Silver halide color photographic material

Disclosed is a silver halide color photographic material having at least one light-sensitive silver halide emulsion layer on a support and containing at least one coupler of formula (I): ##STR1## where R.sub.1 represents an alkyl group; R.sub.2 and R.sub.3 each represent a hydrogen atom, an alkyl group or an aryl group, provided that both R.sub.2 and R.sub.3 are not hydrogen atoms at the same time; R.sub.4 and R.sub.5 each represent an alkyl group; X represents a hydrogen atom or a substituent capable of splitting off by coupling with an oxidation product of a developing agent; Y represents a substituent; n represents 0 or 1; and m represents an integer of from 0 to 3. The material has excellent sensitivity and gradation and has improved storage stability, especially latent image stability.

FIELD OF THE INVENTION 
The present invention relates to a silver halide color photographic 
material and to 1H-pyrazolo[1,5-b][1,2,4]triazole magenta couplers used in 
the material. 
BACKGROUND OF THE INVENTION 
1H-pyrazolo[1.5-b][1,2,4]triazole magenta couplers are disclosed in 
JP-A-59-171956 (the term "JP-A" as used herein means an "unexamined 
published Japanese patent application") and U.S. Pat. No. 4,540,654. These 
couplers are known to have excellent color reproducibility and give fast 
color images; they are also known to be easily produced. Various 
investigations have heretofore been made for improving the sensitivity and 
gradation of these couplers. For instance, couplers having a phenolic 
hydroxyl group in the molecule are disclosed in JP-A-61-65248 and U.S. 
Pat. No. 4,443,536; couplers having a sulfonamido group in the molecule 
are disclosed in JP-A-61-65246 and European Patent 176,804; couplers 
having two sulfonamido groups in the molecule are disclosed in 
JP-A-62-125349; and couplers having a sulfonyl group in the molecule are 
disclosed in JP-A-62-209460. However, silver halide photographic materials 
containing the couplers described in these patent publications have a 
problem in that their sensitivity lowers when they are stored for a long 
period of time. Silver halide photographic materials containing couplers 
described in JP-A-62-79451, U.S. Pat. No. 4,900,655 and JP-A-1-106055 
where R.sub.5 is a substituted phenyl group also have the same problem. 
SUMMARY OF THE INVENTION 
The object of the present invention is to provide a silver halide color 
photographic material having excellent sensitivity and gradation and also 
having excellent storage stability. 
The object has been attained by a silver halide color photographic material 
containing a coupler of a general formula (I): 
##STR2## 
where R.sub.1 represents an alkyl group; R.sub.2 and R.sub.3 each 
represent a hydrogen atom, an alkyl group or an aryl group, provided that 
both R.sub.2 and R.sub.3 are not hydrogen atoms at the same time; R.sub.4 
represents an alkyl group; R.sub.5 represents an alkyl group; X 
represents a hydrogen atom or a substituent capable of splitting off by 
coupling with an oxidation product of a developing agent; Y represents a 
substituent; n represents 0 or 1; and m represents an integer of from 0 to 
3. 
DETAILED DESCRIPTION OF THE INVENTION 
Couplers of formula (I) will be explained in more detail. 
In formula (I), R.sub.1 represents an alkyl group, which is a linear or 
branched, substituted or unsubstituted alkyl group. As substituents of the 
substituted alkyl group, mentioned are, for example, a halogen atom (e.g., 
chlorine, fluorine), an aryl group (e.g., phenyl, naphthyl, p-tolyl), a 
heterocyclic group (e.g., 4-pyridyl, 2-furyl), an alkoxy group (e.g,. 
methoxy, ethoxy, butoxy, dodecyloxy, isopropyloxy, t-butoxy), an aryloxy 
group (e.g., phenoxy, 2,4-di-t-amylphenoxy, p-t-octylphenoxy, 
2-methoxyphenoxy), an alkylthio group (e.g., methylthio, ethylthio, 
octylthio, 2-ethylhexylthio, dodecylthio), an arylthio group (e.g., 
phenylthio, 2-butoxy-5-octylphenylthio), an acyl group (e.g., acetyl, 
pivaloyl, benzoyl), a carbamoyl group (e.g., N,N-diethylcarbamoyl, 
N-butylcarbamoyl, N-phenylcarbamoyl ), an amido group (e.g., acetamido, 
pivaloylamido, tetradecanamido, benzamido), an ureido group (e.g., 
N,N-diethylureido, N-phenylureido), a sulfonamido group (e.g., 
methanesulfonamido, p-toluenesulfonamido), an alkoxycarbonyl group (e.g., 
methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, isopropyloxycarbonyl, 
dodecyloxycarbonyl), and a cyano group. 
Preferably, R.sub.1 is an unsubstituted linear or branched alkyl group 
(e.g., C.sub.1-8 alkyl); and most preferably, it is a methyl group or an 
ethyl group. 
In formula (I), R.sub.2 and R.sub.3 each represent a hydrogen atom, an 
alkyl group or an aryl group. The alkyl group of R.sub.2 and R.sub.3 has 
the same meaning as that of the preceding alkyl group defined for R.sub.1. 
The aryl group of R.sub.2 and R.sub.3 is a substituted or unsubstituted 
aryl group (e.g., phenyl). As possible substituents on the substituted 
aryl group, those defined for the substituted alkyl group of R.sub.1 are 
referred to. 
Preferably, at least one of R.sub.2 and R.sub.3 is a C.sub.1-8 alkyl group 
and is most preferably a methyl group. 
In formula (I), R.sub.4 represents an alkyl group, which is a linear or 
branched (e.g., C.sub.1-12 alkyl), substituted or unsubstituted alkyl 
group. As substituents of the substituted alkyl group, those defined for 
the preceding substituted alkyl group of R.sub.1 are referred to. More 
preferably, R.sub.4 is represented by the following general formula (II): 
EQU --(CH.sub.2).sub.2 --(A)--R.sub.6 (II) 
where A represents an oxygen atom, a nitrogen atom or a sulfur atom; and 
R.sub.6 represents an alkyl group, an aryl group or an acyl group. 
The group of formula (II) will be explained in more detail. 
A is most preferably an oxygen atom. 
R.sub.6 represents an alkyl group, an aryl group or an acyl group. The 
alkyl group is a linear or branched, substituted or unsubstituted alkyl 
group (e.g., C.sub.1-8 alkyl). As substituents of the substituted alkyl 
group, those defined for the preceding substituted alkyl group of R.sub.1 
are referred to. The aryl group is a substituted or unsubstituted aryl 
group (e.g., phenyl). As substituents of the substituted aryl group, those 
defined for the preceding substituted alkyl group of R.sub.1 are referred 
to. The acyl group includes, for example, acetylpropanoyl, butanoyl, 
t-butanoyl, cyclohexanoyl, 2-ethylhexanoyl, dodecanoyl, 
.alpha.-(2,4-di-t-amylphenoxy)hexanoyl groups. Most preferably, R.sub.6 is 
a methyl group, an ethyl group, a propyl group, an isopropyl group, a 
butyl group or a phenyl group. 
In formula (I), R.sub.5 represents an alkyl group, which is a linear or 
branched, substituted or unsubstituted alkyl group. As substituents for 
the substituted alkyl group, mentioned are, for example, a halogen atom 
(e.g., fluorine, chlorine), a hydroxyl group, a cyano group, an aryl group 
(e.g., phenyl, naphthyl), an alkoxy group (e.g., methoxy, ethoxy, 
propyloxy, butyloxy, 2-ethylhexyloxy, hexyloxy, octyloxy, dodecyloxy, 
hexadecyloxy, ethoxyethoxy, phenoxyethoxy, 4-methoxyphenoxyethoxy), an 
aryloxy group (e.g., phenoxy, 2,4-di-t-amylphenoxy, 4-methylphenoxy, 
4-ethoxycarbonylphenoxy, 4-methoxyphenoxy, 4-ethoxyphenoxy), an alkylthio 
group (e.g., methylthio, ethylthio, propylthio, butylthio, octylthio, 
dodecylthio, hexadecylthio), an arylthio group (e.g., phenylthio, 
2-pivaloylamidophenylthio, 2-butoxy-5-t-octylphenylthio, 
4-dodecyloxyphenylthio), an acyl group (e.g., acetyl, benzoyl), an amido 
group (e.g., acetamido, butanamido, tetradecanamido, hexadecanamido, 
benzamido, 2-butoxybenzamido, 2-hexadecyloxybenzamido, 
4-dodecyloxybenzamido, 4-t-butylbenzamido, 
.alpha.-(2,4-di-t-amylphenoxy)butanamido), a sulfonamido group (e.g., 
methanesulfonamido, ethanesulfonamido, octanesulfonamido, 
hexadecanesulfonamido, benzenesulfonamido, 4-methylbenzenesulfonamido, 
4-dodecyloxybenzenesulfonamido, 2-octyloxy-5-t-octylbenzenesulfonamido), a 
carbamoyl group (e.g., N-methylcarbamoyl, N-ethylcarbamoyl, 
N-butylcarbamoyl, N-dodecylcarbamoyl, N-cyclohexylcarbamoyl, 
N,N-diethylcarbamoyl, N,N-diisopropylcarbamoyl, N, N-dibutylcarbamoyl, 
N-octadecyl-N-methylcarbamoyl, N-phenylcarbamoyl), a sulfamoyl group 
(e.g., N-ethylsulfamoyl, N-butylsulfamoyl, N-hexylsulfamoyl, 
N-dodecylsulfamoyl, N-cyclohexylsulfamoyl, N,N-diethylsulfamoyl, 
N,N-dibutylsulfamoyl), an ureido group (e.g., N-ethylureido, 
N-butylureido, N-hexadecylureido, N-phenylureido, N,N-dimethylureido, 
N,N-dibutylureido), an urethane group (e.g., methylurethane, 
ethylurethane, propylurethane, butylurethane, dodecylurethane, 
phenylurethane), an alkoxycarbonyl group (e.g., methoxycarbonyl, 
ethoxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butoxycarbonyl, 
dodecyloxycarbonyl, hexadecyloxycarbonyl), and a sulfonyl group (e.g., 
methylsulfonyl, ethylsulfonyl, butylsulfonyl, dodecylsulfonyl, 
hexadecylsulfonyl, octadecylsulfonyl). 
Preferably, R.sub.5 is an alkyl group having from 14 to 50 carbon atoms in 
total, and more preferably, it is an alkyl group having from 18 to 35 
carbon atoms in total. 
In formula (I), X represents a hydrogen atom or a substituent capable of 
splitting off by coupling with an oxidation product of a developing agent. 
The substituent is, for example, a halogen atom or a monovalent group 
having at least two atoms selected from the group consisting of C, N, O, 
S, P and H. Preferably, it is a hydrogen atom, a halogen atom, an alkoxy 
group, an aryloxy group, an alkylthio group, an arylthio group, a 
3-membered to 10-membered heterocyclic group containing hetero atom(s) 
selected from the group consisting of O, N and/or S; or an acyloxy group. 
More precisely, X is a hydrogen atom, a halogen atom (e.g., fluorine, 
chlorine, bromine), an alkoxy group (e.g., methoxy, ethoxy, 
methoxycarbonylmethoxy, methoxyethoxy), an aryloxy group (e.g., phenoxy, 
4-methylphenoxy, 4-methoxycarbonylphenoxy, 4-t-octylphenoxy, 
4-cyanophenoxy), an alkylthio group (e.g., dodecylthio, hexadecylthio, 
1-ethoxycarbonyldodecylthio), an arylthio group (e.g., 
2-pivaloylamidophenylthio, 2-butoxy-5-t-octylthio, 
2-benzyloxycarbonylaminophenylthio), a heterocyclic group (e.g., 
1-pyrazolyl, 4-methoxy-1-pyrazolyl, 4-chloro-1-pyrazolyl, 
4-cyano-1-pyrazolyl, 4-acetylamino-1-pyrazolyl, 1-imidazolyl), or an 
acyloxy group (e.g., acetoxy, pivaloyloxy). Most preferably, X is a 
chlorine atom or an aryloxy group. 
In formula (I), Y represents a substituent, which has the same meaning 
defined for the substituent of the substituted alkyl group of R.sub.1. 
n represents 0 or 1; and it is preferably 1. m represents an integer of 
from 0 to 3; and it is preferably 0. 
In formula (I), the substituent --NHCOR.sub.5 is preferably para-positioned 
to --OR.sub.4. 
Specific examples of couplers of formula (I) for use in the present 
invention are mentioned below, which, however, are not limitative. 
##STR3## 
The general production methods for couplers of formula (I), which are used 
in the present invention is mentioned below. 
Production of the 1H-pyrazolo[1,5-b][1,2,4]triazole skeleton is described 
in JP-A-60-197688 and JP-A-3-184980. For example, the skeleton may be 
produced in accordance with the following reaction scheme (A): 
##STR4## 
Couplers of formula (I) where the split-off group is bonded to the formula 
via an oxygen atom may be produced by first preparing 
2-acyl-2-aryloxyacetonitriles by the method described in JP-A-2-300155 
followed by applying them to the process mentioned above. Precisely, they 
may be produced, for example, in accordance with the following reaction 
scheme (B): 
##STR5## 
Introduction of an N-heterocyclic group is described in JP-A-2-59584. 
Precisely, N-heterocyclic group-containing couplers of formula (I) are 
produced, for example, in accordance with the following reaction scheme 
(C): 
##STR6## 
(The starting compounds are produced in accordance with the preceding 
reaction scheme (A).) 
For production of couplers of formula (I) in which the split-off group is 
bonded to the formula via a sulfur atom, the method described in U.S. Pat. 
No. 3,227,554 is referred to. They may also be produced by reacting a 
coupler having a halogen atom (e.g., chlorine, bromine) at the 
coupling-active position and a mercaptan compound in the presence of a 
base.

Examples of production of couplers of formula (I) are mentioned below. 
PRODUCTION EXAMPLE 1 
Production of Coupler M-1 
Coupler M-1 is produced in accordance with the following reaction scheme 
(D): 
##STR7## 
1000 ml of ethylene glycol monoethyl ether and 54 g of sodium hydroxide 
were added to 311 g of sodium 2-chloro-5-nitrobenzenesulfonate (compound 
(I)) and stirred under heat at 75.degree. to 80.degree. C. After stirred 
under heat for 3 hours, the resulting mixture was cooled to 50.degree. C., 
and 50 ml of water and 20 ml of concentrated hydrochloric acid were added 
thereto. After further stirring, the insoluble substances were removed by 
filtration. 
The filtrate was gradually and dropwise added to a hot liquid comprising 
320 g of reduced iron, 32 g of ammonium chloride and 200 ml of water. 
After the addition, the liquid mixture was stirred under heat for about 3 
hours. The reaction liquid was then filtered under reduced pressure while 
heating to remove the insoluble substances therefrom. The filtrate was 
concentrated under reduced pressure to precipitate crystals. 500 ml of 
ethanol was added to the residue so that the crystals were dispersed. They 
were taken out by filtration to obtain 182 g (53.5%) of sodium 
5-amino-2-(2-ethoxyethoxy)benzenesulfonate (compound (III)); the compound 
had a melting point of 230.degree. C. or higher. 
550 ml of DMAc was added to 182 g of compound (III) obtained above and 
stirred while cooling with water. To the resulting solution was dropwise 
added 216 g of 2-(2,4-di-t-amylphenoxy)octanoic acid chloride (compound 
(IV)). After the addition, 49 ml of pyridine was dropwise added thereto. 
The resulting mixture was stirred for 2 hours while cooling with water, 
and 1000 ml of ethyl acetate and 1500 ml of water were added thereto. The 
aqueous layer was removed, and the remaining ethyl acetate phase was 
washed three times with a saline solution. The ethyl acetate phase was 
then dried with anhydrous magnesium sulfate, and ethyl acetate was removed 
therefrom by distillation under reduced pressure. Thus, compound (V) was 
obtained. 
400 ml of DMAc and 500 ml of acetonitrile were added to 400 g of compound 
(V) obtained above and stirred at room temperature. To the resulting 
solution was gradually and dropwise added 220 ml of phosphorus 
oxychloride. After the addition, the mixture was heated up to 40.degree. 
to 50.degree. C. and stirred for 2 hours with heating. Thereafter, the 
reaction liquid was gradually poured into 1 kg of ice with stirring. The 
separated oily product was extracted with 1000 ml of ethyl acetate. The 
ethyl acetate extract was washed with a saline solution and dried with 
anhydrous magnesium sulfate. Ethyl acetate was removed from it by 
distillation under reduced pressure, and 306 g (74.7%) of the sulfonic 
acid chloride product (compound (VI)) was obtained as an oil. Compound 
(VI) had the following physical data. 
Proton NMR Spectrum (CDCl.sub.3) .delta.(ppm) (multiplicity, integral 
values): 8.0-7.83 (m, 3H), 7.25 (d, 1H), 7.2-7.0 (m, 2H), 6.65 (d, 1H), 
4.69 (t, 1H), 4.30 (t, 2H), 3,87 (t, 2H), 3.63 (q, 2H), 2.20-0.55 (m, 
38H). 
300 ml of DMAc and 600 ml of ethyl acetate were added to 165.5 g of the 
amine (compound (VII)) as obtained by the method described in 
JP-A-60-197688, and stirred while cooling with ice. To the solution was 
dropwise added 255 g of the sulfonic acid chloride (compound (VI)) 
obtained above. After the addition, the mixture was stirred for 30 
minutes, and 62.8 ml of triethylamine was added thereto. After the 
addition, the mixture was stirred for 4 hours. Then the solution were 
added 10 ml of hydrochloric acid and 1000 ml of water, and this mixture 
was stirred for 30 minutes before the insoluble substances were removed 
therefrom by filtration under reduced pressure. The filtrate was extracted 
with 500 ml of ethyl acetate. The ethyl acetate extract was washed three 
times with a saline solution and then stirred with anhydrous magnesium 
sulfate. Ethyl acetate was removed from the extract by distillation under 
reduced pressure, and 2000 ml of n-hexane and 150 ml of ethyl acetate were 
added to the residue to precipitate crystals. The crystals were taken out 
by filtration and dried to obtain 202 g (56.3 %) of coupler (M-1), which 
had a melting point of 105.degree. to 106.degree. C. The compound was 
obtained as a mixture of diastereomers, and had the following physical 
data. 
Proton NMR Spectrum (CDCl.sub.3) .delta.(ppm) (multiplicity, integral 
values): 10.75 (s, 0.7H), 10.65 (s, 0.3H), 8.0 (s, 0.7H), 7.96 (s, 0.3H), 
7.70 (d, d, 1H), 7.30-6.95 (m, 3H), 6.87-6.18 (m, 2H), 6.38 (d, 0.7H), 
6.31 (d, 0.3H), 4.86-4.70 (m, 1H), 4.10-3.20 (m, 9H), 2.31 (s, 3H), 
2.21-2.03 (m, 2H), 1.94 (q, 2H), 1.8-1.10 (m, 28H), 1,89 (t, 3H), 
0.75-0.55 (m, 6H). 
PRODUCTION EXAMPLES 2 TO 11 
Couplers (M-2) to (M-12) were produced in the same manner as provided in 
Production Example 1. NMR data of these couplers are shown in Tables 1 and 
2 below. 
TABLE 1 
__________________________________________________________________________ 
Coupler 
m.p. 
No. (.degree.C.) 
Proton NMR .delta. (ppm) (multiplicity, integral 
__________________________________________________________________________ 
values) 
M-2 118.about.121 
(CDCl.sub.3), 10.75(S, 0.7H), 10.70(S, 0.3H), 8.0(S, 0.7H), 
7.94(S, 0.3H), 7.72(d.d, 1H), 7.35.about.7.00 
(m, 3H), 6.70.about.6.65(m, 2H), 6.42(d, 0.7H), 6.38(d, 0.3H), 
4.87.about.4.70(m, 1H), 4.08.about.3.60(m, 
4H), 3.50(S, 3H), 3.45.about.3.22(m, 3H), 2.33(S, 3H), 
2.22.about.2.03(m, 2H), 1.93(q, 2H), 1.81.about.1.10(m, 
25H), 0.90(t, 3H), 0.69(t, 6H) 
M-3 107.about.110 
(CDCl.sub.3) 10.74(S, 0.7H), 10.67(S, 0.3H), 8.02(S, 0.7H), 
7.94(S, 0.3H), 7.72(d.d, 1H), 7.33.about.6.95 
(m, 3H), 6.33(t, 1H), 6.26(d, (1H), 6.37((d, 0.7H), 6.32(d, 
0.3H), 4.88.about.4.72(m, 1H), 4.10.about.3.23 
(m, 9H), 2.33(S, 3H), 2.23.about.2.03(m, 2H), 1.95(q, 2H), 
1.79.about.1.11(m, 24H), 0.98(t, 3H), 0.69(t, 6H) 
M-4 184.about.186 
(CDCl.sub.3) 10.75(S, 0.6H), 10.68(S, 0.4H), 8.03(S, 0.6H), 
7.95(S, 0.4H), 7.70(d.d, 1H), 7.31.about.6.97 
(m, 3H), 6.82(t, 1H), 6.76(d, 1H), 6.39(d, 0.6H), 6.34(d, 
0.4H), 4.87.about.4.70(m, 1H), 4.09.about.3.20 
(m, 9H) 2.30.about.2.08(m, 2H), 1.95(q, 2H), 1.78.about.1.10(m, 
26H), 0.69(t, 6H) 
M-5 110.about.116 
(CDCl.sub.3) 10.72(S, 1H), 8.87(S, 1H), 7.89(d, 1H), 7.41(d.d, 
1H), 7.27(S, 1H), 7.19(d.d, 1H), 6.83(d, 
1H), 6.69(t, 1H), 6.58(d, 1H), 4.73(S, 2H), 4.18.about.3.65(m, 
4H), 3.49(S, 3H), 3.47.about.3.20(m, 3H), 
2.34(S, 3H), 1.90(q, 2H), 1.64(q, 2H), 1.45(S, 6H), 1.28(d, 
9H), 0.71(t, 6H) 
M-6 121.about.122 
(CDCl.sub.3) 10.93(S, 1H), 7.66.about.7.55(m, 2H), 7.32(d.d, 
1H), 6.70(t, 1H), 6.49(d, 1H), 4.07.about.3.62(m, 4 
H), 3.50(S, 3H), 3.48.about.3.17(m, 3H), 2.45(t, 2H), 2.32(S, 
3H), 1.36.about.1.63(m, 2H), 1.54.about.1.10(m, 
27H), 0.88(t, 3H) 
__________________________________________________________________________ 
TABLE 2 
__________________________________________________________________________ 
Coupler 
m.p. 
No. (.degree.C.) 
Proton NMR .delta. (ppm) (multiplicity, integral 
__________________________________________________________________________ 
values) 
M-8 vitreous 
(CDCl.sub.3) 10.80(S, 0.5H), 10.71(S, 0.5H), 8.37(S, 0.5H), 
8.32(S, 0.5H), 7.72(d.d, 1H), 7.40.about.7.18 
(m, 1H), 6.98(t, 1H), 6.88.about.6.64(m, 3H), 6.43(d.d, 1H), 
4.72.about.4.55(m, 1H), 4.09.about.3.62(m, 7H), 
3.55.about.3.20(m, 6H), 2.32(S, 3H), 2.14.about.1.93(m, 2H), 
1.67.about.1.50(m, 2H), 1.48.about.1.0(m, 30H), 0.88 
(t, 3H) 
M-9 vitreous 
(CDCl.sub.3) 10.79(S, 0.5H), 10.69(S, 0.5H), 8.38(S, 0.5H), 
8.32(S, 0.5H), 7.72(d.d, 1H), 7.39.about.7.20 
(m, 1H), 7.00(t, 1H), 6.86.about.6.65(m, 3H), 6.40(d.d, 1H), 
4.75.about.4.55(m, 1H), 4.09.about.3.60(m, 6H), 
3.50(S, 1.5H), 3.49(S, 1.5H), 3.45.about.3.20(m, 3H), 2.34(S, 
3H), 2.13.about.1.74(m, 4H), 1.65.about.1.05(m, 
58H), 0.89(t, 6H) 
M-10 92.about.98 
(CDCl.sub.3) 10.74(S, 0.5H), 10.65(S, 0.5H), 8.03(S, 0.5H), 
7.90(S, 0.5H), 7.66(d.d, 1H), 7.33.about.7.05 
(m, 3H), 6.93.about.6.70(m, 1H), 6.25(d, 0.5H), 6.20(d, 0.5H), 
5.65(t, 1H), 4.85(t, 0.5H), 4.26(t, 0.5 
H), 3.80.about.3.13(m, 5H), 2.35(S, 3H), 2.23.about.1.10(m, 
4H), 1.0.about.0.77(m, 6H), 0.76.about.0.57(m, 6H) 
M-11 vitreous 
(CDCl.sub.3) 11.26(S, 0.5H), 11.19(S, 0.5H), 7.89(S, 1H), 
7.68.about. 7.50(m, 3H), 7.30.about.7.10(m, 3H), 
6.75.about.6.36(m, 3H), 5.63(t, 1H), 4.76.about.4.63(m, 1H), 
3.90.about.3.03(m, 5H), 2.37(S, 3H), 2.15.about.1.06(m, 
41H), 1.03.about.0.79(m, 6H), 0.76.about.0.57(m, 6H) 
M-12 100.about.102 
(CDCl.sub.3) 10.19(S, 0.5H), 10.13(S, 0.5H), 7.92(S, 0.5H), 
7.90(S, 0.5H), 7.68(d.d, 1H), 7.38.about.7.20 
(m, 1H), 7.20.about.7.0(m, 4H), 6.90.about.6.77(m, 2H), 
6.70.about.6.52(m, 3H), 4.70.about.4.50(m, 1H), 
4.10.about.3.06 
(m, 9H), 2.62(q, 2H), 2.29(S, 3H), 2.08.about.1.14(m, 35H), 
0.90(t, 3H), 0.78.about.0.58(m, 6H) 
__________________________________________________________________________ 
The photographic material of the present invention is not specifically 
defined, provided that it has at least one blue-sensitive silver halide 
emulsion layer, at least one green-sensitive silver halide emulsion layer 
and at least one red-sensitive silver halide emulsion layer on a support. 
In the material, the number of the silver halide emulsion layers and 
non-light-sensitive layers as well as the order of the layers on the 
support is not specifically defined. As one typical example, there is 
mentioned a silver halide color photographic material having plural 
light-sensitive layer units each composed of plural silver halide emulsion 
layers each having a substantially same color-sensitivity but having a 
different sensitivity degree. The respective light-sensitive layers are 
unit light-sensitive layers each having a color-sensitivity to anyone of 
blue light, green light and red light. In such a multi-layer silver halide 
color photographic material, in general, the order of the light-sensitive 
layer units to be on the support comprises a red-sensitive layer unit, a 
green-sensitive layer unit and a blue-sensitive layer unit as formed on 
the support in this order. As the case may be, however, the order may be 
opposite to the above-mentioned one, in accordance with the object of the 
photographic material. As still another embodiment, a different 
color-sensitive layer may be sandwiched between two other layers, 
including the same color-sensitive layers described above. 
various non-light-sensitive layers such as an interlayer may be provided 
between the above-mentioned silver halide light-sensitive layers, or on or 
below the uppermost layer or lowermost layer thereof. 
Such an interlayer may contain various couplers and DIR compounds described 
in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037 and 
JP-A-61-20038, and it may also contain conventional color mixing 
preventing agents. 
As the constitution of the plural silver halide emulsions which constitute 
the respective light-sensitive layer units, preferred is a two-layered 
constitution composed of a high-sensitivity emulsion layer and a 
low-sensitivity emulsion layer as described in German Patent 1,121,470 and 
British Patent 923,045. In general, it is preferred that the plural 
light-sensitive layers are arranged on the support in such a way that the 
sensitivity degree of the layers gradually decreases in the direction of 
the support. In such an embodiment, a non-light-sensitive layer may be 
provided between the plural silver halide emulsion layers. As another 
embodiment, a low-sensitivity emulsion layer is formed at a distance from 
the support and a high-sensitivity emulsion layer is formed near the 
support, as described in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541, 
and JP-A-62-206543. 
As specific examples of the layer constitution on the support, there are 
mentioned an order of low-sensitivity blue-sensitive layer 
(BL)/high-sensitivity blue-sensitive layer (BH)/high-sensitivity 
green-sensitive layer (GH)/low-sensitivity green-sensitive layer 
(GL)/high-sensitivity red-sensitive layer (RH)/low-sensitivity 
red-sensitive layer (RL) from the most distant from the support; and an 
order of BH/BL/GL/GH/RH/RL; and an order of BH/BL/GH/GL/RL/RH. 
As other examples, there are mentioned an order of blue-sensitive 
layer/GH/RH/GL/RL from the most distant side from the support, as 
described in JP-B-55-34932; and an order of blue-sensitive 
layer/GL/RL/GH/RH from the most distant side from the support, as 
described in JP-A-56-25738 and JP-A-62-63936. 
As a further example, there is mentioned a three-layer unit constitution as 
described in JP-B-49-15495, where the uppermost layer is a 
highest-sensitivity silver halide emulsion layer, the intermediate layer 
is a silver halide emulsion layer having a lower sensitivity than the 
uppermost layer, and the lowermost layer is a silver halide emulsion layer 
having a still lower sensitivity than the intermediate layer. That is, in 
the layer constitution of this type, the sensitivity degree of each 
emulsion layer is gradually lowered as one proceeds in the direction of 
the support. Even in the three-layer constitution of the type, each of the 
same color-sensitivity layers may be composed of three layers of 
middle-sensitivity emulsion layer/high-sensitivity emulsion 
layer/low-sensitivity emulsion layer as formed in this order from the most 
distant side from the support, as described in JP-A-59-202464. 
As still other examples of the layer constitution of the photographic 
material of the present invention, there are mentioned an order of 
high-sensitivity emulsion layer/low-sensitivity emulsion 
layer/middle-sensitivity emulsion layer/, and an order of low-sensitivity 
emulsion layer/middle-sensitivity emulsion layer/high-sensitivity emulsion 
layer. Where the photographic material of the invention has four or more 
layers, the layer constitution thereof may be varied in accordance with 
the manner mentioned above. 
In order to improve the color reproducibility, it is desired to provide a 
doner layer (CL) which has an interlayer effect and which has a different 
color sensitivity distribution from that of the essential light-sensitive 
layers of BL, GL and RL, adjacent to or near to the essential 
light-sensitive layers, in the manner described in U.S. Pat. Nos. 
4,663,271, 4,705,744 and 4,707,436 and JP-A-62-160448 and JP-A-63-89850. 
As mentioned above, various layer constitutions and arrangements may be 
selected in accordance with the object of the photographic material of the 
invention. 
The silver halide to be preferably in the photographic emulsion layer of 
constituting the photographic material of the present invention is silver 
iodobromide, silver iodochloride or silver iodochlorobromide having a 
silver iodide content of about 30 mol % or less. Especially preferred is a 
silver iodobromide or silver iodochlorobromide having a silver iodide 
content of from about 2 mol % to about 10 mol %. 
The silver halide grains to be in the photographic emulsion of constituting 
the photographic material of the present invention may be regular 
crystalline ones such as cubic, octahedral or tetradecahedral grains, or 
irregular crystalline ones such as spherical or tabular grains, or 
irregular crystalline ones having a crystal defect such as a twin plane, 
or composite crystalline ones composed of the above-mentioned regular 
and-irregular crystalline forms. 
Regarding the grain size of the silver halide grains, the grains may be 
fine grains having a small grain size of about 0.2 micron or less or may 
be large ones having a large grain size of up to about 10 microns as the 
diameter of the projected area. The emulsion of the grains may be either a 
polydispersed emulsion or a monodispersed emulsion. 
The silver halide photographic emulsions to be used in the present 
invention may be prepared by various methods, for example, those described 
in Research Disclosure (RD) No. 17643 (December, 1978), pages 22 to 23 (I. 
Emulsion Preparation and Types); RD No. 18716 (November, 1979), pages 648; 
RD No. 307105 (November 1989) pages 863 to 865; P. Glafkides, Chimie et 
Physique Photographique (published by Paul Montel, 1967); G. F. Duffin, 
Photographic Emulsion Chemistry (published by Focal Press, 1966); and V. 
L. Zelikman et al, Making and Coating Photographic Emulsion (published by 
Focal Press, 1964). 
Monodispersed emulsions as described in U.S. Pat. Nos. 3,574,628 and 
3,655,394 and British Patent 1,413,748 are also preferably used in the 
present invention. 
Additionally, tabular grains having an aspect ratio of about 3 or more may 
also be used in the present invention. Such tabular grains may easily be 
prepared in accordance with various methods, for example, as described in 
Gutoff, Photographic Science and Engineering, Vol. 14, pages 248 to 257 
(1970); and U.S. Pat. Nos. 4,434,226, 4,414,310, 4,430,048, 4,439,520 and 
British Patent 2,112,157. 
Regarding the crystal structure of the silver halide grains contained in 
the emulsions of the invention, the grains may have the same halogen 
composition throughout the whole grain, or they may have different halogen 
compositions between the inside part and the outside part of one grain, or 
they may have a layered structure. Further, the grains may have different 
halogen compositions as conjugated by epitaxial bond, or they may have 
other components than silver halides, such as silver rhodanide or lead 
oxide, as conjugated with the silver halide matrix. Additionally, a 
mixture of various grains of different crystalline forms may be employed 
in the present invention. 
The above-mentioned emulsions for use in the present invention may be 
either 1) surface latent image type ones capable of forming latent images 
essentially on the surfaces of the grains, or 2) internal latent image 
type ones capable of forming latent images essentially in the insides of 
them, or 3) they may also be surface/inside latent image type ones capable 
of forming latent images both on the surfaces of the grains and in the 
insides of them. In any event, the emulsions utilized should be negative 
emulsions. As internal latent image type emulsions, they may be internal 
latent image type core/shell emulsions as described in JP-A-63-264740. A 
method of preparing such internal latent image type core/shell emulsions 
is described in JP-A-59-133542. The thickness of the shell of the emulsion 
grains of this type varies, depending upon the way of developing them, and 
is preferably from 3 to 40 nm, especially preferably from 5 to 20 nm. 
The emulsions for use in the invention are generally physically ripened, 
chemically ripened and/or spectral-sensitized. Additives to be used in 
such a ripening or sensitizing step are described in Research Disclosure 
Nos. 17643, 18716 and 307105, and the related descriptions in these 
references are shown in the table mentioned below. 
In the photographic material of the present invention, two or more 
emulsions which are different from one another in at least one 
characteristic of the light-sensitive silver halide grains constituting 
them, which is selected from the grain size, the grain size distribution, 
the halogen composition, the shape and the sensitivity of the grains, can 
be incorporated into one and the same layer. 
Surface-fogged silver halide grains as described in U.S. Pat. No. 
4,082,553; inside-fogged silver halide grains as described in U.S. Pat. 
No. 4,626,498 and JP-A-59-214852; as well as colloidal silver may 
preferably be used in light-sensitive silver halide emulsion layers and/or 
substantially non-light-sensitive hydrophilic colloid layers constituting 
the photographic material of the present invention. Inside-fogged or 
surface-fogged silver halide grains are such grains that can be 
non-imagewise uniformly developed irrespective of the non-exposed area and 
the exposed area of the photographic material. A method of preparing such 
inside-fogged or surface-fogged silver halide grains is described in U.S. 
Pat. No. 4,626,498 and JP-A-59-214852. 
The silver halide used to form the inside nucleus of an inside-fogged 
core/shell type silver halide grain may be either one having the same 
halogen composition or one having a different halogen composition than 
that used to form the shell. The inside-fogged or surface-fogged silver 
halide may be any of silver chloride, silver chlorobromide, silver 
iodobromide or silver chloroiodobromide. The grain size of such a fogged 
silver halide grain is not specifically defined, and it is preferably from 
0.01 to 0.75 .mu.m, especially preferably from 0.05 to 0.6 .mu.m (as a 
mean grain size). The shape of the grain is also not specifically defined, 
and it may be either a regular grain or an irregular grain. The emulsion 
containing such fogged grains may be either a monodispersed one or a 
polydispersed one. Preferred is a monodispersed one, in which at least 95% 
by weight or by number of all the silver halide grains therein have a 
grain size falling within the range of the mean grain size +/-40%. 
The photographic material of the present invention preferably contain 
non-light-sensitive fine silver halide grains. Non-light-sensitive fine 
silver halide grains are meant to be fine silver halide grains which are 
not sensitive to the light as imparted to the photographic material for 
imagewise exposure thereof and are substantially not developed in the step 
of development of the exposed material. These fine grains are desirably 
not previously fogged. 
The fine silver halide grains have a silver bromide content of from 0 to 
100 mol % and, if desired, they may additionally contain silver chloride 
and/or silver iodide. Preferably, they contain silver iodide in an amount 
of from 0.5 to 10 mol %. 
The fine silver halide grains are desired to have a mean grain size (as a 
mean value of the circle-corresponding diameter of the projected area) of 
from 0.01 to 0.5 .mu.m, more preferably from 0.02 to 0.2 .mu.m. 
The fine silver halide grains may be prepared by the same method as that 
used for preparing ordinary light-sensitive silver halide grains. In such 
a case, the surfaces of the fine silver halide grains to be prepared do 
not need to be optically sensitized and color sensitization of the grains 
is also unnecessary. However, prior to addition of the fine grains to the 
coating composition, it is desirable to previously add a known stabilizer, 
such as triazole compounds, azaindene compounds, benzothiazolium 
compounds, or mercapto compounds or zinc compounds, to the coating 
composition. The fine silver halide grains-containing layer may preferably 
contain colloidal silver. 
The amount of silver as coated in the photographic material of the present 
invention is preferably 6.0 g/m.sup.2 or less, most preferably 4.5 
g/m.sup.2 or less. 
Various known photographic additives which may be used in preparing the 
photographic materials of the present invention are mentioned in the 
above-mentioned three Research Disclosures RD 17643, RD 18716 and RD 
307105. The related descriptions therein are shown in the following table. 
__________________________________________________________________________ 
Kinds of Additives 
RD 17643 
RD 18716 RD 307105 
__________________________________________________________________________ 
1 Chemical Sensitizer 
page 23 
page 648, right column 
page 866 
2 Sensitivity Enhancer page 648, right column 
3 Color Sensitizing Agent and 
pages 23 to 24 
page 648, right column, 
pages 866 to 868 
Super Color Sensitizing 
to page 649, right 
Agent column 
4 Brightening Agent 
page 24 page 868 
5 Anti-foggant and Stabilizer 
pages 24 to 25 
page 649, right column 
pages 868 to 870 
6 Light Absorbent, Filter Dye 
pages 25 to 26 
page 649, right column 
page 873 
and Ultraviolet Absorbent 
to page 650, left column 
7 Stain Inhibitor 
page 25, right 
page 650, left column to 
page 872 
column right column 
8 Color Image Stabilizer 
page 25 
page 650, left column 
page 872 
9 Hardening Agent 
page 26 
page 651, left column 
pages 874 to 875 
10 
Binder page 26 
page 651, left column 
page 873 to 874 
11 
Plasticizer and Lubricant 
page 27 
page 650, right column 
page 876 
12 
Coating Aid and Surfactant 
pages 26 to 27 
page 650, right column 
pages 875 to 876 
13 
Antistatic Agent 
page 27 
page 650, right column 
pages 876 to 877 
14 
Mat Agent pages 878 to 879 
__________________________________________________________________________ 
In order to prevent deterioration of the photographic property of the 
photographic material of the invention by formaldehyde gas as imparted 
thereto, compounds capable of reacting with formaldehyde so as to solidify 
it, for example, those described in U.S. Pat. Nos. 4,411,987 and 
4,435,503, are preferably incorporated into the materials of the present 
invention. 
It is preferred to incorporate mercapto compounds described in U.S. Pat. 
Nos. 4,740,454 and 4,788,132 and JP-A-62-18539 and JP-A-1-283551 into the 
photographic materials of the present invention. 
It is also preferred to incorporate, into the photographic materials of the 
present invention, compounds capable of releasing a foggant, a development 
accelerator, a silver halide solvent or a precursor thereof, irrespective 
of the amount of the developed silver as formed by development, which are 
described in JP-A-1-106052. 
It is also preferred to incorporate, into the photographic materials of the 
present invention, dyes as dispersed by the method described in 
International Patent Laid-Open No. WO88/04794 and Japanese Patent Kohyo 
Koho Hei-1-5029, or dyes as described in European Patent 317,308A, U.S. 
Pat. No. 4,420,555 and JP-A-1-259358. 
Various color couplers can be incorporated into the photographic material 
of the present invention, and examples of usable color couplers are 
described in patent publications as referred to in the above-mentioned RD 
No. 17643, VII-C to G, and RD No. 307105, VII-C to G. 
As yellow couplers, for example, those described in U.S. Pat. Nos. 
3,933,501, 4,022,620, 4,326,024, 4,401,752, 4,248,961, JP-B-58-10739, 
British Patents 1,425,020, 1,476,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 
4,511,649, and European Patent 249,473A are preferred. 
As magenta couplers, 5-pyrazolone compounds and pyrazoloazole compounds are 
preferred. For instance, those described in U.S. Pat. Nos. 4,310,619, 
4,351,897, European Patent 73,636, U.S. Pat. Nos. 3,061,432, 3,725,045, RD 
No. 24220 (June, 1984), JP-A-60-33552, RD No. 24230 (June, 1984), 
JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, 
JP-A-60-185951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and 
WO(PCT)88/04795 are preferably used in the present invention, in addition 
to the preceding couplers of formula (I) of the present invention. 
As cyan couplers, phenol couplers and naphthol couplers are preferred. For 
instance, those described in U.S. Pat. Nos. 4,052,212, 4,146,396, 
4,228,122, 4,296,200, 2,369,929, 2,801,171, 2,771,162, 2,895,816, 
3,772,002, 3,758,308, 4,334,011, 4,327,173, German Patent (OLS) No. 
3,329,729, European Patents 121,365A, 249,453A, U.S. Pat. Nos. 3,446,622, 
4,333,999, 4,753,871, 4,451,559, 4,427,767, 4,690,889, 4,254,212, 
4,296,199, and JP-A-61-42658 are preferred. In addition, pyrazoloazole 
couplers described in JP-A-64-553, JP-A-64-554, JP-A-64-555 and 
JP-A-64-556 and imidazole couplers as described in U.S. Pat. No. 4,818,672 
are also usable. 
Polymerized dye-forming couplers may also be used, and typical examples of 
such couplers are described in U.S. Pat. Nos. 3,451,820, 4,080,211, 
4,367,282, 4,409,320, 4,576,910, British Patent 2,102,137 and European 
Patent 341,188A. 
Couplers capable of forming-a colored dyes having a pertinent diffusibility 
may also be used, and those described in U.S. Pat. No. 4,366,237, British 
Patent 2,125,570, European Patent 96,570, and German Patent OLS No. 
3,234,533 are preferred. 
As colored couplers for correcting the unnecessary absorption of colored 
dyes, those described in RD No. 17643, VII-G, RD No. 307105, VII-G, U.S. 
Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. Nos. 4,004,929, 4,138,258, 
and British Patent 1,146,368 are preferred. Additionally, couplers capable 
of correcting the unnecessary absorption of the colored dyed by a phosphor 
dye released during coupling, as described in U.S. Pat. No. 4,774,181, as 
well as couplers having a dye precursor group capable of reacting with a 
developing agent to form a dye, as a split-off group, as described in U.S. 
Pat. No. 4,777,120 are also preferably used. 
Couplers capable of releasing a photographically useful residue along with 
coupling may also be used in the present invention. For instance, as DIR 
couplers capable of releasing a development inhibitor, those described in 
the patent publications as referred to in the above-mentioned RD No. 
17643, Item VII-F, RD No. 307105, Item VII-F, as well as those described 
in JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346 and 
JP-A-63-37350 and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred. 
Couplers capable of releasing a bleaching accelerator, as described in RD 
Nos. 11449 and 24241 and JP-A-61-201247, are effective for shortening the 
time for the processing step with a processing solution having a bleaching 
capacity, and the effect is especially noticeable when they are added to a 
photographic material of the present invention containing the 
above-mentioned tabular silver halide grains. 
As couplers capable of imagewise releasing a nucleating agent or 
development accelerator during development, those described in British 
Patents 2,097,140 and 2,131,188, and JP-A-59-157638 and JP-A-59-170840 are 
preferred. In addition, compounds capable of releasing a foggant, a 
development accelerator or a silver halide solvent by redox reaction with 
an oxidation product of a developing agent, as described in 
JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-45687, are also 
preferably used. 
Additionally, as examples of compounds which may be incorporated into the 
photographic materials of the present invention, there are further 
mentioned competing couplers described in U.S. Pat. No. 4,130,427; 
poly-valent couplers described in U.S. Pat. Nos. 4,238,472, 4,338,393 and 
4,310,618; DIR redox compound-releasing couplers, DIR coupler-releasing 
couplers, DIR coupler-releasing redox compounds and DIR redox-releasing 
redox compounds described in JP-A-60-185950 and JP-A-62-24252; couplers 
capable of releasing a dye which recolors after released from the coupler, 
as described in European Patents 173,302A and 313,308A; ligand-releasing 
couplers described in U.S. Pat. No. 4,553,477; leuco dye-releasing 
couplers described in JP-A-63-75747; and couplers capable of releasing a 
phosphor dye as described in U.S. Pat. No. 4,774,181. 
The above-mentioned couplers can be incorporated into the photographic 
materials of the present invention by various known dispersion methods. 
For instance, an oil-in-water dispersion method may be employed for the 
purpose. Examples of high boiling point solvents usable in the method are 
described in U.S. Pat. No. 2,322,027. As examples of high boiling point 
organic solvents having a boiling point of 175.degree. C. or higher at 
normal pressure, which are used in an oil-in-water dispersion, there are 
mentioned phthalates (e.g., dibutyl phthalate, dicyclohexyl phthalate, 
di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) 
phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl) 
phthalate), phosphates or phosphonates (e.g., triphenyl phosphate, 
tricresyl phosphate, 2-ethylhexyl diphenylphosphate, tricyclohexyl 
phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, 
tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl 
phosphonate), benzoates (e.g., 2-ethylhexyl benzoate, dodecyl benzoate, 
2-ethylhexyl p-hydroxybenzoate), amides (e.g., N,N-diethyldodecanamide, 
N,N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols 
(e.g., isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylates 
(e.g., bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributylate, 
isostearyl lactate, trioctyl citrate), aniline derivatives (e.g., 
N,N-dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (e.g., paraffin, 
dodecylbenzene, diisopropylnaphthalene). As an auxiliary solvent, organic 
solvents having a boiling point of approximately from 30.degree. to 
160.degree. C., preferably from 50.degree. to 160.degree. C. can be used. 
As examples of such auxiliary organic solvents, there are mentioned ethyl 
acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, 
cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide. 
A latex dispersion method may also be employed for incorporating couplers 
into the photographic material of the present invention. The steps of 
carrying out the dispersion method, the effect of the method and examples 
of latexes usable in the method for impregnation are described in U.S. 
Pat. No. 4,199,363, German Patent (OLS) Nos. 2,541,274 and 2,541,230. 
The color photographic material of the present invention preferably 
contains an antiseptic or fungicide of various kinds, for example, 
selected from phenethyl alcohol and those described in JP-A-63-257747, 
JP-A-62-272248 and JP-A-1-80941, such as 1,2-benzisothiazolin-3-one, 
n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 
2-phenoxyethanol or 2-(4-thiazolyl)benzimidazole. 
The present invention may apply to various color photographic materials. 
For instance, there are mentioned, as typical examples, color negative 
films for general use or for movie use, color reversal films for slide use 
or for television use, as well as color papers, color positive films and 
color reversal papers. 
Suitable supports which are usable in the present invention are described 
in, for example, the above-mentioned RD No. 17643, page 28, RD No. 18716, 
from page 647, right column to page 648, left column, and RD No. 307105, 
page 897. 
It is desired that the total film thickness of all the hydrophilic colloid 
layers as provided on the surface of the support having emulsion layers is 
28 microns or less, preferably 23 microns or less, more preferably 18 
microns or less, especially preferably 16 microns or less, in the 
photographic material of the present invention. It is also desired that 
the photographic materials of the invention possess a film swelling rate 
(T.sub.1/2) of 30 seconds or less, preferably 20 seconds or less. The film 
thickness as referred to herein is one as measured under the controlled 
condition of a temperature of 25.degree. C. and a relative humidity of 55% 
(for 2 days); and the film swelling rate as referred to herein may be 
measured by any means known in this technical field. For instance, it may 
be measured by the use of a swellometer of the model as described in A. 
Green et al., Photographic Science Engineering, Vol. 19, No. 2, pages 124 
to 129. The film swelling rate (T.sub.1/2) is defined as follows: 90% of 
the maximum swollen thickness of the photographic material as processed in 
a color developer under the condition of 30.degree. C. and 3 minutes and 
15 seconds is called a saturated swollen thickness. The time necessary for 
attaining a half of the saturated swollen thickness is defined to be a 
film swelling rate (T.sub.1/2). 
The film swelling rate (T.sub.1/2) can be adjusted by adding a hardening 
agent to gelatin of a binder or by varying the condition of storing the 
coated photographic material. Additionally, the photographic material of 
the present invention is desired to have a swelling degree of from 150 to 
400%. The swelling degree as referred to herein is calculated from the 
maximum swollen film thickness as obtained under the above-mentioned 
condition, on the basis of a formula of: 
EQU (maximum swollen film thickness--original film thickness)/(original film 
thickness). 
It is preferred that the photographic material of the present invention 
possess a hydrophilic colloid layer having a total dry thickness of from 2 
.mu.m to 20 .mu.m on the side opposite to the side of having the emulsion 
layers. The layer is referred to as a backing layer. It is preferred that 
the backing layer contains various additives of the above-mentioned light 
absorbent, filter dye, ultraviolet absorbent, antistatic agent, hardening 
agent, binder, plasticizer, swelling agent, coating aid and surfactant. 
The backing layer is desired to have a swelling degree of from 150 to 
500%. 
The color photographic material of the present invention can be developed 
by any ordinary method, for example, in accordance with the process 
described in the above-mentioned RD No. 17643, pages 28 and 29, RD No. 
18716, page 615, from left column to right column, and RD No. 307105, 
pages 880 to 881. 
The color developer to be used for development of the photographic material 
of the present invention is preferably an aqueous alkaline solution 
consisting essentially of an aromatic primary amine color-developing 
agent. As the color-developing agent, p-phenylenediamine compounds are 
preferably used, though aminophenol compounds are also useful. Specific 
examples of p-phenylenediamine compounds usable as the color-developing 
agent include 3-methyl-4-amino-N,N-diethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-methanesulfonamidoethylaniline, 
3-methyl-4-amino-N-ethyl-.beta.-methoxyethylaniline, 
4-amino-3-methyl-N-methyl-N-(3-hydroxypropyl)aniline, 
4-amino-3-methyl-N-ethyl-N-(3-hydroxypropyl)aniline, 
4-amino-3-methyl-N-ethyl-N-(2-hydroxypropyl)aniline, 
4-amino-3-ethyl-N-ethyl-N-(3-hydroxypropyl)aniline, 
4-amino-3-methyl-N-propyl-N-(3-hydroxypropyl)aniline, 
4-amino-3-propyl-N-methyl-N-(3-hydroxypropyl)aniline, 
4-amino-3-methyl-N-methyl-N-(4-hydroxybutyl)aniline, 
4-amino-3-methyl-N-methyl-N-(4-hydroxybutyl)aniline, 
4-amino-3-methyl-N-propyl-N-(4-hydroxybutyl)aniline, 
4-amino-3-ethyl-N-ethyl-N-(3-hydroxy-2-methylpropyl)aniline, 
4-amino-3-methyl-N,N-bis(4-hydroxybutyl)aniline, 
4-amino-3-methyl-N,N-bis(5-hydroxypentyl)aniline, 
4-amino-3-methyl-N-(5-hydroxypentyl)-N-(4-hydroxybutyl)aniline, 
4-amino-3-methoxy-N-ethyl-N-(4-hydroxybutyl)aniline, 
4-amino-3-ethoxy-N,N-bis(5-hydroxypentyl)aniline, 
4-amino-3-propyl-N-(4-hydroxybutyl)aniline, as well as sulfates, 
hydrochlorides and p-toluenesulfonates of the compounds. Above all, 
especially preferred are 
3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethylaniline, 
4-amino-3-methyl-N-ethyl-N-(3-hydroxypropyl)aniline, 
4-amino-3-methyl-N-ethyl-N-(4-hydroxybutyl)aniline, and their 
hydrochlorides, p-toluenesulfonates and sulfates, These compounds can be 
used in combination of two or more of them, in accordance with the object. 
The color developer generally contains a pH buffer such as alkali metal 
carbonates, borates or phosphates, and a development inhibitor or 
anti-foggant such as chlorides, bromides, iodides, benzimidazoles, 
benzothiazoles or mercapto compounds. If desired, it may also contain 
various preservatives such as hydroxylamine, diethylhydroxylamine, 
sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, 
phenylsemicarbazides, triethanolamine, catechol-sulfonic acids; an organic 
solvent such as ethylene glycol, and diethylene glycol; a development 
accelerator such as benzyl alcohol, polyethylene glycol, quaternary 
ammonium salts, and amines; a dye-forming coupler; a competing coupler; an 
auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a tackifier; 
as well as various chelating agents such as aminopolycarboxylic acids, 
aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic 
acids. As specific examples of chelating agents which may be incorporated 
into the color developer, there are mentioned ethylenediamine-tetraacetic 
acid, nitrilo-triacetic acid, diethylenetriamine-pentaacetic acid, 
cyclohexanediaminetetraacetic acid, hydroxylethylimino-diacetic acid, 
1-hydroxyethylidene-1,1-diphosphonic acid, 
nitrilo-N,N,N-trimethylenephosphonic acid, 
ethylenediamine-N,N,N,N-tetramethylene-phosphonic acid, 
ethylenediamine-di(o-hydroxyphenylacetic acid) and their salts. 
Where the photographic material is processed for reversal finish, in 
general, it is first subjected to black-and-white development and then 
subjected to color development. For the first black-and-white development 
is used a black-and-white developer, which contains a conventional 
black-and-white developing agent, for example, dihydroxybenzenes such as 
hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or 
aminophenols such as N-methyl-p-aminophenol, singularly or in combination. 
The color developer and the black-and-white developer generally has a pH 
value of from 9 to 12. The amount of the replenisher to the developer is, 
though depending upon the the color photographic material to be processed, 
generally 3 liters or less per m.sup.2 of the material to be processed. It 
may be reduced to 500 ml or less per m.sup.2 of the material to be 
processed, by lowering the bromide ion concentration in the replenisher. 
Where the amount of the replenisher is reduced, it is preferred to reduce 
the contact area of the surface of the processing solution in the 
processing tank with air so as to prevent vaporization and aerial 
oxidation of the solution. 
The contact surface area of the processing solution with air in the 
processing tank is represented by the opening ratio which is defined by 
the following formula: 
______________________________________ 
Opening Ratio = 
(Contact Surface Area (cm.sup.2) of Processing 
Solution with Air)/(Volume (cm.sup.3) of Processing 
Tank) 
______________________________________ 
The above-mentioned opening ratio is preferably 0.1 or less, more 
preferably from 0.001 to 0.05. Various means can be employed for the 
purpose of reducing the opening ratio, which include, for example, 
provision of a masking substance such as a floating lid on the surface of 
the processing solution in the processing tank, employment of the mobile 
lid described in JP-A 1-82033 and employment of the slit-developing method 
described in JP-A 63-216050. Reduction of the opening ratio is preferably 
applied to not only the both steps of color development and 
black-and-white development but also all the subsequent steps such as 
bleaching, bleach-fixation, fixation, rinsing and stabilization steps. In 
addition, the amount of the replenisher to be added may also be reduced by 
means of suppressing accumulation of bromide ions in the developer. 
The time for color development is generally within the range of from 2 
minutes to 5 minutes, but the processing time may be shortened by 
elevating the processing temperature, elevating the pH value of the 
processing solution and elevating the concentration of the processing 
solution. 
After color development, the photographic emulsion layer is generally 
bleached. Bleaching may be effected simultaneously with fixation 
(bleach-fixation) or separately therefrom. In order to accelerate the 
processing speed, a system of bleaching followed by bleach-fixation may 
also be employed. If desired, a system of using a continuous bleach-fixing 
bath having two tanks, a system of fixation followed by bleach-fixation, 
or a system of bleach-fixation followed by bleaching may also be employed. 
As the bleaching agent there can be used, for example, compounds of 
polyvalent metals such as iron(III), as well as peracids, quinones and 
nitro compounds. Specific examples of the bleaching agent usable in the 
present invention include organic complexes of iron(III), such as 
complexes thereof with amino-polycarboxylic acids such as 
ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 
cyclohexanediamine-tetraacetic acid, methyliminodiacetic acid, 
1,3-diaminopropane-tetraacetic acid or glycol ether-diamine-tetraacetic 
acid or with organic acids such as citric acid, tartaric acid or malic 
acid. Among them, aminopolycarboxylato/iron(III) complexes such as 
ethylenediaminetetraacetato/iron(III) complex and 
1,3-diaminopropane-tetraacetato/iron(III) complex are preferred in view of 
the rapid processability thereof and of prevention of environmental 
pollution. The aminopolycarboxylato/iron(III) complexes are especially 
useful both in a bleaching solution and in a bleach-fixing solution. The 
bleaching solution or bleach-fixing solution containing such 
aminopolycarboxylato/iron(III) complexes generally has a pH value of from 
4.0 to 8.0, but the solution may have a lower pH value for rapid 
processing. 
The bleaching solution, the bleach-fixing solution and the previous bath 
may contain a bleaching accelerating agent, if desired. Various bleaching 
accelerating agents are known, and examples of the agents which are 
advantageously used in the present invention include mercapto group- or 
disulfide group-containing compounds described in U.S. Pat. No. 3,893,858, 
German Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, 
JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, 
JP-A-53-104232, JP-A-53-124424, JP-A-53-141623 and JP-A-53-28426, RD No. 
17129 (July, 1978); thiazolidine derivatives as described in 
JP-A-50-140129; thiourea derivatives as described in JP-B-45-8506, 
JP-A-52-20832 and JP-A-53-32735 and U.S. Pat. No. 3,706,561; iodide salts 
as described in German Patent 1,127,715 and JP-A-58-16235; polyoxyethylene 
compounds as described in German Patents 966,410 and 2,748,4.30; polyamine 
compounds as described in JP-B-45-8836; other compounds as described in 
JP-A-49-40943, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506 
and JP-A-58-163940; and bromide ions. Above all, mercapto group- or 
disulfide group-containing compounds, in particular, those as described in 
U.S. Pat. No. 3,893,858, German Patent 1,290,812 and JP-A-53-95630 are 
preferred, as having a large accelerating effect. In addition, compounds 
described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching 
accelerators may be incorporated into the photographic material of the 
invention. Where the material of the invention is a picture-taking color 
photographic material and it is bleach-fixed, these bleaching accelerators 
are especially effective. 
The bleaching solution and bleach-fixing solution may further contain, in 
addition to the above-mentioned components, various organic acids for the 
purpose of preventing bleaching stains. Especially preferred organic acids 
for the purpose are those having an acid dissociating constant (pKa) of 
from 2 to 5. For instance, acetic acid, propionic acid and hydroxyacetic 
acid are preferably used. 
As the fixing agent in the fixing solution or bleach-fixing solution 
applied to the photographic materials of the invention, those usable are 
thiosulfates, thiocyanates, thioether compounds, thioureas, and a large 
amount of iodide salts. Generally, thiosulfates are used for the purpose. 
Above all, ammonium thiosulfate is most widely used. Additionally, the 
combination of thiosulfates and thiocyanates, thioether compounds or 
thioureas is also preferred. As the preservative to be used in the fixing 
solution or bleach-fixing solution, preferred are sulfites, bisulfites and 
carbonyl-bisulfite adducts, as well as sulfinic acid compounds as 
described in European Patent 294769A. Further, the fixing solution or 
bleach-fixing solution may preferably contain various aminopolycarboxylic 
acids or organic phosphonic acids for the purpose of stabilizing the 
solution. 
It is preferred that the fixing solution or bleach-fixing solution used for 
processing the photographic materials of the present invention contain 
compounds having a pKa value of from 6.0 to 9.0, for the purpose of 
adjusting the pH value of the solution. As such compounds, preferably 
added are imidazoles such as imidazole, 1-methylimidazole, 
1-ethylimidaozle or 2-methylimidazole, in an amount of from 0.1 to 10 
mol/liter. 
The total time for the desilvering process is preferably shorter within the 
range of not causing desilvering insufficiency. For instance, the time is 
preferably from 1 minute to 3 minutes, more preferably from 1 minute to 2 
minutes. The processing temperature may be from 25.degree. C. to 
50.degree. C., preferably from 35.degree. C. to 45.degree. C. In such a 
preferred temperature range, the desilvering speed is accelerated and 
generation of stains in the processed material may effectively be 
prevented. 
In the desilvering process, it is desired that stirring of the processing 
solution during the process be promoted as much as possible. As examples 
of reinforced stirring means for forcedly stirring the photographic 
material during the desilvering step, there are mentioned: a method of 
running a jet stream of the processing solution to the emulsion-coated 
surface of the material, as described in JP-A-62-183460; a method of 
promoting the stirring effect by the use of a rotating means, as described 
in JP-A-62-183461; a method of moving the photographic material being 
processed in the processing bath while the emulsion-coated surface of the 
material is brought into contact with a wiper blade as provided in the 
processing bath, whereby the processing solution as applied to the 
emulsion-coated surface of the material is made turbulent and the stirring 
effect is promoted; and a method of increasing the total circulating 
amount of the processing solution. Such reinforced stirring means are 
effective as to the bleaching solution, bleach-fixing solution and fixing 
solution described above. It is considered that a reinforcement of 
stirring for the processing solution would promote penetration of the 
bleaching agent and fixing agent into the emulsion layer of the 
photographic material being processed and, as a result, the desilvering 
rate in processing the material would be elevated. The above-mentioned 
reinforced stirring means is more effectives when a bleaching accelerator 
is incorporated into the processing solution. Using such means, therefore, 
the bleaching accelerating effect could remarkably be augmented, and the 
fixation preventing effect caused by the bleaching accelerator could be 
evaded. 
The photographic material of the present invention can be processed with an 
automatic developing machine. It is desirable that the automatic 
developing machine used for processing the material of the present 
invention be equipped with a photographic material-conveying means as 
described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259. As is 
noted from the related disclosure of JP-A-60-191257, the conveying means 
may noticeably reduce the carry-over amount from the previous bath to the 
subsequent bath and therefore it is extremely effective for preventing 
deterioration of the processing solution being used. Because of these 
reasons, the conveying means is especially effective for shortening the 
processing time in each processing step-and for reducing the amount of the 
replenisher added to each processing bath. 
The silver halide color photographic material of the present invention is 
generally rinsed in water and/or stabilized, after being desilvered. The 
amount of the water to be used in the rinsing step can be set in a broad 
range, in accordance with the characteristic of the photographic material 
being processed (for example, depending upon the raw material components, 
such as the coupler and so on) or the use of the material, as well as the 
temperature of the rinsing water, the number of the rinsing tanks (the 
number of the rinsing stages), the replenishment system being either a 
normal current or countercurrent system, and other various kinds of 
conditions. Among these conditions, the relation between the number of the 
rinsing tanks and the amount of the rinsing water in a multi-stage 
countercurrent rinsing system can be obtained by the method described in 
Journal of the Society of Motion Picture and Television Engineers, Vol. 
64, pages 248 to 253 (May, 1955). 
According to the multi-stage countercurrent system described in the 
above-mentioned reference, the amount of the rinsing water to be used can 
be reduced noticeably, but because of the prolongation of the residence 
time of the water in the rinsing tank, bacteria would propagate in the 
tank so that the floating substances generated by the propagation of 
bacteria would adhere to the surface of the material as it was processed. 
Accordingly, the above system would often have a problem. In the practice 
of processing the photographic material of the present invention, the 
method of reducing calcium and magnesium ions, which is described in 
JP-A-62-288838, can extremely effectively be used for overcoming this 
problem. In addition, isothiazolone compounds and thiabendazoles described 
in JP-A-57-8542; chlorine-containing bactericides such as chlorinated 
sodium isocyanurates; and benzotriazoles and other bactericides described 
in H. Horiguchi, Chemistry of Bactericidal and Fungicidal Agents (1986, by 
Sankyo Publishing Co., Japan), Bactericidal and Fungicidal Techniques to 
Microorganisms, edited by Association of Sanitary Technique, Japan (1982, 
by Kogyo Gijutsu-kai, Japan), and Encyclopeadia of Bactericidal and 
Fungicidal Agents, edited by Nippon Bactericide and Fungicide Association, 
Japan (1986), can also be used. 
The pH value of the rinsing water to be used for processing the 
photographic material of the present invention is from 4 to 9, preferably 
from 5 to 8. The temperature of the rinsing water and the rinsing time can 
also be set variously in accordance with the characteristics of the 
photographic material being processed as well as the use thereof, and in 
general, the temperature is from 15.degree. to 45.degree. C. and the time 
is from 20 seconds to 10 minutes, and preferably the temperature is from 
25.degree. to 40.degree. C. and the time is from 30 seconds to 5 minutes. 
Alternatively, the photographic material of the present invention may also 
be processed directly with a stabilizing solution in place of being rinsed 
with water. For the stabilization, any known methods, for example, as 
described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345, can be 
employed. 
In addition, the material can also be stabilized, following the rinsing 
step. As one example of the case, there may be mentioned a stabilizing 
bath containing a dye stabilizer and a surfactant, which is used as a 
final bath for picture-taking color photographic materials. As examples of 
dye stabilizers usable for the purpose, there are mentioned aldehydes such 
as formalin and glutaraldehyde, N-methylol compounds, 
hexamethylenetetramine and aldehyde-sulfite adducts. The stabilizing bath 
may also contain various chelating agents and fungicides. 
The overflow from the rinsing and/or stabilizing solutions because of 
addition of replenishers thereto may be re-used in the other steps such as 
the previous desilvering step. 
Where the photographic material of the present invention is processed with 
an automatic developing machine system and wherein the processing 
solutions being used in the step are evaporated and thickened, it is 
desirable to add water to the solutions so as to correct the concentration 
of the solutions. 
The silver halide color photographic material of the present invention can 
contain a color developing agent for the purpose of simplifying and 
accelerating the processing of the material. For incorporation of a color 
developing agent into the photographic material, various precursors of the 
agent are preferably used. For example, there are mentioned indoaniline 
compounds described in U.S. Pat. No. 3,342,597, Schiff base compounds 
described in U.S. Pat. No. 3,342,599 and RD Nos. 14850 and 15159, aldole 
compounds described in RD No. 13924, metal complexes described in U.S. 
Pat. No. 3,719,492 and urethane compounds described in JP-A-53-135628, as 
the precursors. 
The silver halide color photographic material of the present invention can 
contain various kinds of 1-phenyl-3-pyrazolidones, if desired, for the 
purpose of accelerating the color developability thereof. Specific 
examples of these compounds are described in JP-A-56-64339, JP-A-57-144547 
and JP-A-58-115438. 
The processing solutions for the photographic material of the invention are 
used at 10.degree. C. to 50.degree. C. In general, a processing 
temperature of from 33.degree. C. to 38.degree. C. is standard, but the 
temperature may be made higher so as to accelerate the processing or to 
shorten the processing time. Alternatively, the temperature may be made 
lower so as to improve the quality of images formed and to improve the 
stability of the processing solution used. 
The silver halide color photographic material of the present invention is 
especially effectively applied to lens-combined film units such as those 
described in JP-B-2-32615 and Japanese Utility Model Publication No. 
3-39784, as easily expressing the effect. 
Next, the present invention will be explained in more detail by way of the 
following examples, which, however, are not intended to restrict the scope 
of the present invention. 
EXAMPLE 1 
Plural layers each having the composition mentioned below were coated on a 
subbing layer-coated cellulose triacetate support, to prepare a 
multi-layer color photographic material sample 101. 
Compositions of Photographic Layers 
Essential components of constituting the photographic layers are grouped as 
follows: 
ExC: Cyan Coupler 
UV: Ultraviolet Absorbent 
ExM: Magenta Coupler 
HBS: High Boiling Point Organic Solvent 
ExY: Yellow Coupler 
H: Gelatin Hardening Agent 
ExS: Sensitizing Dye 
The number for each component indicates the amount coated by way of a unit 
of g/m.sup.2. The amount of silver halide coated is represented as the 
amount of silver therein coated. The amount of sensitizing dye coated is 
represented by way of a molar unit to mol of silver halide in the same 
layer. 
______________________________________ 
Sample 101: 
______________________________________ 
First Layer: Anti-halation Layer 
Black Colloidal Silver 0.18 as Ag 
Gelatin 1.40 
ExM-1 0.18 
ExF-1 2.0 .times. 10.sup.-3 
Second Layer: Interlayer 
Emulsion G 0.065 as Ag 
2,5-Di-t-pentadecylhydroquinone 
0.18 
ExC-2 0.020 
UV-1 0.060 
UV-2 0.080 
UV-3 0.10 
HBS-1 0.10 
HBS-2 0.020 
Gelatin 1.04 
Third Layer: Low-sensitivity Red-sensitive Emulsion Layer 
Emulsion A 0.25 as Ag 
Emulsion B 0.25 as Ag 
ExS-1 6.9 .times. 10.sup.-5 
ExS-2 1.8 .times. 10.sup.-5 
ExS-3 3.1 .times. 10.sup.-4 
ExC-1 0.17 
ExC-4 0.17 
ExC-7 0.020 
UV-1 0.070 
UV-2 0.050 
UV-3 0.070 
HBS-1 0.060 
Gelatin 0.87 
Fourth Layer: Middle-sensitivity Red-sensitive Emulsion Layer 
Emulsion D 0.80 as Ag 
ExS-1 3.5 .times. 10.sup.-4 
EXS-2 1.6 .times. 10.sup.-5 
ExS-3 5.1 .times. 10.sup.-4 
ExC-1 0.20 
ExC-2 0.050 
ExC-4 0.20 
ExC-5 0.050 
ExC-7 0.015 
UV-1 0.070 
UV-2 0.050 
UV-3 0.070 
Gelatin 1.30 
Fifth Layer: High-sensitivity Red-sensitive Emulsion Layer 
Emulsion E 1.40 as Ag 
ExS-1 2.4 .times. 10.sup.-4 
ExS-2 1.0 .times. 10.sup.-4 
ExS-3 3.4 .times. 10.sup.-4 
ExC-1 0.097 
ExC-2 0.010 
ExC-3 0.065 
ExC-6 0.020 
HBS-1 0.22 
HBS-2 0.10 
Gelatin 1.63 
Sixth Layer: Interlayer 
Cpd-1 0.040 
HBS-1 0.020 
Gelatin 0.80 
Seventh Layer: Low-sensitivity Green-sensitive Emulsion Layer 
Emulsion C 0.30 as Ag 
ExS-4 2.6 .times. 10.sup.-5 
ExS-5 1.8 .times. 10.sup.-4 
ExS-6 6.9 .times. 10.sup.-4 
ExM-1 0.021 
ExM-2 0.26 
ExM-3 0.030 
ExY-1 0.025 
HBS-1 0.10 
HBS-3 0.010 
Gelatin 0.63 
Eighth Layer: Middle-sensitivity Green-sensitive Emulsion Layer 
Emulsion D 0.55 as Ag 
ExS-4 2.2 .times. 10.sup.-5 
ExS-5 1.5 .times. 10.sup.-4 
ExS-6 5.8 .times. 10.sup.-4 
ExM-2 0.094 
ExM-3 0.026 
ExY-1 0.018 
HBS-1 0.16 
HBS-3 8.0 .times. 10.sup.-3 
Gelatin 0.50 
Ninth Layer: High-sensitivity Green-sensitive Emulsion Layer 
Emulsion E 1.40 as Ag 
ExS-4 4.3 .times. 10.sup.-5 
ExS-5 1.0 .times. 10.sup.-4 
ExS-6 3.3 .times. 10.sup.-4 
ExC-1 0.005 
ExM-1 0.013 
Comparative Coupler (a) 0.080 
HBS-1 0.25 
HBS-2 0.10 
Gelatin 1.30 
Tenth Layer: Yellow Filter Layer 
Yellow Colloidal Silver 0.035 as Ag 
Cpd-1 0.080 
HBS-1 0.030 
Gelatin 0.95 
Eleventh Layer: Low-sensitivity Blue-sensitive Emulsion Layer 
Emulsion C 0.18 as Ag 
ExS-7 8.6 .times. 10.sup.-4 
ExY-1 0.042 
ExY-2 0.72 
HBS-1 0.28 
Gelatin 1.10 
Twelfth Layer: Middle-sensitivity Blue-sensitive Emulsion Layer 
Emulsion D 0.40 as Ag 
ExS-7 7.4 .times. 10.sup.-4 
ExC-7 7.0 .times. 10.sup.-3 
ExY-2 0.15 
HBS-1 0.050 
Gelatin 0.78 
Thirteenth Layer: High-sensitivity Blue-sensitive 
Emulsion Layer 
Emulsion F 0.70 as Ag 
ExS-7 2.8 .times. 10.sup.-4 
ExY-2 0.20 
HBS-1 0.070 
Gelatin 0.69 
Fourteenth Layer: First Protective Layer 
Emulsion G 0.20 as Ag 
UV-4 0.11 
UV-5 0.17 
HBS-1 5.0 .times. 10.sup.-2 
Gelatin 1.00 
Fifteenth Layer: Second Protective Layer 
H-1 0.40 
B-1 (diameter 1.7 .mu.m) 
5.0 .times. 10.sup.-2 
B-2 (diameter 1.7 .mu.m) 
0.10 
B-3 0.10 
S-1 0.20 
Gelatin 1.20 
______________________________________ 
In addition, the respective layers may contain any of W-1 through W-3, B-4 
through B-6, F-1 through F-17, and iron salt, lead salt, gold salt, 
platinum salt, iridium salt and rhodium salt, so as to have improved 
storability, processability, pressure resistance, fungicidal and 
bactericidal property, antistatic property and coatability. 
Structural formulae of the compounds used as well as the the emulsions used 
are shown below. 
TABLE 3 
__________________________________________________________________________ 
Coefficient 
Mean 
of Variation 
Mean AgI 
Grain 
to Grain 
Ratio of 
Ratio of Silver Contents 
Content 
Size 
Size Diameter/ 
[core/interlayer/shell] (as 
Structure and Shape of 
(%) (.mu.m) 
(%) Thickness 
AgI content %) 
Grains 
__________________________________________________________________________ 
Emulsion A 
4.0 0.45 
27 1 [1/3] (13/1) two-layer structural 
octahedral grains 
Emulsion B 
8.9 0.70 
14 1 [3/7] (25/2) two-layer structural 
octahedral grains 
Emulsion C 
2.0 0.55 
25 7 -- uniform structural tabular 
grains 
Emulsion D 
9.0 0.65 
25 6 [12/59/29] (0/11/8) 
three-layer structural 
tabular grains 
Emulsion E 
9.0 0.85 
23 5 [8/59/33] (0/11/8) 
three-layer structural 
tabular grains 
Emulsion F 
14.5 1.25 
25 3 [37/63] (34/3) 
two-layer structural 
tabular grains 
Emulsion G 
1.0 0.07 
15 1 -- uniform structural fine 
grains 
__________________________________________________________________________ 
In Table 3, Emulsions A to F are subjected to reduction sensitization using 
thiourea dioxide and thiosulfonic acid during the formation of the grains 
in accordance with the example of JP-A-2-191938. In addition, Emulsions A 
to F are subjected to gold-sensitization, sulfur sensitization and selen 
sensitization in the presence of the spectral sensitizing dye(s) recited 
in each of the light-sensitive layers above and sodium thiocyanate. In the 
formation of the tabular grains, a low molecular gelatin is used in 
accordance with the example of JP-A-1-158426. In the tabular grains and 
the normal crystal grains, dislocation lines as disclosed in JP-A-3-237450 
are observed using a high-pressure electron microscope. 
##STR8## 
Sample 102 was prepared in the same manner as in preparation of the 
preceding sample 101, except that the comparative coupler (a) in the ninth 
layer was replaced by the same molar amount of comparative coupler (b). 
Samples 103 to 107 were prepared also in the same manner as in preparation 
of the preceding sample 101, except that the comparative coupler (a) in 
the ninth layer was replaced by the magenta coupler of the present 
invention as indicated in Table 4 below. Samples 108 to 114 were prepared 
in the same manner as in preparation of the preceding samples 101 to 107, 
except that the coupler ExM-2 in the seventh layer and the eighth layer 
was replaced by the comparative coupler or the magenta coupler of the 
present invention as indicated in Table 4. 
The thus prepared samples 101 to 114 were wedgewise exposed with a white 
light for 1/100 second and then subjected to color development in 
accordance with the process mentioned below. 
______________________________________ 
Color Development Process: 
Step Time Temperature 
______________________________________ 
Color Development 
3 min 15 sec 
38.degree. C. 
Bleaching 1 min 00 sec 
38.degree. C. 
Bleach-fixation 
3 min 15 sec 
38.degree. C. 
Rinsing (1) 40 sec 35.degree. C. 
Rinsing (2) 1 min 00 sec 
35.degree. C. 
Stabilization 40 sec 38.degree. C. 
Drying 2 min 15 sec 
55.degree. C. 
______________________________________ 
Compositions of the processing solutions used above are mentioned below. 
______________________________________ 
Color Developer: 
Diethylenetriaminepentaacetic 
1.0 g 
Acid 
1-Hydroxyethylidene-1,1-diphosphonic 
3.0 g 
Acid 
Sodium Sulfite 4.0 g 
Potassium Carbonate 30.0 g 
Potassium Bromide 1.4 g 
Potassium Iodide 1.5 mg 
Hydroxylamine Sulfate 2.4 g 
4-[N-ethyl-N-.beta.-hydroxyethylaminol- 
4.5 g 
2-methylaniline Sulfate 
Water to make 1.0 liter 
pH 10.05 
Bleaching Solution: 
Ammonium Ethylenediaminetetraacetato/ 
120.0 g 
Ferric Complex Dehydrate 
Disodium Ethylenediaminetetraacetate 
10.0 g 
Ammonium Bromide 100.0 g 
Ammonium Nitrate 10.0 g 
Bleaching Accelerator 0.005 mol 
(CH.sub.3).sub.2 N--CH.sub.2 --CH.sub.2 --S--S--CH.sub.2 -- 
CH.sub.2 --N(CH.sub.3).sub.2.2HCl 
Aqueous Ammonia (27%) 15.0 ml 
Water to make 1.0 liter 
pH 6.3 
Bleach-Fixing Solution: 
Ammonium Ethylenediaminetetraacetato/ 
50.0 g 
Ferric Complex Dehydrate 
Disodium Ethylenediaminetetraacetate 
5.0 g 
Sodium Sulfite 12.0 g 
Ammonium Thiosulfate 240.0 ml 
Aqueous Solution (700 g/liter) 
Aqueous Ammonia (27%) 6.0 ml 
Water to make 1.0 liter 
pH 7.2 
______________________________________ 
Rinsing Solution: 
A city water was passed through a mixed bed type column as filled with an 
H-type strong acidic cation-exchange resin (Amberlite IR-120B, produced by 
Rhom & Haas Co.) and an OH-type basic anion-exchange resin (Amberlite 
IR-400, produced by Rhom & Haas Co.) so that both the calcium ion 
concentration and the magnesium ion concentration in the water were 
reduced to 3 mg/liter, individually. Next, 20 ml/liter of sodium 
dichloroisocyanurate and 0.15 g/liter of sodium sulfate were added to the 
resulting water, which had a pH value falling within the range of from 6.5 
to 7.5. This was used as the rinsing water. 
______________________________________ 
Stabilizing Solution: 
______________________________________ 
Sodium P-toluenesulfinate 
0.03 g 
Polyoxyethylene P-monononylphenyl 
0.2 g 
Ether (mean polymerization degree 10) 
Disodium Ethylenediaminetetraacetate 
0.05 g 
1,2,4-Triazole 1.3 g 
1,4-Bis(1,2,4-triazol-1-ylmethyl)- 
0.75 g 
piperazine 
Water to make 1.0 liter 
pH 8.5 
______________________________________ 
The density of each of the processed samples was measured through a green 
filter, and the reciprocal of the exposure amount to give a density of 
(minimum density+0.2) was obtained. The obtained value was represented as 
a relative sensitivity of each sample on the basis of the control 
sensitivity (100) of sample 101. 
Apart from the preceding processed samples, two other groups of samples 101 
to 114 were prepared and these were wedgewise exposed to a white light for 
1/100 second. One group of the samples was stored under the condition of 
50.degree. C. and 30% RH for 10 days, while the other group of them was 
stored under the condition of 5.degree. C. and 55% RH for 10 days. Then, 
these two groups of samples were processed at the same time in accordance 
with the process mentioned above. The density of each of the processed 
samples was measured through a green filter. 
The value of the exposure amount giving a density of (minimum density+0.2) 
for each of the samples of the latter group (stored at 5.degree. C. and 
55% RH) was read out, and the logarithmic number of the reciprocal of the 
value was represented by S.sup.r.sub.G. 
Also, the value of the exposure amount giving a density of (minimum 
density+0.2) for each of the samples of the former group (stored at 
50.degree. C. and 30% RH) was read out, and the logarithmic number of the 
reciprocal of the value was represented by S.sup.s.sub.G. 
The difference between them (.DELTA.S=S.sup.s.sub.G -S.sup.r.sub.G) was 
used as a criterion for evaluating the latent image stability. 
The results obtained are shown in Table 4 below. 
TABLE 4 
__________________________________________________________________________ 
Latent 
Image 
Sample 
Coupler in 
Coupler in 
Coupler in 
Relative 
Stability 
No. 7th Layer 
8th Layer 
9th Layer 
Sensitivity 
(.DELTA.S) 
Remarks 
__________________________________________________________________________ 
101 ExM-2 ExM-2 Comparative 
100 -0.04 Comparative Sample 
coupler (a) 
102 ExM-2 ExM-2 Comparative 
89 -0.06 Comparative Sample 
coupler (b) 
103 ExM-2 ExM-2 M-1 107 +0.01 Sample of the Invention 
104 ExM-2 ExM-2 M-6 105 +/-0.0 Sample of the Invention 
105 ExM-2 ExM-2 M-13 105 -0.01 Sample of the Invention 
106 ExM-2 ExM-2 M-19 107 +0.02 Sample of the Invention 
107 ExM-2 ExM-2 M-11 105 +0.01 Sample of the Invention 
108 Comparative 
Comparative 
Comparative 
85 -0.04 Comparative Sample 
coupler (c) 
coupler (c) 
coupler (c) 
109 M-9 M-9 M-1 107 +0.01 Sample of the Invention 
110 M-24 M-24 M-11 105 +0.01 Sample of the Invention 
111 Comparative 
Comparative 
Comparative 
100 -0.06 Comparative Sample 
coupler (d) 
coupler (d) 
coupler (d) 
112 Comparative 
Comparative 
Comparative 
95 -0.03 Comparative Sample 
coupler (e) 
coupler (e) 
coupler (e) 
113 Comparative 
Comparative 
Comparative 
92 -0.05 Comparative Sample 
coupler (f) 
coupler (f) 
coupler (f) 
114 Comparative 
Comparative 
Comparative 
85 -0.06 Comparative Sample 
coupler (g) 
coupler (g) 
coupler (g) 
__________________________________________________________________________ 
Comparative couplers used above are mentioned and shown below. 
##STR9## 
From the results in Table 4 above, it is understood that the samples of the 
present invention all have elevated sensitivity and elevated latent image 
storability. The reason may be that conventional couplers (such as the 
comparative couplers used above) interact with the silver halide emulsions 
which constitute the photographic materials--during processing or during 
storage of the materials after exposure--to cause a retardation in the 
developability of the materials. The couplers of formula (I) of the 
present invention are free from such unfavorable interactions and 
therefore do not cause a reduction in their color forming capacity during 
processing or in stored photographic materials. 
EXAMPLE 2 
Sample No. 214 (multi-layer color paper) of Example 2 of European Patent 
No. 355,660A2 (corresponding JP-A-2-139544 and U.S. Ser. No. 07/393,747) 
is modified in such a way that the bisphenol compound (III-23) is replaced 
by compound (III-10), that the yellow coupler (ExY), the cyan coupler 
(ExC), the image stabilizer (Cpd-8), the solvent (Solv-6) and the oxonole 
dyes are replaced by the following compounds, respectively, and that the 
antiseptics (bactericidal and fungicidal component) mentioned below are 
incorporated therein. 
##STR10## 
The modified sample is exposed in the same manner as in Example 2 of EP 
Patent No. 355,660A2 specification, and is stored under the condition of 
50.degree. C. and 30% RH for 2 days, and is processed in the same manner 
as in Example 2 of the same. 
The variation of the photographic properties of the sample before and after 
storage under the preceding condition is determined and is favorably 
little, like the samples of the present as described in the preceding 
Example 1. 
While the invention has been described in detail and with reference to 
specific embodiments thereof, it will be apparent to one skilled in the 
art that various changes and modifications can be made therein without 
departing from the spirit and scope thereof.