other.) 
The examples of stabilizers represented by general formulas [XXV], [XXVI] 
and [XXVII] are listed below. However, the scope of the invention is not 
limited only to these examples. More than two types of stabilizers may be 
used combinedly in compliance with a specific requirement. 
##STR85## 
When incorporating the cyan coupler of the invention as well as the 
respective couplers according to the invention, a rate of addition is 
usually approximately 0.005 to 2, or, preferably, 0.01 to 0.5 mol per mol 
silver halide. 
The type of silver halide incorporated into the silver halide emulsion used 
in embodying the invention is arbitrarily selected from those used in a 
conventional silver halide emulsion, for example, silver bromide, silver 
chloride, silver iodo-bromide, silver chloro-bromide, and silver 
chloro-iodo-bromide. 
The silver halide emulsion for composing a silver halide emulsion layer of 
the invention may be prepared using any of diverse methods including a 
conventional method. Such methods are as follows: a method, which is the 
method for preparing the so-called conversion emulsion, described in 
Japanese Patent Publication No. 7772/1971 wherein an emulsion of silver 
salt particles, a part of which is comprised of a silver salt having a 
solubility of greater than that of silver bromide, is prepared, thereby at 
least a portion of these silver salt particles are converted into silver 
bromide or silver iodo-bromide; and a method for preparing a Lippmann 
emulsion comprising fine particle silver halide with an average particle 
size of less than 0.1 .mu.m. Additionally, the silver halide emulsion of 
the invention may be chemically sensitized by using certain compounds 
singly or combinedly. The examples of such compounds are as follows: 
sulfur sensitizers such as arylthiocarbamide, thiourea, and cystine; 
active or inactive selenium sensitizers; reduction sensitizers such as 
stannous salt, and polyamine; noble metal sensitizers such as potassium 
aurithiocyanate, potassium chloroaurate, and 2-aurosulfobenzthiazole 
methylchloride; water soluble salt sensitizers of ruthenium, rhodium, and 
iridium, and, more specifically, ammonium chloropalladate, potassium 
chloroplatinate, and sedium chloropalladite. 
A silver halide emulsion used in embodying the invention may have various 
known photographic additives. Such additives are described, for example, 
in Research Disclosure Dec. 1978, No. 17643. 
Silver halide used in embodying the invention is spectrally sensitized 
using an appropriate sensitizing dye in order to provide the silver halide 
with sensitivity in a required spectral band. Various spectral sensitizing 
dyes are singly or combinedly used for this purpose. 
The typical spectral sensitizing dyes advantageously used in the invention 
are cyanine dyes, merocyanine dyes, and complex cyanine dyes described in 
U.S. Pat. Nos. 2,269,234, 2,270,378, 2,442,710, 2,454,620 and 2,776,280. 
The support according to the invention is selected, in compliance with a 
specific requirement for the photographic light-sensitive material, from 
those known in the art, for example, a plastic film, plastic-laminated 
paper, baryta paper, and synthetic paper. These supports are usually 
subjected to subbing process in order to enhance adhesion between a 
support and a photographic emulsion layer. 
The prepared silver halide color photographic light-sensitive material of 
the invention is, once exposed, subjected to various photographic 
processes for color developing. The preferred color developer used in the 
invention is one comprising an aromatic primary amine color developing 
agent as a principal component. The typical examples of such a color 
developing agent are p-phenylenediamine color developing agents, for 
example, diethyl-p-phenylenediamine hydrochloride, 
monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine 
hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 
2-amino-5-(N-ethyl-.beta.-hydroxylethylamino)-toluene, 
2-amino-5-(N-ethyl-.beta.-methanesulfonamideethyl)aminotoluene sulfate, 
2-amino-5-N-ethyl-N-.beta.-methanesulfonamideethylamino) toluene, 
4-(N-ethyl-N-.beta.-hydroxyethylamino)aniline, and 
2-amino-5-(N-ethyl-.beta.-methoxyethyl)aminotoluene. The especially 
preferred color developing agent is selected from 
2-amino-5-(N-ethyl-N-.beta.-hydroxyethylamino)toluene, and 
2-amino-5-(N-ethyl-N-.beta.-methanesulfonamideethylamino)-toluene. These 
color developing agents are singly used or two or more of them may be 
combinedly used. Additionally, these agents are used, in compliance with a 
specific requirement, together with a black-and-white developing agent, 
such as hydroquinone. Furthermore, the color developer usually contains an 
alkali agent such as sodium hydroxide, ammonium hydroxide, sodium sulfite, 
and may further contain various additives such as alkali metal halide like 
potassium bromide, and a development control agent like citrazinic acid. 
The silver halide color photogrphic light-sensitive material of the 
invention may contain, in a hydrophilic colloid layer, the previously 
mentioned color developing agent in the form of either the color 
developing agent itself or a precursor thereof. A precursor of color 
developing agent is a compound being capable of forming a color developing 
agent in the presence of an alkali. The examples of such a precursor 
include a Schiff base type precursor of an aromatic aldehyde derivative, 
multi-valent metal-ion complex precursor, phthalic imido derivative 
precursor, phosphoric amide derivatives precursor, sugar-amine reaction 
product precursor, and urethane precursor. These precursors of aromatic 
primary amine color developing agent are described in, for example, U.S. 
Pat. Nos. 3,342,599, 2,507,114, 2,695,234 and 3,719,492, British Patent 
No. 803,783, Japanese Patent O.P.I. Publication Nos. 135628/1978 and 
79035/1979, Research Disclosure Nos. 15,159, 12,146 and 13,924. 
These aromatic primary amine color developing agents or precursors thereof 
should be added in an amount to ensure satisfactory coloration in color 
developing. The amount greatly differs depending on a type of 
light-sensitive material. However, the usual amount is 0.1 to 5 mol, or, 
preferably, 0.5 to 3 mol per mol light-sensitive silver halide. These 
color developing agents or the precursors thereof may be used singly or 
combinedly. Incorporating such compounds into a photographic 
light-sensitive material is effected by dissolving such compounds in an 
arbitary solvent such as water, methanol, ethanol, and acetone. Otherwise, 
such compounds may be incorporated in the form of emulsification 
comprising a high-boiling organic solvent such as dibutyl phthalate, 
dioctyl phthalate, or tricresyl phosphate; or the compounds may be 
incorporated after being absorbed in a latex polymer as described in 
Research Disclosure No. 14850. 
After color developing, the silver halide color photographic 
light-sensitive material is usually subjected to various processing steps 
such as bleaching and fixing, or bleach-fixing, and then washing with 
water. Various compounds are used as a bleacher. The typical examples of 
bleacher are multivalent metal compounds of iron (III), cobalt (III), and 
tin (II), in particular, complex salts of such multivalent metal cation 
and organic acid. Such complex salts include metal complex salts of 
aminopolycarboxylic acids such as ethylenediamine tetraacetic acid, 
nitrilo triacetic acid, and N-hydroxyethylenediamine diacetic acid; metal 
complex salts of malonic acid, tartaric acid, malic acid, diglycolic acid, 
and dithioglycolic acid; and ferricianates, and bichromates.

EXAMPLES 
The present invention is hereinunder described in detail by referring to 
the preferred examples. However, the scope of the effective embodiment of 
the invention is not limited only to these examples. 
EXAMPLE 1 
As listed in Table 1, each amount of the cyan coupler of the invention was 
weighed at a rate of 0.1 mol per 1 mol silver, and added to dibutyl 
phthalate, serving as a high-boiling solvent, of which weight equivalent 
to that of the coupler, as well as to ethyl acetate of which weight three 
times as much as the cyan coupler, whereby each mixture was heated to 
60.degree. C. to solve the coupler completely. Additionally, to prepare 
comparative sample, each amount of a respective known comparative coupler 
was weighed at a rate of 0.1 mol per 1 mol silver, and added to dibutyl 
phthalate of which weight equivalent to that of the coupler, as well as to 
ethyl acetate of which weight three times as much as the cyan coupler, 
whereby each mixture was heated to 60.degree. C. to solve the coupler 
completely. Each of these solutions was mixed with 1200 ml of 5% aqueous 
gelatin soluton comprising 120 ml of 5% aqueous solution of Alkanol B 
(alkylnaphthalene sulfonate, manufactured by DuPont), thereby the mixture 
was homogenized with an ultrasonic homogenized, thus each emulsification 
product was prepared. Then, each of this dispersion was added to 4 kg of 
red-sensitive silver iodo-bromide emulsion (containing 7 mol% silver 
iodide), to which 120 ml of 2% aqueous solution of 1,2-bis(vinylsulfonyl) 
ethane (water:methanol=1:1) serving as a hardener was added, thereby the 
emulsion was applied onto and dried over a transparent polyester base 
having a subbing layer, and thus each sample having a stable coating layer 
was prepared (amount of coated silver was 15 mg/100 cm.sup.2). 
Each of samples thus prepared was subjected to wedge exposing in compliance 
with a conventional method, and treated in the following developing 
process. The results are listed in Table 1. 
The sensitivity and maximum color density of each sample were determined 
with Model PDA-65 photographic densitometer manufactured by Konica 
Corporation. 
______________________________________ 
[Processing] (38.degree. C.) 
Processing time 
______________________________________ 
Color developing 
3 min. 15 sec. 
Bleaching 1 min. 30 sec. 
Washing 3 min. 15 sec. 
Fixing 6 min. 30 sec. 
Washing 3 min. 15 sec. 
Stabilizing 1 min. 30 sec. 
______________________________________ 
The compositions of the respective processing solutions are as follows. 
______________________________________ 
[Color developer composition] 
______________________________________ 
4-amino-3-methyl-N--ethyl-N--(.beta.-hydroxylethyl)- 
aniline sulfate 4.75 g 
Sodium sulfite anhydride 4.25 g 
Hydroxyamino 1/2 sulfate 2.0 g 
Potassium carbonate anhydride 
37.0 g 
Sodium bromide 1.3 g 
Trisodium nitrilotriacetate, monohydride 
2.5 g 
Potassium hydroxide 1.0 g 
______________________________________ 
Water was added to the ingredients to prepare one liter solution, of which 
pH was adjusted to 10.0 with potassium hydroxide. 
______________________________________ 
[Bleacher composition] 
______________________________________ 
Ferric ammonium ethylenediaminetetraacetate 
100.0 g 
Diammonium ethylenediaminetetraacete 
10.0 g 
Ammonium bromide 150.0 g 
Glacial acetic acid 10.0 ml 
______________________________________ 
Water was added to the ingredients to prepare one liter solution, of which 
pH was adjusted to 6.0 with aqueous ammonium solution. 
______________________________________ 
[Fixer composition] 
______________________________________ 
Ammonium thiosulfate (50% aqueous solution) 
162 ml 
Sodium sulfite anhydride 12.4 g 
______________________________________ 
Water was added to the ingredients to prepare one liter solution, of which 
pH was adjusted to 6.5 with acetic acid. 
______________________________________ 
[Stabilizer] 
______________________________________ 
Formalin (37% aqueous solution) 
5.0 ml 
Konidax (Konica Coporation) 
7.0 ml 
Water was added to the ingredients to prepare one liter solution. 
TABLE 1 
______________________________________ 
Relative Maximum Maximum 
Sample sensi- color absorption 
No. Coupler No. 
tivity density wavelength 
.DELTA..lambda.s 
______________________________________ 
1 C-2 100 2.98 696 123 
2 Comparative 
97 2.75 692 127 
coupler (A) 
3 Comparative 
95 2.60 691 128 
coupler (B) 
4 Comparative 
89 2.73 690 128 
coupler (C) 
5 Comparative 
85 2.52 690 129 
coupler (D) 
6 Comparative 
89 2.61 689 130 
coupler (E) 
7 (1) 130 3.30 693 128 
8 (2) 127 3.21 692 127 
9 (9) 110 3.17 690 127 
10 (11) 108 3.02 691 126 
11 (13) 112 3.15 691 125 
12 (20) 131 3.40 694 128 
13 (22) 129 3.38 693 127 
14 (23) 125 3.30 690 126 
15 (25) 127 3.32 692 127 
16 (26) 120 3.19 694 127 
17 (29) 135 3.50 693 128 
18 (30) 120 3.20 695 127 
19 (32) 138 3.55 695 128 
20 (34) 118 3.10 691 126 
21 (36) 132 3.35 692 126 
______________________________________ 
In the table above, the respective relative sensitivity values are based on 
the sensitivity of Sample No. 1 i.e. 100. The maximum absorption 
wavelength values (.lambda..sub.max) are wavelengths respectively giving 
density of 1.0, while .DELTA..lambda..sub.s indicates values respectively 
obtained by subtracting, from .lambda..sub.max, an absorption wavelength 
in a short-wave side corresponding with 20% of the spectral absorption 
property obtainable from the density 1.0. 
##STR86## 
Table 1 shows that the comparative couplers are inferior to coupler C-2 
both in terms of sensitivity and maximum color density, and that, when 
compared to coupler C-2 as well as the comparative couplers, each of 
coupler sample Nos. 7 through 21 according to the invention has remarkably 
high sensitivity as well as high maximum color density. 
EXAMPLE 2 
The respective samples prepared in Example 1 L were subjected to wedge 
exposing, and then, to color developing in Example. Each sample was 
treated with bleach-fixer having the following compositions, whereby the 
fading of cyan dye due to fatigued bleach-fixer was examined. 
______________________________________ 
[Bleach-fixer composition] 
______________________________________ 
Ferric ammonium ethylenediaminetetraacetate 
50 g 
Ammonium sulfite (40% solution) 
50 ml 
Ammonium thiosulfate (70% solution) 
140 ml 
Ammonium water (28% solution) 
20 ml 
Ethylenediaminetetraacetic acid 
4 g 
Hydrosulfite 5 g 
______________________________________ 
Water was added to the ingredients to prepare one liter solution. 
Each of the obtained samples were examined for maximum color density. Table 
2 lists the results. The dye residue percent at maximum density was 
determined by the following expression. 
##EQU1## 
TABLE 2 
______________________________________ 
Con- Con- 
centration centration 
Dye residue 
Sample of fresh of fatigued 
percent 
No. Coupler No. 
bleach-fixer 
bleach-fixer 
(%) 
______________________________________ 
22 C - 2 2.98 2.24 75 
23 Comparative 
2.75 2.53 94 
coupler (A) 
24 Comparative 
2.60 2.32 95 
coupler (B) 
25 Comparative 
2.73 2.64 96 
coupler (C) 
26 Comparative 
2.52 2.30 96 
coupler (D) 
27 Comparative 
2.61 2.47 95 
coupler (E) 
28 (1) 3.30 3.17 96 
29 (2) 3.21 3.05 95 
30 (9) 3.17 3.02 95 
31 (11) 3.02 2.90 96 
32 (13) 3.15 3.06 97 
33 (20) 3.40 3.25 96 
34 (22) 3.38 3.24 96 
35 (23) 3.30 3.18 96 
36 (25) 3.32 3.17 95 
37 (26) 3.19 3.10 97 
38 (29) 3.50 3.40 97 
39 (30) 3.20 3.00 94 
40 (32) 3.55 3.32 94 
41 (34) 3.10 2.98 96 
42 (36) 3.35 3.21 96 
______________________________________ 
Table 2 shows that the sample having a naphthol coupler (C-1) indicates 
greatly faded cyan dye when treated with a fatigued bleach-fixer. In 
contrast, it is apparent from the table that the samples (Nos. 28 through 
42) using a coupler of the invention show less faded cyan dye, as 
comparable to the samples using comparative couplers (A) through (E). 
EXAMPLE 3 
Upon a treatment polyester base having a subbing layer, the following 
layers were disposed, in the following order, in order to prepare each of 
the samples respectively having the constitution specified in Table 3. 
First layer (anti-halation layer) 
Aqueous gelatin solution containing black colloidal silver was applied at a 
rate of 0.5 g/m.sup.2 in terms of amount of silver in order to form a 
layer with a dry thickness of 3.0.mu.. 
Second layer (intermediate layer) 
Aqueous gelatin solution was applied in order to form a layer with a dry 
thickness of 1.0.mu.. Third layer (red-sensitive low-sensitivity silver 
halide emulsion layer) 
First, a red-sensitive low-sensitivity silver halide emulsion was prepared 
in the following manner: an iodo-bromide emulsion (a mixture comprising, 
at a ratio of 2:1, an iodo-bromide emulsion having an average particle 
size of 0.6.mu. with 4 mol% of silver iodide and an iodo-bromide emulsion 
having an average particle size of 0.3.mu. with 4 mol% of silver iodide) 
was chemically sensitized using a gold-sensitizer and sulfur-sensitizer, 
to which were added, as red-sensitive sensitizing dyes, 
9-ethyl-3,3'di-(3-sulfopropyl)-4,5,4',5'-dibenzothiacarbo-cyanine 
hydroxide anhydride, 
5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfobutyl)thiacarbocyanine hydroxide 
anhydride, and 
2-[2-{(5-chloro-3-ethyl-2(3H)-benzothiazolydene)methyl}-1-butenyl-5-chloro 
-3-(4-sulfobutyl)]-benzoxazolium; thereby added were 1.0 g of 
4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and 20.0 mg of 
1-phenyl-5-mercaptotetraazole. 
Next, a cyan coupler, DIR compound, colored cyan coupler, anti-fogging 
agent and high-boiling solvent were added to 150 ml of ethyl acetate, and 
then, dissolved by heating, thereby the solution was added to 550 ml of 
7.5% aqueous gelatin solution containing 5 g of sodium 
triisopropylnaphthalenesulfonate, and the mixture was homogenized using a 
colloid mill. The resultant dispersion was heated to remove ethyl acetate, 
thereby to the dispersion was added the red-sensitive low-sensitivity 
emulsion mentioned above. The resultant emulsion was applied in order to 
form a layer with a dry thickness of 4.0 .mu.m (100 g gelatin contained 
per mol silver halide.) 
Fourth layer (red-sensitive high-sensitivity silver halide emulsion layer) 
First, a red-sensitive low-sensitivity silver halide emulsion was prepared 
in the following manner; an iodo-bromide emulsion (an average particle 
size of 1.2.mu. with 7 mol% of silver) was chemically sensitized using a 
gold-sensitizer and sulfur-sensitizer, to which were added, as 
red-sensitive sensitizing dyes, 
9-ethyl-3,3'-di-(3-sulfopropyl)-4,5,4',5'-dibenzothiacarbocyanine 
hydroxide anhydride, 
3,3'-dichloro-9-ethyl-3,3'-di-(3-sulfobutyl)thiacarbocyanine hydroxide 
anhydride, and 
2-[2-{(5-chloro-3-ethyl-2(3H)-benzothiazolydene)methyl}-1-butenyl-5-chloro 
-2-(4-sulfobutyl)benzoxazolium anhydride; thereby added were 1.0 g of 
4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and 10.0 mg of 
1-phenyl-5-mercaptotetraazole. 
Next, a cyan coupler, DIR compound, anti-fogging agent and high-boiling 
solvent were added to 60 ml of ethyl acetate, and then, dissolved by 
heating, thereby the solution was added to 30 ml of 7.5% aqueous solution 
containing 1.5 g of sodium triisopropylnaphthalenesulfonate, and the 
mixture was homogenized using a colloid mill. To the resultant dispersion 
was added the red-sensitive high-sensitivity emulsion mentioned above. The 
resultant emulsion was applied in order to form a layer with a dry 
thickness of 2.0 .mu.m (100 g gelatin contained per mol silver halide). 
Fifth layer (intermediate layer) 
Identical with the second layer. Sixth layer (green-sensitive 
low-sensitivity silver halide emulsion layer) 
First, a green-sensitive low-sensitivity silver halide emulsion was 
prepared in the following manner: an iodo-bromide emulsion having an 
average particle size of 0.6 .mu.m with 4 mol% of silver iodide and an 
iodo-bromide emulsion having an average particle size of 0.3 .mu.m with 7 
mol% of silver iodide were independently chemically sensitized using a 
gold-sensitizer and sulfur-sensitizer, thereby to the respective emulsions 
were added, as green-sensitive sensitizing dyes, 
5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfobutyl)oxacarbocyanine hydroxide 
anhydride, and 3,3-diphenyl-9-ethyl-3,3'-di-(3-sulfobutyl)oxacarbocyanine 
hydroxide anhydride, and 
9-ethyl-3,3'-di-(3-sulfopropyl)-5,6,5',6'-dibenzoxycarnocyanine hydroxide 
anhydride; thereby added were 1.0 g of 
4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and 20.0 mg of 
1-phenyl-5-mercaptotetrazole; then, the two types of silver halide 
emulsions prepared were mixed together at a ratio of 1:1. 
Next, a magenta coupler, DIR coupler, colored magenta coupler, anti-fogging 
agent and high-boiling solvent were added to 240 ml of ethyl acetate, and 
then, dissolved by heating, thereby the solution was added to 7.5% aqueous 
gelatin solution containing sodium triisopropylnaphthalenesulfonate, and 
the mixture was homogenized using a colloid mill. To the resultant 
dispersion was added the green-sensitive low-sensitivity emulsion 
mentioned above. The resultant emulsion was applied in order to form a 
layer with a dry thickness of 4.0 .mu.m (100 g gelation contained per mol 
silver halide). 
Seventh layer (green-sensitive high-sensitivity silver halide emulsion 
layer) 
First, a green-sensitive high-sensitivity silver halide emulsion was 
prepared in the following manner: an iodo-bromide emulsion (having an 
average particle size of 1.2.mu. with 7mol% of silver iodide) was 
chemically sensitized using a gold-sensitizer and sulfur-sensitizer, to 
which were added, as green-sensitive sensitizing dyes, 
5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfobutyl)oxacarbocyanine hydroxide 
anhydride, and 5,5'-diphenyl-9-ethyl-3,3'-di-(3-sulfobutyl)oxacarbocyanine 
hydroxide anhydride, and 
9-ethyl-3,3'-di-(3-sulfopropyl)-5,6,5'6'-benzoxacarbocyanine hydroxide 
anhydride; thereby added were 1.0 g of 
4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and 10.0 mg of 
1-phenyl-5-mercaptotetraazole. 
Next, a magenta coupler, DIR coupler, colored magenta coupler, anti-fogging 
agent and high-boiling solvent were added to 200 ml of ethyl acetate, and 
then, dissolved by heating, thereby the solution was added to 7.5% aqueous 
gelatin solution containing sodium triisopropylnaphthalenesulfonate, and 
the mixture was homogenized using a colloid mill. To the resultant 
dispersion was added the green-sensitive high-sensitivity emulsion 
mentioned above. The resultant emulsion was applied in order to form a 
layer with a dry thickness of 2.0 .mu.m (100 g gelatin contained per mol 
silver halide). 
Eighth layer (intermediate layer) 
Identical with the second layer. 
Ninth layer (yellow filter layer) 
To an aqueous gelatin solution having dispersed yellow colloidal silver 
were added a solution prepared by dissolving 3 g of 
2,3-di-t-octylhydroquinone and 1.5 g of di-2-ethylhexyphthalate in 10 ml 
of ethyl acetate, as well as a dispersion prepared by dissolving 0.3 g of 
sodium triisopropylnaphthalenesulfonate, thereby the resultant emulsion 
was applied so that a dry thickness was 1.2 .mu. containing gelatin at a 
rate of 0.9 g/m.sup.2, and 2,5-di-t-octylhydroquinone at a rate of 0.10 
g/m.sup.2. 
Tenth layer (Blue-sensitive low-sensitivity silver halide emulsion layer) 
An iodo-bromide emulsion having an average particle size of 0.6 .mu.m with 
6 mol% of silver iodide was chemically sensitized using a gold-sensitizer 
and sulfur-sensitizer, thereby to the emulsions was added, as sensitizing 
dyes, 5,5'-dimethoxy 3,3'-di-(3-sulfopropyl)thiacyanine hydroxide 
anhydride, and then 1.0 g of 4-hydroxy-6-methyl-2,3,3a,7-tetraazaindene 
and 20.0 mg of 1-phenyl-5-mercaptotetraazole. Then the mixture was 
treated with a conventional technique, and a blue-sensitive 
low-sensitivity silver halide emulsion was prepared. 
Next, a yellow coupler, and high-boiling solvent were added to 300 ml of 
ethyl acetate, and then, dissolvent by heating, thereby the solution was 
added to 7.5% aqueous gelatin solution containing sodium 
triisopropylnaphthalenesulfonate, and the mixture was homogenized using a 
colloid mill. To the resultant dispersion was added the blue-sensitive 
low-sensitivity emulsion mentioned above. The resultant emulsion was 
applied in order to form a layer with a dry thickness of 4.0 .mu.m (240 g 
gelatin contained per mol silver halide). Eleventh layer (blue-sensitive 
high-sensitivity silver halide emulsion layer) 
An iodo-bromide emulsion (an average particle size of 1.2.mu. with 7 mol% 
of silver iodide was chemically sensitized using a gold-sensitizer and 
sulfur-sensitizer, thereby to the emulsion were added, as sensitizing 
dyes, 5,5'-dimethoxy-3,3'-di-(3-sulfopropyl)thiacyanine hydroxide 
anhydride, and then 1.0 g of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene 
and 10.0 mg of 1-phenyl-5-mercaptotetraazole. Then the mixture was treated 
with a conventional technique, and a blue-sensitive high-sensitivity 
silver halide emulsion was prepared. 
Next, a yellow coupler, and high-boiling solvent were added to 240 ml of 
ethyl acetate, and then, dissolved by heating, thereby the solution was 
added to 7.5% aqueous gelatin solution containing sodium 
triisopropylnaphthalenesulfonate, and the mixture was homogenized using a 
colloid mill. To the resultant dispersion was added the blue-sensitive 
high-sensitivity emulsion mentioned above. The resultant emulsion was 
applied in order to form a layer with a dry thickness of 2.0 .mu.m (160 g 
gelatin contained per mol silver halide). 
Twelfth layer (intermediate layer) 
To 2 ml of ethyl acetate were added a high-boiling solvent and ultraviolet 
absorbent, thereby the solution was added to 7.5% aqueous gelatin solution 
containing sodium triisopropylnaphthalene sulfonate, and the mixture was 
homogenized with a colloid mill. The resultant emulsion was applied in 
order to form a layer with a dry thickness of 1.0 .mu.m and rate of 
gelatin applied was 1.0 g/m.sup.2. 
Thirteenth layer (protective layer) 
An aqueous gelatin solution containing 4 g gelatin per 100 ml and 0.2 g of 
1,2-bisvinylsulfonylethane per 100 ml was applied so that amount of 
gelatin applied was at a rate of 1.3 g/m.sup.2 and a dry thickness was 1.2 
.mu.m. 
TABLE 3 
__________________________________________________________________________ 
Sample No. 43 
High- Anti- Ultra- 
Coupler 
boiling 
DIR Colored 
fogging 
violet 
No. solvent 
coupler 
coupler 
agent absorbent 
Amount 
Amount 
Amount 
Amount 
Amount 
Amount 
applied 
applied 
applied 
applied 
applied 
applied 
__________________________________________________________________________ 
13th layer 
(protective layer) 
12th layer HBS-9 U-5 
(intermediate layer) 
2 2 
11th layer Y-3 HBS-9 
(blue-sensitive high- 
11 50 
sensitivity layer) 
10th layer Y-3 HBS-9 
(blue-sensitive low- 
34 50 
sensitivity layer) 
9th layer 
(yellow filter layer) 
8th layer 
(intermediate layer) 
7th layer M-3 HBS-26 
D-5 CM-3 A-1 
(green-sensitive high- 
1.0 100 0.04 0.3 1.8 
sensitivity layer) 
6th layer M-1 HBS-26 
D-6 CM-3 A-1 
(green-sensitive high- 
7.9 100 0.4 0.8 0.5 
sensitivity layer) 
5th layer HBS-9 A-1 
(intermediate layer) 
0.06 0.06 
4th layer (1) HBS-9 D-13 A-1 
(red-sensitive high- 
1.8 100 0.4 0.5 
sensitivity layer) 
3rd layer C-3 HBS-9 D-2 CC-3 A-1 
(red-sensitive low- 
10.0 100 0.4 0.3 0.5 
sensitivity layer) 
2nd layer 
(intermediate layer) 
1st layer 
(anti-halation layer) 
Support 
__________________________________________________________________________ 
In Table 3, the amounts applied indicate amounts per mol silver halide, 
whereby the amounts of coupler, DIR coupler and colored coupler are in 
mol%, the amounts of high-boiling solvent and ultraviolet absorbent are in 
weights per m.sup.2. The amount (g per m.sup.2) of high-boiling solvent 
was equal to that of ultraviolet absorbent. Additionally, the amount (g 
per m.sup.2) of anti-fogging agent in the fifth layer is in weight (g) per 
m.sup.2 ; and the amount by weight of high-boiling solvent used is the 
same as anti-fogging agent. 
Each sample prepared with a constitution specified in Table 3 was treated 
with the processing steps in Example 1. As a result, each sample was 
found to be a silver halide color photographic light-sensitive material 
having satisfactory color balance. 
In contrast to a conventional technique, the present invention, by using a 
cyan coupler represented by general formula [I], provides a cyan dye image 
with high sensitivity and high color density free from dye loss even 
treated with a fatigued bleaching bath or bleach-fixing bath. 
This photographic light-sensitive material also excels in spectral property 
and is capable of providing a cyan coupler with excellent dispersion 
stability.